Chemical Arithmetic 1
Chapter
Chemistry is basically an experimental science. In
it we study physical and chemical properties of
substance and measure it upto possibility. The results
of measurement can we reported in two steps,
(a) Arithmetic number, (b) Unit of measurement.
Every experimental measurement vary slightly
from one another and involves some error or
uncertainty depending upon the skill of person making
the measurements and measuring instrument. The
closeness of the set of values obtained from identical
measurement called precision and a related term,
refers to the closeness of a single measurement to its
true value called accuracy.
Significant figures
In the measured value of a physical quantity, the
digits about the correctness of which we are surplus
the last digit which is doubtful, are called the
significant figures. Number of significant figures in a
physical quantity depends upon the least count of the
instrument used for its measurement.
(1) Common rules for counting significant
figures Following are some of the common rules for
counting significant figures in a given expression
Rule 1. All non zero digits are significant.
Example : x  1234 has four significant figures.
Again x  189 has only three significant figures.
Rule 2. All zeros occurring between two non zero
digits are significant.
Example : x  1007 has four significant figures.
Again x  1 .0809 has five significant figures.
1
Chemical Arithmetic
Rule 3. In a number less than one, all zeros to the
right of decimal point and to the left of a non zero digit
are not significant.
Example : x  0 . 0084 has only two significant
digits. Again, x  1 .0084 has five significant figures.
This is on account of rule 2.
Rule 4. All zeros on the right of the last non zero
digit in the decimal part are significant.
Example : x  0 .00800 has three significant figures
8, 0, 0. The zeros before 8 are not significant again
1.00 has three significant figures.
Rule 5. All zeros on the right of the non zero digit
are not significant.
Example : x  1000 has only one significant figure.
Again x  378000 has three significant figures.
Rule 6. All zeros on the right of the last non zero
digit become significant, when they come from a
measurement.
Example : Suppose distance between two stations
is measured to be 3050 m. It has four significant
figures. The same distance can be expressed as 3.050
km or 3 . 050  10 5 cm . In all these expressions, number
of significant figures continues to be four. Thus we
conclude that change in the units of measurement of a
quantity does not change the number of significant
figures. By changing the position of the decimal point,
the number of significant digits in the results does not
change. Larger the number of significant figures
obtained in a measurement, greater is the accuracy of
the measurement. The reverse is also true.
 2 Chemical Arithmetic
(2) Rounding off : While rounding off
measurements, we use the following rules by
convention
Rule 1. If the digit to be dropped is less than 5,
then the preceding digit is left unchanged.
Example : x  7.82 is rounded off to 7.8, again
x  3 . 94 is rounded off to 3.9.
Rule 2. If the digit to be dropped is more than 5,
then the preceding digit is raised by one.
Example : x = 6.87 is rounded off to 6.9, again x =
12.78 is rounded off to 12.8.
Rule 3. If the digit to be dropped is 5 followed by
digits other than zero, then the preceding digit is raised
by one.
Example : x = 16.351 is rounded off to 16.4, again
x  6.758 is rounded off to 6.8.
Rule 4. If digit to be dropped is 5 or 5 followed by
zeros, then preceding digit is left unchanged, if it is even.
Example : x = 3.250 becomes 3.2 on rounding off,
again x  12 .650 becomes 12.6 on rounding off.
Rule 5. If digit to be dropped is 5 or 5 followed by
zeros, then the preceding digit is raised by one, if it is
odd.
Example : x = 3.750 is rounded off to 3.8, again
x  16 .150 is rounded off to 16.2.
(3) Significant figure in calculation
(i) Addition and subtraction : In addition and
subtraction the following points should be remembered
(a) Every quantity should be changed into same
unit.
(b) If a quantity is expressed in the power of 10,
then all the quantities should be changed into power of
10.
(c) The result obtained after addition or
subtraction, the number of figure should be equal to that
of least, after decimal point.
(ii) Multiplication and division
Table 1.1 Seven basic S.I. units
Length Mass Time Temperature
metre (m) Kilogram (kg) Second (s) Kelvin (K)
Table 1.2 Derived Units
Physical quantity
Area square metre
Volume cubic metre
(a) The number of significant figures will be same
if any number is multiplied by a constant.
(b) The product or division of two significant
figures, will contain the significant figures equal to
that of least.
Units for measurement
The chosen standard of measurement of a
quantity which has essentially the same nature as that
of the quantity is called the unit of the quantity.
Following are the important types of system for unit,
(1) C.G.S. System : Length (centimetre), Mass
(gram), Time (second)
(2) M.K.S. System : Length (metre), Mass
(kilogram), Time (second)
(3) F.P.S. System : Length (foot), Mass (pound),
Time (second)
(4) S.I. System : The 11th general conference of
weights and measures (October 1960) adopted
International system of units, popularly known as the SI
units. The SI has seven basic units from which all other
units are derived called derived units. The standard
prefixes which helps to reduce the basic units are now
widely used.
Dimensional analysis : The seven basic quantities
lead to a number of derived quantities such as
pressure, volume, force, density, speed etc. The units
for such quantities can be obtained by defining the
derived quantity in terms of the base quantities using
the base units. For example, speed (velocity) is
expressed in distance/time. So the unit is m / s or ms 1 .
The unit of force (mass  accelerati on) is kg ms 2 and the
unit for acceleration is ms 2 .
Electric Luminous Amount of
Current Intensity substance
Ampere (A) Candela (Cd) Mole (mol)
Unit Symbol
m2
m3
 Chemical Arithmetic 3

Velocity metre per second ms–1

Acceleration metre per second square ms–2

Density kilogram per cubic metre kg m–3

Molar mass kilogram per mole kg mol–1

Molar volume cubic metre per mole m3 mol–1

Molar concentration mole per cubic metre mol m–3

Force newton (N) kg m s–2

Pressure pascal (Pa) N m–2

Energy work joule (J) kg m2 s–2, Nm

Table 1.3 Standard prefixes use to reduce the basic units

Multiple Prefix Symbol Submultiple Prefix Symbol
1024 yotta Y 10–1 deci d
1021 zetta Z 10–2 centi c
1018 exa E 10–3 milli m
1015 peta P 10–6 micro 
1012 tera T 10–9 nano n
109 giga G 10–12 pico p
106 mega M 10–15 femto f
103 kilo k 10–18 atto a
102 hecto h 10–21 zeto z
101 deca da 10–24 yocto y

Table 1.4 Conversion factors

1 m = 39.37 inch 1 cal = 4.184 J 1 e.s.u. = 3.3356  10–10 C 1 mole of a gas = 22.4 L at STP

1 inch = 2.54 cm 1 eV = 1.602  10–19 J 1 dyne = 10–5 N 1 mole a substance = N0

molecules

1 litre = 1000 mL 1 eV/atom =96.5 kJ 1 atm = 101325 Pa 1 g atom = N0 atoms

mol–1

1 gallon (US) = 3.79 L 1 amu = 931.5016 MeV 1 bar = 1  105 N m–2 t (oF) = 9/5 t (oC) + 32

1 lb = 453.59237 g 1 kilo watt hour = 1 litre atm = 101.3 J 1 g cm–3 = 1000 kg m–3
3600 kJ

1 newton =1 kg m s–2 1 horse power = 746 1 year = 3.1536  107 s 1Å = 10–10 m

watt

1 J = 1 Nm =1 kg m2 s–2 1 joule = 107 erg 1 debye (D) = 1  10 –18 esu 1nm = 10–9 m
cm

Laws of chemical combination Various chemical reactions take place according

to the certain laws, known as the Laws of chemical
combination.
 4 Chemical Arithmetic
(1) Law of conservation of mass : It was
proposed by Lavoisier and verified by Landolt. According
to this law, Matter is neither created nor destroyed in
the course of chemical reaction though it may change
from one form to other. The total mass of materials
after a chemical reaction is same as the total mass
before reaction.
(2) Law of constant or definite proportion : It
was proposed by Proust. According to this law, A pure
chemical compound always contains the same elements
combined together in the fixed ratio of their weights
whatever its methods of preparation may be.
(3) Law of multiple proportion : It was proposed
by Dalton and verified by Berzelius. According to this
law, When two elements A and B combine to form more
than one chemical compounds then different weights of
A, which combine with a fixed weight of B, are in
proportion of simple whole numbers.
(4) Law of equivalent proportion or law of
reciprocal proportion : It was proposed by Ritcher.
According to this law, The weights of the two or more
elements which separately react with same weight of a
third element are also the weights of these elements
which react with each other or in simple multiple of
them.
(5) Gay-Lussac’s law : It was proposed by
Gay–Lussac and is applicable only for gases.
According to this law, When gases combine, they
do so in volumes, which bear a simple ratio to each
other and also to the product formed provided all
gases are measured under similar conditions. The
Gay-Lussac’s law, was based on experimental
observation.
Important hypothesis
(1) Atomic hypothesis : Keeping in view various
law of chemical combinations, a theoretical proof for
the validity of different laws was given by John Dalton
in the form of hypothesis called Dalton's atomic
hypothesis. Postulates of Dalton's hypothesis is as
followes,
(i) Each element is composed of extremely
small particles called atoms which can take part in
chemical combination.
(ii) All atoms of a given element are identical i.e.,
atoms of a particular element are all alike but differ
from atoms of other element.
(iii) Atoms of different elements possess different
properties (including different masses).
(iv) Atoms are indestructible i.e., atoms are
neither created nor destroyed in chemical reactions.
(v) Atoms of elements take part to form molecules
i.e., compounds are formed when atoms of more than
one element combine.
(vi) In a given compound, the relative number and
kinds of atoms are constant.
(2) Modern atomic hypothesis : The main
modifications made in Dalton’s hypothesis as a result of
new discoveries about atoms are,
(i) Atom is no longer considered to be indivisible.
(ii) Atoms of the same element may have different
atomic weights. e.g., isotopes of oxygen
O 16 , O 17 , and O 18 .
(iii) Atoms of different element may have same
atomic weights. e.g., isobars Ca 40 and Ar 40 .
(iv) Atom is no longer indestructible. In many
nuclear reactions, a certain mass of the nucleus is
converted into energy in the form of ,  and  rays.
(v) Atoms may not always combine in simple
whole number ratios. e.g., in sucrose (C12 H 22O11 ) , the
elements carbon, hydrogen and oxygen are present in
the ratio of 12 : 22 : 11 and the ratio is not a simple
whole number ratio.
(3) Berzelius hypothesis : “Equal volumes of all
gases contain equal number of atoms under same
conditions of temperature and pressure”. When
applied to law of combining volumes, this hypothesis
predicts that atoms are divisible and hence it is
contrary to Dalton's hypothesis.
(4) Avogadro’s hypothesis : “Equal volumes of
all gases under similar conditions of temperature and
pressure contain equal number of molecules.” Avogadro
hypothesis has been found to explain as follows,
(i) Provides a method to determine the atomic
weight of gaseous elements.
(ii) Provides a relationship between vapour density
(V.D.) and molecular masses of substances.
Molecular mass  2  vapour density
(iii) It helps in the determination of mass of fixed
volume of a particular gas.
Mass of 1 ml gas = V.D.  0.0000897 gm.
(iv) It also helps in the determination of molar
volume at N.T.P.
 V.D.  0.0000897 gm. gas has volume = 1 ml
 2 V.D.(i.e., molecular mass) gm. has
1  2  V .D.
volume  ml  22400 ml
V .D.  0.0000897
 Molar mass of a gas or its 1 mole occupies 22.4
L volume at S.T.P.
 Chemical Arithmetic 5
(v) It helps in determination of molecular Atomic mass = Equivalent mass  Valency
formulae of gases and is very useful in gas analysis. By Approximat e atomic mass
knowing the molecular volumes of reactants and Valency 
Equivalent mass
products of reaction, molecular composition can be
determined easily. (ii) Vapour density method : It is suitable for
elements whose chlorides are volatile.
Atomic, Molecular and Equivalent masses
Molecular mass of chloride
(1) Atomic mass : It is the average relative mass Valency of the element =
Equivalent mass of chloride
of atom of element as compared with an atom of
carbon –12 isotope taken as 12. 2  Vapour density of chloride
=
Equivalent mass of metal  35.5
Average mass of an atom
Atomic mass 
1/12  Mass of an atom of C 12 Atomic mass = Equivalent mass of metal
 Valency
Average atomic mass : If an elements exists in
two isotopes having atomic masses ‘a’ and ‘b’ in the ratio (iii) Specific heat method : It is suitable only for
(m  a)  (n  b) gases. The two types of specific heats of gases are CP
m : n, then average atomic mass = . Since (at constant pressure) and C v (at constant volume).
m n
the atomic mass is a ratio, it has no units and is expressed Their ratio is known as  whose value is constant (1.66
in amu, 1 amu = 1.66  10 24
g . One atomic mass unit for monoatomic, 1.40 for diatomic and 1.33 for triatomic
gases).
1
(amu) is equal to th of the mass of an atom of carbon-
12 Molecular mass
Atomic mass of a gaseous element 
12 isotope. Atomicity
Gram atomic mass (GAM) : Atomic mass of an (iv) Isomorphism method : It is based on law of
element expressed in grams is called Gram atomic mass isomorphism which states that compounds having
or gram atom or mole atom. identical crystal structure have similar constitution and
Mass of an element chemical formulae.
(i) Number of gram atoms =
GAM Example : K 2 SO 4 , K 2 CrO4 and K 2 SeO 4
(ii) Mass of an element in gm. = No. of gm. atom (valency of S, Cr, Se = 6),
 GAM
ZnSO 4 . 7 H 2 O, MgSO4 .7 H 2 O, FeSO4 . 7 H 2 O
(iii) Number of atoms in 1 GAM = 6.02  10 23
(valency of Zn, Mg, Fe = 2).
 Number of atoms in a given substance
(2) Molecular mass : Molecular mass of a
Mass
= No. of GAM  6.02  10 23
=  6.02 molecule, of an element or a compound may be defined
GAM as a number which indicates how many times heavier is
 10 23 a molecule of that element or compound as compared
(iv) Number of atoms in 1gm of element 1
with of the mass of an atom of carbon–12. Molecular
12
6.02  10 23
= mass is a ratio and hence has no units. It is expressed
Atomic mass
in a.m.u.
(v) Mass of one atom of the element (in gm.)
Mass of one molecule of the substance
GAM Molecular mass 
 1 / 12  Mass of one atom of C - 12
6.02  10 23
Actual mass of one molecule = Mol. mass
Methods of determination of atomic mass
1 .66 10 24 gm .
(i) Dulong and Pettit's method :
According to Dulong and Pettit's law Molecular mass of a substances is the additive
property and can be calculated by adding the atomic
Atomic mass  Specific heat = 6.4 (approx.)
masses present in one molecule.
6 .4
Atomic mass (approx.) = Gram molecular mass (GMM) and Gram molar
Specific heat (in cals.)
volume : Molecular mass of an element or compound
This law is applicable to solid elements only except when expressed in gm. is called its gram molecular
Be, B, C and Si because their specific heat is variable mass, gram molecule or mole molecule.
with temperature.
 6 Chemical Arithmetic
Mass of substances  Mi Xi
Number of gm molecules = M (Average molecular mass) =
GMM  X total
Mass of substances in gm = No. of gm. molecules Where A1 , A2 , A3 ..... are atomic mass of species 1,
 GMM 2, 3,…. etc. with % ratio as X1 , X 2 , X 3 ..... etc. Similar
Volume occupied by one mole of any gas at STP is terms are for molecular masses.
called Gram molar volume. The value of gram molar
(3) Equivalent mass : The number of parts by
volume is 22.4 litres. Volume of 1 mole of any gas at STP
mass of a substance that combines with or displaces
= 22.4 litres
1.008 parts by mass of hydrogen or 8.0 parts of oxygen
Expression for mass and density or 35.5 parts of chlorine is called its equivalent mass
Mass of 11 .2 L of any gas at STP = V.D. of that gas (EM). On the other hand quantity of a substance in
in gm. grams numerically equal to its equivalent mass is called
its gram equivalent mass (GEM) or gram equivalent.
Mol. mass in gm.
Density of a gas at NTP = Mass of the substancein grams
22400 ml Number of GEM 
GEM of the substance
Important generalisations
Expressions for equivalent mass (EM)
Number of atoms in a substance
Atomic mass
(i) EM of an element 
= Number of GMM  6.02  1023  Atomicity Valency
Number of electrons in given substance Molecular mass
(ii) EM of an acid 
= Number of GMM  6.02  1023  Number of electrons Basicity
Methods of determination of molecular mass (Basicity of acid is the number of replaceable
Following methods are used to determine hydrogen atoms in one molecule of the acid).
molecular mass, Molecular mass
(iii) EM of a base 
(i) Diffusion method (For gases) : The ratio of Acidity
rates of diffusion of two gases is inversely proportional
(Acidity of a base is the number of replaceable–
to the square root of their molecular masses.
OH groups in one molecule of the base).
r1 M2
 (iv) EM of a salt =
Formula mass
r2 M1 Total posi tive or negative charge
(ii) Vapour density method (For gases only) : (v) EM of an oxidising agent
Mass of a fixed volume of the vapour is compared with
Formula mass
the mass of the same volume of hydrogen under same 
conditions. The ratio of these masses is called Vapour Number of electrons gained per molecule or Total change in O.N.
density or Relative density. Equivalent mass of common oxidising agent
Molecular mass  2  Vapour desity changes with the medium of the reaction.

(iii) Victor Meyer method (For volatile liquids or Methods of determination of equivalent mass
solids) (i) Hydrogen displacement method : The mass of
It is based on Dalton's law of partial pressure and metal which displaces 11200 ml of hydrogen at NTP
Avogadro's hypothesis (gram molar volume). from an acid, alkali or alcohol is the equivalent mass of
22400 ml of vapours of a substance = Molecular the metal.
mass of that substance (a) Equivalent mass of metal
(iv) Colligative property method (For non- Massof metal W
volatile solids)  1.008   1 .008 g
Massof H 2 displaced M
Discussed in colligative properties of solutions.
(b) Equivalent mass of metal
Average atomic mass and molecular mass
Mass of metal W
 Ai X i  11200 = 11200
A (Average atomic mass) = Vol. (ml) of H 2 displaced at STP V
 X total
 Chemical Arithmetic 7
This method is useful for metals which can displace W1 E
 1
hydrogen from acids or can combine with hydrogen W2 E2
(Mg, Zn, Na, Ca etc.)
(vii) Double decomposition method
(ii) Oxide formation method : The mass of the AB  CD  AD   CB
element which combines with 8 grams of oxygen is the
Mass of compound AB Eq. mass of A  Eq. mass of B
equivalent mass of the element. 
Mass of compound AD Eq. mass of A  Eq. mass of D
Mass of metal
(a) Equivalent mass of metal = 8 Massof salt taken (W1 ) Eq. mass of salt (E1 )
Mass of oxygen or 
Massof ppt. obtained (W2 ) Eq. mass of salt in ppt. (E 2 )
(b) Equivalent mass of metal (viii) Conversion method : When one compound
Mass of metal of a metal is converted to another compound of the
=  5600 same metal, then
Vol. of O 2 at S.T.P. in ml
Mass of compound I (W1 ) E  Eq. mass of radical I
(iii) Chloride formation method : The mass of an 
Mass of compound II (W2 ) E  Eq. mass of radical II
element which reacts with 35.5 gm. of chlorine is the
(E = Eq. mass of the metal)
equivalent mass of that element.
(ix) Volatile chloride method
(a) Equivalent mass of metal
Valency of metal
Mass of metal
  35 .5 2  V.D. of Chloride 2  V.D.
Mass of chlorine  
Eq. mass of metal chloride E  35.5
(b) Equivalent mass of metal 2  V.D. of Chloride
E   35 . 5
Mass of metal Valency
  11200
Vol. of Cl 2 (in ml.) at STP (x) Silver salt method (For organic acids)

(iv) Neutralisation method : (For acids and Equivalent Mass of acid

108  Massof silver salt
bases). =  107
Massof Ag metal
W
Equivalent mass of acid (or base)  Molecular mass of acid = Equivalent mass of acid
VN
 Basicity
Where , The mole concept
W = Mass of acid or base in gm., One mole of any substance contains a fixed
V = Vol. of base or acid in litre required for number (6.022  10 23 ) of any type of particles (atoms or
neutralisation molecules or ions) and has a mass equal to the atomic
or molecular weight, in grams. Thus it is correct to
N is Normality of base or acid
refer to a mole of helium, a mole of electrons, or a mole
(v) Metal displacement method : It is based on
of Na  , meaning respectively Avogadro’s number of
the fact that one gm. equivalent of a more electropositive
atoms, electrons or ions.
metal displaces one gm equivalent of a less
Weight (grams)
electropositive metal from its salt solution.  Number of moles 
Weight of one mole (g/mole)
Mass of metal added Eq. mass of metal added
 Weight
Mass of metal displaced Eq. mass of metal displaced 
Atomic or molecular weight
W1 E
 1
W2 E2 Percentage composition & Molecular formula
(vi) Electrolytic method : The quantity of (1) Percentage composition of a compound
substance that reacts at electrode when 1 faraday of
Percentage composition of the compound is the relative
electricity is passed is equal to its gram equivalent
mass of each of the constituent element in 100 parts of
mass.
it. If the molecular mass of a compound is M and B is
Gram equivalent mass = Electrochemical equivalent the mass of an element in the molecule, then
 96500
Mass of element X
The ratio of masses of two metals deposited by Percentage of element   100   100
Molecular mass M
the same quantity of electricity will be in the ratio of
their equivalent masses.
 8 Chemical Arithmetic
(2) Determination of empirical formula : The (1) Gravimetric analysis : In gravimetric
empirical formula of a molecule is determined using analysis we relate the weights of two substances or
the % of elements present in it. Following method is a weight of a substance with a volume of a gas or
adopted. volumes of two or more gases.
Elemen % Relative no. of Simplest Empirical
Problems Involving Mass-Mass Relationship
t atoms = %/at. wt. Ratio Formula
Proceed for solving such problems according to
Relative no. of atoms : Divide the percentage of
the following instructions,
each element present in compound by its at. weight.
This gives the relative no. of atoms of element in (i) Write down the balanced equation to represent
molecule. the chemical change.
Simplest ratio : Find out lowest value of relative
(ii) Write the number of moles below the formula
no. of atoms and divide each value of relative no. of
of the reactants and products. Also write the relative
atoms by this value to estimate simplest ratio of
weights of the reactants and products (calculated from
elements.
the respective molecular formula), below the respective
It the simplest ratio obtained are not complete formula.
integers, multiply them by a common factor to get
integer values of simplest ratio. (iii) Apply the unitary method to calculate the
unknown factor (s).
Empirical formula : Write all constituent atoms
with their respective no. of atoms derived in simplest Problems Involving Mass-Volume Relationship
ratio. This gives empirical formula of compound.
For solving problems involving mass-volume
Molecular formula : Molecular formula relationship, proceed according to the following
 n  empirical formula where ' n' is the whole no. instructions,
obtained by
(i) Write down the relevant balanced chemical
molecular weight of compound
n equations (s).
empirical formula weight of compound
(ii) Write the weights of various solid reactants
Chemical stoichiometry
and products.
Stoichiometry (pronounced “stoy-key om-e-tree”)
(iii) Gases are usually expressed in terms of
is the calculation of the quantities of reactants and
volumes. In case the volume of the gas is measured at
products involved in a chemical reaction. That means
room temperature and pressure (or under conditions
quantitative calculations of chemical composition and
reaction are referred to as stoichiometry. other than N.T.P.), convert it into N.T.P. by applying
gas equation.
Basically, this topic involves two types of
calculations. (iv) Volume of a gas at any temperature and
pressure can be converted into its weight and vice-
(a) Simple calculations (gravimetric analysis) and
g
versa with the help of the relation, by PV   RT
(b) More complex calculations involving M
concentration and volume of solutions (volumetric where g is weight of gas, M is mole. wt. of gas, R is
analysis).
gas constant.
There is no borderline, which can distinguish the
Calculate the unknown factor by unitary method.
set of laws applicable to gravimetric and volumetric
analysis. All the laws used in one are equally applicable Problems Based on Volume-Volume
to the other i.e., mole as well as equivalent concept. But Relationship
in actual practise, the problems on gravimetric involves
simpler reactions, thus mole concept is convenient to Such problems can be solved according to
apply while volumetric reactions being complex and chemical equation as,
unknown (unknown simple means that it is not known (i) Write down the relevant balanced chemical
to you, as it’s not possible for you to remember all
equation.
possible reactions), equivalent concept is easier to
apply as it does not require the knowledge of balanced (ii) Write down the volume of reactants and
equation. products below the formula to each reactant and
 Chemical Arithmetic 9
product with the help of the fact that 1 gm molecule of I 2  2 Na2 S 2 O3  2 NaI  Na2 S 4 O6
every gaseous substance occupies 22.4 litres at N.T.P.
n  2, n 1
(iii) In case volume of the gas is measured under
Equivalents of I 2  Equivalent of Na2 S 2 O3
particular (or room) temperature, convert it to volume
at NTP by using ideal gas equation.  Equivalents of I 2  N  V  10 3
Take the help of Avogadro’s hypothesis “Equal
N  V  10 3
volume of different gases under the similar conditions of Moles of I 2 
2
temperature and pressure contain the same number of
molecules”. Mass of free I2 in the solution

 N  V  10 3 
(2) Volumetric analysis : It is a method which   254  g .
involves quantitative determination of the amount of  2 
any substance present in a solution through volume
(iv) Iodometric titrations : This is an indirect
measurements. For the analysis a standard solution is
method of estimation of iodine. An oxidising agent is
required. (A solution which contains a known weight of
made to react with excess of solid KI . The oxidising
the solute present in known volume of the solution is
agent oxidises I  to I 2 . This iodine is then made to
known as standard solution.)
react with Na2 S 2 O3 solution.
To determine the strength of unknown solution
with the help of known (standard) solution is known as Oxidising Agent
titration. Different types of titrations are possible ( A)  KI  I 2    2 NaI  Na 2 S 4 O 6
2 Na 2 S 2 O 3

which are summerised as follows,

Let the normality of Na2 S 2 O3 solution is N and
(i) Redox titrations : To determine the strength of
the volume of thiosulphate consumed to V ml .
oxidising agents or reducing agents by titration with
the help of standard solution of reducing agents or Equivalent of A  Equivalent of I 2  Equivalents of
oxidising agents. Na2 S 2 O3
Examples:
Equivalents of I 2 liberated from KI  N  V  10 3
K 2 Cr2 O7  4 H 2 SO 4  K 2 SO 4  Cr2 (SO 4 )3  4 H 2 O  3[O]
[2 FeSO 4  H 2 SO 4  O  Fe 2 (SO 4 )3  H 2 O]  3 N  V  10 3
Moles of I 2 liberated from KI 
6 FeSO 4  K 2 Cr2 O7  7 H 2 SO 4  3 Fe(SO 4 )3  K 2 SO 4  Cr2 (SO 4 )3 7 H 2 O 2
2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO 4  3 H 2 O  5[O]
[2 FeSO 4  H 2 SO 4  O  Fe 2 (SO 4 )3  H 2 O]  5 Mass of I2 liberated from
10 FeSO 4  2 KMnO4  8 H 2 SO 4  5 Fe 2 (SO 4 )3  K 2 SO 4  2 MnSO 4  8 H 2 O  N  V  10 3 
KI    254  g .
Similarly with H 2 C2 O4  2 

2 KMnO4  3 H 2 SO 4  5 H 2 C2 O4  (v) Precipitation titrations : To determine the

anions like CN  , AsO 33  , PO 43  , X  etc, by precipitating
K2 SO 4  2MnSO 4  8 H 2 O  10 CO2 etc.
with AgNO3 provides examples of precipitation
(ii) Acid-base titrations : To determine the titrations.
strength of acid or base with the help of standard
NaCl  AgNO3  AgCl   NaNO3
solution of base or acid.
KSCN  AgNO3  AgSCN   KNO3
Example: NaOH  HCl  NaCl  H 2 O
End point and equivalence point : The point
and NaOH  CH 3 COOH  CH 3 COONa  H 2 O etc. at which titration is stopped is known as end point,
while the point at which the acid and base (or
(iii) Iodiometric titrations : This is a simple
oxidising and reducing agents) have been added in
titration involving free iodine. This involves the
equivalent quantities is known as equivalence point .
titration of iodine solution with known sodium
Since the purpose of the indicator is to stop the
thiosulphate solution whose normality is N . Let the
titration close to the point at which the reacting
volume of sodium thiosulphate is V ml .
substances were added in equivalent quantities, it
 10 Chemical Arithmetic
is important that the equivalent point and the end Mol. wt.
where x  , x = valency or change in oxi.
point be as close as possible. Eq. wt.
Normal solution : A solution containing one Number.
gram equivalent weight of the solute dissolved per (10) Normality formula, N1V1  N 2 V2
litre is called a normal solution; e.g. when 40 g of
NaOH are present in one litre of NaOH solution, Wt.of solvent
(11) % by weight   100
the solution is known as normal (N) solution of Wt.of solution
NaOH. Similarly, a solution containing a fraction of Wt. of solvent
gram equivalent weight of the solute dissolved per (12) % by volume   100
Vol. of solution
litre is known as subnormal solution. For example,
Vol. of solvent
a solution of NaOH containing 20 g (1/2 of g eq. (13) % by strength   100
wt.) of NaOH dissolved per litre is a sub-normal Vol. of solution
solution. It is written as N/2 or 0.5 N solution. (14) Specific gravity
Formula used in solving numerical problems on Wt. of solution
volumetric analysis   Wt. of 1 ml . of solution
Vol. of solution
(1) Strength of solution = Amount of substance in
Wt. of ionic solute
g litre 1 (15) Formality 
Formula Wt. of solute  Vin l
(2) Strength of solution = Amount of substance in
(16) Mol. Wt. = V.D  2 (For gases only)
g moles litre 1
(3) Strength of solution = Normality  Eq. wt. of Limiting reagent or reactant
the solute In many situations, an excess of one or more
= molarity  Mol. wt. of substance is available for chemical reaction. Some of
solute these excess substances will therefore be left over
Moles of solute when the reaction is complete; the reaction stops
(4) Molarity 
Volume in litre immediately as soon as one of the reactant is totally
consumed.
Wt. in gm
(5) Number of moles   M  V(in l)
Mol.wt. The substance that is totally consumed in a
reaction is called limiting reagent because it determines
Volume in litres
 at NTP (only for gases) or limits the amount of product. The other reactant
22 .4
present in excess are called as excess reagents.
Wt.in gm  1000
(6) Number of millimoles  Let us consider a chemical reaction which is
mol. wt.
initiated by passing a spark through a reaction vessel
 Molarity  Volume in ml . containing 10 mole of H2 and 7 mole of O2.

(7) Number of equivalents 2 H 2 (g)  O2 (g)  2 H 2 O (v)

Wt. in gm
  x  No. of moles  Normality  Volume in litre Moles before 10 7 0
Eq. wt.
reaction
(8) Number of milliequivalents (meq.)
Moles after 0 2 10
Wt. in gm  1000 reaction
  normality  Volume in ml .
Eq. wt.
The reaction stops only after consumption of 5
(9) Normality  x  No. of millimoles moles of O2 as no further amount of H2 is left to react
with unreacted O2. Thus H2 is a limiting reagent in this
Strength in gm litre1
 x  Molarity  reaction.
Eq. wt.
 Chemical Arithmetic 11

 Law of conservation of mass does not hold good

for nuclear reactions.

 Law of definite proportions do not hold good for

non-stoichiometric compounds e.g., Wusitite
Fe0.95O.

 Law of definite proportions, law of multiple

proportions and law of reciprocal proportions do
not hold good when same compounds is obtained
by using different isotopes of te same element
e.g. H2O and D2O.

 The term atom was introduced by Ostwald and

the term molecule was introduced by Avogadro.

 The concept of element was introduced by Robert

Boyle.

 The number of atoms present in a molecule of a

gaseous element is called Atomicity.

 Both atomic mass and molecular mass are just

rations and hence have no units.

 1 mol of H2O  22400 cc of H2O (because it is a

liquid). Instead,
1 mol of H2O = 18cc of H2O
(because density of H2O = 1
g/cc)

 1 M H2SO4 = 2NH2SO4.
 Minimum molecular mass of a macromolecular
substance can be calculated by analysing it for
one of the minar components. Minimum
molecular mass is obtained when it is supposed
that one molecule of the macromolecule contains
only one atom or molecule of the minor
component.

Minimum molecular mass

Atomic/mol ecular mass of minor component


Mass of minor component per gram of macromolec ule
 10 Chemical Arithmetic
13. In known elements, the maximum number is of
[CPMT 1985]
(a) Metals (b) Non-metals
(c) Metalloids (d) None of these
14. Which one of the following is not an element
(a) Diamond (b) Graphite
Significant figures, Units for measurement, (c) Silica (d) Ozone
Matter and Separation of mixture 15. A mixture of ZnCl 2 and PbCl2 can be separated by

1. One fermi is [Haryana CEET 1994; DPMT 2004] [AFMC 1989]

(a) Distillation (b) Crystallization
(a) 10 13 cm (b) 10 15 cm
(c) Sublimation (d) Adding aceitic acid
(c) 10 10 cm (d) 10 12 cm 16. A mixture of methyl alcohol and acetone can be separated by
2. A picometre is written as (a) Distillation
(a) 10 9 m (b) 10 10 m (b) Fractional distillation
(c) 10 11 m (d) 10 12 m (c) Steam distillation
3. One atmosphere is equal to (d) Distillation under reduced pressure
(a) 101.325 K pa (b) 1013.25 K pa 17. In the final answer of the expression
(29 .2  20 .2) (1.79  10 5 )
(c) 10 5 Nm (d) None of these . The number of significant figures
1.37
4. Dimensions of pressure are same as that of
is [CBSE PMT 1994]
[CBSE PMT 1995]
(a) 1 (b) 2
(a) Energy (b) Force
(c) 3 (d) 4
(c) Energy per unit volume (d) Force per unit volume
18. 81.4 g sample of ethyl alcohol contains 0.002 g of water. The
5. The prefix 10 18 is [Kerala MEE 2002] amount of pure ethyl alcohol to the proper number of
(a) Giga (b) Nano significant figures is
(c) Mega (d) Exa (a) 81.398 g (b) 71.40 g
6. Given the numbers : 161cm, 0.161cm, 0.0161 cm. The number (c) 91.4 g (d) 81 g
of significant figures for the three numbers are 19. The unit J Pa 1 is equivalent to
[CBSE PMT 1998]
(a) m 3 (b) cm 3
(a) 3, 4 and 5 respectively (b) 3, 3 and 3 respectively
(c) 3, 3 and 4 respectively (d) 3, 4 and 4 respectively (c) dm 3 (d) None of these
7. Significant figures in 0.00051 are 20. From the following masses, the one which is expressed nearest
to the milligram is
(a) 5 (b) 3
(a) 16 g (b) 16.4 g
(c) 2 (d) 4
(c) 16.428 g (d) 16.4284 g
8. Which of the following halogen can be purified by sublimation [Manipal PMT 2001]
21. The number of significant figures in 6.02  10 23 is
(a) F2 (b) Cl 2
(a) 23 (b) 3
(c) Br2 (d) I2 (c) 4 (d) 26
9. Difference in density is the basis of [Kerala MEE 2002] 22. The prefix zepto stands for [DPMT 2004]
(a) Ultrafiltration (b) Molecular sieving (a) 10 9 (b) 10 12
(c) Gravity Separation (d) Molecular attraction
(c) 10 15 (d) 10 21
10. Which of the following elements of matter would best convey
23. The significant figures in 3400 are [BHU 2004]
that there is life on earth
(a) 2 (b) 5
(a) Oxygen (b) Hydrogen
(c) 6 (d) 4
(c) Carbon (d) Iron
24. The number of significant figures in 6.0023 are
11. The compound which is added to table salt for maintaining
[Pb.CET 2001]
proper health is
(a) 5 (b) 4
(a) KCl (b) KBr
(c) 3 (d) 1
(c) NaI (d) MgBr2
25. Given P  0 . 0030 m , Q  2 .40 m , R  3000 m , Significant
12. Which of the following contains only one element figures in P, Q and R are respectively [Pb. CET 2002]
(a) Marble (b) Diamond
(a) 2, 2, 1 (b) 2, 3, 4
(c) Glass (d) Sand
(c) 4, 2, 1 (d) 4, 2, 3
 Chemical Arithmetic 11
26. The number of significant figures in 60.0001 is 9. Two elements X and Y have atomic weights of 14 and 16. They
[Pb. CET 2000] form a series of compounds A, B, C, D and E in which the same
(a) 5 (b) 6 amount of element X, Y is present in the ratio 1 : 2 : 3 : 4 : 5. If
(c) 3 (d) 2 the compound A has 28 parts by weight of X and 16 parts by
weight of Y, then the compound of C will have 28 parts weight
27. A sample was weighted using two different balances. The
of X and [NCERT 1971]
result’s were (i) 3.929 g (ii) 4.0 g. How would the weight of the
sample be reported (a) 32 parts by weight of Y (b) 48 parts by weight of Y
(a) 3.929 g (b) 3 g (c) 64 parts by weight of Y (d) 80 parts by weight of Y
(c) 3.9 g (d) 3.93 g 10. Carbon and oxygen combine to form two oxides, carbon
monoxide and carbon dioxide in which the ratio of the weights
Laws of chemical combination of carbon and oxygen is respectively 12 : 16 and 12 : 32. These
figures illustrate the
1. Which of the following pairs of substances illustrate the law of (a) Law of multiple proportions
multiple proportions [CPMT 1972, 78]
(b) Law of reciprocal proportions
(a) CO and CO2 (b) H 2 O and D2 O (c) Law of conservation of mass
(c) NaCl and NaBr (d) MgO and Mg(OH )2 (d) Law of constant proportions
11. A sample of calcium carbonate (CaCO3 ) has the following
2. 1.0 g of an oxide of A contained 0.5 g of A. 4.0 g of another
oxide of A contained 1.6 g of A. The data indicate the law of percentage composition : Ca = 40%; C = 12%; O = 48%
(a) Reciprocal proportions (b) Constant proportions If the law of constant proportions is true, then the weight of
calcium in 4 g of a sample of calcium carbonate obtained from
(c) Conservation of energy (d) Multiple proportions
another source will be
3. Among the following pairs of compounds, the one that (a) 0.016 g (b) 0.16 g
illustrates the law of multiple proportions is
(c) 1.6 g (d) 16 g
(a) NH 3 and NCl 3 (b) H 2 S and SO 2 12. n g of substance X reacts with m g of substance Y to form p g of
(c) CuO and Cu 2 O (d) CS 2 and FeSO 4 substance R and q g of substance S. This reaction can be
represented as, X  Y  R  S . The relation which can be
4. The percentage of copper and oxygen in samples of CuO established in the amounts of the reactants and the products will be
obtained by different methods were found to be the same. This
(a) n  m  p  q (b) n  m  p  q
illustrates the law of [AMU 1982, 92]
(c) n  m (d) pq
(a) Constant proportions (b) Conservation of mass
(c) Multiple proportions (d) Reciprocal proportions 13. Which of the following is the best example of law of
conservation of mass [NCERT 1975]
5. Two samples of lead oxide were separately reduced to metallic
lead by heating in a current of hydrogen. The weight of lead (a) 12 g of carbon combines with 32 g of oxygen to form 44 g
from one oxide was half the weight of lead obtained from the of CO2
other oxide. The data illustrates [AMU 1983] (b) When 12 g of carbon is heated in a vacuum there is no
(a) Law of reciprocal proportions change in mass
(b) Law of constant proportions (c) A sample of air increases in volume when heated at
(c) Law of multiple proportions constant pressure but its mass remains unaltered
(d) Law of equivalent proportions (d) The weight of a piece of platinum is the same before and
6. Chemical equation is balanced according to the law of after heating in air
[AMU 1984] 14. The law of multiple proportions is illustrated by the two
(a) Multiple proportion (b) Reciprocal proportion compounds [NCERT 1972]
(c) Conservation of mass (d) Definite proportions (a) Sodium chloride and sodium bromide
7. Avogadro number is (b) Ordinary water and heavy water
(a) Number of atoms in one gram of element (c) Caustic soda and caustic potash
(b) Number of millilitres which one mole of a gaseous (d) Sulphur dioxide and sulphur trioxide
substances occupies at NTP 15. In compound A, 1.00 g nitrogen unites with 0.57 g oxygen. In
(c) Number of molecules present in one gram molecular mass compound B, 2.00 g nitrogen combines with 2.24 g oxygen. In
of a substance compound C, 3.00 g nitrogen combines with 5.11 g oxygen.
(d) All of these These results obey the following law [CPMT 1971]
8. Different propartions of oxygen in the various oxides of (a) Law of constant proportion
nitrogen prove the [MP PMT 1985] (b) Law of multiple proportion
(a) Equivalent proportion (b) Multiple proportion (c) Law of reciprocal proportion
(c) Constant proportion (d) Conservation of matter (d) Dalton's law of partial pressure
 12 Chemical Arithmetic
16. Hydrogen combines with oxygen to form H 2 O in which 16 g 4. 1 amu is equal to
of oxygen combine with 2 g of hydrogen. Hydrogen also 1 1
(a) of C  12 (b) of O - 16
combines with carbon to form CH 4 in which 2 g of hydrogen 12 14
combine with 6 g of carbon. If carbon and oxygen combine (c) 1g of H 2 (d) 1 .66  10 23 kg
together then they will do show in the ratio of
5. Sulphur forms the chlorides S 2 Cl 2 and SCl 2 . The equivalent
(a) 6 : 16 or 12 : 32 (b) 6 : 18
mass of sulphur in SCl 2 is
(c) 1 : 2 (d) 12 : 24
17. 2 g of hydrogen combine with 16 g of oxygen to form water [EAMCET 1985; Pb. CET 2001]
and with 6 g of carbon to form methane. In carbon dioxide 12 g (a) 8 g/mole (b) 16 g/mole
of carbon are combined with 32 g of oxygen. These figures (c) 64.8 g/mole (d) 32 g/mole
illustrate the law of 6. The sulphate of a metal M contains 9.87% of M. This sulphate
(a) Multiple proportions (b) Constant proportions is isomorphous with ZnSO 4 .7 H 2 O . The atomic weight of M
(c) Reciprocal proportions (d) Conservation of mass is [IIT 1991]
18. An element forms two oxides containing respectively 53.33 and (a) 40.3 (b) 36.3
36.36 percent of oxygen. These figures illustrate the law of (c) 24.3 (d) 11.3
(a) Conservation of mass (b) Constant proportions 7. When 100 ml of 1 M NaOH solution and 10 ml of
(c) Reciprocal proportions (d) Multiple proportions 10 N H 2 SO 4 solution are mixed together, the resulting solution
19. After a chemical reaction, the total mass of reactants and will be [DPMT 1982]
products [MP PMT 1989]
(a) Alkaline (b) Acidic
(a) Is always increased (b) Is always decreased
(c) Strongly acidic (d) Neutral
(c) Is not changed (d) Is always less or more
8. In chemical scale, the relative mass of the isotopic mixture of
20. A sample of pure carbon dioxide, irrespective of its source
oxygen atoms (O 16 , O 17 , O 18 ) is assumed to be equal to
contains 27.27% carbon and 72.73% oxygen. The data support
[AIIMS 1992] [Bihar MADT 1981]

(a) Law of constant composition (a) 16.002 (b) 16.00

(c) 17.00 (d) 11.00
(b) Law of conservation of mass
9. For preparing 0.1 N solution of a compound from its impure
(c) Law of reciprocal proportions
sample of which the percentage purity is known, the weight of
(d) Law of multiple proportions the substance required will be [MP PET 1996]
21. The law of definite proportions is not applicable to nitrogen (a) More than the theoretical weight
oxide because [EAMCET 1981]
(b) Less than the theoretical weight
(a) Nitrogen atomic weight is not constant
(c) Same as the theoretical weight
(b) Nitrogen molecular weight is variable (d) None of these
(c) Nitrogen equivalent weight is variable 10. 1 mol of CH 4 contains
(d) Oxygen atomic weight is variable
(a) 6.02  10 23 atoms of H
22. Which one of the following pairs of compounds illustrates the
law of multiple proportion [EAMCET 1989]
(b) 4 g atom of Hydrogen

(a) H 2O, Na2O (b) MgO, Na2O (c) 1.81  10 23 molecules of CH 4

(d) 3.0 g of carbon
(c) Na2O, BaO (d) SnCl 2 , SnCl4
11. In the reaction 2 Na2 S 2O3  I2  Na2S 4 O6  2 NaI , the
Atomic, Molecular and Equivalent masses equivalent weight of Na2 S 2 O3 (mol. wt. = M) is equal to
(a) M (b) M / 2
1. Which property of an element is always a whole number
(c) M / 3 (d) M / 4
[MP PMT 1986]
12. When potassium permanganate is titrated against ferrous
(a) Atomic weight (b) Equivalent weight
ammonium sulphate, the equivalent weight of potassium
(c) Atomic number (d) Atomic volume permanganate is [CPMT 1988]
2. Which one of the following properties of an element is not (a) Molecular weight /10 (b) Molecular weight /5
variable [Bihar MADT 1981] (c) Molecular weight /2 (d) Molecular weight
(a) Valency (b) Atomic weight
13. Boron has two stable isotopes, 10 B (19%) and 11 B (81%). The
(c) Equivalent weight (d) All of these atomic mass that should appear for boron in the periodic table
3. The modern atomic weight scale is based on is [CBSE PMT 1990]
[MP PMT 2002] (a) 10.8 (b) 10.2
12 16
(a) C (b) O (c) 11.2 (d) 10.0
(c) H1 (d) C 13
 Chemical Arithmetic 13
14. What is the concentration of nitrate ions if equal volumes of 0.1 27. The atomic weights of two elements A and B are 40 and 80
M AgNO3 and 0.1 M NaCl are mixed together respectively. If x g of A contains y atoms, how many atoms are
[CPMT 1983; NCERT 1985] present in 2x g of B
(a) 0.1 M (b) 0.2 M y y
(a) (b)
(c) 0.05 M (d) 0.25 M 2 4
15. Total number of atoms represented by the compound (c) y (d) 2y
CuSO4.5H2O is [BHU 2005]
28. Assuming fully decomposed, the volume of CO2 released at
(a) 27 (b) 21
(c) 5 (d) 8 STP on heating 9.85g of BaCO3 (Atomic mass of Ba=137)
16. 74.5 g of a metallic chloride contain 35.5 g of chlorine. The will be [CBSE PMT 2000]
equivalent weight of the metal is [CPMT 1986] (a) 0.84 L (b) 2.24 L
(a) 19.5 (b) 35.5 (c) 4.06 L (d) 1.12 L
(c) 39.0 (d) 78.0
29. If N A is Avogadro’s number then number of valence electrons
17. 7.5 grams of a gas occupy 5.8 litres of volume at STP the gas is
(a) NO (b) N 2 O in 4.2 g of nitride ions ( N 3 )

(c) CO (d) CO2 (a) 2.4 N A (b) 4.2 N A

18. The number of atoms in 4.25 g of NH 3 is approximately (c) 1.6 N A (d) 3.2 N A
[CBSE PMT 1999; MH CET 2003] 30. The weight of 1  10 22 molecules of CuSO 4 .5 H 2 O is
(a) 1  10 23 (b) 2  10 23
[IIT 1991]
(c) 4  10 23 (d) 6  10 23 (a) 41.59 g (b) 415.9 g
19. One litre of a gas at STP weight 1.16 g it can possible be
(c) 4.159 g (d) None of these
[AMU 1992]
31. Rearrange the following (I to IV) in the order of increasing
(a) C2 H 2 (b) CO
masses and choose the correct answer from (a), (b), (c) and (d)
(c) O2 (d) CH 4 (Atomic mass: N=14, O=16, Cu=63).
20. The vapour density of a gas is 11.2. The volume occupied by I. 1 molecule of oxygen
11.2 g of the gas at ATP will be [Bihar CET 1995]
II. 1 atom of nitrogen
(a) 11.2 L (b) 22.4 L
(c) 1 L (d) 44.8 L III. 1  10 10 g molecular weight of oxygen
21. Equivalent weight of crystalline oxalic acid is IV. 1  10 10 g atomic weight of copper
[MP PMT 1995]
(a) 30 (b) 63 (a) II<I<III<IV (b) IV<III<II<I
(c) 53 (d) 45 (c) II<III<I<IV (d) III<IV<I<II
22. The equivalent weight of an element is 4. Its chloride has a V.D 32. 1.520 g of the hydroxide of a metal on ignition gave 0.995
59.25. Then the valency of the element is [BHU 1997] gm of oxide. The equivalent weight of metal is
(a) 4 (b) 3 [DPMT 1984]

(c) 2 (d) 1 (a) 1.520 (b) 0.995

(c) 19.00 (d) 9.00
23. 1.25 g of a solid dibasic acid is completely neutralised by 25 ml
of 0.25 molar Ba(OH )2 solution. Molecular mass of the acid is 33. How much coulomb charge is present on 1g ion of N 3 
(a) 100 (b) 150 (a) 5.2  10 6 Couloumb (b) 2 .894  10 5 Couloumb
(c) 120 (d) 200 (c) 6 . 6  10 6 Couloumb (d) 8.2  10 6 Couloumb
24. The oxide of a metal has 32% oxygen. Its equivalent weight 34. Ratio of C p and Cv of a gas X is 1.4, the number of atom of
would be [MP PMT 1985] the gas ‘X’ present in 11.2 litres of it at NTP will be
(a) 34 (b) 32 [CBSE 1999]
(c) 17 (d) 8 (a) 6.02  10 23 (b) 1.2  10 23
25. The mass of a molecule of water is [Bihar CEE 1995]
(c) 3.01  10 23 (d) 2.01  10 23
26 25
(a) 3  10 kg (b) 3  10 kg 35. If we consider that 1/6, in place of 1/12, mass of carbon atom is
26 26
(c) 1 . 5  10 kg (d) 2 .5  10 kg taken to be the relative atomic mass unit, the mass of one mole
of a substance will [AIEEE 2005]
26. 1.24 gm P is present in 2.2 gm
(a) Decrease twice
(a) P4 S 3 (b) P2 S 2
(b) Increase two fold
(c) PS 2 (d) P2 S 4 (c) Remain unchanged
(d) Be a function of the molecular mass of the substance
 14 Chemical Arithmetic
36. What should be the equivalent weight of phosphorous acid, if (a) 21 (b) 54
P=31; O=16; H=1 (c) 27.06 (d) 2.086
(a) 82 (b) 41 49. One gram of hydrogen is found to combine with 80g of
(c) 20.5 (d) None of these bromine one gram of calcium valency=2 combines with 4g of
37. The number of molecule at NTP in 1 ml of an ideal gas will be bromine the equivalent weight of calcium is
(a) 6  10 23 (b) 2.69  10 19 (a) 10 (b) 20
(c) 40 (d) 80
(c) 2 .69  10 23 (d) None of these
50. The equivalent weight of MnSO 4 is half its molecular weight
38. The specific heat of a metal is 0.16 its approximate atomic
weight would be when it is converted to [IIT 1988; CPMT 1994]
(a) 32 (b) 16 (a) Mn 2 O 3 (b) MnO2
(c) 40 (d) 64
(c) MnO4 (d) MnO 42 
39. The weight of a molecule of the compound C60 H 122 is
51. 100 mL of PH3 on decomposition produced phosphorus and
[AIIMS 2000]
hydrogen. The change in volume is [MNR 1986]
(a) 1 . 4  10 21 g (b) 1 .09  10 21 g
(a) 50 mL increase (b) 500 mL decrease
(c) 5 .025  10 23 g (d) 16 .023  10 23 g
(c) 900 mL decrease (d) Nil.
40. What is the weight of oxygen required for the complete
combustion of 2.8 kg of ethylene [CBSE PMT 1989] 52. 12 g of Mg (at. mass 24) on reacting completely with acid
(a) 2.8 kg (b) 6.4 kg gives hydrogen gas, the volume of which at STP would be
(c) 9.6 kg (d) 96 kg [CPMT 1978]
41. What volume of NH 3 gas at STP would be needed to prepare (a) 22 .4 L (b) 11 .2 L
100ml of 2.5 molal (2.5m) ammonium hydroxide solution (c) (d) 6.1 L
44 .8 L
(a) 0.056 litres (b) 0.56 litres
53. Which of the following has least mass [Pb. PET 1985]
(c) 5.6 litres (d) 11.2 litres
(a) 2 g atom of nitrogen (b) 3  10 23
atoms of C
42. If the density of water is 1 g cm 3 then the volume occupied
by one molecule of water is approximately [Pb. PMT 2004] (c) 1 mole of S (d) 7.0 g of Ag
(a) 18 cm 3 (b) 22400 cm 3 54. How many mole of helium gas occupy 22 .4 L at 0 o C at 1
(c) 6 . 02  10 23 cm 3 (d) 3 . 0  10 23 cm 3 atm. pressure [Kurukshetra CEE 1992; CET 1992]
(a) 0.11 (b) 0.90
43. Caffeine has a molecular weight of 194. If it contains 28.9% by
mass of nitrogen, number of atoms of nitrogen in one molecule (c) 1.0 (d) 1.11
of caffeine is 55. Volume of a gas at STP is 1 . 12  10 7 cc. Calculate the number
(a) 4 (b) 6 of molecules in it [BHU 1997]
(c) 2 (d) 3
(a) 3 .01  10 20 (b) 3 . 01  10 12
44. A 400 mg iron capsule contains 100 mg of ferrous fumarate,
(CHCOO )2 Fe . The percentage of iron pasent in it is (c) 3 .01  10 23 (d) 3 .01  10 24

approximately 56. 4.4 g of an unknown gas occupies 2 . 24 L of volume at

(a) 33% (b) 25% standard temperature and pressure. The gas may be
(c) 14% (d) 8% [MP PMT 1995]
26
45. The element whose a atom has mass of 10 .86  10 kg is (a) Carbon dioxide (b) Carbon monoxide
(a) Boron (b) Calcium (c) Oxygen (d) Sulphur dioxide
(c) Silver (d) Zinc 57. The number of moles of oxygen in 1 L of air containing 21%
46. The number of gram atoms of oxygen present in 0.3 gram mole oxygen by volume, in standard conditions, is
of (COOH )2 .2 H 2 O is
[CBSE PMT 1995; Pb. PMT 2004]
(a) 0.6 (b) 1.8 (a) 0.186 mol (b) 0.21 mol
(c) 1.2 (d) 3.6
(c) 2.10 mol (d) 0.0093 mol
47. A gaseous mixture contains CH 4 and C 2 H 6 in equimolecular
58. The number of molecules in 8.96 L of a gas at 0 o C and 1
proportion. The weight of 2.24 litres of this mixture at NTP is
(a) 4.6 g (b) 1.6 g atmosphere pressure is approximately [BHU 1993]

(c) 2.3 g (d) 23 g (a) 6 .02  10 23

(b) 12 .04  10 23

48. Vapour density of a metal chloride is 66. Its oxide contains (c) 18 . 06  10 23
(d) 24 .08  10 22
53% metal. The atomic weight of the metal is
[Bihar MADT 1982]
 Chemical Arithmetic 15
59. The equivalent weight of a metal is 9 and vapour density of its (c) 6  10 23 (d) 12  10 23
chloride is 59.25. The atomic weight of metal is 6. The volume occupied by 4.4 g of CO2 at STP is
[Pb. CET 2002]
[AFMC 1997, 2004; Pb. CET 1997, 2002]
(a) 23.9 (b) 27.3 (a) 22.4 L (b) 2.24 L
(c) 36.3 (d) 48.3 (c) 0.224 L (d) 0.1 L
60. The molecular weight of a gas is 45. Its density at STP is 7. The number of water molecules present in a drop of water
[Pb. PMT 2004] (volume 0.0018 ml) at room temperature is [DCE 2000]
(a) 22.4 (b) 11.2 (a) 6.023  10 19 (b) 1.084  10 18
(c) 5.7 (d) 2.0 (c) 4 .84  10 17 (d) 6.023  10 23
61. Equivalent weight of a bivalent metal is 37.2. The molecular 8. One mole of calcium phosphide on reaction with excess of
weight of its chloride is [MH CET 2003] water gives [IIT 1999]
(a) 412.2 (b) 216 (a) One mole of phosphine
(c) 145.4 (d) 108.2 (b) Two moles of phosphoric acid
62. On reduction with hydrogen, 3.6 g of an oxide of metal left 3.2 (c) Two moles of phosphine
g of metal. If the vapour density of metal is 32, the simplest (d) One mole of phosphorus pentoxide
formula of the oxide would be 9. 19.7 kg of gold was recovered from a smuggler. How many
[DPMT 2004] atoms of gold were recovered (Au =197) [Pb. CET 1985]

(a) MO (b) M 2 O 3 (a) 100 (b) 6.02  10 23

(c) 6 .02  10 24 (d) 6.02  10 25
(c) M2O (d) M 2 O5
10. The total number of protons in 10 g of calcium carbonate is
63. The number of molecules in 4.25 g of ammonia are ( N 0  6 .023  10 23 )
[Pb. CET 2000]
(a) 1.5057  10 24 (b) 2.0478  10 24
(a) 0 .5  10 23
(b) 1.5  10 23

(c) 3 .0115  10 24 (d) 4 .0956  10 24

(c) 3 .5  10 23 (d) 1.8  10 32 11. The number of molecules in 16 g of methane is
The mole concept (a) 3 .0  10 23 (b) 6.02  10 23
16 16
(c)  10 23 (d)  10 23
1. Which one of the following pairs of gases contains the same 6 .02 3 .0
number of molecules [EAMCET 1987] 12. Number of molecules in 100 ml of each of
(a) 16 g of O 2 and 14 g of N 2 O 2 , NH 3 and CO 2 at STP are [Bihar MADT 1985]
(b) 8 g of O 2 and 22 g of CO2 (a) In the order CO2  O2  NH 3
(c) 28 g of N 2 and 22 g of CO2 (b) In the order NH 3  O 2  CO2
(d) 32 g of O 2 and 32 g of N 2 (c) The same
2. Number of gm of oxygen in 32.2 g Na 2 SO 4 .10 H 2 O is (d) NH 3  CO2  O 2
[Haryana PMT 2000] 13. The molecular weight of hydrogen peroxide is 34. What is the
(a) 20.8 (b) 22.4 unit of molecular weight [MP PMT 1986]
(c) 2.24 (d) 2.08 (a) g (b) mol
3. 250 ml of a sodium carbonate solution contains 2.65 grams of (c) g mol 1 (d) mol g 1
Na 2 CO 3 . If 10 ml of this solution is diluted to one litre, what
14. The number of water molecules in 1 litre of water is
is the concentration of the resultant solution (mol. wt. of [EAMCET 1990]
Na 2 CO 3 =106) [EAMCET 2001]
(a) 18 (b) 18  1000
(a) 0.1 M (b) 0.001 M (c) N A (d) 55 .55 N A
(c) 0.01 M (d) 10 4 M 15. The number of electrons in a mole of hydrogen molecule is
4. A molar solution is one that contains one mole of a solute in [CPMT 1987]
[IIT 1986] (a) 6.02  10 23
(b) 12 .046  10 23

(a) 1000 g of the solvent (b) One litre of the solvent

(c) 3 .0115  10 23
(d) Indefinite
(c) One litre of the solution (d) 22.4 litres of the solution
16. The numbers of moles of BaCO3 which contain 1.5 moles of
5. The number of oxygen atoms in 4.4 g of CO 2 is approx.
oxygen atoms is [EAMCET 1991]
[CBSE PMT 1990]
(a) 0.5 (b) 1
(a) 1.2  10 23 (b) 6  10 22
(c) 3 (d) 6.02  10 23
 16 Chemical Arithmetic
17. Which of the following is Loschmidt number (a) 40 (b) 60
(a) 6  10 23
(b) 2.69  10 19 (c) 8 (d) 10
(c) 3  10 23
(d) None of these 2. The percentage of nitrogen in urea is about [KCET 2001]

18. How many molecules are present in one gram of hydrogen (a) 46 (b) 85
[AIIMS 1982] (c) 18 (d) 28
(a) 6 .02  10 23 (b) 3 .01  10 23 3. If two compounds have the same empirical formula but
different molecular formula, they must have
(c) 2 .5  10 23 (d) 1 .5  10 23 [MP PMT 1986]
19. The total number of gm-molecules of SO 2Cl2 in 13 .5 g of (a) Different percentage composition
sulphuryl chloride is [CPMT 1992] (b) Different molecular weights
(a) 0.1 (b) 0.2 (c) Same viscosity
(c) 0.3 (d) 0.4 (d) Same vapour density
20. The largest number of molecules is in [BHU 1997] 4. A compound (80 g) on analysis gave C = 24 g, H = 4 g, O =
(a) 34 g of water (b) 28 g of CO2 32 g. Its empirical formula is [CPMT 1981]
(c) 46 g of CH 3OH (d) 54 g of N 2O5 (a) C 2 H 2 O2 (b) C 2 H 2 O
21. The number of moles of sodium oxide in 620 g of it is (c) CH 2 O2 (d) CH 2 O
[BHU 1992] 5. The empirical formula of a compound is CH 2 O. 0.0835 moles
(a) 1 mol (b) 10 moles
of the compound contains 1.0 g of hydrogen. Molecular
(c) 18 moles (d) 100 moles formula of the compound is
22. 2 g of oxygen contains number of atoms equal to that in (a) C 2 H 12 O6 (b) C5 H 10 O5
[BHU 1992] (c) C 4 H 8 O8 (d) C 3 H 6 O3
(a) 0 . 5 g of hydrogen (b) 4 g of sulphur
6. The empirical formula of an acid is CH2O2 , the probable
(c) 7 g of nitrogen (d) 2 . 3 g of sodium
molecular formula of acid may be [AFMC 2000]
23. Molarity of liquid HCl with density equal to 1.17 g / cc is
(a) CH 2O (b) CH2O2
[CBSE PMT 2001]
(a) 36.5 (b) 18.25 (c) C2 H 4 O2 (d) C3 H6 O4
(c) 32.05 (d) 4.65 7. In which of the following pairs of compounds the ratio of C, H
24. How many atoms are contained in one mole of sucrose and O is same
(C12 H 22O11) [Pb. PMT 2002]
(a) Acetic acid and methyl alcohol
(a) 45  6 .02  10 23 atoms/mole (b) Glucose and acetic acid
(b) 5  6 .62  10 23 atoms/mole (c) Fructose and sucrose
(c) 5  6 .02  10 23 atoms/mole (d) All of these
(d) None of these
25. The number of molecules of CO2 present in 44g of CO2 is Chemical stoichiometry
[BCECE 2005]
1. How much of NaOH is required to neutralise 1500 cm 3 of 0.1
(a) 6.0  10 23
(b) 3  10 23
N HCl (Na = 23) [KCET 2001]
(c) 12  10 23 (d) 3  10 10
(a) 40 g (b) 4 g
26. A sample of phosphorus trichloride (PCl3 ) contains 1.4 moles
(c) 6 g (d) 60 g
of the substance. How many atoms are there in the sample[Kerala PMT 2004]
2. How much water should be added to 200 c.c of semi normal
(a) 4 (b) 5.6
solution of NaOH to make it exactly deci normal
(c) 8.431  10 23 (d) 3.372  10 24
[AFMC 1983]
(e) 2 .409  10 24 (a) 200 cc (b) 400 cc
27. The number of sodium atoms in 2 moles of sodium
(c) 800 cc (d) 600 cc
ferrocyanide is [BHU 2004]
3. 2.76 g of silver carbonate on being strongly heated yield a
(a) 12  10 23 (b) 26  10 23
residue weighing [Pb. CET 2003]
(c) 34  10 23 (d) 48  10 23
(a) 2.16 g (b) 2.48 g
(c) 2.64 g (d) 2.32 g
Percentage composition & Molecular formula

1. The percentage of oxygen in NaOH is [CPMT 1979]

 Chemical Arithmetic 17
4. In the reaction, 4 NH 3 (g)  5O 2 (g)  4 NO(g)  6 H 2 O(g) , (c) 80 grams (d) 320 grams
When 1 mole of ammonia and 1 mole of O 2 are made to react 13. What is the normality of a 1 M solution of H 3 PO4
to completion [AIIMS 1982]

(a) 1.0 mole of H 2 O is produced (a) 0.5 N (b) 1.0 N

(c) 2.0 N (d) 3.0 N
(b) 1.0 mole of NO will be produced
14. Normality of 2M sulphuric acid is [AIIMS 1992]
(c) All the oxygen will be consumed
(a) 2N (b) 4N
(d) All the ammonia will be consumed
N N
(c) (d)
5. Haemoglobin contains 0.33% of iron by weight. The molecular 2 4
weight of haemoglobin is approximately 67200. The number of
15. How many g of a dibasic acid (Mol. wt. = 200) should be
iron atoms (At. wt. of Fe = 56) present in one molecule of present in 100 ml of its aqueous solution to give decinormal
haemoglobin is [CBSE PMT 1998] strength [AIIMS 1992]
(a) 6 (b) 1 (a) 1 g (b) 2 g
(c) 4 (d) 2 (c) 10 g (d) 20 g
6. What quantity of ammonium sulphate is necessary for the 16. The solution of sulphuric acid contains 80% by weight
production of NH 3 gas sufficient to neutralize a solution H 2 SO 4 . Specific gravity of this solution is 1.71. Its normality
containing 292 g of HCl ? [HCl=36.5; (NH 4 )2 SO 4 =132; is about [CBSE 1991]

NH 3 =17] [CPMT 1992] (a) 18.0 (b) 27.9

(c) 1.0 (d) 10.0
(a) 272 g (b) 403 g
(c) 528 g (d) 1056 g 17. Mohr's salt is dissolved in dil. H 2 SO 4 instead of distilled
7. The percentage of P2 O 5 in diammonium hydrogen phosphate water to

(NH 4 )2 HPO 4 is [CPMT 1992] (a) Enhance the rate of dissolution

(b) Prevent cationic hydrolysis
(a) 23.48 (b) 46.96
(c) 53.78 (d) 71.00 (c) Increase the rate of ionisation
(d) Increase its reducing strength
1
8. If 1 moles of oxygen combine with Al to form Al 2 O3 the 18. Acidified potassium permanganate solution is decolourised by
2
weight of Al used in the reaction is (Al=27) [EAMCET 1980] (a) Bleaching powder (b) White vitriol
(a) 27 g (b) 54 g (c) Mohr's salt (d) Microcosmic salt
(c) 49.5 g (d) 31 g 19. Approximate atomic weight of an element is 26.89. If its
equivalent weight is 8.9, the exact atomic weight of element
9. The percentage of Se in peroxidase anhydrous enzyme is 0.5% would be [DPMT 1984]
by weight (atomic weight=78.4). Then minimum molecular
(a) 26.89 (b) 8.9
weight of peroxidase anhydrous enzyme is
(c) 17.8 (d) 26.7
[CBSE PMT 2001]
20. Vapour density of a gas is 22. What is its molecular mass
(a) 1 .568  10 4 (b) 1 .568  10 3
[AFMC 2000]
(c) 15 .68 (d) 3 .136  10 4 (a) 33 (b) 22
10. H 2 evolved at STP on complete reaction of 27 g of (c) 44 (d) 11
Aluminium with excess of aqueous NaOH would be 21. Equivalent weight of KMnO4 acting as an oxidant in acidic
[CPMT 1991] medium is [CPMT 1990; MP PET 1999]
(a) 22.4 (b) 44.8 (a) The same as its molecular weight
(c) 67.2 (d) 33.6 litres (b) Half of its molecular weight

11. What is the % of H 2 O in Fe(CNS )3 .3 H 2O (c) One-third of its molecular weight

(d) One-fifth of its molecular weight
(a) 45 (b) 30
22. 0.16 g of dibasic acid required 25 ml of decinormal NaOH
(c) 19 (d) 25 solution for complete neutralisation. The molecular weight of
12. What weight of SO 2 can be made by burning sulphur in 5.0 the acid will be [CPMT 1989]

moles of oxygen (a) 32 (b) 64

(a) 640 grams (b) 160 grams (c) 128 (d) 256
 18 Chemical Arithmetic
23. To neutralise 20 ml of M / 10 sodium hydroxide, the volume [CPMT 1992]
of M / 20 hydrochloric acid required is (a) 0.6 g (b) 1.0 g
[Andhra MBBS 1980] (c) 1.5 g (d) 2.0 g
(a) 10 ml (b) 15 ml 32. In the preceeding question, the amount of Na2CO3 present in
(c) 20 ml (d) 40 ml the solution is [CPMT 1992]
24. Hydrochloric acid solutions A and B have concentration of 0.5 (a) 2.650 g (b) 1.060 g
N and 0.1 N respectively. The volume of solutions A and B
(c) 0.530 g (d) 0.265 g
required to make 2 litres of 0.2 N hydrochloric are
[KCET 1993]
33. How many ml of 1 (M) H 2 SO 4 is required to neutralise 10 ml
(a) 0.5 l of A + 1.5 l of B of 1 (M) NaOH solution
[MP PET 1998; MNR 1982; MP PMT 1987]
(b) 1.5 l of A + 0.5 l of B
(a) 2.5 (b) 5.0
(c) 1.0 l of A + 1.0 l of B
(c) 10.0 (d) 20.0
(d) 0.75 l of A + 1.25 l of B
34. Which of the following cannot give iodometric titrations
25. 5 ml of N HCl, 20 ml of N / 2 H 2 SO 4 and 30 ml of
[AIIMS 1997]
N / 3 HNO3 are mixed together and volume made to one litre.
3 2
(a) Fe (b) Cu
The normality of the resulting solution is [MNR 1991]
(a) N /5 (b) N / 10 (c) Pb2 (d) Ag 
(c) N / 20 (d) N / 40 35. KMnO4 reacts with ferrous ammonium sulphate according to
26. Under similar conditions of pressure and temperature, 40 ml of the equation
slightly moist hydrogen chloride gas is mixed with 20 ml of MnO4  5 Fe 2   8 H   Mn2   5 Fe3   4 H 2O , here 10
ammonia gas, the final volume of gas at the same temperature
and pressure will be [CBSE PMT 1993] ml of 0.1 M KMnO4 is equivalent to [CPMT 1999]

(a) 100 ml (b) 20 ml (a) 20 ml of 0.1 M FeSO4

(c) 40 ml (d) 60 ml
(b) 30 ml of 0.1 M FeSO4
27. KMnO4 reacts with oxalic acid according to the equation,
(c) 40 ml of 0.1 M FeSO4
2 MnO 4  5 C 2 O42   16 H   2 Mn 2   10 CO 2  8 H 2 O , here
20 ml of 0.1 M KMnO4 is equivalent to [CBSE PMT 1996] (d) 50 ml of 0.1 M FeSO4

(a) 20 ml of 0.5 M H 2C2O4 (b) 50 ml of 0.1 M H 2C2O4 36. Ca(OH )2  H 3 PO4  CaHPO4  2 H 2 O the equivalent
(c) 50 ml of 0.5 M H 2C2O4 (d) 20 ml of 0.1 M H 2C2O4 weight of H 3 PO4 in the above reaction is [Pb. PMT 2004]

28. In order to prepare one litre normal solution of KMnO4 , how (a) 21 (b) 27
many grams of KMnO4 are required if the solution is used in (c) 38 (d) 49
acidic medium for oxidation [MP PET 2002] 37. The mass of BaCO3 produced when excess CO2 is bubbled
(a) 158 g (b) 31.6 g through a solution of 0.205 mol Ba(OH )2 is
(c) 790 g (d) 62 g [UPSEAT 2004]
29. What is the concentration of nitrate ions if equal volumes of 0.1
(a) 81 g (b) 40.5 g
M AgNO3 and 0.1 M NaCl are mixed together
(c) 20.25 g (d) 162 g
[NCERT 1981; CPMT 1983]
38. The amount of water that should be added to 500 ml of 0.5 N
(a) 0.1 N (b) 0.2 M
solution of NaOH to give a concentration of 10 mg per ml is
(c) 0.05 M (d) 0.25 M
30. 30 ml of acid solution is neutralized by 15 ml of a 0.2 N base. (a) 100 (b) 200
The strength of acid solution is [CPMT 1986] (c) 250 (d) 500
(a) 0.1 N (b) 0.15 N
39. Number of moles of KMnO4 required to oxidize one mole of
(c) 0.3 N (d) 0.4 N
Fe(C 2 O 4 ) in acidic medium is [Haryana CEE 1996]
31. A solution containing Na2CO3 and NaOH requires 300 ml of
0.1 N HCl using phenolpthalein as an indicator. Methyl orange (a) 0.6 (b) 0.167
is then added to the above titrated solution when a further 25 ml (c) 0.2 (d) 0.4
of 0.2 N HCl is required. The amount of NaOH present in
40. A hydrocarbon contains 86% carbon, 488ml of the hydrocarbon
solution is (NaOH  40 , Na2CO3  106 )
weight 1.68 g at STP. Then the hydrocarbon is an
 Chemical Arithmetic 19
(a) Alkane (b) Alkene (c) 18 g (d) 19 g
(c) Alkyne (d) Arene M
50. A solution of 10 ml FeSO 4 was titrated with
41. The ratio of amounts of H 2 S needed to precipitate all the metal 10
KMnO4 solution in acidic medium. The amount of
ions from 100 ml of 1 M AgNO3 and 100 ml of 1 M
KMnO4 used will be [CPMT 1984]
CuSO 4 will be
(a) 5 ml of 0.1 M (b) 10 ml of 1.1 M
(a) 1:1 (b) 1:2
(c) 10 ml of 0.5 M (d) 10 ml of 0.02 M
(c) 2:1 (d) None of these
51. 1.12 ml of a gas is produced at STP by the action of 4.12 mg of
42. An electric discharge is passed through a mixture containing 50 alcohol, with methyl magnesium iodide. The molecular mass of
c.c. of O 2 and 50 c.c. of H 2 . The volume of the gases formed alcohol is [Roorkee 1992; IIT 1993]

(i) at room temperature and (ii) at 1100C will be (a) 16.0 (b) 41.2
(a) (i) 25 c.c. (ii) 50 c.c. (b) (i) 50 c.c. (ii) 75 c.c. (c) 82.4 (d) 156.0
(c) (i) 25 c.c. (ii) 75 c.c. (d) (i) 75 c.c. (ii) 75 c.c. 52. The simplest formula of a compound containing 50% of
43. 100 ml of 0.1 N hypo decolourised iodine by the addition of x g element X (atomic mass 10) and 50% of element Y (atomic
of crystalline copper sulphate to excess of KI. The value of ‘x’ mass 20) is [Roorkee 1994]

is (molecular wt. of CuSO 4 .5 H 2 O is 250) (a) XY (b) X 2Y

(a) 5.0 g (b) 1.25 g (c) XY 3 (d) X 2 Y3

(c) 2.5 g (d) 4 g 53. A compound contains atoms of three elements in A, B and C. If
the oxidation number of A is +2, B is +5 and that of C is – 2, the
44. How many grams of caustic potash required to completely
possible formula of the compound is
neutralise 12.6 gm HNO3
[CBSE PMT 2000]
(a) 22.4 KOH (b) 1.01 KOH (a) A3 (BC 4 )2
(c) 6.02 KOH (d) 11.2 KOH
(b) A3 (B4 C)2
45. If isobutane and n-butane are present in a gas, then how much
oxygen should be required for complete combustion of 5 kg of (c) ABC 2
this gas (d) A 2 (BC 3 )2
(a) 17.9 kg (b) 9 kg
54. What will be the volume of CO2 at NTP obtained on heating
(c) 27 kg (d) 1.8 kg 10 grams of (90% pure) limestone [Pb. CET 2001]
46. 16.8 litre gas containing H 2 and O 2 is formed at NTP on (a) 22.4 litre
electrolysis of water. What should be the weight of electrolysed (b) 2.016 litre
water
(c) 2.24 litre
(a) 5 g (b) 9 g (d) 20.16 litre
(c) 10 g (d) 12 g 55. The ratio of the molar amounts of H 2S needed to precipitate
47. On electrical decomposition of 150 ml dry and pure O 2 , 10% the metal ions from 20 mL each of 1M Cd(NO3 )2 and
of O 2 gets changed to O, then the volume of gaseous mixture 0.5 M CuSO4 is [CPMT 1997]
after reaction and volume of remaining gas left after passing in
(a) 1 : 1
turpentine oil will be
(b) 2 : 1
(a) 145 ml (b) 149 ml
(c) 1 : 2
(c) 128 ml (d) 125 ml
(d) Indefinite
48. What should be the weight of 50% HCl which reacts with 100 g
56. 12 g of Mg (at. mass 24) will react completely with acid to
of limestone
give [MNR 1985]
(a) 50% pure (b) 25% pure
(a) One mole of H 2
(c) 10% pure (d) 8% pure
(b) 1/2 mole of H 2
49. What should be the weight and moles of AgCl precipitate
obtained on adding 500ml of 0.20 M HCl in 30 g of (c) 2/3 mole of O 2
AgNO3 solution? ( AgNO3 = 170) (d) Both 1/2 mol of H 2 and 1/2 mol of O 2
(a) 14.35 g (b) 15 g
 20 Chemical Arithmetic
57. 1 .5 mol of O 2 combine with Mg to form oxide MgO . The (b) 22.4 L of CO2 at STP
mass of Mg (at. mass 24) that has combined is (c) 0.44 g of CO2
[KCET 2001] (d) None of these
(a) 72 g (b) 36 g 8. In a mole of water vapour at STP, the volume actually occupied
or taken by the molecules (i.e., Avogadro’s No.  Volume
(c) 48 g (d) 24 g of one molecule) is [Kerala EEE 2000]
58. 100 g CaCO3 reacts with 1litre 1 N HCl. On completion of (a) Zero
reaction how much weight of CO2 will be obtain (b) Less than 1% of 22.4 litres
(c) About 10% of the volume of container
[Kerala CET 2005]
(d) 1% to 2% of 22.4 litres
(a) 5.5 g (b) 11 g
(e) Between 2% to 5% of 22.4 litres
(c) 22 g (d) 33 g 9. If 10 21 molecules are removed from 200mg of CO2 , then the
(e) 44 g number of moles of CO2 left are [IIT 1983]

(a) 2 .85  10 3 (b) 28 .8  10 3

(c) 0 .288  10 3 (d) 1.68  10 2
10. The set of numerical coefficient that balances the
equation K 2 CrO4  HCl  K 2 Cr2 O7  KCl  H 2 O is
[Kerala CEE 2001]
1. Mixture of sand and sulphur may best be separated by (a) 1, 1, 2, 2, 1 (b) 2, 2, 1, 1, 1
[Kerala CET 2001] (c) 2, 1, 1, 2, 1 (d) 2, 2, 1, 2, 1
(a) Fractional crystallisation from aqueous solution 11. One litre hard water contains 12.00 mg Mg 2  milli equivalent
(b) Magnetic method of washing soda required to remove its hardness is [
(c) Fractional distillation (a) 1 (b) 12.15
(d) Dissolving in CS 2 and filtering
(c) 1  10 3 (d) 12 .15  10 3
2. Irrespective of the source, pure sample of water always yields 12. In standardization of using by
Na2S 2O3 K2Cr2O7
88.89% mass of oxygen and 11.11% mass of hydrogen. This is
explained by the law of [Kerala CEE 2002] iodometry, the equivalent weight of K2Cr2O7 is [IIT 2000]

(a) Conservation of mass (b) Constant composition (a) MW / 2 (b) MW / 3

(c) Multiple proportions (d) Constant volume (c) MW / 6 (d) MW / 1
3. Zinc sulphate contains 22.65% of zinc and 43.9% of water of 13. 3.92 g of ferrous ammonium sulphate crystals are dissolved in
crystallization. If the law of constant proportions is true, then 100 ml of water, 20 ml of this solution requires 18 ml of
the weight of zinc required to produce 20 g of the crystals will
KMnO4 during titration for complete oxidation. The weight of
be
(a) 45.3 g (b) 4.53 g KMnO4 present in one litre of the solution is
(c) 0.453 g (d) 453 g [Tamilnadu CET 2002]
4. 3 3
10 dm of N 2 gas and 10 dm of gas X at the same temperature (a) 3.476 g (b) 12.38 g
contain the same number of molecules. The gas X is (c) 34.76 g (d) 1.238 g
(a) CO (b) CO2 14. A 100 ml solution of 0.1 n HCl was titrated with 0.2 N NaOH
solution. The titration was discontinued after adding 30 ml of
(c) H2 (d) NO NaOH solution. The remaining titration was completed by
5. The molar heat capacity of water at constant pressure is 75 adding 0.25 N KOH solution. The volume of KOH required for
JK 1 mol 1 . When 1.0 kJ of heat is supplied to 100 g of water completing the titration is [DCE 1999]

which is free to expand, the increases in temperature of water is (a) 70[CBSE

ml PMT 2003] (b) 32 ml
(a) 6.6 K (b) 1.2 K (c) 35 ml (d) 16 ml
(c) 2.4 K (d) 4.8 K 15. What volume of Hydrogen gas, at 273 K and 1 atm pressure
6. A compound possesses 8% sulphur by mass. The least will be consumed in obtaining 21.6 g of elemental boron
molecular mass is [AIIMS 2002] (atomic mass = 10.8) from the reduction of boron trichloride by
(a) 200 (b) 400 Hydrogen [AIEEE 2003]

(c) 155 (d) 355 (a) 22.4 L (b) 89.6 L

7. Which of the following contains maximum number of atoms (c) 67.2 L (d) 44.8 L
[JIPMER 2000] 16. The mass of 112 cm 3 of CH 4 gas at STP is
(a) 6.023  10 21
molecules of CO 2 [Karnataka CET 2001]
 Chemical Arithmetic 21
(a) 0.16 g (b) 0.8 g Reason : Under similar conditions of temperature and
pressure all gases contain equal number of
(c) 0.08 g (d) 1.6 g
molecules.
17. Complete combustion of 0.858 g of compound X gives 7. Assertion : One atomic mass unit (amu) is mass of an
2.63 g of CO2 and 1.28 g of H 2O . The lowest molecular atom equal to exactly one-twelfth the mass of
a carbon-12 atom.
mass X can have [Kerala MEE 2000]
Reason : Carbon-12 isotope was selected as standard.
(a) 43 g (b) 86 g
M
(c) 129 g (d) 172 g 8. Assertion : Molecular mass of A is if the molecular
4
18. In the following reaction, which choice has value twice that of mass of B is M.
the equivalent mass of the oxidising agent Reason : Vapour density of A four times that of B.
SO 2  H 2 O  3 S  2 H 2 O [DPMT 2000] 9. Assertion : Pure water obtained from different sources
such as, river, well, spring, sea etc. always
(a) 64 (b) 32 contains hydrogen and oxygen combined in
(c) 16 (d) 48 the ratio 1 : 8 by mass.
Reason : A chemical compound always contains
elements combined together in same
proportion by mass, it was discovered by
French chemist, Joseph Proust (1799).
10. Assertion : As mole is the basic chemical unit, the
concentration of the dissolved solute is
Read the assertion and reason carefully to mark the correct option out usually specified in terms of number of moles
of the options given below : of solute.
Reason : The total number of molecules of reactants
(a) If both assertion and reason are true and the reason is the
correct explanation of the assertion. involved in a balanced chemical equation is
(b) If both assertion and reason are true but reason is not the known as molecularity of the reaction.
correct explanation of the assertion. 11. Assertion : A certain element X, forms three binary
(c) If assertion is true but reason is false. compounds with chlorine containing
(d) If the assertion and reason both are false. 59.68%,68.95% and 74.75% chlorine
(e) If assertion is false but reason is true. respectively. These data illustrate the law of
multiple proportions.
1. Assertion : Volume of a gas is inversely proportional to
Reason : According to law of multiple proportions, the
the number of moles of a gas.
relative amounts of an element combining
Reason : The ratio by volume of gaseous reactants and with some fixed amount of a second element
products is in agreement with their mole in a series of compounds are the ratios of
ratio. [AIIMS 1995] small whole numbers.
2. Assertion : Molecular weight of oxygen is 16. 12. Assertion : Equivalent weight of Cu in CuO is 63.6
Reason : Atomic weight of oxygen is 16. and in Cu2O 31.8.
[AIIMS 1996] Reason : Equivalent weight of an element
3. Assertion : Atoms can neither be created nor destroyed. Atomic wei ght of the element

Reason : Under similar condition of temperature and Valency of the element
pressure, equal volume of gases does not 13. Assertion : Mass spectrometer is used for the
contain equal number of atoms. determination of isotopes.
[AIIMS 1994,2002] Reason : Isotopes are the atoms of same element
4. Assertion : One mole of SO 2 contains double the number of differing in mass numbers.
14. Assertion : Gases combine in simple ratio of their
molecules present in one mole of O 2 .
volume but, not always.
Reason : Molecular weight of SO 2 is double to that of Reason : Gases deviate from ideal behaviour.
O2 . 15. Assertion : Isomorphous substances form crystals of
same shape and can grow in saturated
5. Assertion : 1.231 has three significant figures.
solution of each other.
Reason : All numbers right to the decimal point are Reason : They have similar constitution and chemical
significant. formulae.
6. Assertion : 22.4 L of N 2 at NTP and 5.6 L O 2 at NTP 16. Assertion : Atomicity of oxygen is 2.
contain equal number of molecules.
 22 Chemical Arithmetic
Reason : 1 mole of an element contains 6 .023  10 23 1 a 2 b 3 b 4 c 5 a
atoms. 6 b 7 a 8 c 9 d 10 c
17. Assertion : 1 amu equals to 1 .66  10 24 g .
11 b 12 c 13 c 14 d 15 a
24 1 16 a 17 b 18 b 19 a 20 a
Reason : 1 .66  10 g equals to th of mass of a
12
21 b 22 b 23 c 24 a 25 a
C 12 atom.
26 c 27 d

Percentage composition & Molecular formula

1 a 2 a 3 b 4 d 5 a
6 b 7 b

Significant figures, Units for measurement,

Matter and Separation of mixture Chemical stoichiometry

1 a 2 d 3 a 4 c 5 d 1 c 2 c 3 a 4 c 5 c

6 b 7 c 8 d 9 c 10 c 6 c 7 c 8 b 9 a 10 d

11 c 12 b 13 a 14 c 15 b 11 c 12 d 13 d 14 b 15 a

16 b 17 b 18 a 19 a 20 c 16 b 17 b 18 c 19 d 20 c

21 b 22 d 23 a 24 a 25 b 21 d 22 c 23 d 24 a 25 d

26 b 27 d 26 b 27 b 28 b 29 c 30 a
31 b 32 c 33 b 34 c 35 d
Laws of chemical combination 36 d 37 b 38 d 39 a 40 b
41 b 42 c 43 c 44 d 45 a
1 a 2 d 3 c 4 a 5 c
46 b 47 a 48 a 49 a 50 d
6 c 7 c 8 b 9 b 10 a
51 c 52 b 53 a 54 b 55 b
11 c 12 b 13 a 14 d 15 b
56 b 57 a 58 c
16 a 17 c 18 d 19 c 20 a
21 c 22 d
Critical Thinking Questions
Atomic, Molecular and Equivalent masses
1 d 2 b 3 b 4 a 5 c

1 c 2 b 3 a 4 a 5 b 6 b 7 b 8 b 9 a 10 d

6 c 7 d 8 b 9 a 10 b 11 a 12 c 13 a 14 d 15 c

11 a 12 b 13 a 14 c 15 b 16 c 17 a 18 b

16 c 17 a 18 d 19 a 20 a
Assertion & Reason
21 b 22 b 23 d 24 c 25 a
26 a 27 c 28 d 29 a 30 c 1 e 2 e 3 c 4 e 5 d
31 a 32 d 33 b 34 a 35 c 6 d 7 a 8 c 9 a 10 b
36 b 37 b 38 c 39 a 40 b 11 a 12 e 13 e 14 a 15 a
41 c 42 d 43 a 44 d 45 d 16 b 17 a
46 b 47 c 48 c 49 b 50 b
51 a 52 b 53 b 54 c 55 b
56 a 57 d 58 d 59 a 60 d
61 c 62 d 63 b

The mole concept

 Chemical Arithmetic 23
Significant figures, Units of measurement, 6. (c) As the given sulphate is isomorphous with ZnSO 4 .7 H 2 O
Matter and Separation of mixture its formula would be MSO 4 .7 H 2 O .m is the atomic
weight of M, molecular weight of MSO 4 .7 H 2 O
Force [MLT 2 ]  m  32  64  126  m  222
4. (c) Pressure    [ML1 T  2 ]
Area [L2 ] m
Hence % of M   100  9.87 (given) or
m  222
[ML2 T 2 ]
Energy per unit volume   [ML1 T  2 ] 100 m  9.87 m  222  9.87 or 90 .13 m  222  9.87
[L3 ]
222  9 .87
or m   24 .3 .
(29 .2  20 .2) (1 .79  10 5 ) 9 .0  1 .79  10 5 90 .13
17. (b) 
1 .37 1 .37
Least precise terms i.e., 9.0 has only two significant figures.
Hence, final answer will have two significant figures.
18. (a) Pure ethyl alcohol  81 .4  0 .002  81 .398 .
19. (a) JPa–1; Unit of work is Joule and unit of pressure is Pascal.
Dimension of Joule i.e. work  F  L  MLT 2  L

 ML2 T 2 
1

1

Pa Pressure F
1 1 A

F
 MLT 1  
A
     
So, JPa–1  ML2 T 2  L2  L  L3 .

22. (d) 1 zepto  10 21

23. (a) As we know that all non zero unit are significant number.
Therefore significant figure is 2.
24. (a) Number of significant figures in 6.0023 are 5 because all
the zeroes stand between two non zero digit are counted
towards significant figures.
25. (b) Given P  0 . 0030 m , Q  2 .40 m & R  3000 m In
P(0 . 0030 ) initial zeros after the decimal point are not
significant. Therefore, significant figures in P(0 . 0030 ) are 2.
Similarly in Q(2 .40 ) significant figures are 3 as in this case
final zero is significant. In R  (3000 ) all the zeroes are
significant hence, in R significant figures are 4.
26. (b) All the zeroes between two non zero digit are significatn.
Hence in 60.0001 significant figures is 6.
27. (d) Round off the digit at 2nd position of decimal 3.929
= 3.93.

Laws of chemical combination

12. (b) X Y ⇌ R S
ng mg pg qg

n  m  p  q by low of conservation of mass.

Atomic, Molecular and Equivalent masses

5. (b) The atomic weight of sulphur =32

In SCl 2 valency of sulphur =2
32
So equivalent mass of sulphur   16 .
2
 24 Chemical Arithmetic
7. (d) For NaOH, M  N  22.4 L of gas at S.T.P. weight  22 . 4  1 . 16
N1 V1  100 ml  1N  100 ml (N )  25 . 984  26
This molecular weight indicates that given
For H 2 SO 4 , N 2 V2  10 ml  10 N  100 ml (N )
compound is C2 H 2 .
Hence, N1 V1  N 2 V2 .
20. (a) Molecular weight  2  V. D  2  11 .2  22 .4
10. (b) 1 mole of CH 4 contains 4 mole of hydrogen  22.4gm of gas occupies 22.4L at S.T.P.
atom i.e. 4g atom of hydrogen. 22 .4
 11.2gm of gas occupies  11 .2  11 .2 L .
2 2.5
22 .4
11. (a) Na 2 SO 3  I 2  Na 2 S 4 O 6  NaI Molecular weight
21. (b) Equivalent weight 
Valency
n  2  0 .5  1
COOH 126
M M Molecular weight of |  2H 2O   63 .
E  M C OOH 2
n  factor 1
2  V .D 2  59 .25
M 22. (b) Valency of the element  
12. (b) E  E  35 .5 4  35 .5
5
118 .50
 =3.
10  19  81  11 190  891 39 .5
13. (a) Atomic mass  
100 100 W (gm )  1000
23. (d) Molarity 

1081 V (ml )  molecular weight
100 1 . 25  1000
0 . 25 
 10 . 81 25  molecular weight

14. (c) 0.1M AgNO3 will react with 0.1M NaCl to form 1.25  1000
 Molecular weight   200 .
0.25  25
0.1M NaNO3 . But as the volume doubled, conc.
24. (c) Let weight of metal oxide = 100gm
0.1
of NO 3   0 .05 M . Weight of oxygen = 32gm
2
 weight of metal  100  32  68 gm
16. (c) wt. of metallic chloride  74 .5 wt. of metal
Equivalent weight of oxide  8
wt. of chlorine = 35.5 wt. of oxygen
68
 wt. of metal  74 .5  35 .5  39   8  17 .
32
Equivalent weight of metal
25. (a) 6  10 23 molecules has mass  18 gm
weight of metal
  35 .5 18
weight of chlorine 1 molecules has mass   3  10 23 gm
6  10 23
39
  35 .5  39  3  10 26 kg .
35 .5
26. (a) Choice (a) is P4 S 3
17. (a)  5.8L of gas has mass  7 .5 gm
31  4
 gm P is present in 220gm P4 S 3
7.5 (124 )
 22.4L " " " =  22 .4  28 .96
5.8 220
 1.24gm P is present in =  1 .24  2 .2 gm
So molecular weight = 29 124
x
So, molecular formula of compound is NO 27. (c) Number of moles of A 
40
18. (d)  17gm NH 3 contains 6  10 23 molecules of Number of atoms of
x
NH 3 A  Avogadro no.  y (say)
40
6  10 23 40 y
 4.25gm NH 3 contains =  4 .25 Or x 
17 Avogadro no.
2x
6  10 23  4 .25 Number of moles of B 
 No. of atoms   4  6  10 23 . 80
17
19. (a)  1L of gas at S.T.P. weight 1.16g
 Chemical Arithmetic 25
Number of atoms of B 33. (b) One ion carries 3  1 . 6  10 19 coulomb
2x 2 40 y
  Av.no.    Av.no.  y
80 80 Av.no. Then 1 gm ion N 3  (1 mole) carries
28. (d) BaCO3  BaO  CO2   3  1.6  10 19  6.02  10 23
Molecular weight of
 2 . 89  10 5 coulomb
BaCO3  137  12  3  16 =197
 197gm produces 22.4L at S.T.P. CP
34. (a)  1 .4 so, given gas is diatomic
22 .4 CV
 9.85gm produces  9 .85  1 .12 L at
197
S.T.P. 11.2L  3 .01  10 23 molecules

29. (a) 14 gm N 3  ions have  8 N A valence electrons  No. of atoms  3 .01  10 23  2

 6.023  10 23 atoms
3 8 N A  4.2
4.2gm of N ions have   2.4 N A
14 36. (b) The acid is dibasic.

30. (c) [  Molecular weight of CuSO 4 .5 H 2O Molecular weight of H 3 PO3  3  31  48  82

 63 . 5  32  64  90  249 . 5 ] Molecular weight 82

 Equivalent weight   =
Basicity 2
6  10 23 molecules has weight  249 .5 gm
41.
249 .5  1  10 22
1  10 22
molecules has weight  37. (b)  22400 ml at NTP has 6.023  10 23 molecule
6  10 23
6 .023  10 23
 41 .58  10 1  1 ml at NTP has =
22400
 4 . 158
31. (a) (I) 1 molecule of oxygen
= 0.0002688  10 23  2 .69  10 19 .
 6  10 23 molecule has mass  32 gm
38. (c) Sp. heat × atomic wt.= 6.4
32 0.16 × atomic wt.= 6.4
 1 molecule of O 2 has mass 
6  10 23 6 .4
Atomic wt.   40 .
 5.3  10 23 gm 0.16

(II) 1 atom of nitrogen 39.
 2  6  10 23 atoms of N 2 has mass = 28gm
28
 1 atom of N 2 has mass  842
2  6  10 23
 2.3  10 23 gm
(III) 1  10 10 g molecular weight of oxygen 40.
(a) Molecular weight of C60 H122  12  60  122  1
 720  122  842
 6  10 23
molecule C60 H122 has mass = 842gm
 1 molecule C60 H122 has mass
6  10 23
 140 .333  10 23 gm  1 .4  10 21 gm .
(b) C2 H 4  2O2  2CO2  2 H 2O

g atomic weight  2  1  10 10

 2  10 10
g  28gm C2 H 4 requires 64gm oxygen

(IV) 1  10 10 g atomic weight of copper  2 .8  10 3 gm C2 H 4 requires

64
So, order of increasing masses II  I  III  IV . =  2 .8  10 3 gm  6.4  10 3 gm = 6.4kg.
28
wt. of metal hydroxide EM  EOH  41. (c) 2.5 molal NH 4 OH means 2.5 moles of NH 3 in
32. (d) 
wt. of metal oxide EM  EO 
1000g H 2 O (1000cc of solution)
1 .520 x  17
  Hence, 100cc solution of NH 3 requires = 0.25
0.995 x 8
 1 . 520 x  1 . 520  8  0.995 x  0.995  17 mole
 0 .25  22 .4 L  5 .6 L .
1 . 520 x  12 .160  0 .995 x  16 .915
M M
or 0.525 x  4.755 42. (d) d  ; 1 or M = V; 18gm = 18ml
V V
4 .755
x 9. 6  10 23 molecule of water has volume =18cc
0 .525
 26 Chemical Arithmetic
18 49. (b) One gram of hydrogen combines with 80gm of
1 molecule of water has volume 
6  10 23 bromine.
 3  10 23 cm 3 . So, equivalent weight of bromine = 80gm
43. (a) 100gm caffeine has 28.9gm nitrogen  4gm of bromine combines with 1gm of Ca
28 .9  80gm of bromine combines with =
194gm caffeine has =  194  56 .06 gm 1
100  80  20 .
4
56 .06
 No. of atoms in caffeine  4. 2 4
14 50. (b) Mn SO 4  Mn O2
44. (d) Molecular weight of (CHCOO )2 Fe  170 Change of valency  4  2  2
Fe present in 100mg of (CHCOO )2 Fe M
 Equivalent weight  .
56 2
  100 mg  32 .9 mg 51. (a) 2 PH 3  2 P  3 H 2
170 (solid)
2ml 3ml
This is present in 400mg of capsule 100 ml 150 ml
32 .9 Increase in volume
% of Fe in capsule   100  8 .2 .
400  150 ml  100 ml  50 ml increase.
45. (d) 1 atom has mass  10 .86  10 26 kg 52. (b) Mg  2 HCl  MgCl2  H 2
 10 .86  10 23
gm  24g Mg evolves 22.4L H 2 at STP

6.023  10 23 atoms has mass  12g Mg evolves H 2 at STP

22 .4
 12
= 10 .86  10 23
 6 .023  10 23
= 65 .40 gm 24
=11.2L at STP.
This is the atomic weight of Zn.
46. (b)  1mole (COOH )2 . 2H 2O has 96gm oxygen 53. (b) (a) 2gm atom of nitrogen = 28gm

 0.3 mole (COOH )2 . 2H 2O has (b) 6  10 23 atoms of C has mass  12 gm

96  0 .3  28 .8 gm 3  10 23 atoms of C has mass

28 .8 12  3  10 23
 No. of gram atoms of oxygen   1 .8 .   6 gm
16 6  10 23
47. (c) Equimolecular proportion means both gases (c) 1mole of S has mass = 32gm
2 .24
occupied equal volume   1 .12 L (d) 7.0gm of Ag
2
So, lowest mass = 6gm of C.
For CH4 :
22.4L CH4 has mass  16 gm 54. (c) 1mole of any gas at STP occupies 22.4L.

16 55. (b)  22400cc of gas at STP has

1.12L CH 4 has mass   1.12  0.8 gm .
22 .4 6  10 23 molecules
For C2 H 6  1.12  10 7 of gas at STP has
22.4L C2 H 6 has mass = 30gm 6  10 23  1 .12  10 7
 .03  10 14  3  10 12 .
1.12L C2 H 6 has mass 22400
30 3 .0 56. (a)  2.24L of gas has mass = 4.4gm
  1 .12  gm  1 .5 gm
22 .4 2
4 .4
Total mass  1 .5 gm  0 .8 gm  2 .3 gm .  22.4L of gas has mass   22 .4  44
2 .24
48. (c) Let wt. of metal oxide = 100gm
wt. of metal = 53gm So given gas is CO2 because CO2 has molecular
wt. of oxygen = 47gm mass=44.
wt. of metal 57. (d) 1L of air =210cc O 2
Equivalent weight of oxygen  8
wt. of oxygen
22400cc = 1 mole
53
  8  9 .02 1
47 210 cc   210  0 .0093 .
22400
2  V .D 2  66 132
Valency     2 .96  3 58. (d)  22.4L of a gas at STP has no. of molecules
E  35 .5 9  35 .5 44 .5
 Atomic weight  Equivalent weight  Valency  6.023  10 23
 9.02  3  27 .06
 Chemical Arithmetic 27
 8.96L of a gas at STP has no. of molecules The mole concept
6.02  10 23  8.96
  2 .408  10 23  24 .08  10 22 .
22 .4 16 1
1. (a) 16g O 2 has no. of moles  
59. (a) Given equivalent weight of metal = 9 32 2
Vapour density of metal chloride = 59.25 14 1
14g N 2 has no. of moles  
 molecular weight of metal chloride 28 2

 2  V .D  2  59 .25  118 .5 No. of moles are same, so no. of molecules are

same.
 valency of metal
2. (b) Na2 SO 4 . 10 H 2O  2  23  32  4  16  10  18
molecular weight of metal chloride

equivalnet weight of metal  35.5  46  32  64  180  322 gm
118 . 5 118 . 5 322gm Na2 SO 4 .10 H 2O contains = 224 gm
Valency of metal    2 . 66
9  35 . 5 44 . 5 oxygen
Therefore atomic weight of the metal 32.2gm Na2 SO 4 .10 H 2O contains
=equivalent weight  valency
32 .2  224
 9  2 . 66  23 . 9 =  22 .4 gm
322
molecular wt. of metal
60. (d) The density of gas  W (gm )  1000
volume 3. (b) Molarity 
molecular wt.  V(ml .)
45
  2 gm litre  1 2 .65  1000
22 . 4   0 .1 M
106  250
61. (c) Equivalent weight of bivalent metal = 37.2
10ml of this solution is diluted to 1000ml
 Atomic weight of metal  37 .2  2  74 .4
N1V1  N 2 V2
 Formula of chloride  MCl2
10  0 .1  1000  x
Hence, molecular weight of chloride
0 .1  10
(MCl2 )  74 .4  2  35 .5  145 .4 x  0 .001 M .
1000
62. (c) As we know that
4. (c) According to definition of molar solution  A
weight of metal
Equivalent weight  8 molar solution is one that contains one mole
weight of oxygen of a solute in one litre of the solution.
32
  8  64 5. (a) 44g of CO2 has 2  6  10 23 atoms of oxygen
0 .4
12  10 23
mol. wt 4.4g of CO2 has =  4 .4
Vapour density  44
2
Mol. wt  2  V .D  2  32  64  1 .2  10 23 atoms.
6. (b) 44g CO2 occupies 22.4L at STP
mol. wt 64
As we know that n   1
eq. wt 64 22 .4
4.4g CO2 occupies   4 .4 = 2.24L.
Suppose, the formula of metal oxide be M 2 On . 44

Hence the formula of metal oxide  M 2 O . Mass g

7. (a) Density  ; 1 or g  ml
Volume ml
63. (b) Molecular weight of NH 3 is 17
0.0018ml = 0.0018gm
According to the mole concept No. of
17 gm NH 3 has molecules  6 .02  10 23
moles 
weight

0 . 0018
 1  10  4
Molecular weight 18
6 .02  10 23
 1 gm NH 3 has molecules   No. of water molecules
17
= 6.023  10 23  1  10 4
 4.25 gm NH 3 has molecules
 6 .023  10 19 .
6.02  10 23  4.25 (c) Ca3 P2  6 H 2 O  2PH3  3Ca(OH )2
  1.5  10 23 molecule 8.
17
 28 Chemical Arithmetic
9. (d) Amount of  32  32  2  35 .5 = 135gm
gold  19 . 7 kg  19 .7  1000 gm =19700gm  135 gm of SO 2Cl2 = 1gm molecule
19700 1
No. of moles   100  13.5gm of SO 2 Cl2   13 .5  0 .1 .
197 135
 No. of atoms  100  6 .023  10 23 20. (a) (a) 34gm of water

 6 .023  10 25 atoms.  18gm H 2O = 6 .023  10 23 molecule

10. (c)  100gm CaCO 3  6 .023  10 23 molecules 6.023  10 23

 34gm H 2O =  34
18
6 .023  10 23
 10gm CaCO3 =  10  11 .37  10 23 mole
100
(b) 28gm of CO2
 6 .023  10 22 molecule
1 molecule of CaCO3 = 50 protons  44gm CO2  6  10 23 molecules
6  10 23
6 .023  10 22 molecule of CaCO3  50  6 .023  10 22  28gm CO2   28  3.8  10 23
44
 3 .0115  10 24 (c) 46gm of CH 3OH
11. (b) 16gm of CH4 = 1mole  6 .023  10 23 molecules.
 32gm CH 3 OH  6  10 23 molecules
12. (c) According to avogadro's hypothesis equal
6  10 23
volumes of all gases under similar conditions  46gm CH 3 OH   46  8.625  10 23
32
of temperature and pressure contains equal
no. of molecules. (d)  108gm of N 2 O5  6  10 23 molecules

(d) d 
M 6  10 23
14. (d = density, M= mass, V =volume)  54gm of N 2 O5   54  3  10 23
V 108
Since d = 1 molecules.
So, M  V 21. (b) Sodium oxide  Na2O
18gm = 18ml Molecular weight = 46 +16 = 62
18ml = NA molecules (NA = avogadro's no.) 62gm of Na2O = 1 mole
NA 620gm of Na2O = 10 mole.
1000ml   1000 = 55.555 NA.
18 2 1
22. (b) 2gm of oxygen contains atom   mole
15. (a) This is fact. 16 8
16. (a)  3 moles of oxygen is that in 1 mole of 4 1
also 4g of sulphur   mole.
BaCO3 32 8
23. (c) Molarity = mole/litre
 1.5 moles of oxygen is that in mole of
1 1  1cc contains 1.17gm
BaCO3   1 .5   0 .5 . 1170 gm
3 2  1000cc contains 1170gm
Mol. wt.
17. (b) The no. of molecules present in 1ml of gas at
1170
STP is known as Laschmidt number.   32 .05 mole / litre (Mol. wt. of
36 .5
22400ml of gas has total no. of molecules
HCl=36.5)
 6 .023  10 23 24. (a) 1 mole of sucrose contains
1ml of gas has total no. of molecules
6 .023  10 23 molecules
6 .023  10 23
  1 molecule of sucrose has 45 atoms
22400
 6 .023  10 23 molecule of sucrose has
45  6 .023  10 23 atoms/mole
 2 .69  10 19 .
25. (a) wt of CO2  44
18. (b)  2gm of hydrogen  6 .02  10 23 molecules
 1gm of hydrogen mol wt of CO2  44

6 .02  10 23 wt. of CO2

  3 .01  10 23 molecule. No. of molecule   6.02  10 23
2 mol wt of CO2
19. (a) Molecular weight of SO 2Cl2
 Chemical Arithmetic 29
44 W(gm)  1000 150  40
  6 .02  10 23  6 .02  10 23 1 , W (gm)   6 gm .
44 150  40 1000
26. (c) No. of atoms in one molecule 1 1
2. (c) N 1 V1  N 2 V2 ;  200   V2 ; V2  1000 ml
= no. of moles  6 .022  10 23 2 10
Volume of water added  1000  200  800 ml .
 1.4  6.022  10 23  8.432  10 23

27. (d) As we know that four sodium atom are 3. (a) 2 Ag 2 CO 3  4 Ag  2CO 2  O2
present in sodium ferrocyanide [Na4 Fe(CN )6 ] 2  276 gm 4  108 gm
Hence, number of Na atoms = No. of moles   2  276 gm of Ag2CO3 gives 4  108 gm
number of atom  Avogadro’s number
4  108
2  4  6.023  10 23  48  10 23  1 gm of Ag2CO3 gives 
2  276
Percentage composition & Molecular formula  2.76 gm of Ag2CO3 gives
4  108  2 .76
1. (a)  40gm NaOH contains 16gm of oxygen  2 .16 gm
2  276
16
 100gm of NaOH contains  100 =40% 4. (c)
40
4 NH 3( g )  5 O 2( g )  4 NO( g )  6 H 2 O( g )
oxygen.
t0 1 1 0 0
2. (a) Urea- NH 2  CO  NH 2
tt 1  4x 1  5x 4x 6x
 60gm of urea contains 28gm of nitrogen
Oxygen is limiting reagent
28
 100gm of urea contains  100  46 .66 . 1
60 So, X   0 .2 all oxygen consumed
5
3. (b) Based on facts.
4. (d) C  24 gm , H  4 gm , O  32 gm Left NH 3  1  4  0.2  0.2 .

So, Molecular formula  C2 H 4 O2 5. (c)  100gm Hb contain = 0.33gm Fe

So, Empirical formula  CH 2O 67200  0 .33
 67200gm Hb = gm Fe
100
(Simplest formula).
(a)  0.0835 mole of compound contains 1gm of 672  0 .33
5. gm atom of Fe = 4.
hydrogen 56
 1gm mole of compound contain = 6. (c) ( NH 4 )2 SO 4  2 NH 3  2 HCl
132 2(36 .5 )73 gm
1
 11 .97 73 g HCl  132 g(NH 4 )2 SO 4
0 .0835
=12gm of hydrogen. 292 g HCl  528 g(NH 4 )2 SO 4
12 gm of H 2 is present in C2 H12O6 7. (c) 2( NH 4 )2 HPO 4  P2 O5
2(36 1  31  64 ) 264 62  80 142
6. (b) Empirical formula of an acid is CH2O2
wt. of P2 O 5
(Empirical formula)n  Molecular formula % of P2 O 5   100
wt of salt
n = whole no. multiple i.e. 1,2,3,4..............
142
If n  1 molecular formula CH2O2 .   100  53 .78 % .
264
7. (b) Glucose - C6 H12 O6
3
Ratio of C, H and O  1 : 2 : 1 8. (b) 2 Al  O 2  Al 2 O 3
2
In acetic acid CH 3  C  O  H
|| 3
O According to equation mole of O 2
2
Ratio of C, H and O 1 : 2 : 1 . combines with 2 mole Al.
2 mole Al = 54gm
Chemical stoichiometry
9. (a) 0.5gm Se  100gm peroxidase anhydrous
enzyme
W( gm )  1000
1. (c) N  100  78 .4
V  Eq.wt. 78.4gm Se   1 .568  10 4
0 .5
1500ml of 0.1N HCl = 150ml (N)
 30 Chemical Arithmetic
Minimum m.w.  molecule at least contain 24. (a) NV  N 1 V1  N 2 V2
one selenium. 0.2  2  0.5 x  0.1(2  x )
3
10. (d) H 2 O  Al  NaOH  NaAlO2  H2 0 .4  0 .5 x  0 .2  0 .1 x
27 gm 2
3
22 .4  33 .6 L 0 .2  0 .4 x
2
1
11. (c) In Fe(CNS )3 . 3 H 2 O x L  0 .5 L
2
3  18
% of H 2 O   100  19 % . 25. (d) NV  N1V1  N 2 V2  N 3 V3
284
1 1
12. (d) 5 S  5O2  5 SO 2 ; 5 O2  5 SO 2 ; 5  64  320 gm . N  1000  1  5   20   30  5  10  10  25
2 3
13. (d) H 3 PO4 is tribasic so N  3 M  3  1  3 .
N
14. (b) H 2 SO 4 is dibasic N  2 M  2  2  4 . N  0 .025  .
40
M 200 26. (b) NH 3( g )  HCl ( g )  NH 4 Cl(s )
15. (a) For Dibasic acid E    100
2 2 t0 20 ml 40 ml 0
t t 0 20 ml solid
W  1000
N
E  V (in ml ) Final volume = 20ml.
1 W  1000 27. (b) KMnO4 Oxalic acid
  W  1 gm .
10 100  100 M 1 V1 M V 20  0 . 1 M 2 V2
 2 2 ;  ; M2 V2  5 .
10  sp. gr. of the solution  wt. % of solute  Mol. wt. n1 n2 2 5
16. (b) N 
Molecular wt. of solute  Eq. wt.
M 158
28. (b) Acidic medium E    31 .6 gm .
10  1 .71  80  98 5 5
N   27 .9
98  49 29. (c) 0.1 M AgNO3 will react with 0.1 M NaCl to
18. (c) 2KMnO4  3 H 2 SO 4 
form 0.1 M NaNO3 . But as the volume is
K2 SO 4  2MnSO4  3 H 2O  [O] 0 .1
doubled, conc. of NO3   0 .05 M
2 FeSO 4  H 2 SO 4  [O]  Fe2 (SO 4 )3  H 2 O]  5 2
[Mohrsalt]
30. (a) Acid base
2 KMnO4  10 FeSO 4  8 H 2 SO 4 
N1 V1 = N 2 V2 ; N1  30  0.2  15 ; N1  0.1 N
31. (b) (I) Phenopthalein indicate partial
K 2 SO 4  2MnSO 4  5 Fe2 (SO 4 )3  8 H 2 O
neutralisation of Na2 CO3  NaHCO3
Mohr-salt reducing agent
Meq. of Na2 CO3 + Meq. of NaOH = Meq. of HCl
KMnO 4 / H   oxidising agent
W W
19. (d) Atomic weight = Equivalent weight × Valency  1000   1000  NV
E E
(Suppose Na2 CO3  a gm , NaOH = b gm)
 26.89 
 8.9  3  26 .7  Valency   3 . a b
 8.9   1000   1000  300  0 . 1 .....(1)
106 40
20. (c) MW  2  V .D.  2  22  44 .
(II) Methyl orange indicate complete
21. (d) 2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO 4  3 H 2 O  5[O]
2 neutralisation
7
Change by 5 HCl HCl
N1 V1  N 2 V2 ,
Mol.wt.
Eq. wt.  25  0 . 2  0 . 1  V2 so V2  50 ml excess
5
22. (c) Dibasic acid NaOH; N 1 V1  N 2 V2 
a
 1000 
b
 1000  350  0 .1 .....(2)
53 40
W 1 0 .16 25
 1000   25 ;  1000  From (1) and (2) b =1gm.
E 10 E 10
M  2  E  2  64  128 . 32. (c) From solution of (31)
From equation (1)
23. (d) NaOH HCl
a  Na2 CO3  0.53 gm .
1 1
N1 V1  N 2 V2 ; 20    V ; V = 40ml.
10 20
 Chemical Arithmetic 31

33. (b) (H 2 SO 4 )
M1V1 M 2 V2
 ( NaOH ) 41. (b) AgNO3  2 Ag   S 2   Ag 2 S
n1 n2 (H 2 S )

1  V1 1  10  2 mole  1 mole [100×1 =100

 ; V1  5ml . millimole]
1 2
34. (c) Atom in highest oxidation state can oxidize  100 miliimole  50 millimole H2S
iodide to liberate I2 which is volumetrically required
measured by iodometric titration using hypo. CuSO 4  Cu 2  S 2   CuS
(H 2 S )
2 I   I2
 1 mole  1 mole [100×1=100
Pb2  Lowest oxidation state can not oxidise millimole]
iodide to I2 .  100 millimole  100 millimole H2S
35. (d) KMnO4  Mohr salt required
M1 V1 M 2 V2 0 .1  10 M 2 V2 50 1
 .
 ;  ; M2 V2  5 . Ratio
n1 n2 1 5 100 2
36. (d) The equivalent weight of 42. (c) At room temperature
molecular weight 2 H 2(g)  O2(g)  2 H 2 O(l)
H 3 PO4 
2 t =0 50ml 50ml 0
 mole wt of H3 PO4 = 3 + 31 + 64 = 98 t =t 50 – 2x 50 – x 2x
98 =0 25gases
  49
2 (50)liquid
37. (b) Ba(OH )2  CO2  BaCO3  H2O In this case H 2 is limiting reagent
Atomic wt. of BaCO3 = 137  12  16  3 = 197 x = 25ml
wt. of substance At 110°C 2 H 2(g)  O2(g)  2 H 2 O(g) Vgas  75 ml
No. of mole 
mol wt. t =t 0 25ml 50ml
 1 mole of Ba(OH )2 gives 1 mole of BaCO3 2 2 2 1
43. (c) CuSO 4  2 KI  K 2 SO 4  CuI 2 ; 2 CuI 2  CuI 2  I2
 205 mole of Ba(OH )2 will give .205 mole of
BaCO3 I2  2 Na2 S 2O3  2 NaI  Na2 S 4 O6

 wt. of 0.205 mole of BaCO3 will be Eq. wt. Of CuSO4 .5 H 2O  Mol.wt.  250
.205  197  40 .385 gm  40 .5 gm 100 ml of 0.1 N hypo  100 ml of 0.1 N
38. (d) N1  0.5 N  10 mg per mL CuSO 4 .5 H 2O
250  0.1  100
10  10 3 gm   2 .5 gm
N2   1000 =0.25N 100
40  1
44. (d) HNO3  KOH  KNO3  H 2O
V1  500 ml , V2  ?
N1V1  N 2 V2 ; 0.5  500  0.25  V2 12 .6
 0.2 mole; HNO 3  KOH
63
V2  1000 mL final volume water added = 1000
0.2 mole  0.2 mole
– 500
0 .2  56  11 .2 gm .
= 500mL.
39. (a) eq. of KMnO4 = eq. of Fe(C2O4 ) 45. (a) Isobutane and n-butane C4 H10  have same

x 5  13 molecular formula;

x  0 .6 C4 H10 
13
O2  4 CO2  5 H 2 O
40. (b) 2
Element At.w Mol Rati Empirical For 58gm of C4 H10 208 gm O 2 is required
t. e o formula 5  208
C =86% 12 7.1 1 CH2 then for 5 kg of C4 H10 O2   17 .9 k g
58
H =14% 1 14 2 Beleongs
16 .8
to 46. (b) n   0 .75 mole of H 2 and O 2
22 .4
alkene
0 .25 O2
Cn H 2n 2 H 2 O  2 H 2  O 2 0 .75
0 .25 H2
2:1
 32 Chemical Arithmetic
2 mole H 2 – 2 mole H 2 O 55. (b) Cd 2  S 2   CdS
0.5 mole H 2 – 0.5 mole H 2 O = 9gm. 20×1= 20
47. (a)  3ml (O)  1ml O 3 Cu 2  S 2   CuS
30ml (O)  10ml O 3 20×0.5 =10
150  10 Ratio = 2 : 1
x  15 ml
100
56. (b) Mg 2  H 2
V of O2  V of O3  135  10  145 ml
12 gm 1
Turpentine oil absorb ozone. n  mole of H 2
24 gm 2
48. (a) 50% HCl itself means 50gm HCl react with
100gm sample 1
57. (a) Mg  O2  MgO
50 1mole 2
% Purity   100  50 % . 0 .5 mole
100
0.5 mole of oxygen react with 1 mole of Mg
49. (a) AgNO3  HCl  AgCl  HNO 3
1 .5
30 500  0 . 2 1.5 mole of oxygen react with  3 mole
0 .5
170 1000
24  3  72 gm .
t =0 0.176 mole 0.1 mole limiting
=14.345gm 58. (c) CaCO 3  2 HCl  CaCl 2  CO 2  H 2 O
100 g 2N 44 g
t =t 0.076 mole 0 0.1mole
100 g CaCO3 with 2 N HCl gives 44 g CO2
50. (d) KMnO4 FeSO 4
100 g CaCO3 with 1 N HCl gives 22 g CO2
M 1 V1 M 2 V2 n
= ; M1V1  1 M 2 V2
n1 n2 n2 Critical Thinking Questions
2 1 1
  10    0.2 2. (b) H 2 O contains H and O in a fixed ratio by
10 10 5
1 mass. It illustrates the law of constant
For (d), M1 V1  0 .02  10  composition.
5
3. (b) 100 g of ZnSO4 crystals are obtained from
OR
51. (c) ROH  CH 3 MgI  CH 4  Mg =22.65g Zn
I
1 mol. 1 mol  22400 cc 1g ofZnSO4 crystals will be obtained
22 .65
1.12 mL is obtained from 4.12 mg from  g Zn
100
 22400 mL will be obtained from
20 g of ZnSO4 crystals obtained from
4 .12 22 .65
 22400 mg  84 .2 g   20  4 .53 g
1 .12 100
52. (b) 4. (a) If same volume is occupied by the gas, the no.
of molecules are same, so no. of moles are
Element %(a) At.wt.( a/b Rati
same.
b) o
1 mole of N 2 gas  2  14  28 gm
X 50 10 5 2
1 mole of CO gas  12  16  28 gm
Y 50 20 2.5 1
75
Simplest formula  X 2Y 5. (c) Heat capacity of water per gram   4 .17
18
53. (a) A3 (BC4 )2  3  2  [5  (2  4)]2  0 .
Q = mST
54. (b) CaCO3  CaO  CO 2 1000  100  4.17  t
10 gm
1000
t  2 .4 K .
9 100  4 .17
90% pure 9gm  mole
100 6. (b)  8gm sulphur is present in 100gm of
CaCO3  CO2  0.09 mole substance
100
At NTP Vol. CO2  0.09  22 .4  2.016 L .  32gm sulphur will present =  32  400 .
8
 Chemical Arithmetic 33
7. (b) (a) 6.023  10 23 molecules of CO2 N1V1  N 2 V2 ; 0.1  V1  0.2  30 ; V1  60 ml

No. of atoms  3  6.023  10 21 = 18 .069  10 21 V total (HCl) = 100ml

atoms V1 = 60ml
(b) 22.4L of CO2 40ml
No. of atoms 40ml 0.1N HCl is now neutralised by KOH
= 6 .023  10 23  3  18 .069  10 23 atoms (0.25N) 
(c) 0.44gm of CO2 (HCl) N1V1  N 2 V2 (KOH)
0 .44 1 0.1  40  0.25  V2 ; V2  16 ml .
No. of moles    6 .023  10 23 moles
44 100 15. (c) BCl3  3[H ]  B  3 HCl
 6.023  10 21 moles  3  6.023  10 21 atoms
3 21 .6
BCl3  H 2  B  3 HCl ; B   2 mole
18 .069  10 21 atoms 2 10 .8
8. (b) It is about 22.4L. 3
3
B H2
9. (a) 200mg of CO2 = 200  10  0.2 gm 2
3
44gm of CO2 = 6  10 23 molecules 1mole  mole ; 2 mole – 3 mole
2
6  10 23 V  3  22 .4  67 .2 L .
0.2gm of CO2 =  0.2  0.0272  10 23
44
W V W 112
16. (c) n   ;  ; W  0 .08 gm .
 2.72  10 21 molecule M 22400 16 22400
Now 10 21 molecule are removed. 12 WCO 2 12 2 .63
17. (a) %C    100    100  83 .6 %
So remaining molecules  2.72  10 21  10 21 44 W 44 0 .858

 10 21 (2.72  1) = 1.72  10 21 molecules 2 WH 2 O 2 1 .28

%H    100    100  16 .4 %
18 W 18 .858
Now, 6 .023  10 23 molecules = 1mole
Element
%(a At.wt.( a/b Rati
1.72  10 21 molecules ) b) o ×3
1  1.72  10 21 C 83. 12 6.96 1
  0.285  10  2 7
6.023  10 23 6
 2 .85  10 3 . H 16.4 1 16.4 2.3
10. (d) 2K 2 Cr2 O4  2HCl  K 2 Cr2 O7  2KCl  H 2 O C3 H7  12  3  7  43 gm .

11. (a) Meq of Mg 2  Meq of washing soda 18. (b) SO 2  2 H 2 O  S  2 H 2 O 2

4 0
W 24
1000  Mg 2 ; EW   12 M 64
E 2 EW    16 ; Twice 16  2  32
4 4
3
12  10
 1000  1 .
12 Assertion & Reason
12. (c) K 2 Cr 2 O 7  4 H 2 SO 4  K 2 SO 4  Cr 2 (SO 4 )3
 12/two atom  6/two atom 1. (e) We know that from the reaction
Change by 6 H 2  Cl2  2 HCl that the ratio of the volume of
4 H 2 O  3[O]
gaseous reactants and products is in
Mol.wt.
Eq. wt.  agreement with their molar ratio. The ratio of
6
H2 : Cl2 : HCl volumes is 1 : 1 : 2 which is the
13. (a) KMnO4 = Mohr salt
same as their molar ratio. Thus volume of gas
M 1 V1 M 2 V2  W  V
   1000   2 is directly related to the number of moles.
1 5  M  V  5 Therefore, the assertion is false but reason is
 W  1000  3 .92  1000 20 true.
 58  1000   18  
  392  1000 5
2. (e) We know that molecular weight of substance
W=3.476gm/L.
is calculated by adding the atomic weight of
14. (d) Volume m of HCl neutralised by NaOH =
atoms present in one molecules. We also know
(Caustic soda) = V1
 34 Chemical Arithmetic
that molecular weight of oxygen (O2 ) =2x M
8. (c) Vapour density of B  ,
(Atomic weight of oxygen)  2  16  32 a.m.u. 2

Atomic weight of oxygen is 16, because it is 16 M

Vapour density of A  4   2M
times heavier than1/12th
of carbon atom. 4
Therefore assertion is false but reason is true. Molecular mass of A  2  2 M  4 M .
3. (c) According to Dalton's atomic theory atoms can 9. (a) Pure water always contains hydrogen and
neither be created nor destroyed and oxygen in the ratio 1 : 8 by mass. This is in
according to berzelius hypothesis, under accordance with the law of constant
similar condition of temperature and pressure composition.
equal volumes of all gases contain equal no. of
10. (b) The number of moles of a solute present in
atom. Therefore assertion is true but reason is
litre of solution is known is as molarity (M).
false.
The total no. of molecules of reactants present
4. (e) One mole of any substance corresponding to in a balanced chemical equation is known as
6 .023  10 23 entities is respective of its weight. molecularity. For example,

Molecular weight of SO 2  32  2  16  64 gm . PCl5  PCl3  Cl2 (Unimolecular)

Molecular weight of O2  16  2  32 gm . 2HCl  H2  I2 (Bimolecular)

 Molarity and molecularity are used in

 Molecular weight of SO 2 is double to that
different sense.
of O 2 .
11. (a) Both assertion and reason are true and reason
5. (d) 1.231 has four significant figures all no. from is the correct explanation of assertion.
left to right are counted, starting with the
12. (e) Equivalent wt. of Cu in CuO
first digit that is not zero for calculating the
63 . 6 At.wt.
no. of significant figure. =  =31.8
2 Valency
6. (d) Molar volume (at NTP) = 22.4L 63 .6
Equivalent wt. of Cu in Cu 2 O  =63.6
Now 22.4L of N 2  volume occupied by one 1

mole of N 2  28 gm  6 . 023  10 23 molecules. (Valency of Cu =1).

13. (e) Mass spectrometer is the instrument used for
Similarly, O2  2  16  32 gm ,
the determination of accurate atomic mass
32 gm  6.023  10 23 molecules = 22.4L and the relative abundance of the isotopes.
14. (a) Both assertion and reason are true and reason
 22 .4 L  6.023  10 23 or
is the correct explanation of assertion.
6.023  10 23  5.6
5.6 L 
22 .4 15. (a) Example of isomorphous compounds are
K2 SO3 , K2CrO4 , K2 SeO 4 (valency of S, Cr, Se =
6) and
1
  6 .023  10 23 ZnSO4 . 7 H2O, MgSO4 . 7 H2O, FeSO4 . 7 H2O
4
(valency of Zn, Mg, Fe =2).
According to avagadro's hypothesis equal
16. (b) No. of atoms present in a molecules of a
volume of all gases contain equal no. of
gaseous element is called atomicity.
molecules under similar condition of
temperature and pressure. For example, O 2 has two atoms and hence its

7. (a) For universally accepted atomic mass unit in atomicity is 2.

1961, C-12 was selected as standard. 17. (a) 12gm of C-12 contain 6 .023  10 23 atom
However the new symbol used is 'v' (unified
12
mass) in place of amu.   10  23  1 .66  10  24 .
6.023
 34 Chemical Arithmetic

1. A mixture of sand and iodine can be separated by 7. The maximum amount of BaSO 4 precipitated on
[Kerala CEE 2002] mixing equal volumes of BaCl2 (0.5 M) with
(a) Crystallisation (b) Sublimation H 2SO4 (1M) will correspond to
(c) Distillation (d) Fractional (a) 0.5 M (b) 1.0 M
distillation
(c) 1.5 M (d) 2.0 M
2. The element similar to carbon is
8. Crystals of which pair are isomorphous[MP PMT 1985]
(a) Mg (b) Mn
(a) ZnSO4 , SnSO 4 (b) MgSO4 , CaSO4
(c) Sn (d) Po
(c) ZnSO4 , MgSO4 (d) PbSO4 , NiSO4
2. The law of multiple proportions was proposed by
9. M is the molecular weight of KMnO4 . The
[IIT 1992]
equivalent weight of KMnO4 when it is converted
(a) Lavoisier (b) Dalton
into K2 MnO4 is
(c) Proust (d) Gay-Lussac
(a) M (b) M / 3
4. 1 L of N 2 combines with 3 L of H 2 to form 2L of
(c) M / 5 (d) M / 7
NH 3 under the same conditions. This illustrates
the 10. An aqueous solution of 6.3 g of oxalic acid
dihydrate is made up of to 250 ml. The volume of
(a) Law of constant composition
0.1 N NaOH required to completely neutralise 10
(b) Law of multiple proportions
ml of this solution is [IIT 2001]
(c) Law of reciprocal proportions
(a) 40 ml (b) 20 ml
(d) Gay-Lussac’s law of gaseous volumes
(c) 10 ml (d) 4 ml
5. One sample of atmospheric air is found to have 11. The normality of orthophosphoric acid having
0.03% of carbon dioxide and another sample purity of 70% by weight and specific gravity 1.54
0.04%. This is evidence that would be [CPMT 1992]
(a) The law of constant composition is not always (a) 11N (b) 22N
true
(c) 33N (d) 44N
(b) The law of multiple proportions is true
12. The equivalent weight of phosphoric acid (H 3 PO4 )
(c) Air is a compound
in the reaction, NaOH  H3 PO4  NaH2 PO4  H2O
(d) Air is a mixture
is
6. One part of an element A combines with two parts [AIIMS 1999; BHU 2005]
of another B. Six parts of the element C combine
(a) 25 (b) 49
with four parts of the element B. if A and C
(c) 59 (d) 98
combine together the ratio of their weights will
be governed by [AMU 1984] 13. Volume of 0.6 M NaOH required to neutralize

(a) Law of definite proportion 30 cm 3 of 0.4 M HCl is [KCET 1995]

(b) Law of multiple proportion (a) 30 cm 3 (b) 20 cm 3

(c) Law of reciprocal proportion
(c) 50 cm 3 (d) 45 cm 3
(d) Law of conservation of mass
 Chemical Arithmetic 35
14. One mole of potassium dichromate completely 15. The number of equivalents of Na2 S 2O3 required
oxidises the following number of moles of ferrous for the volumetric estimation of one equivalent of
sulphate in acidic medium [MP 2  1998]
CuPET is
(a) 1 (b) 3 [Kerala MEE 2000]
(c) 5 (d) 6 (a) 1 (b) 2
(c) 3/2 (d) 3

(SET -1)

1. (b) Iodine shows sublimation and hence

volatalizes on heating, the vapour condenses
on cooling to give pure iodine.
2. (c) Carbon and tin both are same group elements
so have similarities in properties.
3. (b) Law of multiple proportions was proposed by
Dalton and verified by Berzelius.
4. (d) Gay- Lussac's law : The volumes of the
reacting gases and those of the gaseous
products bear the simple ratio (also called the
law of gaseous volumes).
10. (a) Oxalic acid NaOH
5. (d)
N 1 V1  N 2 V2
6. (c) The weights of two elements combining with a
fixed amount of the third element will bear  W 1000 
the same ratio(or simple multiple of it) in E  V   V1  N 2 V2
 
which they themselves react.
6 .3 1000
7. (a) BaCl2  H 2 SO 4  BaSO4  2 HCl   10  0 .1  V V= 40ml.
63 250
One mole of BaCl2 reacts with one mole of
11. (a) 70% by weight 70 gm H 3 PO4  100 gm
H 2 SO 4 . Hence 0.5 mole will react with 0.5
solution/sample
mole of H 2 SO 4 i.e. BaCl2 is the limiting
W 100 70  1000
reagent. V  N  11 N .
d 1 .54 98  100 / 1 .54
8. (c) Isomorphous substance molecules contain the
same number of atoms bonded in similar 12. (d) NaOH  H 3 PO 4  NaH 2 PO 4
(PO 43 ) ( NaPO 4 2 )
fashion.
7 6 MW 98
9. (a) KMnO4  K 2 MnO4 EW   .
no. of ionisable H  1
Change in 0.5 per atom  7  6  1 13. (b) NaOH HCl
 Equivalent weight of KMnO4 N1V1  N 2 V2 ; 0.6  V1  0.4  30 ; V1  20 ml .
Molecular weight of KMnO 4 M
  M. 14. (d) Cr2 O7  Cr 3  ; Fe    Fe   
Change of 0.5 per atom 1
n6 n 1

eq. of K2Cr2O7 = eq. of FeSO4

*** 1  6  x 1
2 
15. (b) Cu  2 I  CuI 2 2CuI2  Cu2 I2  I2

I2  2 Na2S 2 O3  2 NaI  Na2 S 4 O6

36 Chemical Arithmetic
Cu 2   2 Na 2 S 2 O3
 36 Structure of atom
John Dalton 1808, believed that matter is made
up of extremely minute indivisible particles, called
atom which can takes part in chemical reactions. These
can neither be created nor be destroyed. However,
modern researches have conclusively proved that atom
is no longer an indivisible particle. Modern structure of
atom is based on Rutherford’s scattering experiment on
atoms and on the concepts of quantization of energy.
Composition of atom
The works of J.J. Thomson and Ernst Rutherford
actually laid the foundation of the modern picture of the
atom. It is now believed that the atom consists of several
sub-atomic particles like electron, proton, neutron,
positron, neutrino, meson etc. Out of these particles, the
electron, proton and the neutron are called fundamental
subatomic particles and others are non-fundamental
particles.
Electron (–1eo)
(1) It was discovered by J.J. Thomson (1897) and
is negatively charged particle. Electron is a component
particle of cathode rays.
(2) Cathode rays were discovered by William
Crooke's & J.J. Thomson (1880) using a cylindrical
hard glass tube fitted with two metallic electrodes. The
tube has a side tube with a stop cock. This tube was
known as discharge tube. They passed electricity
(10,000V) through a discharge tube at very low
pressure ( 10 2 to 10 3 mm Hg ) . Blue rays were emerged
from the cathode. These rays were termed as Cathode
rays.
(3) Properties of Cathode rays
(i) Cathode rays travel in straight line.
Chapter
2
Structure of atom
(ii) Cathode rays produce mechanical effect, as
they can rotate the wheel placed in their
path.
(iii) Cathode rays consist of negatively charged
particles known as electron.
(iv) Cathode rays travel with high speed
approaching that of light (ranging between
10 9 to 10 11 cm/sec)
(v) Cathode rays can cause fluorescence.
(vi) Cathode rays heat the object on which they
fall due to transfer of kinetic energy to the
object.
(vii) When cathode rays fall on solids such
as Cu, X  rays are produced.
(viii) Cathode rays possess ionizing power i.e.,
they ionize the gas through which they pass.
(ix) The cathode rays produce scintillation on the
photographic plates.
(x) They can penetrate through thin metallic
sheets.
(xi) The nature of these rays does not depend upon
the nature of gas or the cathode material used
in discharge tube.
(xii) The e/m (charge to mass ratio) for
cathode rays was found to be the same as that
for an e  (1.76  10 8 coloumb per gm). Thus,
the cathode rays are a stream of electrons.
(xiii) According to Einstein’s theory of
relativity, mass of electron in motion is, m 
Rest mass of electron(m)

[1  (u / c) 2 ]
 Structure of atom 37
Where u = velocity of electron, c= velocity of and observed the formation of anode rays. These rays
light. also termed as positive or canal rays.
When u=c than mass of moving electron =. (3) Properties of anode rays

Proton (1H1, H+, P) (i) Anode rays travel in straight line.

(ii) Anode rays are material particles.
(1) Proton was discovered by Goldstein and is
positively charged particle. It is a component particle (iii) Anode rays are positively charged.
of anode rays.
(2) Goldstein (1886) used perforated cathode in
the discharge tube and repeated Thomson's experiment
Table : 2.1 Comparison of mass, charge and specific charge of electron, proton and neutron

Name of constant Unit Electron(e–) Proton(p+) Neutron(n)

Amu 0.000546 1.00728 1.00899
Mass (m) Kg 9.109 × 10–31 1.673 × 10–27 1.675 × 10–27
Relative 1/1837 1 1

Coulomb (C) – 1.602 × 10–19 +1.602 × 10–19 Zero

Charge(e) Esu – 4.8 × 10–10 +4.8 × 10–10 Zero
Relative –1 +1 Zero
Specific charge (e/m) C/g 1.76 × 108 9.58 × 104 Zero
Density Gram / cc 2.17  10 17 1 .114  10 14 1 .5  10 14

 The atomic mass unit (amu) is 1/12 of the mass of an individual atom of 6 C 12 , i.e. 1.660  10 27 kg .
Table : 2.2 Other non fundamental particles
Particle Symbol Nature Charge esu Mass Discovered by
10–10
(amu)
 
Positron e , 1e , 
0 + + 4.8029 0.0005486 Anderson (1932)

Neutrino  0 0 < 0.00002 Pauli (1933) and Fermi (1934)

Anti-proton p – – 4.8029 1.00787 Chamberlain Sugri (1956) and Weighland
(1955)
Positive mu meson
 + + 4.8029 0.1152 Yukawa (1935)

Negative mu meson
 – – 4.8029 0.1152 Anderson (1937)

Positive pi meson  + + 4.8029 0.1514

Negative pi meson  – – 4.8029 0.1514 Powell (1947)

Neutral pi meson 0 0 0 0.1454

(iv) Anode rays may get deflected by external (viii) These rays produce flashes of light on ZnS
magnetic field. screen.

(v) Anode rays also affect the photographic plate. Neutron (on1, N)

(vi) The e/m ratio of these rays is smaller than (1) Neutron was discovered by James Chadwick
that of electrons. (1932) according to the following nuclear reaction,

(vii) Unlike cathode rays, their e/m value is 4 Be 9  2 He 4  6 C 12  o n 1

dependent upon the nature of the gas taken in the tube.
It is maximum when gas present in the tube is or 5 B 11  2 He 4  7 N 14  o n 1
hydrogen.
 38 Structure of atom
(2) Neutron is an unstable particle. It decays as (iii) Atomic number = Number of positive charge
follows, on nucleus = Number of protons in nucleus = Number
of electrons in nutral atom.
 1 H 1   0
1 0 0
0n 1 e (iv) Two different elements can never have
neutron Proton electon antinutrin o
identical atomic number.
Atomic number, Mass number and Atomic species (2) Mass number
(1) Atomic number or Nuclear charge Mass number (A) = Number of protons or Atomic
(i) The number of protons present in the nucleus number (Z) + Number of neutrons or Number of
of the atom is called atomic number (Z). neutrons = A – Z .
(i) Since mass of a proton or a neutron is not a
(ii) It was determined by Moseley as,
1
s whole number (on atomic weight scale), weight is not
  a(Z  b ) or aZ  ab necessarily a whole number.
Z
Where,   X  ray’s frequency Fig. 2.1
(ii) The atom of an element X having mass
Z= atomic number of the metal a&b are number (A) and atomic number (Z) may be represented
constant. by a symbol, Z XA .

Table: 2.3 Different types of atomic species

Atomic species Similarities Differences Examples

(i) Atomic No. (Z) (i) Mass No. (A) (i) 11 H , 12 H , 13 H
(ii) No. of protons (ii) No. of neutrons 16
(ii) 8 O, 17 18
8 O, 8 O
(iii) No. of electrons (iii) Physical properties
Isotopes 35 37
(iii) 17 Cl , 17 Cl
(iv) Electronic configuration
(Soddy)
(v) Chemical properties
(vi) Position in the periodic
table
(i) Mass No. (A) (i) Atomic No. (Z) (i) 40
18
40
Ar , 19 K , 40
20 Ca

(ii) No. of nucleons (ii) No. of protons, electrons 130

(ii) 52 Te , 130 130
54 Xe , 56 Ba
and neutrons
Isobars (iii)Electronic configuration
(iv) Chemical properties
(v) Position in the perodic
table.
No. of neutrons (i) Atomic No. (i) 30
14
31
Si , 15 32
P, 16 S
(ii) Mass No., protons and 39
(ii) 19 K , 40
20 Ca
electrons.
3
(iii) Electronic configuration (iii) 1 H , 42 He
Isotones
(iv) Physical and chemical (iv) 13
C , 14
6 7 N
properties
(v) Position in the periodic
table.
Isotopic No. (i) At No., mass No., (i) 92 U 235 , 90 Th 231
(N – Z) or (A – 2Z) electrons, protons, neutrons.
Isodiaphers (ii) 19 K 39 , 9 F 19
(ii) Physical and chemical
properties. (iii) 29 Cu 65 , 24 Cr 55
 Structure of atom 39
(i) No. of electrons At. No., mass No. (i) N 2 O, CO 2 , CNO  (22 e  )
(ii) Electronic configuration
(ii) CO , CN  , N 2 (14 e  )
Isoelectronic
species (iii) H  , He , Li  , Be 2  (2e  )

(iv)
P 3  , S 2  , Cl  , Ar , K  and Ca 2  (18 e  )

(i) No. of atoms (i) N 2 and CO

(ii) No. of electrons (ii) CO2 and N 2 O
(iii) Physical and chemical
Isosters (iii) HCl and F2
properties.
(iv) CaO and MgS

(v) C6 H 6 and B3 N 3 H 6

denoted by the symbol  (nu) and is expressed in terms

Electromagnetic radiations of cycles (or waves) per second (cps) or hertz (Hz).
(1) Light and other forms of radiant energy   distance travelled in one second = velocity =c
propagate without any medium in the space in the form c
of waves are known as electromagnetic radiations. 

These waves can be produced by a charged body
(iii) Velocity : It is defined as the distance
moving in a magnetic field or a magnet in a electric
covered in one second by the wave. It is denoted by the
field. e.g.   rays,   rays, cosmic rays, ordinary light
letter ‘c’. All electromagnetic waves travel with the
rays etc.
same velocity, i.e., 3  10 10 cm / sec .
(2) Characteristics
c    3  10 10 cm / sec
(i) All electromagnetic radiations travel with the
velocity of light. (iv) Wave number : This is the reciprocal of
wavelength, i.e., the number of wavelengths per
(ii) These consist of electric and magnetic
centimetre. It is denoted by the symbol  (nu bar). It is
fields components that oscillate in directions
perpendicular to each other and perpendicular to expressed in cm 1 or m 1 .
the direction in which the wave is travelling. 1
 
(3) A wave is always characterized by the 
following five characteristics, (v) Amplitude : It is defined as the height of the
(i) Wavelength : The distance between two crest or depth of the trough of a wave. It is denoted by
nearest crests or nearest troughs is called the the letter ‘A’. It determines the intensity of the
wavelength. It is denoted by  (lambda) and is radiation.
measured is terms of centimeter(cm), angstrom(Å), The arrangement of various types of
micron(  ) or nanometre
Crest (nm).
Wavelengt electromagnetic radiations in the order of their
h increasing or decreasing wavelengths or frequencies is
Vibrating
source known as electromagnetic spectrum.
Energy Table: 2.4
Name Wavelength (Å) Frequency (Hz)
Radio wave 3  10 14  3  10 7 1  10 5  1  10 9
Trough Microwave 3  10 7  6  10 6 1  10 9  5  10 11
Fig. 2.2
Infrared (IR) 6  10 6  7600 5  10 11  3 .95  10 16
Visible 7600  3800 3.95  10 16  7.9  10 14
1 Å  10 8 cm  10 10 m ; 1  10 4 cm  10 6 m ;
Ultraviolet 3800  150 7.9  10 14  2  10 16
7 9
1nm  10 cm  10 m ; 1cm  10 Å  10   10 nm
8 4 7 (UV)
X-Rays 150  0 . 1 2  10 16  3  10 19
(ii) Frequency : It is defined as the number of
  Rays 0 . 1  0 . 01 3  10 19  3  10 20
waves which pass through a point in one second. It is
Cosmic Rays 0.01- zero 3  10 20  infinity
 40 Structure of atom
Atomic spectrum - Hydrogen spectrum

Atomic spectrum
Spectrum is the impression produced on a
photographic film when the radiation (s) of particular (2) This model failed to explain the line spectrum
wavelength (s) is (are) analysed through a prism or of an element and the scattering experiment of
diffraction grating. Rutherford.
Types of spectrum Rutherford's nuclear model
(1) Emission spectrum : Spectrum produced by
(1) Rutherford carried out experiment on the
the emitted radiation is known as emission spectrum.
bombardment of thin (10–4 mm) Au foil with high speed
This spectrum corresponds to the radiation emitted
(energy evolved) when an excited electron returns back positively charged   particles emitted from Ra and
to the ground state. gave the following observations based on this
(i) Continuous spectrum : When sunlight is passed experiment,
through a prism, it gets dispersed into continuous bands (i) Most of the  particles passed without any
of different colours. If the light of an incandescent object deflection.
resolved through prism or spectroscope, it also gives (ii) Some of them were deflected away from their
continuous spectrum of colours.
path.
(ii) Line spectrum : If the radiation’s obtained by
(iii) Only a few (one in about 10,000) were
the excitation of a substance are analysed with help of
returned back to their original direction of
a spectroscope a series of thin bright lines of specific
propagation. Deflecte
colours are obtained. There is dark space in between d
two consecutive lines. This type of spectrum is called -
line spectrum or atomic spectrum.. particles
-rays
(2) Absorption spectrum : Spectrum produced by +ve
the absorbed radiations is called absorption spectrum. Nucleus
Hydrogen spectrum
(1) Hydrogen spectrum is an example of line
emission spectrum or atomic emission spectrum.
Fig. 2.4 ZnS
(2) When an electric discharge is passed through screen
hydrogen gas at low pressure, a bluish light is emitted.
(3) This light shows discontinuous line spectrum (2) From the above observations he concluded
of several isolated sharp lines through prism. that, an atom consists of
(4) All these lines of H-spectrum have Lyman, (i) Nucleus which is small in size but carries the
Balmer, Paschen, Barckett, Pfund and Humphrey series. entire mass i.e. contains all the neutrons and protons.
These spectral series were named by the name of (ii) Extra nuclear part which contains electrons.
scientist discovered them. This model was similar to the solar system.
(5) To evaluate wavelength of various H-lines Ritz (3) Properties of the nucleus
introduced the following expression, (i) Nucleus is a small, heavy, positively charged
1 portion of the atom and located at the centre of the
1  1 
    R 2  2  atom.
 c  n1 n 2 
(ii) All the positive charge of atom (i.e. protons)
Where R is universal constant known as Rydberg’s are present in nucleus.
constant its value is 109, 678 cm 1 . (iii) Nucleus contains neutrons and protons, and
Plum pudding model of Thomson hence these particles collectively are also referred to as
nucleons.
(1) He suggected that atom is a positively
(iv) The size of nucleus is measured in Fermi (1
charged sphere having electrons embedded uniformly
Fermi = 10–13 cm).
giving an overall picture of plum pudding.
Positively (v) The radius of nucleus is of the order of
+ – + charged sphere 1 .5  10 13 cm . to 6 .5  10 13 cm . i.e. 1 .5 to 6 .5 Fermi.
– + –
– + Electron
+
+ – unifromly
– + embedded
Positive charge spreaded throughout the
sphere
Fig. 2.3

Generally the radius of the nucleus ( rn ) is given by the
following relation,
rn  ro ( 1 . 4  10 13 cm )  A 1 / 3
This exhibited that nucleus is 10 5 times small in
size as compared to the total size of atom.
(vi) The Volume of the nucleus is about 10 39 cm 3
and that of atom is 10 24 cm 3 , i.e., volume of the nucleus
is 10 15 times that of an atom.
(vii) The density of the nucleus is of the order of
10 15 g cm 3 or 10 8 tonnes cm 3 or 10 12 k g / cc . If nucleus
is spherical than,
Density
mass of the nucleus mass number
= 
volume of the nucleus 4
6 . 023  10 23  r 3
3
(4) Drawbacks of Rutherford's model
(i) It does not obey the Maxwell theory of
electrodynamics, according to it “A small charged
particle moving around an oppositely charged centre
continuously loses its energy”. If an electron does so, it
should also continuously lose its energy and should set
up spiral motion ultimately failing into the nucleus.
(ii) It could not explain the line spectra of H 
atom and discontinuous spectrum nature.
Planck's quantum theory
When black body is heated, it emits thermal
radiation’s of different wavelengths or frequency. To
explain these radiations, max planck put forward a
theory known as planck’s quantum theory.
(i) The radiant energy which is emitted or
absorbed by the black body is not continuous but
discontinuous in the form of small discrete packets of
energy, each such packet of energy is called a
'quantum'. In case of light, the quantum of energy is
called a 'photon'.
(ii) The energy of each quantum is directly
proportional to the frequency (  ) of the radiation, i.e.
hc
E   or E  hv 
 2
Where, h  Planck's constant = 6.62×10–27 erg.
sec. or 6 . 62  10 34 Joules sec .
(iii)The total amount of energy emitted or
absorbed by a body will be some whole number quanta.
Hence E  nh  , where n is an integer.
Photoelectric effect
(1) When radiations with certain minimum
frequency ( 0 ) strike the surface of a metal, the
electrons are ejected from the surface of the metal.
Structure of atom 41
This phenomenon is called photoelectric effect and the
electrons emitted are called photo-electrons. The
current constituted by photoelectrons is known as
photoelectric current.
(2) The electrons are ejected only if the radiation
striking the surface of the metal has at least a
minimum frequency ( 0 ) called Threshold frequency.
The minimum potential at which the plate photoelectric
current becomes zero is called stopping potential.
(3) The velocity or kinetic energy of the electron
ejected depend upon the frequency of the incident
radiation and is independent of its intensity.
(4) The number of photoelectrons ejected is
proportional to the intensity of incident radiation.
(5) Einstein’s photoelectric effect equation
According to Einstein,
Maximum kinetic energy of the ejected electron =
absorbed energy – threshold energy
1 1 1 
2
mv max  h   h  0  hc   
2    0 
Where,  0 and 0 are threshold frequency and
threshold wavelength.
Bohr’s atomic model
Bohr retained the essential features of the
Rutherford model of the atom. However, in order to
account for the stability of the atom he introduced the
concept of the stationary orbits. The Bohr postulates
are,
(1) An atom consists of positively charged nucleus
responsible for almost the entire mass of the atom
(This assumption is retention of Rutherford model).
(2) The electrons revolve around the nucleus in
certain permitted circular orbits of definite radii.
(3) The permitted orbits are those for which the
angular momentum of an electron is an intergral
multiple of h / 2 where h is the Planck’s constant. If
m is the mass and v is the velocity of the electron in a
permitted orbit of radius r , then
nh
L  mvr  ; n  1 , 2, 3, …… 
Where L is the orbital angular momentum and n
is the number of orbit. The integer n is called the
principal quantum number. This equation is known as
the Bohr quantization postulate.
(4) When electrons move in permitted discrete
orbits they do not radiate or lose energy. Such orbits
are called stationary or non-radiating orbits. In this
manner, Bohr overcame Rutherford’s difficulty to
account for the stability of the atom. Greater the
distance of energy level from the nucleus, the more is
 42 Structure of atom
the energy associated with it. The different energy Z2
levels were numbered as 1,2,3,4 .. and called as  21 .8  10 19  J per atom (1 J  10 7 erg)
n2
K, L, M, N, …. etc.
Z2
E  13 .6  eV per atom(1eV  1.6  10 -19 J )
(5) Ordinarily an electron continues to move n2
in a particular stationary state or orbit. Such a state Z2
of atom is called ground state. When energy is given  13 .6  k .cal / mole (1 cal = 4.18J)
n2
to the electron it jumps to any higher energy level
1312
and is said to be in the excited state. When the or Z 2 k Jmol 1
electron jumps from higher to lower energy state, n2
the energy is radiated. When an electron jumps from an outer orbit
(higher energy) n2 to an inner orbit (lower
Advantages of Bohr’s theory
energy) n1 , then the energy emitted in form of radiation
(i) Bohr’s theory satisfactorily explains the
spectra of species having one electron, viz. hydrogen is given by

atom, He  , Li 2  etc. 2 2 k 2 me 4 Z 2  1 1 
E  En2  En1  
h2  n2  n2 
(ii) Calculation of radius of Bohr’s orbit :  1 2 

According to Bohr, radius of nth orbit in which electron  1 1 

moves is  E  13 . 6 Z 2  2  2 eV / atom

 n1 n 2 
 h2  n2 E
rn   2 2 . As we know that E  h  , c   and  
1
 ,
 4 me k  Z  hc

Where, n  Orbit number, m  Mass number 2 2 k 2 me 4 Z 2  1 1 

  
9.1  10 31

kg , e  Charge 1.6  10 19 ch 3  n2  n2 
on the electron  1 2 

Z  Atomic number of element, k = Coulombic constant  1 

1 1
9  10 9
Nm 2 c 2  This can be represented as

   RZ 2  2  2
 n1 n 2



After putting the values of m,e,k,h, we get. 2 2k 2me 4
Where, R  ; R is known as Rydberg
n2 ch3
rn   0 . 529 Å
Z constant. Its value to be used is 109678 cm1 .

(iii) Calculation of velocity of electron The negative sign in the above equations shows
1/2
that the electron and nucleus form a bound system, i.e.,
2e 2 ZK  Ze 2  the electron is attracted towards the nucleus. Thus, if
Vn  , Vn    ;
nh  mr  electron is to be taken away from the nucleus, energy
2 . 188  10 8 Z has to be supplied. The energy of the electron in n  1
Vn  cm . sec 1 orbit is called the ground state energy; that in the n  2
n
orbit is called the first excited state energy, etc. When
(iv) Calculation of energy of electron in Bohr’s
n   then E  0 which corresponds to ionized atom
orbit
i.e., the electron and nucleus are infinitely separated
Total energy of electron = K.E. + P.E. of electron H  H   e  (ionization).
kZe 2 kZe 2 kZe 2
   (6) Spectral evidence for quantisation (Explanation
2r r 2r
for hydrogen spectrum on the basisof bohr atomic model)
 2 2 mZ 2 e 4 k 2
Substituting of r, gives us E (i) The light absorbed or emitted as a result of an
n 2h2 electron changing orbits produces characteristic
Where, n=1, 2, 3……….  absorption or emission spectra which can be recorded
Putting the value of m, e, k, h,  we get on the photographic plates as a series of lines, the
optical spectrum of hydrogen consists of several series
Z2
E  21 .8  10 12  erg per atom of lines called Lyman, Balmar, Paschen, Brackett,
n2
Pfund and Humphrey. These spectral series were
named by the name of scientist who discovered them.
(ii) To evaluate wavelength of various H-lines
Ritz introduced the following expression,
 Structure of atom 43
1  1 1  (vi) Thus, at least for the hydrogen atom, the Bohr
    R 2  2 
 c  n1 n 2  theory accurately describes the origin of atomic spectral
lines.
2 2me 4
Where, R is =  Rydberg's constant (7) Failure of Bohr model
ch3
(i) Bohr theory was very successful in predicting
It's theoritical value = 109,737 cm–1 and It's and accounting the energies of line spectra of hydrogen
experimental value = 109 ,677 .581 cm 1 i.e. one electron system. It could not explain the line
spectra of atoms containing more than one electron.
This remarkable agreement between the
(ii) This theory could not explain the presence of
theoretical and experimental value was great
multiple spectral lines.
achievment of the Bohr model.
(iii) This theory could not explain the splitting of
(iii) Although H-atom consists of only one electron
spectral lines in magnetic field (Zeeman effect) and in
yet it's spectra consist of many spectral lines.
electric field (Stark effect). The intensity of these
(iv) Comparative study of important spectral
spectral lines was also not explained by the Bohr
series of Hydrogen is shown in following table.
atomic model.
(v) If an electron from nth excited state comes to
(iv) This theory was unable to explain of dual
various energy states, the maximum spectral lines
nature of matter as explained on the basis of De
n(n  1)
obtained will be = . n= principal quantum broglies concept.
2
(v) This theory could not explain uncertainty
number.
principle. (vi) No conclusion was given for the
As n=6 than total number of spectral lines
6(6  1) 30 concept of quantisation of energy.
=   15 .
2 2
Table: 2.5

S.No Spectral Lies in Transition n12 n 22 n12  max n2

max   min   2 2 2
. series the n2  n1 (n 22 n12 )R R  min n 2  n1
region
(1) Lymen Ultraviole n1  1 n1  1 and n 2  2 n1  1 and n 2  
series t region 4
n 2  2,3,4....  4 1
 max   min  3
3R R

(2) Balmer Visible n1  2 n1  2 and n 2  3 n1  2 and n2  

series region
n 2  3,4,5....  36 4 9
 max   min 
5R R 5

(3) Paschen Infra red n1 = 3 n1  3 and n 2  4 n1  3 and n 2  

16
series region n 2  4,5,6....  144 9
 max   min  7
7R R
(4) Brackett Infra red n1  4 n1  4 and n2  5 n1  4 and n 2  
series region 25
n 2  5,6,7....  16  25 16
max   min  9
9R R

(5) Pfund Infra red n1  5 n1  5 and n 2  6 n1  5 and n 2  

36
series region n 2  6,7,8....  25  36 25
 max   min  11
11 R R
(6) Humphrey Far n1  6 n1  6 and n 2  7 n1  6 and n 2  
49
series infrared n 2  7,8....  36  49 36
region  max   min  13
13 R R

Bohr–Sommerfeild’s model
 44 Structure of atom
It is an extension of Bohr’s model. The electrons
in an atom revolve around the nuclei in elliptical orbit.
The circular path is a special case of ellipse.
Association of elliptical orbits with circular orbit
explains the fine line spectrum of atoms.
(7) The de-Broglie equation is applicable to all
material objects but it has significance only in case of
microscopic particles. Since, we come across
macroscopic objects in our everyday life, de-broglie
relationship has no significance in everyday life.

Dual nature of electron Heisenberg’s uncertainty principle

(1) In 1924, the French physicist, Louis de Broglie This principle states “It is impossible to specify
suggested that if light has both particle and wave like at any given moment both the position and momentum
nature, the similar duality must be true for matter. (velocity) of an electron”.
Thus an electron, behaves both as a material particle
h
and as a wave. Mathematically it is represented as , x . p 
4
(2) This presented a new wave mechanical theory
Where x  uncertainty is position of the particle,
of matter. According to this theory, small particles like
p  uncertainty in the momentum of the particle
electrons when in motion possess wave properties.
Now since p  m v
(3) According to de-broglie, the wavelength
associated with a particle of mass m, moving with h
So equation becomes, x . m v  or
velocity v is given by the relation 4
h

h
, where h = Planck’s constant. x  v 
mv 4m
In terms of uncertainty in energy, E and
(4) This can be derived as follows according to
uncertainty in time t, this principle is written as,
h.c  c
Planck’s equation, E  h       h
   E . t 
4
energy of photon (on the basis of Einstein’s mass
Schrödinger wave equation
energy relationship), E  mc 2
(1) Schrodinger wave equation is given by Erwin
hc h Schrödinger in 1926 and based on dual nature of
Equating both  mc or  
2
which is same
 mc electron.
as de-Broglie relation.  mc  p 
(2) In it electron is described as a three dimensional
(5) This was experimentally verified by Davisson wave in the electric field of a positively charged nucleus.
and Germer by observing diffraction effects with an
(3) The probability of finding an electron at any
electron beam. Let the electron is accelerated with a
potential of V than the Kinetic energy is point around the nucleus can be determined by the help
of Schrodinger wave equation which is,
1
mv 2  eV ; m 2 v 2  2eVm
2 2 2 2 8 2m
   (E  V )   0
x 2 y 2 z 2 h2
h
mv  2eVm  P ;  
2eVm Where x, y and z are the 3 space co-ordinates, m

(6) If Bohr’s theory is associated with de-Broglie’s = mass of electron, h = Planck’s constant, E = Total
equation then wave length of an electron can be energy, V = potential energy of electron,  =
determined in bohr’s orbit and relate it with amplitude of wave also called as wave function,  = for
circumference and multiply with a whole number an infinitesimal change.
2r (4) The Schrodinger wave equation can also be
2r  n  or  
n written as,
h 8 2m
From de-Broglie equation,   . 2   (E  V )   0
mv
h2
h 2r nh Where  = laplacian operator.
Thus  or mvr 
mv n 2
(5) Physical significance of  and  2
 Structure of atom 45
(i) The wave function  represents the (v) It gives the information of orbit K, L, M, N-----
amplitude of the electron wave. The amplitude  is -------.
thus a function of space co-ordinates and time i.e.
(vi) Angular momentum can also be calculated
  (x, y, z...... times)
using principle quantum number
(ii) For a single particle, the square of the wave (2) Azimuthal quantum number (l)
function ( 2 ) at any point is proportional to the
(i) Azimuthal quantum number is also known
probability of finding the particle at that point. as angular quantum number. Proposed by
(iii) If  2 is maximum than probability of finding Sommerfield and denoted by ‘l’.

e  is maximum around nucleus and the place where (ii) It determines the number of sub shells or
probability of finding e 
is maximum is called electron sublevels to which the electron belongs.
density, electron cloud or an atomic orbital. It is (iii) It tells about the shape of subshells.
different from the Bohr’s orbit.
(iv) It also expresses the energies of subshells
(iv) The solution of this equation provides a set of s  p  d  f (increasing energy).
number called quantum numbers which describe
(v) The value of l  (n  1) always. Where ‘n’ is the
specific or definite energy state of the electron in atom
number of principle shell.
and information about the shapes and orientations of
the most probable distribution of electrons around the (vi) Value = 0 1 2 3…..(n-
of l 1)
nucleus.
Radial probability distribution curves : Radial Name of = s p d f
subshell
probability is R  4r 2 dr 2 . The plats of R distance
Shape of = Spher Dumbb Double Comple
from nucleus as follows subshell ical ell dumbbe x
ll
14
12 (vii) It represent the orbital angular momentum.
10 5 5
4r2 dr 2

4r2 dr 2

4r2 dr 2

h
8 4 4 Which is equal to l(l  1)
6 3 3 2
4 2 2
2 1 1 (viii) The maximum number of electrons in
0
2 4 6 8
0
2 4 6 8
0
2 4 6 8 subshell  2(2l  1)
0.53Å r(Å) 0.53Å 2.7Å r(Å) 2.1Å r(Å)
1s 2s 2s s  subshell 2 electrons d  subshell 10 electrons
Fig. 2.5
p  subshell 6 electrons f  subshell 14 electrons.
Quantum numbers
(ix) For a given value of ‘n’ the total values of ‘l’ is
Each orbital in an atom is specified by a set of
always equal to the value of ‘n’.
three quantum numbers (n, l, m) and each electron is
designated by a set of four quantum numbers (n, l, m (3) Magnetic quantum number (m)
and s).
(i) It was proposed by Zeeman and denoted by ‘m’.
(1) Principle quantum number (n)
(ii) It gives the number of permitted orientation
(i) It was proposed by Bohr and denoted by ‘n’. of subshells.
(ii) It determines the average distance between (iii) The value of m varies from –l to +l through
electron and nucleus, means it denotes the size of atom. zero.
(iii) It determine the energy of the electron in an (iv) It tells about the splitting of spectral lines in
orbit where electron is present. the magnetic field i.e. this quantum number proves the
(iv) The maximum number of an electron in Zeeman effect.
an orbit represented by this quantum number as
(v) For a given value of ‘n’ the total value of ’m’ is
2n 2 . No energy shell in atoms of known elements
equal to n 2 .
possess more than 32 electrons.
 46 Structure of atom
(vi) For a given value of ‘l’ the total value of ‘m’ is (ii) The value of ' s' is  1/2 and - 1/2, which signifies
equal to (2l  1). the spin or rotation or direction of electron on it’s axis
during movement.
(vii) Degenerate orbitals : Orbitals having the
same energy are known as degenerate orbitals. e.g. for (iii) The spin may be clockwise or anticlockwise.
p subshell p x p y p z
(iv) It represents the value of spin angular
(viii) The number of degenerate orbitals of s h
momentum is equal to s(s  1).
subshell =0. 2

(4) Spin quantum numbers (s) (v) Maximum spin of an atom  1 / 2  number of
unpaired electron.
(i) It was proposed by Goldshmidt & Ulen Back
and denoted by the symbol of ‘s’. (vi) This quantum number is not the result of
solution of schrodinger equation as solved for H-atom.

Table : 2.6 Distribution of electrons among the quantum levels

Designation of Number of Orbitals in the

n l m
orbitals subshell

1 0 0 1s 1

2 0 0 2s 1

2 1 –1, 0, +1 2p 3

3 0 0 3s 1

3 1 –1, 0, +1 3p 3

3 2 –2, –1, 0, +1, +2 3d 5

4 0 0 4s 1

4 1 –1, 0, +1 4p 3

4 2 –2, –1, 0, +1, +2 4d 5

4 3 –3, –2, –1, 0, +1, +2, +3 4f 7

Shape of orbitals (i) For ‘p’ orbital l=1, & m=+1,0,–1 means there
are three ‘p’ orbitals, which is symbolised as p x , p y , p z .
(1) Shape of ‘s’ orbital
(ii) Shape of ‘p’ orbital is dumb bell in which the
(i) For ‘s’ orbital l=0 & m=0 so ‘s’ orbital have
two lobes on opposite side separated by the nodal
only one unidirectional orientation i.e. the probability
plane.
of finding the electrons is same in all directions.
(iii) p-orbital has directional properties.
(ii) The size and energy of ‘s’ orbital with
increasing ‘n’ will be 1s  2 s  3 s  4 s. Z Z Z

(iii) s-orbitals known as radial node or modal Y Y Y

surface. But there is no radial node for 1s orbital since
it is starting from the nucleus.
X X X

Px PY Pz

Fig. 2.7
(3) Shape of ‘d’ orbital
(i) For the ‘d’ orbital l =2 then the values of ‘m’
1S 2S are –2, –1, 0, +1, +2. It shows that the ‘d’ orbitals has
Fig. 2.6 five orbitals as d xy , d yz , d zx , d x 2 y 2 , d z 2 .
(2) Shape of ‘p’ orbitals

(ii) Each ‘d’ orbital identical in shape, size and
energy.
(iii) The shape of d orbital is double dumb bell .
(iv) It has directional properties.
Z Z
Y Y
X X
dZX dXY
Structure of atom 47
(3) Pauli’s exclusion principle
According to this principle “no two electrons in an
atom will have same value of all the four quantum
numbers”.
If one electron in an atom has the quantum
numbers n  1 , l  0 , m  0 and s  1 / 2 , no other
electron can have the same four quantum numbers. In
other words, we cannot place two electrons with the
same value of s in a 1 s orbital.

Z Z
Y Y The orbital diagram does not represent a
Z possible arrangement of 1s
electrons

X X Because there are only two possible values of s,

an orbital can hold not more than two electrons.

dYZ
(4) Hund’s Rule of maximum multiplicity
dX2–Y2
Z This rule deals with the filling of electrons in the
Y
orbitals having equal energy (degenerate orbitals).
According to this rule,

X “Electron pairing in p, d and f orbitals cannot

occur until each orbitals of a given subshell contains
d one electron each or is singly occupied”.
z2
This is due to the fact that electrons being
Fig. 2.8
identical in charge, repel each other when present in
(4) Shape of ‘f’ orbital the same orbital. This repulsion can however be
(i) For the ‘f’ orbital l=3 then the values of ‘m’ minimised if two electrons move as far apart as
are –3, –2, –1,0,+1,+2,+3. It shows that the ‘f’ orbitals possible by occupying different degenerate orbitals. All
have seven orientation as the unpaired electrons in a degenerate set of orbitals
fx ( x 2  y 2 ) , fy( x 2  y 2 ) , fz ( x 2  y 2 ), fxyz , fz 3 , fyz 2 and fxz 2 . will have same spin.
(ii) The ‘f’ orbital is complicated in shape. As we now know the Hund’s rule, let us see how
Rules for filling of electrons in various orbitals the three electrons are arranged in p orbitals.

The atom is built up by filling electrons in various The important point ot be remembered is that all
orbitals according to the following rules, the singly occupied orbitals should have electrons with
parallel spins i.e in the same direction either-clockwise
(1) Aufbau’s principle
or anticlockwise.
This principle states that the electrons are added
one by one to the various orbitals in order of their
2px 2py 2pz 2px 2py 2pz
increasing energy starting with the orbital of lowest or
energy. The increasing order of energy of various Electronic configurations of elements
orbitals is On the basis of the elecronic configuration
1s  2 s  2 p  3 s  3 p  4 s  3 d  4 p  5 s  4 d  5 p  6 s  4 f principles the electronic configuration of various
elements are given in the following table :
 5d  6 p  7 s  5 f  6d  7 p.........
The above method of writing the electronic
(2) (n+l) Rule
configurations is quite cumbersome. Hence, usually the
In neutral isolated atom, the lower the value of (n electronic configuration of the atom of any element is
+ l) for an orbital, lower is its energy. However, if the simply represented by the notation.
two different types of orbitals have the same value of Number of
(n + l), the orbitals with lower value of n has lower electrons
Present
energy.
number
of
nlx symbol of
principal subshell
shell
 48 Structure of atom
 The d orbital which does not have four lobes is
dz 2

 The d orbital whose lobes lie along the axis is

Some Unexpected Electronic Configuration d x 2 y 2
Some of the exceptions are important though,
h
because they occur with common elements, notably  Spin angular momentum  s(s  1)
2
chromium and copper.
n
Cu has 29 electrons. Its excepted electronic  Total spin   ; where n is no of unpaired e 
2
configuration is 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 9 but in reality
 Magnetic moment  n(n  2) B.M. (Bohr
the configuration is 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s1 3d 10 as this

configuration is more stable. Similarly Cr has the magnetron) of n unpaired e

configuration of 1s 2 2 s 2 sp 6 3 s 2 3 p 6 4 s 1 3d 5 instead of  Ion with unpaired electron in d or f orbital will be

1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3 d 4 .
Factors responsible for the extra stability of half-
filled and completely filled subshells,
(i) Symmetrical distribution : It is well known fact
that symmetry leads to stability. Thus the electronic
configuration in which all the orbitals of the same
subshell are either completely filled or are exactly half
filled are more stable because of symmetrical
distribution of electrons.
(ii) Exchange energy : The electrons with parallel
spins present in the degenerate orbitals tend to
exchange their position. The energy released during
this exchange is called exchange energy. The number of
exchanges that can take place is maximum when the
degenerate orbtials (orbitals of same subshell having
equal energy) are exactly half-filled or completely. As a
result, the exchange energy is maximum and so it the
stability.
 All lines in the visible region are of Balmer series
but reverse is not true i.e., all Balmer lines will not
fall in visible region.
 A part of an atom up to penultimate shell is a
kernel or atomic core.
 If the energy supplied to hydrogen atom is less
than 13.6 eV it will awpt or absorb only those quanta
which can take it to a certain higher energy level i.e.,
all those photons having energy less than or more
than a particular energy level will not be absorbed by
hydrogen atom, but if energy supplied to hydrogen
atom is more than 13.6eV then all photons are
absorbed and excess energy appear as kinetic energy
of emitted photo electron.
 No of nodes in any orbital  (n  l  1)
 No of nodal planes in an orbitals
coloured.
 Exception of E.C. are Cr (24 ) , Cu (29 ) , Mo (42 ) ,
Ag (47 ) , W (74 ) , Au (79 ) .
2r h
 No. of waves n  (where   )
 mv
v
 No. of revolutions of e  per second is  .
2r
 The solution of schrodinger wave equation gives
principal, azimuthal and magnetic quantum numbers
but not the spin quantum number.
 In the Rydberg formula, when n 2   the line
produced is called the limiting line of that series.
 Among various forms of visible light, violet
colour has shortest wavelength, highest frequency
and highest energy.
 Red coloured light has largest wavelength, least
frequency and lowest energy in visible light.
 Elements give line spectra. The line spectrum is
characteristic of the excited atom producing it. No
two elements have identical line spectrum.
 The line spectrum results from the emission of
radiations from the atoms of the elements and is
therefore called as atomic spectrum.
 Atoms give line spectra (known as atomic
spectrum) and the molecules give band spectra (known
as molecular spectrum).
 The negative potential at which the photoelectric
current becomes zero is called cut off potential or
stopping potential.
 When energy or frequency of scattered ray is
lesser than the incident ray, it is known as Compton
effect.
 The instrument used to record solar spectrum is
called spectrometer or spectrograph developed by
Bunsen and Kirchoff in 1859.
 The intensities of spectral lines decreases with
l
 Structure of atom 49
increase in the value of n . For example, the intensity [IIT 1982; BITS 1988;CPMT 1977; NCERT 1974;
of first Lyman line (2  1) is greater than second line MP PMT 1992; MP PET 2002]
(3  1) and so on. (a) James Chadwick (b) William Crooks
 In Balmer series of hydrogen spectrum the first (c) J.J. Thomson (d) Rutherford
line (3  2) is also known as L line. The second line 7. The ratio of charge and mass would be greater for
(4  2) is L  line. The line from infinity energy shell [BHU 2005]
is called limiting line. (a) Proton (b) Electron
(c) Neutron (d) Alpha

Discovery and Properties of anode, cathode rays

neutron and Nuclear structure

1. A neutral atom (Atomic no. > 1) consists of

[CPMT 1982]
(a) Only protons
(b) Neutrons + protons
(c) Neutrons + electrons
(d) Neutron + proton + electron
2. The nucleus of the atom consists of
[CPMT 1973, 74, 78, 83, 84; MADT Bihar 1980;
DPMT 1982, 85; MP PMT 1999]
(a) Proton and neutron
(b) Proton and electron
(c) Neutron and electron
(d) Proton, neutron and electron
3. The size of nucleus is of the order of
[CPMT 1982; MP PMT 1991]
12
(a) 10 m (b) 10 8 m

(c) 10 15 m (d) 10 10 m

4. Positive ions are formed from the neutral atom by
the
[CPMT 1976]
(a) Increase of nuclear charge
(b) Gain of protons
(c) Loss of electrons
(d) Loss of protons
5. The electron is
[DPMT 1982; MADT Bihar 1980]
(a)  -ray particle (b)  -ray particle
(c) Hydrogen ion (d) Positron
6. Who discovered neutron
 48 Structure of atom
8. Magnitude of K.E. in an orbit is equal to [BCECE 2005]
(a) Half of the potential energy
(b) Twice of the potential energy
(c) One fourth of the potential energy
(c) Two neutrons and two protons
(d) Four protons and two electrons
19. Which is correct statement about proton
[CPMT 1979; MP PMT 1985; NCERT 1985; MP PET 1999]

(d) None of these (a) Proton is nucleus of deuterium

9. The density of neutrons is of the order[NCERT 1980] (b) Proton is ionized hydrogen molecule
3
(a) 10 kg / cc 6
(b) 10 kg / cc (c) Proton is ionized hydrogen atom
(d) Proton is  -particle
(c) 10 9 kg / cc (d) 10 11 kg / cc
20. Cathode rays are made up of [AMU 1983]
10. The discovery of neutron becomes very late
because (a) Positively charged particles
[CPMT 1987; AIIMS 1998] (b) Negatively charged particles
(a) Neutrons are present in nucleus (c) Neutral particles
(b) Neutrons are highly unstable particles (d) None of these
(c) Neutrons are chargeless 21. Anode rays were discovered by [DPMT 1985]
(d) Neutrons do not move (a) Goldstein (b) J. Stoney
11. The fundamental particles present in the nucleus
(c) Rutherford (d) J.J. Thomson
of an atom are [CPMT 1983, 84]
22. The radius of an atom is of the order of
(a) Alpha particles and electrons
[AMU 1982; IIT 1985; MP PMT 1995]
(b) Neutrons and protons 10
(a) 10 cm (b) 10 13 cm
(c) Neutrons and electrons
(d) Electrons, neutrons and protons (c) 10 15 cm (d) 10 8 cm

12. The order of density in nucleus is 23. Neutron possesses [CPMT 1982]

[NCERT 1981, CPMT 1981, 2003] (a) Positive charge (b) Negative charge
(c) No charge (d) All are correct
8
(a) 10 kg / cc (b) 10 8 kg / cc
24. Neutron is a fundamental particle carrying
(c) 10 9 kg / cc (d) 10 12 k g / cc [CPMT 1990]
13. Cathode rays are [JIPMER 1991; NCERT 1976] (a) A charge of +1 unit and a mass of 1 unit
(a) Protons (b) Electrons (b) No charge and a mass of 1 unit
(c) Neutrons (d)  -particles (c) No charge and no mass
14. Number of neutron in C 12 is [BCECE 2005] (d) A charg of –1 and a mass of 1 unit
(a) 6 (b) 7 25. Cathode rays have [CPMT 1982]

(c) 8 (d) 9 (a) Mass only (b) Charge only

15. Heaviest particle is [DPMT 1983; MP PET 1999] (c) No mass and charge (d) Mass and charge
both
(a) Meson (b) Neutron
26. The size of nucleus is measured in
(c) Proton (d) Electron
[EAMCET 1988; CPMT 1994]
16. Penetration power of proton is
(a) amu (b) Angstrom
[BHU 1985; CPMT 1982, 88]
(c) Fermi (d) cm
(a) More than electron (b) Less than electron
27. Which phrase would be incorrect to use
(c) More than neutron (d) None
[AMU (Engg.) 1999]
17. An elementary particle is [CPMT 1973]
(a) A molecular of a compound
(a) An element present in a compound
(b) A molecule of an element
(b) An atom present in an element
(c) An atom of an element
(c) A sub-atomic particle
(d) None of these
(d) A fragment of an atom
28. Which one of the following pairs is not correctly
18. The nucleus of helium contains
matched
[CPMT 1972; DPMT 1982]
[MP PET 2002]
(a) Four protons (a) Rutherford-Proton
(b) Four neutrons (b) J.J. Thomsom-Electron
 Structure of atom 49
(c) J.H. Chadwick-Neutron 40. Which of the following has the same mass as that
(d) Bohr-Isotope of an electron [AFMC 2002]

29. Proton was discovered by (a) Photon

[AFMC 2004] (b) Neutron
(a) Chadwick (b) Thomson (c) Positron (d) Proton
(c) Goldstein (d) Bohr 41. What is the ratio of mass of an electron to the mass
30. The minimum real charge on any particle which of a proton
can exist is [UPSEAT 2004]
[RPMT 2000] (a) 1 : 2 (b) 1 : 1
19 10
(a) 1 . 6  10 Coulomb (b) 1 . 6  10 Coulomb (c) 1 : 1837 (d) 1 : 3

(c) 4 .8  10 10 Coulomb (d) Zero Atomic number, Mass number, Atomic species
31. The nature of anode rays depends upon
1. The number of electrons in an atom of an element
[MP PET 2004]
is equal to its [BHU 1979]
(a) Nature of electrode (b) Nature of residual (a) Atomic weight (b) Atomic number
gas
(c) Equivalent weight (d) Electron affinity
(c) Nature of discharge tube (d) All the above 2. The nucleus of the element having atomic number
32. One would expect proton to have very large 25 and atomic weight 55 will contain
[Pb. CET 2004] [CPMT 1986; MP PMT 1987]

(a) Ionization potential (b) Radius (a) 25 protons and 30 neutrons

(b) 25 neutrons and 30 protons
(c) Charge (d) Hydration energy
(c) 55 protons
33. The mass of a mol of proton and electron is
(d) 55 neutrons
(a) 6.023  10 23 g (b) 1.008 g and 0 .55 mg 3. If W is atomic weight and N is the atomic number
of an element, then [CPMT 1971, 80, 89]
(c) 9 .1  10 28 kg (d) 2 gm
(a) Number of e 1  W  N
34. The average distance of an electron in an atom
from its nucleus is of the order of (b)
[MP Number
PET 1996] of 0n
1
W N

(a) 10 6 m (b) 10 6 m (c) Number of 1 H 1  W  N

(c) 10 10 m (d) 10 15 m (d) Number of 0n

1
N
35. The mass of 1 mole of electrons is [Pb. CET 2004] 4. The total number of neutrons in dipositive zinc
ions with mass number 70 is[IIT 1979; Bihar MEE 1997]
(a) 9.1  10 28 g (b) 1.008 mg
(a) 34 (b) 40
(c) 0.55 mg (d) 9.1  10 27 g (c) 36 (d) 38
36. The ratio of specific charge of a proton and an  - 5. Which of the following are isoelectronic with one
particle is another
[NCERT 1983; EAMCET 1989]
[MP PET 1999]
(a) Na  and Ne (b) K  and O
(a) 2 : 1 (b) 1 : 2
(c) Ne and O (d) Na  and K 
(c) 1 : 4 (d) 1 : 1
6. The number of electrons in one molecule of
37. Ratio of masses of proton and electron is[BHU 1998]
CO2 are
(a) Infinite (b) 1 .8  10 3 [IIT 1979; MP PMT 1994; RPMT 1999]
(c) 1.8 (d) None of these (a) 22 (b) 44
38. Splitting of signals is caused by [Pb. PMT 2000] (c) 66 (d) 88
(a) Proton (b) Neutron 7. Chlorine atom differs from chloride ion in the
number of
(c) Positron (d) Electron
[NCERT 1972; MP PMT 1995]
39. The proton and neutron are collectively called as (a) Proton (b) Neutron
[MP PET 2001] (c) Electrons (d) Protons and
(a) Deutron (b) Positron electrons
(c) Meson (d) Nucleon
 50 Structure of atom
8. CO has same electrons as or the ion that is 18. An atom has the electronic configuration of
isoelectronic with CO is [CPMT 1984; IIT 1982; 1s 2 ,2 s 2 2 p 6 , 3 s 2 3 p 6 3d 10 ,4 s 2 4 p 5 . Its atomic weight
EAMCET 1990; CBSE PMT 1997] is 80. Its atomic number and the number of
(a) N 2 (b) CN 
neutrons in its nucleus shall be
[MP PMT 1987]
(c) O 2 (d) O 2
(a) 35 and 45 (b) 45 and 35
9. The mass of an atom is constituted mainly by (c) 40 and 40 (d) 30 and 50
[DPMT 1984, 91; AFMC 1990]
19. Which of the following particles has more
(a) Neutron and neutrino (b)Neutron and electron electrons than neutrons
(c) Neutron and proton (d) Proton and electron
(a) C (b) F 
10. The atomic number of an element represents
(c) O 2 (d) Al 3
[CPMT 1983; CBSE PMT 1990; NCERT 1973; AMU 1984]
20. Compared with an atom of atomic weight 12 and
(a) Number of neutrons in the nucleus
atomic number 6, the atom of atomic weight 13
(b) Number of protons in the nucleus
and atomic number 6 [NCERT 1971]
(c) Atomic weight of element
(a) Contains more neutrons (b)Contains more electrons
(d) Valency of element (c) Contains more protons (d)Is a different element
11. An atom has 26 electrons and its atomic weight is
21. In the nucleus of 20 Ca 40 there are
56. The number of neutrons in the nucleus of the
[CPMT 1990; EAMCET 1991]
atom will be
(a) 40 protons and 20 electrons
[CPMT 1980]
(b) 20 protons and 40 electrons
(a) 26 (b) 30
(c) 20 protons and 20 neutrons
(c) 36 (d) 56
(d) 20 protons and 40 neutrons
12. The most probable radius (in pm) for finding the
electron in He  is [AIIMS 2005]
22. Na  ion is isoelectronic with [CPMT 1990]

(a) 0.0 (b) 52.9 (a) Li  (b) Mg 2

(c) 26.5 (d) 105.8 (c) Ca 2 (d) Ba 2
2 23. Ca has atomic no. 20 and atomic weight 40.
13. The number of unpaired electrons in the Fe ion
is Which of the following statements is not correct
[MP PET 1989; KCET 2000]
about Ca atom
[MP PET 1993]
(a) 0 (b) 4
(a) The number of electrons is same as the number
(c) 6 (d) 3
of neutrons
14. A sodium cation has different number of electrons
(b) The number of nucleons is double of the number of
from electrons
(a) O 2  (b) F  (c) The number of protons is half of the number of
(c) Li  (d) Al 3 neutrons
15. An atom which has lost one electron would be (d) The number of nucleons is double of the atomic
[CPMT 1986]
number
(a) Negatively charged 24. Pick out the isoelectronic structures from the
following
(b) Positively charged
(c) Electrically neutral CH 3 H3O NH 3 CH 3 [IIT 1993]
I II III IV
(d) Carry double positive charge
(a) I and II (b) I and IV
16. Number of electrons in the outermost orbit of the
(c) I and III (d) II, III and IV
element of atomic number 15 is [CPMT 1988, 93]
25. Number of electrons in CONH 2 is [AMU 1988]
(a) 1 (b) 3
(c) 5 (d) 7 (a) 22 (b) 24
17. The atomic weight of an element is double its (c) 20 (d) 28
atomic number. If there are four electrons in 2 p 26. The atomic number of an element having the
orbital, the element is [AMU 1983] valency shell electronic configuration 4 s 2 4 p 6 is[MP PMT 1
(a) C (b) N (a) 35 (b) 36
(c) O (d) Ca (c) 37 (d) 38
27. The present atomic weight scale is based on
 Structure of atom 51
[EAMCET 1988; MP PMT 2002] (a) 30 (b) 32
(a) C 12
(b) O 16 (c) 34 (d) 33
(c) H 1 (d) C 13 38. The nucleus of the element 21 E 45 contains
28. Isoelectronic species are [EAMCET 1989] (a) 45 protons and 21 neutrons
    (b) 21 protons and 24 neutrons
(a) K , Cl (b) Na , Cl
(c) 21 protons and 45 neutrons
(c) Na, Ar (d) Na  , Ar
(d) 24 protons and 21 neutrons
29. If the atomic weight of an element is 23 times 39. Neutrons are found in atoms of all elements
that of the lightest element and it has 11 protons, except in
then it contains [MP PMT 1997]
[EAMCET 1986; AFMC 1989] (a) Chlorine (b) Oxygen
(a) 11 protons, 23 neutrons, 11 electrons (c) Argon (d) Hydrogen
(b) 11 protons, 11 neutrons, 11 electrons 40. The mass number of an anion, X 3  , is 14. If there
(c) 11 protons, 12 neutrons, 11 electrons are ten electrons in the anion, the number of
(d) 11 protons, 11 neutrons, 23 electrons neutrons in the nucleus of atom, X 2 of the
30. Which of the following oxides of nitrogen is element will be
isoelectronic with CO2 [CBSE PMT 1990] [MP PMT 1999]

(a) NO2 (b) N 2 O (a) 10 (b) 14

(c) 7 (d) 5
(c) NO (d) N 2 O2
41. Which of the following are isoelectronic species
31. The ratio between the neutrons in C and Si with I  CH 3 , II  NH 2 , III  NH 4 , IV  NH 3 [CPMT 1999]
respect to atomic masses 12 and 28 is [EAMCET 1990]
(a) I, II, III (b) II, III, IV
(a) 2 : 3 (b) 3 : 2
(c) I, II, IV (d) I and II
(c) 3 : 7 (d) 7 : 3
32. The atomic number of an element is always equal 42. The charge on the atom containing 17 protons, 18
neutrons and 18 electrons is [AIIMS 1996]
to
[MP PMT 1994] (a) 1 (b)  2
(a) Atomic weight divided by 2 (c) 1 (d) Zero
(b) Number of neutrons in the nucleus 43. Number of unpaired electrons in inert gas is[CPMT 1996]
(c) Weight of the nucleus (a) Zero (b) 8
(d) Electrical charge of the nucleus (c) 4 (d) 18
44. In neutral atom, which particles are equivalent
33. Which of the following is isoelectronic with
[RPMT 1997]
carbon atom
(a) p  , e  (b) e  , e 
[MP PMT 1994; UPSEAT 2000]
(a) Na 
(b) Al 3  (c) e  , p  (d) p  , n o
45. Nuclei tend to have more neutrons than protons
(c) O 2  (d) N 
at high mass numbers because[Roorkee Qualifying 1998]
34. CO2 is isostructural with
(a) Neutrons are neutral particles
[IIT 1986; MP PMT 1986, 94, 95] (b) Neutrons have more mass than protons
(a) SnCl 2 (b) SO 2 (c) More neutrons minimize the coulomb
(c) HgCl2 (d) All the above repulsion
(d) Neutrons decrease the binding energy
35. The hydride ions (H  ) are isoelectronic with
46. Which one of the following is not isoelectronic
[AFMC 1995; Bihar MEE 1997]
with O 2 
(a) Li (b) He  [CBSE PMT 1994]
(c) He (d) Be 3 
(a) N (b) F
36. The number of electrons in the nucleus of C 12 is (c) Tl  (d) Na 
[AFMC 1995] 47. 40
The number of electrons in [19 K ] 1 is
(a) 6 (b) 12 [CPMT 1997; AFMC 1999]
(c) 0 (d) 3 (a) 19 (b) 20
37. An element has electronic configuration 2, 8, 18, (c) 18 (d) 40
1. If its atomic weight is 63, then how many
neutrons will be present in its nucleus
 52 Structure of atom
48. The number of electrons and neutrons of an (a) F  , O 2 (b) F  , O
element is 18 and 20 respectively. Its mass
number is (c) F  , O  (d) F  , O 2
[CPMT 1997; Pb. PMT 1999; MP PMT 1999] 60. An element have atomic weight 40 and it’s
(a) 17 (b) 37 electronic configuration is 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 . Then
(c) 2 (d) 38 its atomic number and number of neutrons will be
49. Number of protons, neutrons and electrons in the [RPMT 2002]
231
element 89 Y is [AFMC 1997] (a) 18 and 22 (b) 22 and 18
(a) 89, 231, 89 (b) 89, 89, 242 (c) 26 and 20 (d) 40 and 18
(c) 89, 142, 89 (d) 89, 71, 89 61. The nucleus of tritium contains [MP PMT 2002]
50. Be 2  is isoelectronic with [EAMCET 1998] (a) 1 proton + 1 neutron (b) 1 proton + 3 neutron
(a) Mg 2  (b) Na  (c) 1 proton + 0 neutron (d) 1 proton + 2 neutron
62. Which one of the following groupings represents
(c) Li  (d) H 
a collection of isoelectronic species [AIEEE 2003]
51. An isostere is [UPSEAT 1999]
  (a) Na  , Ca 2  , Mg 2  (b) N 3  , F  , Na 
(a) NO 2 and O 3 (b) NO 2 and PO 43 
(c) Be , Al 3  , Cl  (d) Ca 2  , Cs  , Br
(c) CO 2 , N 2 O, NO 3 (d) ClO 4 and OCN 

63. Which of the following are isoelectronic and

52. Nitrogen atom has an atomic number of 7 and
oxygen has an atomic number 8. The total number isostructural NO 3 , CO 32  , ClO 3 , SO 3 [IIT Screening 2003]
of electrons in a nitrate ion will be [Pb. PMT 2000] (a) NO 3 , CO 32  (b) SO 3 , NO 3
(a) 8 (b) 16
(c) 32 (d) 64 (c) ClO 3 , CO 32  (d) CO 32  , SO 3
53. If molecular mass and atomic mass of sulphur are 64. The number of electrons in Cl  ion is [MP PMT 2003]
256 and 32 respectively, its atomicity is [RPET 2000]
(a) 19 (b) 20
(a) 2 (b) 8
(c) 18 (d) 35
(c) 4 (d) 16
65. The number of neutron in tritium is [CPMT 2003]
54. The nitride ion in lithium nitride is composed of
(a) 1 (b) 2
[KCET 2000]
(a) 7 protons + 10 electrons (c) 3 (d) 0
(b) 10 protons + 10 electrons 66. Tritium is the isotope of [CPMT 2003]
(c) 7 protons + 7 protons (a) Hydrogen (b) Oxygen
(d) 10 protons + 7 electrons (c) Carbon (d) Sulpher
55. The atomic number of an element is 17. The 67. The atomic number of an element is 35. What is
number of orbitals containing electron pairs in its the total number of electrons present in all the p-
valence shell is orbitals of the ground state atom of that element
[CPMT 2001] [EAMCET (Engg.) 2003]
(a) Eight (b) Six (a) 6 (b) 11
(c) Three (d) Two (c) 17 (d) 23
56. The atomic number of an element is 35 and mass 68. The nucleus of an element contain 9 protons. Its
number is 81. The number of electrons in the valency would be [
outer most shell is (a) 1 (b) 3
[UPSEAT 2001] (c) 2 (d) 5
(a) 7 (b) 6 69. The compound in which cation is isoelectronic with
(c) 5 (d) 3 anion is
57. Which of the following is not isoelectronic[MP PET 2002] [UPSEAT 2004]
(a) NaCl (b) CsF
(a) Na  (b) Mg 2 
(c) NaI (d) K 2 S
(c) O 2  (d) Cl 
70. Which among the following species have the same
58. The charge of an electron is  1 .6  10 19 C. The number of electrons in its outermost as well as

value of free charge on Li ion will be penultimate shell
[AFMC 2002; KCET (Engg.) 2002] [DCE 2004]
19 19 2 2
(a) 3 .6  10 C (b) 1  10 C (a) Mg (b) O
19 19
(c) 1 .6  10 C (d) 2.6  10 C (c) F  (d) Ca 2 
59. Iso-electronic species is [RPMT 2002] 71. Six protons are found in the nucleus of
 Structure of atom 53
[CPMT 1977, 80, 81; NCERT 1975, 78] (a) The force of repulsion on the moving alpha
(a) Boron (b) Lithium particle is small
(c) Carbon (d) Helium (b) The force of attraction on the alpha particle to
72. The nitrogen atom has 7 protons and 7 electrons, the oppositely charged electrons is very small
the nitride ion ( N 3 ) will have [NCERT
(c) There 1977]one nucleus and large number of
is only
(a) 7 protons and 10 electrons electrons
(b) 4 protons and 7 electrons (d) The nucleus occupies much smaller volume
(c) 4 protons and 10 electrons compared to the volume of the atom
(d) 10 protons and 7 electrons 6. Positronium consists of an electron and a positron
73. Number of neutrons in heavy hydrogen atom is (a particle which has the same mass as an
[MP PMT 1986] electron, but opposite charge) orbiting round
their common centre of mass. Calculate the value
(a) 0 (b) 1
of the Rydberg constant for this system.
(c) 2 (d) 3
(a) R / 4 (b) R / 2
74. Which of the following is always a whole number
[CPMT 1976, 81, 86] (c) 2 R (d) R
(a) Atomic weight (b) Atomic radii 7. When  -particles are sent through a thin metal
(c) Equivalent weight (d) Atomic number foil, most of them go straight through the foil
because (one or more are correct)
Atomic models and Planck's quantum theory (a) Alpha particles are much heavier than
electrons
1. Rutherford's experiment on scattering of particles (b) Alpha particles are positively charged
showed for the first time that the atom has
(c) Most part of the atom is empty space
[IIT 1981; NCERT 1981; CMC Vellore 1991;
(d) Alpha particles move with high velocity
CPMT 1984; Kurukshetra CEE 1998]
8. When an electron jumps from L to K shell
(a) Electrons (b) Protons
[CPMT 1983]
(c) Nucleus (d) Neutrons
(a) Energy is absorbed
2. Rutherford's scattering experiment is related to (b) Energy is released
the size of the
(c) Energy is sometimes absorbed and sometimes
[IIT 1983; MADT Bihar 1995; BHU 1995] released
(a) Nucleus (b) Atom (d) Energy is neither absorbed nor released
(c) Electron (d) Neutron 9. When beryllium is bombarded with  -particles,
3. Rutherford's alpha particle scattering experiment extremely penetrating radiations which cannot be
eventually led to the conclusion that[IIT 1986; RPMT 2002] deflected by electrical or magnetic field are given
out. These are
(a) Mass and energy are related
[CPMT 1983]
(b) Electrons occupy space around the nucleus
(a) A beam of protons (b)  -rays
(c) Neutrons are buried deep in the nucleus
(c) A beam of neutrons (d) X-rays
(d) The point of impact with matter can be
10. Which one of the following is not the
precisely determined
characteristic of Planck's quantum theory of
4. Bohr's model can explain [IIT 1985] radiation [AIIMS 1991]
(a) The spectrum of hydrogen atom only (a) The energy is not absorbed or emitted in
whole number or multiple of quantum
(b) Spectrum of atom or ion containing one
electron only (b) Radiation is associated with energy

(c) The spectrum of hydrogen molecule (c) Radiation energy is not emitted or absorbed
conti- nuously but in the form of small packets
(d) The solar spectrum called quanta
5. When atoms are bombarded with alpha particles, (d) This magnitude of energy associated with a
only a few in million suffer deflection, others pass quantum is proportional to the frequency
out undeflected. This is because[MNR 1979; NCERT 1980; AFMC 1995]
11. The spectrum of He is expected to be similar to
 54 Structure of atom
[AIIMS 1980, 91; DPMT 1983; MP PMT 2002] (a) Increases (b) Decreases
(a) H (b) Li  (c) Remains the same (d) None of these
20. Experimental evidence for the existence of the
(c) Na (d) He 
atomic nucleus comes from [
12. Energy of orbit [DPMT 1984, 91]
(a) Millikan's oil drop experiment
(a) Increases as we move away from nucleus (b) Atomic emission spectroscopy
(b) Decreases as we move away from nucleus (c) The magnetic bending of cathode rays
(c) Remains same as we move away from nucleus (d) Alpha scattering by a thin metal foil
(d) None of these 21. Which of the following statements does not form
13. Bohr model of an atom could not account for part of Bohr's model of the hydrogen atom[CBSE PMT 1989
(a) Emission spectrum (a) Energy of the electrons in the orbit is
(b) Absorption spectrum quantized

(c) Line spectrum of hydrogen (b) The electron in the orbit nearest the nucleus
has the lowest energy
(d) Fine spectrum
(c) Electrons revolve in different orbits around
14. Existence of positively charged nucleus was
the nucleus
established by
(d) The position and velocity of the electrons in
[CBSE PMT 1991]
the orbit cannot be determined
(a) Positive ray analysis
simultaneously
(b)  -ray scattering experiments
22. When  -particles are sent through a tin metal
(c) X-ray analysis
foil, most of them go straight through the foil as[EAMCET
(d) Discharge tube experiments (a)  -particles are much heavier than electrons
15. Electron occupies the available orbital singly
(b)  -particles are positively charged
before pairing in any one orbital occurs, it is[CBSE PMT 1991]
(a) Pauli's exclusion principle (c) Most part of the atom is empty space

(b) Hund's Rule (d)  -particles move with high velocity

(c) Heisenberg's principle 23. The energy of second Bohr orbit of the hydrogen
atom is –328 kJ mol–1, hence the energy of fourth
(b) Prout's hypothesis
Bohr orbit would be
16. The wavelength of a spectral line for an electronic
[CBSE PMT 2005]
transition is inversely related to [IIT 1988]
(a) – 41 kJ mol–1 (b) –1312 kJ mol–1
(a) The number of electrons undergoing the
transition (c) –164 kJ mol–1 (d) – 82 kJ mol–1
(b) The nuclear charge of the atom 24. When an electron revolves in a stationary orbit
then
(c) The difference in the energy of the energy
levels involved in the transition [MP PET 1994]
(a) It absorbs energy
(d) The velocity of the electron undergoing the
transition (b) It gains kinetic energy
17. When an electron drops from a higher energy (c) It emits radiation
level to a low energy level, then [AMU 1985] (d) Its energy remains constant
(a) Energy is emitted 25. A moving particle may have wave motion, if
(b) Energy is absorbed (a) Its mass is very high
(c) Atomic number increases (b) Its velocity is negligible
(d) Atomic number decreases (c) Its mass is negligible
18. Davisson and Germer's experiment showed that (d) Its mass is very high and velocity is negligible
[MADT Bihar 1983] 26. The postulate of Bohr theory that electrons jump
(a)  -particles are electrons from one orbit to the other, rather than flow is
according to
(b) Electrons come from nucleus
(a) The quantisation concept
(c) Electrons show wave nature
(b) The wave nature of electron
(d) None of the above
(c) The probability expression for electron
19. When an electron jumps from lower to higher
orbit, its energy [MADT Bihar 1982]
(d) Heisenberg uncertainty principle
 Structure of atom 55
27. The frequency of an electromagnetic radiation is (c) Both release or absorption of energy
2  10 6 Hz . What is its wavelength in metres (d) Unpredictable
1 37. In an element going away from nucleus, the
(Velocity of light  3  10 ms 8
)
energy of particle [RPMT 1997]
(a) 6.0  10 14
(b) 1 .5  10 4
(a) Decreases (b) Not changing
(c) 1 .5  10 2
(d) 0.66  10 2
(c) Increases (d) None of these
28. What is the packet of energy called [AFMC 2005]
38. The  -particle scattering experiment of
(a) Electron (b) Photon Rutherford concluded that [
(c) Positron (d) Proton (a) The nucleus is made up of protons and
29. The energy of an electron in n th orbit of hydrogen neutrons
atom is (b) The number of electrons is exactly equal to
[MP PET 1999] number of protons in atom
13 .6 13 .6 (c) The positive charge of the atom is
(a) eV (b) eV
n 4
n 3 concentrated in a very small space
13 .6 13 .6 (d) Electrons occupy discrete energy levels
(c) eV (d) eV
n 2
n 39. Wavelength associated with electron motion[BHU 1998]
30. If wavelength of photon (a) Increases with increase in speed of electron
is 2.2  10 11 m, h  6.6  10 34 J-sec, then momentum (b) Remains same irrespective of speed of
electron
of photon is [MP PET 1999]
23 1
(c) Decreases with increase in speed of e 
(a) 3  10 kg ms (b) 3 . 33  10 22 kg ms 1
(d) Is zero
(c) 1 . 452  10 44 kg ms 1 (d) 6 . 89  10 43 kg ms 1 40. The element used by Rutherford in his famous
scattering experiment was [
31. The expression for Bohr's radius of an atom is
(a) Gold (b) Tin
[MP PMT 1999]
2 2
(c) Silver (d) Lead
n h n h2
2
(a) r  (b) r  41. If electron falls from n  3 to n  2 , then emitted
4 2 me 4 z 2 4 2 me 2 z energy is
n2h2 n2h2 [AFMC 1997; MP PET 2003]
(c) r  (d) r 
4 me z
2 2 2
4 m 2 e 2 z 2
2 (a) 10 .2eV (b) 12 .09 eV
32. The energy of an electron revolving in n th Bohr's (c) 1 . 9 eV (d) 0 . 65 eV
42.
orbit of an atom is given by the expression[MP PMT 1999] The radius of the nucleus is related to the mass
number A by [
2 2 m 4 e 2 z 2 2 2 me 2 z 2
(a) En   (b) En   (a) R  R o A 1/2
(b) R  Ro A
n2h2 n2h2
2 2 me 4 z 2 2m 2 e 2 z 4 (c) R  R o A 2 (d) R  R o A 1 / 3
(c) E n   (d) En  
n2h2 n2h2 43. The specific charge of proton is 9 .6  10 6 C kg 1 then
33. Who modified Bohr's theory by introducing for an -particle it will be [MH CET 1999]
elliptical orbits for electron path[CBSE PMT 1999; AFMC 2003]
(a) 38 .4  10 7 C kg 1 (b) 19 .2  10 7 C kg 1
(a) Hund (b) Thomson
(c) Rutherford (d) Sommerfield (c) 2 . 4  10 7 C kg 1 (d) 4 . 8  10 7 C kg 1
34. Bohr's radius can have [DPMT 1996] 44.
In hydrogen spectrum the different lines of Lyman
(a) Discrete values (b) ve values series are present is [UPSEAT 1999]
(c) ve values (d) Fractional values (a) UV field (b) IR field
35. The first use of quantum theory to explain the (c) Visible field (d) Far IR field
45.
structure of atom was made by[IIT 1997; CPMT 2001; J&K CETWhich
2005] one of the following is considered as the
(a) Heisenberg (b) Bohr main postulate of Bohr’s model of atom[AMU 2000]
(c) Planck (d) Einstein (a) Protons are present in the nucleus
(b) Electrons are revolving around the nucleus
36. An electronic transition from 1s orbital of an atom
causes (c) Centrifugal force produced due to the
[JIPMER 1997]
revolving electrons balances the force of
attraction between the electron and the
(a) Absorption of energy protons
(b) Release of energy
 56 Structure of atom
(d) Angular momentum of electron is an integral 56. The energy of a radiation of wavelength 8000 Å is
h E1 and energy of a radiation of wavelength 16000
multiple of
2 Å is E 2 . What is the relation between these two [Kerala C
46. The electronic energy levels of the hydrogen atom (a) E1  6E2 (b) E1  2E2
in the Bohr’s theory are called [AMU 2000]
(c) E1  4 E2 (d) E1  1 / 2 E2
(a) Rydberg levels (b) Orbits
(e) E1  E2
(c) Ground states (d) Orbitals
47. The energy of a photon is calculated by [Pb. PMT 2000] 57. The formation of energy bonds in solids are in
accordance with [DCE 2001]
(a) E  h (b) h  E
(a) Heisenberg’s uncertainty principle
E h
(c) h  (d) E  (b) Bohr’s theory
  (c) Ohm’s law
48. Visible range of hydrogen spectrum will contain (d) Rutherford’s atomic model
the following series [RPET 2000] 58. The frequency of yellow light having wavelength
(a) Pfund (b) Lyman 600 nm is
(c) Balmer (d) Brackett [MP PET 2002]
49. Radius of the first Bohr’s orbit of hydrogen atom (a) 5 . 0  10 14 Hz (b) 2.5  10 7 Hz
is (c) 5 .0  10 7 Hz (d) 2 .5  10 14 Hz
[RPET 2000] 59. The value of the energy for the first excited state
(a) 1 .06 Å (b) 0 .22 Å of hydrogen atom will be [MP PET 2002]
(a)  13 .6 eV (b)  3.40 eV
(c) 0 . 28 Å (d) 0 . 53 Å
(c)  1.51 eV (d)  0.85 eV
50. In Balmer series of hydrogen atom spectrum
60. Bohr model of atom is contradicted by[MP PMT 2002]
which electronic transition causes third line[MP PMT 2000]
(a) Pauli’s exclusion principle
(a) Fifth Bohr orbit to second one
(b) Planck quantum theory
(b) Fifth Bohr orbit to first one
(c) Heisenberg uncertainty principle
(c) Fourth Bohr orbit to second one
(d) All of these
(d) Fourth Bohr orbit to first one
61. Which of the following is not true in Rutherford’s
51. Energy of electron of hydrogen atom in second nuclear model of atom [Orissa JEE 2002]
Bohr orbit is
(a) Protons and neutrons are present inside
[MP PMT 2000]
19
nucleus
(a)  5 .44  10 J (b)  5 .44  10 19 kJ
(b) Volume of nucleus is very small as compared
(c)  5 . 44  10 19 cal (d)  5 . 44  10 19 eV to volume of atom
52. If change in energy (c) The number of protons and neutrons are
(E)  3  10 8 J , h  6 .64  10 34 J - s and always equal
(d) The number of electrons and protons are
c  3  10 8 m /s, then wavelength of the light is
always equal
[CBSE PMT 2000]
62. The emission spectrum of hydrogen is found to
(a) 6.36  10 3 Å (b) 6.36  10 5 Å satisfy the expression for the energy change. E
(c) 6 .64  10 8 Å (d) 6 . 36  10 18 Å  1 1 
53. The radius of first Bohr’s orbit for hydrogen is (in joules) such that E  2 . 18  10  2  2  J
 n1 n2 
0.53 Å. The radius of third Bohr’s orbit would be[MP PMT 2001]
where n1 = 1, 2, 3….. and n 2 = 2, 3, 4……. The
(a) 0.79 Å (b) 1.59 Å
(c) 3.18 Å (d) 4.77 Å spectral lines correspond to Paschen series to
54. Rutherford’s -particle scattering experiment (a) n1  1 and n 2  2, 3, 4
proved that atom has [MP PMT 2001] (b) n1  3 and n 2  4, 5, 6
(a) Electrons (b) Neutron
(c) n1  1 and n 2  3, 4, 5
(c) Nucleus (d) Orbitals
55. Wavelength of spectral line emitted is inversely (d) n1  2 and n 2  3, 3, 5

1  1 and n 2  infinity
proportional to (e) n2001]
[CPMT
(a) Radius (b) Energy 63. The ratio between kinetic energy and the total
(c) Velocity (d) Quantum number energy of the electrons of hydrogen atom
according to Bohr’s model is
[Pb. PMT 2002]
(a) 2 : 1 (b) 1 : 1
 Structure of atom 57
(c) 1 : – 1 (d) 1 : 2 stationary state 1, would be (Rydberg constant
64. Energy of the electron in Hydrogen atom is given  1 . 097  10 7 m 1 )
by [AIEEE 2004]
[AMU (Engg.) 2002] (a) 406 nm (b) 192 nm
131 .38 131 .33
(a) En   kJ mol 1 (b) En   kJ mol 1 (c) 91 nm (d) 9 . 1 10 8 nm
n2 n
75. In Bohr’s model, atomic radius of the first orbit is
1313 .3 313 .13
(c) En   kJ mol 1 (d) E n   k J mol 1  , the radius of the 3rd orbit, is [MP PET 1997; Pb. CET 2001
2
n n2
(a)  / 3 (b) 
65. Ratio of radii of second and first Bohr orbits of H
atom (c) 3  (d) 9 
[BHU 2003] 76. According to Bohr’s principle, the relation
(a) 2 (b) 4 between principle quantum number (n) and radius
(c) 3 (d) 5 of orbit is [BHU 2004]
66. The frequency corresponding to transition n  2 (a) r  n (b) r  n 2
to n  1 in hydrogen atom is [MP PET 2003] 1 1
(c) r  (d) r  2
(a) 15 .66  10 10 Hz (b) 24 .66  10 14 Hz n n
(c) 30 .57  10 Hz
14
(d) 40 .57  10 24 Hz 77. The ionisation potential of a hydrogen atom is –
13.6 eV. What will be the energy of the atom
67. The mass of a photon with a wavelength equal to
corresponding to n  2
1 .54  10 8 cm is [Pb. PMT 2004] [Pb. CET 2000]
(a) 0.8268  10 34 kg (b) 1.2876  10 33 kg (a) –3.4 eV (b) –6.8 eV
32
(c) 1.4285  10 kg (d) 1.8884  10 kg 32 (c) –1.7 eV (d) – 2.7 eV
78. The energy of electron in hydrogen atom in its
68. Splitting of spectral lines under the influence of
grounds state is –13.6 eV. The energy of the level
magnetic field is called [MP PET 2004]
corresponding to the quantum number equal to 5
(a) Zeeman effect (b) Stark effect is [Pb. CET 2002]
(c) Photoelectric effect (d) None of these (a) –0.54 eV (b) – 0.85 eV
69. The radius of electron in the first excited state of (c) – 0.64 eV (d) – 0.40 eV
hydrogen atom is [MP PMT 2004] 79. The positive charge of an atom is [AFMC 2002]
(a) a0 (b) 4a0 (a) Spread all over the atom
(c) 2a0 (d) 8a0 (b) Distributed around the nucleus
70. The ratio of area covered by second orbital to the (c) Concentrated at the nucleus
first orbital is [AFMC 2004] (d) All of these
(a) 1 : 2 (b) 1 : 16 80. A metal surface is exposed to solar radiations [DPMT 2005
(c) 8 : 1 (d) 16 : 1 (a) The emitted electrons have energy less than a
maximum value of energy depending upon
71. Time taken for an electron to complete one
frequency of incident radiations
revolution in the Bohr orbit of hydrogen atom is [Kerala PMT 2004]
(b) The emitted electrons have energy less than
4 2 mr 2 nh maximum value of energy depending upon
(a) (b)
nh 4  2 mr intensity of incident radiation
nh h (c) The emitted electrons have zero energy
(c) (d)
4  2 mr 2 2mr (d) The emitted electrons have energy equal to
72. The radius of which of the following orbit is same energy of photos of incident light
as that of the first Bohr's orbit of hydrogen atom 81. Which of the following transitions have minimum
[IIT Screening 2004] wavelength [DPMT 2005]
 2 (a) n4  n1 (b) n2  n1
(a) He (n  2) (b) Li (n  2)
2 (c) n4  n2 (d) n3  n1
(c) Li (n  3) (d) Be 3  (n  2)
73. The frequency of radiation emitted when the Dual nature of electron
electron falls from n  4 to n  1 in a hydrogen
atom will be (Given ionization energy of
1. De broglie equation describes the relationship of
H  2 .18  10 18 J atom 1 and h  6.625  10 34 Js ) [CBSE PMT 2004]
wavelength associated with the motion of an electron
(a) 3.08  10 15 s 1 (b) 2.00  10 15 s 1 and its[MP PMT 1986]
1
(c) 1 .54  10 s
15
(d) 1 .03  10 15 s 1 (a) Mass (b) Energy
74. The wavelength of the radiation emitted, when in (c) Momentum (d) Charge
a hydrogen atom electron falls from infinity to 2. The wave nature of an electron was first given by
 58 Structure of atom
[CMC Vellore 1991; Pb. PMT 1998; CPMT 2004] (a) 9 .28  10 4 m (b) 9 .28  10 7 m
(a) De-Broglie (b) Heisenberg
(c) 9 .28  10 8 m (d) 9 . 28  10 10 m
(c) Mosley (d) Sommerfield
3. Among the following for which one mathematical 12. What will be de-Broglie wavelength of an electron
h moving with a velocity of 1 .2  10 5 ms 1 [MP PET 2000]
expression   stands
p
(a) 6.068  10 9 (b) 3 .133  10 37
(a) De Broglie equation (b) Einstein equation
(c) 6.626  10 9 (d) 6.018  10 7
(c) Uncertainty equation (d) Bohr equation
13. The de-Broglie wavelength associated with a
4. Which one of the following explains light both as
particle of mass 10 6 kg moving with a velocity of
a stream of particles and as wave motion
[AIIMS 1983; IIT 1992; UPSEAT 2003] 10 ms 1 , is
(a) Diffraction (b)   h / p [AIIMS 2001]
22 29
(c) Interference (d) Photoelectric effect (a) 6 .63  10 m (b) 6 . 63  10 m
5. In which one of the following pairs of experimental (c) 6 .63  10 31
m (d) 6 . 63  10 34
m
observations and phenomenon does the
experimental observation correctly account for 14. What is the de-Broglie wavelength associated
phenomenon [AIIMS 1983] with the hydrogen electron in its third orbit[AMU (Engg.) 2
Experimental observation Phenomenon (a) 9 .96  10 10 cm (b) 9 .96  10 8 cm
(a) X -ray spectra Charge on the nucleus (c) 9 .96  10 4 cm (d) 9 .96  10 8 cm
(b)  -particle scatteringQuantized electron orbit 15. If the velocity of hydrogen molecule is
(c) Emission spectra The quantization of 5  10 4 cm sec 1 , then its de-Broglie wavelength is [MP PMT
energy
(a) 2 Å (b) 4 Å
(d) The photoelectric effect The nuclear atom
(c) 8 Å (d) 100 Å
6. Which of the following expressions gives the de-
16.
Broglie relationship[MP PMT 1996, 2004; MP PET/PMT 1998] A 200g golf ball is moving with a speed of 5 m per
hour. The associated wave length is
 h
(a) h  (b)   (h  6.625  10 34 J - sec)
mv mv
[MP PET 2003]
m v
(c)   (d)   (a) 10 10
m (b) 10 20
m
hv mh
30 40
7. de-Broglie equation is (c) 10 m (d) 10 m
[MP PMT 1999; CET Pune 1998]
17. A cricket ball of 0.5 kg is moving with a velocity
(a) n  2d sin (b) E  hv
of 100 m / sec . The wavelength associated with its
h
(c) E  mc 2 (d)   motion is
mv
[DCE 2004]
8. The de-Broglie wavelength of a particle with mass
(a) 1 / 100 cm (b) 6 .6  10 34 m
1 gm and velocity 100 m / sec is[CBSE PMT 1999; EAMCET 1997;
(c) 1 .32  10 35 m (d) 6 .6  10 28 m
AFMC 1999; AIIMS 2000]
18. Dual nature of particles was proposed by [DCE 2004]
(a) 6 .63  10 33 m (b) 6 .63  10 34 m (a) Heisenberg (b) Lowry
(c) 6 .63  10 35 m (d) 6 .65  10 35 m (c) de-Broglie (d) Schrodinger
9. Minimum de-Broglie wavelength is associated 19. Calculate de-Broglie wavelength of an electron
with[RPMT 1999] travelling at 1% of the speed of light [DPMT 2004]
(a) Electron (b) Proton (a) 2.73  10 24 (b) 2 .42  10 10
(c) CO2 molecule (d) SO 2 molecule (c) 242 .2  10 10
(d) None of these
10. The de-Broglie wavelength associated with a 20. Which is the correct relationship between
material particle is [JIPMER 2000] wavelength and momentum of particles[Pb. PMT 2000]
h h
(a) Directly proportional to its energy (a)   (b)  
(b) Directly proportional to momentum P P
h P
(c) Inversely proportional to its energy (c) P  (d) h 
(d) Inversely proportional to momentum  
21. The de-Broglie equation applies [MP PMT 2004]
11. An electron has kinetic energy 2 .8  10 23 J . de- (a) To electrons only
Broglie wavelength will be nearly
(b) To neutrons only
(m e  9 .1  10 31 kg ) [MP PET 2000] (c) To protons only
(d) All the material object in motion
 Structure of atom 59
h
Uncertainty principle and Schrodinger wave (a) Zero (b) 
2
equation
h
(c)  (d) Infinite
2
1. The uncertainty principle was enunciated by
[NCERT 1975; Bihar MEE 1997] 9. The possibility of finding an electron in an orbital
was conceived by [MP PMT 1994]
(a) Einstein (b) Heisenberg
(a) Rutherford (b) Bohr
(c) Rutherford (d) Pauli
(c) Heisenberg (d) Schrodinger
2. According to heisenberg uncertainty principle
[AMU 1990; BCECE 2005] 10. Uncertainty principle gave the concept of
h (a) Probability
(a) E  mc 2 (b) x  p 
4 (b) An orbital

(c)  
h
(d) x  p 
h (c) Physical meaning of  the  2
p 6 (d) All the above
3. “The position and velocity of a small particle like 11. The uncertainty principle and the concept of wave
electron cannot be simultaneously determined.” nature of matter was proposed by ...... and ......
This statement is respectively
[NCERT 1979; BHU 1981, 87] [MP PET 1997]
(a) Heisenberg uncertainty principle (a) Heisenberg, de Broglie (b)de-Broglie, Heisenberg
(b) Principle of de Broglie's wave nature of (c) Heisenberg, Planck (d) Planck, Heisenberg
electron
12. The uncertainty in momentum of an electron is
(c) Pauli's exclusion principle
1  10 5 kg  m / s . The uncertainty in its position
(d) Aufbau's principle
will be ( h  6.62  10 34 kg  m 2 / s )
4. In Heisenberg's uncertainty equation
h [AFMC 1998; CBSE PMT 1999; JIPMER 2002]
x  p  ; p stands for
4 (a) 1 .05  10 28 m (b) 1 .05  10 26 m
(a) Uncertainty in energy (c) 5.27  10 30 m (d) 5 .25  10 28 m
(b) Uncertainty in velocity
13. The uncertainty in the position of a moving bullet
(c) Uncertainty in momentum of mass 10 gm is 10 5 m . Calculate the uncertainty
(d) Uncertainty in mass in its velocity
5. Which one is not the correct relation in the [DCE 1999]
following 28 28
(a) 5.2  10 m / sec (b) 3.0  10 m / sec
E
(a) h  (b) E  mc 2
(c) 5.2  10 22
m / sec (d) 3  10 22
m / sec
v
h
(c) x  p 
h
(d)  
h 14. The equation x .p  shows [MP PET 2000]
4 mv 4
(a) de-Broglie relation
6. The maximum probability of finding an electron
in the d xy orbital is [MP PET 1996] (b) Heisenberg’s uncertainty principle
(c) Aufbau principle
(a) Along the x-axis (d) Hund’s rule
(b) Along the y-axis 15. Which quantum number is not related with
(c) At an angle of 45 o
from the x and y-axes Schrodinger equation [RPMT 2002]
o (a) Principal (b) Azimuthal
(d) At an angle of 90 from the x and y-axes
(c) Magnetic (d) Spin
7. Simultaneous determination of exact position and
16. Uncertainty in position of a 0.25 g particle is
momentum of an electron is [BHU 1979]
10 5 . Uncertainty of velocity is (h  6 .6  10 34 Js ) [AIEEE 200
(a) Possible
(b) Impossible (a) 1 .2  10 34 (b) 2 .1  10 29
(c) 1 . 6  10 20 (d) 1.7  10 9
(c) Sometimes possible sometimes impossible
17. The uncertainty in momentum of an electron is
(d) None of the above
1  10 5 kg m / s . The uncertainity in its position will
8. If uncertainty in the position of an electron is 34
zero, the uncertainty in its momentum would be[CPMT 1988]be (h  6.63  10 Js) [Pb. CET 2000]
30
(a) 5 .28  10 m (b) 5 .25  10 28 m
 60 Structure of atom
(c) 1 .05  10 26 m (d) 2.715  10 30 m 5. Nitrogen has the electronic configuration
18. According to Heisenberg’s uncertainty principle, 1s 2 ,2 s 2 2 p 1x 2 p 1y 2 p 1z and not 1s 2 ,2 s 2 2 p x2 2 p1y 2 p z0 which
the product of uncertainties in position and is determined by
velocities for an electron of mass 9 .1  10 31 kg is [DPMT [BHU 2004]
1982, 83, 89; MP PMT/PET 1988; EAMCET 1988]

(a) 2.8  10 3 m 2 s 1 (b) 3.8  10 5 m 2 s 1 (a) Aufbau's principle (b) Pauli's exclusion
5 2 1 6 2 1 principle
(c) 5.8  10 m s (d) 6.8  10 m s
(c) Hund's rule (d) Uncertainty principle
19. For an electron if the uncertainty in velocity is
6. Which one of the following configuration
 , the uncertainty in its position (x ) is given by[DPMT 2005]
represents a noble gas [
hm 4 DPMT 1984]
(a) (b)
4  hm 
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 (b) 1s 2 ,2 s 2 2 p 6 ,3 s1
h 4 m
(c) (d) (c) 1s 2 ,2 s 2 2 p 6 (d) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 ,4 s 2
4m  h . 
7. The electronic configuration of silver atom in
20. Orbital is [DPMT 2005]
ground state is
(a) Circular path around the nucleus in which the
[CPMT 1984, 93]
electron revolves
10 1
(b) Space around the nucleus where the (a) [Kr ]3 d 4 s (b) [ Xe ] 4 f 14 5 d 10 6 s 1
probability of finding the electron is (c) [Kr ] 4 d 10 5 s 1 (d) [Kr ] 4 d 9 5 s 2
maximum
(c) Amplitude of electrons wave 8. Principal, azimuthal and magnetic quantum
numbers are respectively related to[CPMT 1988; AIIMS 199
(d) None of these
(a) Size, shape and orientation
Quantum number, Electronic configuration (b) Shape, size and orientation
(c) Size, orientation and shape
and Shape of orbitals
(d) None of the above
1. Be's 4th electron will have four quantum numbers 9. Correct set of four quantum numbers for valence
[MNR 1985] electron of rubidium (Z = 37) is
n l m s [IIT 1984; JIPMER 1999; UPSEAT 2003]

(a) 1 0 0 +1/2 1 1
(a) 5, 0, 0,  (b) 5, 1, 0, 
(b) 1 1 +1 +1/2 2 2
(c) 2 0 0 – 1/2 1 1
(c) 5, 1, 1,  (d) 6, 0, 0, 
(d) 2 1 0 +1/2 2 2
2. The quantum number which specifies the location 10. The correct ground state electronic configuration of
of an electron as well as energy is [DPMT 1983] chromium atom is[IIT 1989, 94; MP PMT 1993; EAMCET 1997;
(a) Principal quantum number ISM Dhanbad 1994; AFMC 1997; Bihar MEE 1996;
(b) Azimuthal quantum number MP PET 1995, 97; CPMT 1999; Kerala PMT 2003]

(c) Spin quantum number (a) [ Ar ] 3 d 5 4 s 1 (b) [ Ar ] 3 d 4 4 s 2

(d) Magnetic quantum number (c) [ AR]3d 6 4 s 0 (d) [ Ar]4 d 5 4 s 1
3. The shape of an orbital is given by the quantum
11. 2p orbitals have [NCERT 1981; MP PMT 1993, 97]
number
(a) n  1, l  2 (b) n  1, l  0
[NCERT 1984; MP PMT 1996]
(a) n (b) l (c) n  2, l  1 (d) n  2, l  0
(c) m (d) s 12. Electronic configuration of H  is [CPMT 1985]
4. In a given atom no two electrons can have the 0 1
(a) 1s (b) 1s
same values for all the four quantum numbers.
This is called (c) 1s 2
(d) 1 s 1 2 s 1
[BHU 1979; AMU 1983; EAMCET 1980, 83; 13. The quantum numbers for the outermost electron
MADT Bihar 1980; CPMT 1986, 90, 92; NCERT 1978, 84; of an element are given below as
RPMT 1997; CBSE PMT 1991; MP PET 1986, 99] 1
n  2, l  0, m  0, s   . The atoms is
(a) Hund's rule 2
(b) Aufbau's principle (a) Lithium (b) Beryllium
(c) Uncertainty principle (c) Hydrogen (d) Boron
(d) Pauli's exclusion principle 14. Principal quantum number of an atom represents
[EAMCET 1979; IIT 1983; MNR 1990;UPSEAT 2000, 02]
 Structure of atom 61
(a) Size of the orbital (b)
(b) Spin angular momentum (c)
(c) Orbital angular momentum
(d)
(d) Space orientation of the orbital
15. An element has the electronic configuration 24. The following has zero valency [DPMT 1991]
1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 2 . Its valency electrons are (a) Sodium (b) Beryllium
[NCERT 1973] (c) Aluminium (d) Krypton
(a) 6 (b) 2 25. The number of electrons in the valence shell of
(c) 3 (d) 4 calcium is
[IIT 1975]
16. The magnetic quantum number specifies
(a) 6 (b) 8
[MNR 1986; BHU 1982; CPMT 1989, 94;
MP PET 1999; AFMC 1999; AMU (Engg.) 1999]
(c) 2 (d) 4
26. The valence electron in the carbon atom are[MNR 1982]
(a) Size of orbitals (b) Shape of orbitals
(a) 0 (b) 2
(c) Orientation of orbitals (d) Nuclear stability
(c) 4 (d) 6
17. Which of the following sets of quantum numbers
27. For the dumb-bell shaped orbital, the value of l is
represent an impossible arrangement[IIT 1986; MP PET 1995]
[CPMT 1987, 2003]
n l m ms (a) 3 (b) 1
1 (c) 0 (d) 2
(a) 3 2 –2 (+)
2 28. Chromium has the electronic configuration
1 4 s 1 3 d 5 rather than 4 s 2 3 d 4 because
(b) 4 0 0 (–)
2 (a) 4 s and 3 d have the same energy
1 (b) 4 s has a higher energy than 3 d
(c) 3 2 –3 (+)
2 (c) 4 s 1 is more stable than 4 s 2
1 (d) 4 s 1 3 d 5 half-filled is more stable than 4 s 2 3 d 4
(d) 5 3 0 (–)
2 29. The electronic configuration of calcium ion (Ca 2  )
18. If n  3 , then the value of ' l' which is incorrect is
[CPMT 1994] [CMC Vellore 1991]
2 2 6 2 6 2
(a) 0 (b) 1 (a) 1s ,2 s 2 p ,3 s 3 p ,4 s
(c) 2 (d) 3 (b) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 ,4 s 1
19. Which orbital is dumb-bell shaped (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 2
[MP PMT 1986; MP PET/PMT 1998]
(d) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 3d 5
(a) s -orbital (b) p -orbital
(e) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 ,4 s 0
(c) d -orbital (d) f -orbital
30. The structure of external most shell of inert gases
20. The total number of unpaired electrons in d - is
orbitals of atoms of element of atomic number 29 [JIPMER 1991]
is [CPMT 1983] (a) s p 2 3
(b) s p2 6

(a) 10 (b) 1 1 2
(c) s p (d) d 10 s 2
(c) 0 (d) 5
31. The two electrons in K sub-shell will differ in
21. The shape of 2 p orbital is
[MNR 1988; UPSEAT 1999, 2000; Kerala PMT 2003]
[CPMT 1983; NCERT 1979]
(a) Principal quantum number
(a) Spherical (b) Ellipsoidal
(b) Azimuthal quantum number
(c) Dumb-bell (d) Pyramidal
(c) Magnetic quantum number
22. The magnetic quantum number for an electron
(d) Spin quantum number
when the value of principal quantum number is 2
can have 32. A completely filled d -orbital (d 10 ) [MNR 1987]
[CPMT 1984] (a) Spherically symmetrical
(a) 3 values (b) 2 values (b) Has octahedral symmetry
(c) 9 values (d) 6 values (c) Has tetrahedral symmetry
23. Which one is the correct outer configuration of (d) Depends on the atom
chromium 33. If magnetic quantum number of a given atom
[AIIMS 1980, 91; BHU 1995] represented by –3, then what will be its principal
(a)      quantum number

  
     

     
 62 Structure of atom
[BHU 2005] (c) – 1 (d) 0
(a) 2 (b) 3 42. The maximum number of electrons that can be
(c) 4 (d) 5 accommodated in the M th shell is
34. The total number of orbitals in an energy level (a) 2 (b) 8
designated by principal quantum number n is (c) 18 (d) 32
equal to
43. For a given value of quantum number l , the
[AIIMS 1997; J&K CET 2005]
number of allowed values of m is given by
(a) 2n (b) 2n 2 (a) l  2 (b) 2l  2
(c) n (d) n 2 (c) 2 l  1 (d) l  1
35. The number of orbitals in the fourth principal 44. The number of radial nodes of 3s and 2p orbitals
quantum number will be are respectively. [IIT-JEE 2005]
(a) 4 (b) 8 (a) 2, 0 (b) 0, 2
(c) 12 (d) 16 (c) 1, 2 (d) 2, 1
36. Which set of quantum numbers are not possible 45. Which of the sub-shell is circular
from the following
(a) 4 s (b) 4 f
1
(a) n  3, l  2, m  0, s   (c) 4 p (d) 4 d
2
1 46. Which electronic configuration for oxygen is
(b) n  3, l  2, m  2, s   correct according to Hund's rule of multiplicity
2
1 (a) 1s 2 ,2 s 2 2 p x2 2 p 1y 2 p 1z (b) 1s 2 ,2 s 2 2 p x2 2 p y2 2 p z0
(c) n  3, l  3, m  3, s  
2
(c) 1s 2 ,2 s 2 2 p x3 2 p 1y 2 p z0 (d) None of these
1
(d) n  3, l  0, m  0, s  
2 47. If value of azimuthal quantum number l is 2, then
37. The four quantum number for the valence shell total possible values of magnetic quantum number
electron or last electron of sodium (Z = 11) is[MP PMT 1999] will be
1 (a) 7 (b) 5
(a) n  2, l  1, m  1, s  
2 (c) 3 (d) 2
1 48. The type of orbitals present in Fe is
(b) n  3, l  0, m  0, s  
2 (a) s (b) s and p
1
(c) n  3, l  2, m  2, s   (c) s, p and d (d) s, p, d and f
2
49. The shape of d xy orbital will be
1
(d) n  3, l  2, m  2, s  
2 (a) Circular (b) Dumb-bell
38. The explanation for the presence of three (c) Double dumb-bell (d) Trigonal
unpaired electrons in the nitrogen atom can be 50. In any atom which sub-shell will have the highest
given by energy in the following
[NCERT 1979; RPMT 1999; DCE 1999, 2002; (a) 3 p (b) 3 d
CPMT 2001; MP PMT 2002; Pb. PMT / CET 2002]
(c) 4 s (d) 3 s
(a) Pauli's exclusion principle
51. Which electronic configuration is not observing
(b) Hund's rule the ( n  l ) rule
(c) Aufbau's principle
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 1 ,4 s 2
(d) Uncertainty principle
(b) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 3d 7 ,4 s 2
39. The maximum energy is present in any electron at
(a) Nucleus (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 ,4 s 1
(b) Ground state (d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 8 ,4 s 2
(c) First excited state 52. The four quantum numbers of the outermost
(d) Infinite distance from the nucleus orbital of K (atomic no. =19) are[MP PET 1993, 94]
40. The electron density between 1 s and 2 s orbital is 1
(a) n  2, l  0, m  0, s  
(a) High (b) Low 2
(c) Zero (d) None of these 1
(b) n  4 , l  0, m  0, s  
41. For ns orbital, the magnetic quantum number has 2
value 1
(c) n  3, l  1, m  1, s  
(a) 2 (b) 4 2
 Structure of atom 63
1 (c) 4 (d) 9
(d) n  4 , l  2, m  1, s  
2 62. Which of the following ions is not having the
53. The angular momentum of an electron depends on configuration of neon
[BHU 1978; NCERT
1981]
(a) F  (b) Mg 2
(a) Principal quantum number (c) Na  (d) Cl 
(b) Azimuthal quantum number 63. Elements upto atomic number 103 have been
(c) Magnetic quantum number synthesized and studied. If a newly discovered
(d) All of these element is found to have an atomic number 106,
54. The electronic configuration of copper (29 Cu) is its electronic configuration will be
[DPMT 1983; BHU 1980; AFMC 1981; [AIIMS 1980]
14 4 2
CBSE PMT 1991; MP PMT 1995] (a) [Rn]5 f ,6 d ,7 s (b) [Rn]5 f ,6 d 1 ,7 s 2 7 p 3
14

2 2 6 2 6 9 2
(a) 1s ,2 s 2 p ,3 s 3 p 3d ,4 s
(c) [Rn]5 f 14 ,6 d 6 ,7 s 0 (d) [Rn]5 f 14 ,6 d 5 ,7 s 1
2 2 6 2 6 10 1
(b) 1s ,2 s 2 p ,3 s 3 p 3d ,4 s
64. Ions which have the same electronic configuration
(c) 1s 2 .2 s 2 2 p 6 ,3 s 2 3 p 6 ,4 s 2 4 p 6 are those of

(d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 (a) Lithium and sodium (b) Sodium and

potassium
55. The number of orbitals in 2 p sub-shell is
(c) Potassium and calcium (d)Oxygen and chlorine
[NCERT 1973; MP PMT 1996]
(a) 6 (b) 2 65. When the azimuthal quantum number has a value
of l  0 , the shape of the orbital is [MP PET 1995]
(c) 3 (d) 4
56. The number of orbitals in d sub-shell is[MNR 1981] (a) Rectangular (b) Spherical
(a) 1 (b) 3 (c) Dumbbell (d) Unsymmetrical
(c) 5 (d) 7 66. The magnetic quantum number for valency
57. A sub-shell l  2 can take how many electrons electrons of sodium is [CPMT 1988; MH CET 1999]
[NCERT 1973, 78] (a) 3 (b) 2
(a) 3 (b) 10 (c) 1 (d) 0
(c) 5 (d) 6 67. The electronic configuration of an element with
58. Pauli's exclusion principle states that atomic number 7 i.e. nitrogen atom is[CPMT 1982, 84, 87]
[MNR 1983; AMU 1984] (a) 1 s 2 , 2 s 1 , 2 p x3 (b) 1s 2 ,2 s 2 2 p x2 2 p1y
(a) Two electrons in the same atom can have the
(c) 1s 2 ,2 s 2 2 p 1x 2 p 1y 2 p 1z (d) 1s 2 ,2 s 2 2 p 1x 2 p y2
same energy
(b) Two electrons in the same atom cannot have 68. In a multi-electron atom, which of the following
the same spin orbitals described by the three quantum members
will have the same energy in the absence of
(c) The electrons tend to occupy different orbitals
magnetic and electric fields
as far as possible
[AIEEE 2005]
(d) Electrons tend to occupy lower energy orbitals
(1) n  1, l  0, m  0 (2) n  2, l  0, m  0
preferentially
(e) None of the above (3) n  2, l  1, m  1 (4) n  3, l  2, m  0
59. For d electrons, the azimuthal quantum number is (5) n  3, l  2, m  0
[MNR 1983; CPMT 1984] (a) (1) and (2) (b) (2) and (3)
(a) 0 (b) 1 (c) (3) and (4) (d) (4) and (5)
(c) 2 (d) 3 69. Which of the following represents the electronic
60. For p -orbital, the magnetic quantum number has configuration of an element with atomic number
value 17
[AMU 1982]
(a) 2 (b) 4, – 4
2 2 6 1 6
(c) – 1, 0, +1 (d) 0 (a) 1s ,2 s 2 p ,3 s 3 p (b) 1s ,2 s 2 p ,3 s 2 3 p 4 ,4 s1
2 2 6

61. For n  3 energy level, the number of possible (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 5 (d) 1s 2 ,2 s 2 2 p 6 ,3 s 1 3 p 4 ,4 s 2

orbitals (all kinds) are[BHU 1981; CPMT 1985; MP PMT 1995]
70. The shape of s -orbital is [NCERT 1978I]
(a) 1 (b) 3 (a) Pyramidal (b) Spherical
 64 Structure of atom
(c) Tetrahedral (d) Dumb-bell shaped 79. Krypton (36 Kr) has the electronic configuration
71. When 3 d orbital is complete, the new electron (18 Ar) 4 s 2 ,3d 10 ,4 p 6 . The 37 th electron will go into
will enter the which one of the following sub-levels
[EAMCET 1980; MP PMT 1995]
[CBSE PMT 1989; CPMT 1989; EAMCET 1991]
(a) 4 p -orbital (b) 4 f -orbital (a) 4 f (b) 4 d
(c) 4 s -orbital (d) 4 d -orbital (c) 3 p (d) 5 s
72. In a potassium atom, electronic energy levels are
1
in the following order [EAMCET 1979; DPMT 1991] 80. If an electron has spin quantum number of 
2
(a) 4 s  3 d (b) 4 s  4 p and a magnetic quantum number of 1 , it cannot
(c) 4 s  3 d (d) 4 s  3 p be presented in an [CBSE PMT 1989; UPSEAT 2001]
73. Fe (atomic number = 26) atom has the electronic (a) d -orbital (b) f -orbital
arrangement [NCERT 1974; MNR 1980] (c) p -orbital (d) s -orbital
(a) 2, 8, 8, 8 (b) 2, 8, 16 81. The azimuthal quantum number is related to
(c) 2, 8,14, 2 (d) 2, 8, 12, 4 [BHU 1987, 95]
74. Cu 2  will have the following electronic (a) Size (b) Shape
configuration (c) Orientation (d) Spin
[MP PMT 1985] 82. The total number of electrons that can be
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 accommodated in all the orbitals having principal
quantum number 2 and azimuthal quantum
(b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 ,4 s 1 number 1 is [CPMT 1971, 89, 91]
(c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 (a) 2 (b) 4
(c) 6 (d) 8
(d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 ,4 s 1
83. Electronic configuration of C is [CPMT 1975]
75. Which one is the electronic configuration of Fe 2 2 2 2 2 2 3
(a) 1s ,2 s 2 p (b) 1s ,2 s 2 p
[MADT Bihar 1982; AIIMS 1989]
2 2
(c) 1s ,2 s (d) 1s 2 ,2 s 2 2 p 6
(a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6
84. There is no difference between a 2p and a
(b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 4 ,4 s 2
3 p orbital regarding [BHU 1981]
(c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 ,4 s 1 (a) Shape (b) Size
(d) None of these (c) Energy (d) Value of n
76. How many electrons can be fit into the orbitals 85. The electronic configuration of chromium is
that comprise the 3 rd quantum shell n  3 [MP PMT 1993; MP PET 1995; BHU 2001; BCECE 2005]
[MP PMT 1986, 87; Orissa JEE 1997]
(a) [ Ne ]3 s 2 3 p 6 3d 4 ,4 s 2 (b) [ Ne ]3 s 2 3 p 6 3d 5 ,4 s 1
(a) 2 (b) 8
(c) 18 (d) 32 (c) [ Ne ]3 s 2 3 p 6 ,4 s 2 4 p 4 (d) [ Ne ]3 s 2 3 p 6 3d 1 ,4 s 2 4 p 3
77. Which element is represented by the following 86. The shape of p -orbital is [MP PMT 1993]
electronic configuration [MP PMT 1987] (a) Elliptical (b) Spherical
2p
(c) Dumb-bell (d) Complex geometrical
2s    87. The electronic configuration (outermost) of Mn 2
1s  ion (atomic number of Mn  25 ) in its ground
 state is
[MP PET 1993]
(a) Nitrogen (b) Oxygen 5
(a) 3 d ,4 s 0 4
(b) 3 d ,4 s 1

(c) Fluorine (d) Neon 3 2

(c) 3 d ,4 s (d) 3 d 2 ,4 s 2 4 p 2
78. If the value of azimuthal quantum number is 3,
the possible values of magnetic quantum number 88. The principal quantum number represents [CPMT 1991]
would be (a) Shape of an orbital
[MP PMT 1987; RPMT 1999; AFMC 2002; KCET 2002] (b) Distance of electron from nucleus
(a) 0, 1, 2, 3 (b) 0, – 1, – 2, – 3 (c) Number of electrons in an orbit
(c) 0,  1,  2,  3 (d)  1,  2,  3 (d) Number of orbitals in an orbit
 Structure of atom 65
89. When the azimuthal quantum number has a value (c) n  1, l  0, m l  0, m s  1 / 2
of l  1 , the shape of the orbital is [MP PET 1993]
(d) n  2, l  0, m l  0, m s  1 / 2
(a) Unsymmetrical (b) Spherically
symmetrical 98. Correct configuration of Fe 3 [26] is
[CPMT 1994; BHU 1995; KCET 1992]
(c) Dumb-bell (d) Complicated
90. How many electrons can be accommodated in a (a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5
sub-shell for which n  3, l  1 [CBSE PMT 1990] (b) 1s 2 ,2 s 2 sp 6 ,3 s 2 3 p 6 3d 3 ,4 s 2
(a) 8 (b) 6 (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6 ,4 s 2
(c) 18 (d) 32
(d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 ,4 s 1
91. For azimuthal quantum number l3, the
99. Azimuthal quantum number for last electron of
maximum number of electrons will be [CBSE PMT 1991;
Na atom is
EAMCET 1991; RPMT 2002; CBSE PMT 2002]
[BHU 1995]
(a) 2 (b) 6 (a) 1 (b) 2
(c) 0 (d) 14 (c) 3 (d) 0
92. An ion has 18 electrons in the outermost shell, it 100. A 3 p orbital has [IIT 1995]
is
(a) Two spherical nodes
[CBSE PMT 1990]
(b) Two non-spherical nodes
 4
(a) Cu (b) Th (c) One spherical and one non-spherical nodes

(c) Cs (d) K  (d) One spherical and two non-spherical nodes
93. The order of filling of electrons in the orbitals of 101. All electrons on the 4 p sub-shell must be
an atom will be [CBSE PMT 1991] by the quantum number(s)[MP PET 1996]
characterized
(a) 3d, 4 s, 4 p, 4 d, 5 s (b) 4 s, 3d, 4 p, 5 s, 4 d 1
(a) n  4 , m  0, s   (b) l  1
(c) 5 s, 4 p, 3d, 4 d, 5 s (d) 3d, 4 p, 4 s, 4 d, 5 s 2
1 1
94. The quantum number which may be designated by (c) l  0, s   (d) s  
s, p, d and f instead of number is BHU 1980] 2 2
102. The electronic configuration of the element of
(a) n (b) l
atomic number 27 is
(c) m l (d) m s
(a) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s () 4 p ()()() 5 s ()
95. Which of the following represents the correct sets
of the four quantum numbers of a 4 d electron (b) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 3 d ()()(), 4 s () 4 p ()
[MNR 1992; UPSEAT 2001; J&K CET 2005] (c) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 3 d ()()()(), 4 s ()
1
(a) 4 , 3, 2, (b) 4, 2, 1, 0 (d) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 3 d ()()()()() 4 s ()
2
103. When the value of the principal quantum number
1 1
(c) 4 , 3,  2,  (d) 4 , 2, 1,  n is 3, the permitted values of the azimuthal
2 2
quantum numbers l and the magnetic quantum
96. Which of the following statements is not correct numbers m , are
for an electron that has the quantum numbers
l m
n  4 and m  2
0 0
[MNR 1993]
(a) 1  1, 0,  1
(a) The electron may have the quantum number
1 2  2,1, 0,  1,2
s
2 1 1
(b) The electron may have the quantum number (b) 2  2, 1,  1
l2 3  3,2, 1,  2,3
(c) The electron may have the quantum number
0 0
l3
(c) 1 1, 2, 3
(d) The electron may have the quantum number
l  0, 1, 2, 3 2  3,  2, 1,  2,3

97. The set of quantum numbers not applicable for an 1 0, 1

electron in an atom is [MNR 1994] (d) 2 0, 1, 2
(a) n  1, l  1, m l  1, m s  1 / 2 3 0, 1, 2, 3
(b) n  1, l  0, m l  0, m s  1 / 2 104. The number of possible spatial orientations of an
electron in an atom is given by its
 66 Structure of atom
(a) Spin quantum number (c) Magnetic quantum number
(b) Spin angular momentum (d) Spin quantum number
(c) Magnetic quantum number 113. For the n  2 energy level, how many orbitals of
(d) Orbital angular momentum all kinds are possible [Bihar CEE 1995]
105. Which of the following sets of orbitals may (a) 2 (b) 3
degenerate
(c) 4 (d) 5
(a) 2 s, 2 p x , 2 p y (b) 3 s, 3 p x ,3d xy
114. Which one is in the ground state [DPMT 1996]
(c) 1s, 2s, 3 s (d) 2 p x , 2 p y , 2 p z

106. The set of quantum numbers
n  3, l  0, m  0, s  1 / 2 belongs to the element (a   
)
(a) Mg (b) Na

(c) Ne (d) F
107. An electron has principal quantum number 3. The
number of its (i) sub-shells and (ii) orbitals would (b   
be respectively )
[MP PET 1997] 
(a) 3 and 5 (b) 3 and 7 
(c) 3 and 9 (d) 2 and 5 (c   
108. What is the electronic configuration of )
Cu 2  (Z  29 ) of least position[MP PET/PMT 1998; MP PET 2001] 
1
(a) [ Ar ] 4 s 3 d 8 2
(b) [ Ar ] 4 s 3 d 10
4p 1 
(d   
(c) [ Ar ] 4 s 1 3 d 10 (d) [ Ar ] 3 d 9
)
109. The correct electronic configuration of Ti(Z  22 ) 
atom is
[MP PMT 1999] 115. When the principal quantum number (n  3) , the
2 2 6 2
(a) 1s 2 s 2 p 3 s 3 p 4 s 3d 6 2 2 possible values of azimuthal quantum number ( l )
is
(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 4 [Bihar MEE 1996; KCET 2000]
(c) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 4 (a) 0, 1, 2, 3 (b) 0, 1, 2
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 1 3d 3 (c) – 2, – 1, 0, 1, 2 (d) 1, 2, 3
(e) 0, 1
110. Which of the following configuration is correct for
116. Which statement is not correct for n  5 , m  3
iron
[CPMT 1996]
[CBSE PMT 1999]
1
(a) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 5 (a) l  4 (b) l  0, 1, 3; s  
2
(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 5 (c) l  3 (d) All are correct
2 2 6 2 6 2 7
(c) 1s 2 s 2 p 3 s 3 p 4 s 3d 117. 1s 2 2 s 2 2 p 6 3 s 1 shows configuration of [CPMT 1996]
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 6 (a) Al 3  in ground state (b) Ne in excited state
111. Which of the following set of quantum numbers (c) Mg  in excited state (d) None of these
belong to highest energy [CPMT 1999]
118. Five valence electrons of p 15 are labelled as
1
(a) n  4 , l  0, m  0, s   AB X Y Z
2
1 3s 3p
(b) n  3, l  0, m  0, s  
2 1
If the spin quantum of B and Z is  , the group
1 2
(c) n  3, l  1, m  1, s   of electrons with three of the quantum number
2
same are
1
(d) n  3, l  2, m  1, s   [JIPMER 1997]
2
(a) AB, XYZ , BY (b) AB
112. Which quantum number will determine the shape
(c) XYZ , AZ (d) AB, XYZ
of the subshell [CPMT 1999; Pb. PMT 1998]
(a) Principal quantum number 119. Electronic configuration of Sc 21 is [BHU 1997]
2 2 6 2 6 2 1
(b) Azimuthal quantum number (a) 1s 2 s 2 p 3 s 3 p 4 s 3d
 Structure of atom 67
(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 1 3d 2 128. Which one of the following set of quantum
2 2 6 2 6 0 3
numbers is not possible for 4 p electron[EAMCET 1998]
(c) 1s 2 s 2 p 3 s 3 p 4 s 3d
1
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 2 4 s 2 3d 2 (a) n  4 , l  1, m  1, s  
2
120. If n  l  6 , then total possible number of 1
subshells would be [RPMT 1997] (b) n  4 , l  1, m  0, s  
2
(a) 3 (b) 4
1
(c) 2 (d) 5 (c) n  4 , l  1, m  2, s  
2
121. An electron having the quantum numbers 1
1 (d) n  4 , l  1, m  1, s  
n  4, l  3, m  0 , s   would be in the orbital 2
2 129. Which of the following orbital is not possible[RPMT 1999]
[Orissa JEE 1997] (a) 3 f (b) 4 f
(a) 3 s (b) 3 p (c) 5 f (d) 6 f
130. Which set of quantum numbers for an electron of
(c) 4 d (d) 4 f
an atom is not possible [RPMT; DCE 1999]
122. Which of the following sets of quantum numbers (a) n  1, l  0, m  0, s  1 / 2
is not allowed [Orissa JEE 1997] (b) n  1, l  1, m  1, s  1 / 2
1 (c) n  1, l  0, m  0, s  1 / 2
(a) n  1, l  0, m  0, s  
2
(d) n  2, l  1, m  1, s  1 / 2
1
(b) n  1, l  1, m  0, s   131. Electronic configuration of ferric ion is[RPET 2000]
2
(a) [ Ar ] 3 d 5 (b) [ Ar ] 3 d 7
1
(c) n  2, l  1, m  1, s   (c) [ Ar ] 3 d 3 (d) [ Ar ] 3 d 8
2
132. What is the maximum number of electrons which
1 can be accommodated in an atom in which the
(d) n  2, l  1, m  0, s  
2 highest principal quantum number value is 4[MP PMT 2000
123. For which of the following sets of four quantum (a) 10 (b) 18
numbers, an electron will have the highest energy[CBSE PMT(c) 32
1994] (d) 54
l 133. Which of the following electronic configurations is
n m s
not possible
(a) 3 2 1 +1/2 [CPMT 2000]
(b) 4 2 1 +1/2 (a) 1 s 2 2 s 2 (b) 1s 2 2 s 2 2 p 6
(c) 4 1 0 –1/2 (c) 3d 10 4 s 2 4 p 2 (d) 1 s 2 2 s 2 2 p 2 3 s 1
(d) 5 0 0 –1/2 134. The electronic configuration of an element is
124. The electronic configuration of gadolinium 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 5 4 s1 . This represents its
(atomic no. 64) is [CBSE PMT 1997] [IIT Screening 2000]
8
(a) [ Xe ]4 s 5 d 6 s 9 2 7 1
(b) [ Xe ]4 s 5 d 6 s 2 (a) Excited state (b) Ground state
(c) Cationic form (d) Anionic form
(c) [ Xe ]4 s 3 5 d 5 6 s 2 (d) [ Xe ]4 f 6 5 d 2 6 s 2 135. Which of the following set of quantum numbers is
125. An e  has magnetic quantum number as  3 , what possible
[AIIMS 2001]
is its principal quantum number [BHU 1998]
1
(a) 1 (b) 2 (a) n  3; l  2; m  2 and s  
2
(c) 3 (d) 4
1
126. The number of quantum numbers required to (b) n  3; l  4; m  0 and s  
2
describe an electron in an atom completely is[CET Pune 1998]
1
(a) 1 (b) 2 (c) n  4; l  0; m  2 and s  
2
(c) 3 (d) 4 1
(d) n  4; l  4; m  3 and s  
127. The electronic configuration 1s 2 2 s 2 2 p 1x 2 p 1y 2 p 1z 2
136. Which of the following set of quantum number is
[AFMC 1997; Pb. PMT 1999; CBSE PMT 2001; AIIMS 2001]
not valid
(a) Oxygen (b) Nitrogen [AIIMS 2001]
(c) Hydrogen (d) Fluorine (a) n  1, l  2 (b) 3  2, m  1
(c) m  3, l  0 (d) 3  4, l  2
 68 Structure of atom
137. Which one pair of atoms or ions will have same
configuration [JIPMER 2001]
(a) F  and Ne (b) Li  and He  (c)

(c) Cl and Ar (d) Na and K
138. Which of the following sets of quantum number is
not possible [MP PET 2001] (d)
1
(a) n  3; l  2; m  0; s  
2 146. The total magnetic quantum numbers for d-orbital
1 is given by [
(b) n  3; l  0; m  0; s  
2 (a) 2 (b) 0,  1,  2
1 (c) 0, 1, 2 (d) 5
(c) n  3; l  0; m  1; s  
2 147. The outer electronic structure 3 s 2 3 p 5 is possessed
1 by
(d) n  3; l  1; m  0; s  
2 [Pb. PMT 2002; Pb. CET 2001]
139. Which of the following set of quantum numbers is (a) Cl (b) O
correct for the 19th electron of chromium [DCE 2001] (c) Ar (d) Br
n l m s 148. Which of the following set of quantum number is
(a) 3 0 0 1/2 not possible [Pb. PMT 2002]

(b) 3 2 –2 1/2 n l m1 m2

(c) 4 0 0 1/2 (a) 3 2 1 + 1/2

(d) 4 1 –1 1/2 (b) 3 2 1 – 1/2

(c) 3 2 1 0
140. When the value of azimuthal quantum number is (d) 5 2 –1 + 1/2
3, magnetic quantum number can have values[DPMT 2001]
(a) + 1, 0, – 1 149. The configuration 1s 2 , 2 s 2 2 p 5 , 3 s 1 shows[Pb. PMT 2002]
(b) + 2, + 1, 0, – 1, – 2 (a) Excited state of O 2
(c) – 3, – 2, – 1, – 0, + 1, + 2, + 3
(b) Excited state of neon
(d) + 1, – 1
(c) Excited state of fluorine
141. The quantum numbers n  2, l  1 represent [AFMC 2002]
(d) Ground state of fluorine atom
(a) 1s orbital (b) 2s orbital
150. The quantum number ‘m’ of a free gaseous atom is
(c) 2p orbital (d) 3d orbital associated with [AIIMS 2003]
142. The magnetic quantum number of valence
(a) The effective volume of the orbital
electron of sodium (Na) is [RPMT 2002]
(b) The shape of the orbital
(a) 3 (b) 2
(c) 1 (d) 0 (c) The spatial orientation of the orbital
143. Azimuthal quantum number defines [AIIMS 2002] (d) The energy of the orbital in the absence of a
magnetic field
(a) e/m ratio of electron
(b) Spin of electron 151. Correct statement is [BHU 2003]

(c) Angular momentum of electron (a) K  4 s , Cr  3 d 4 s , Cu  3 d

1 4 2 10
4s 2

(d) Magnetic momentum of electron

(b) K  4 s , Cr  3 d 4 s , Cu  3 d
2 4 2 10
4s2
144. Quantum numbers of an atom can be defined on
the basis of [AIIMS  4 s 2 , Cr  3 d 5 4 s 1 , Cu  3 d 10 4 s 2
(c) K2002]
(a) Hund’s rule
(d) K  4 s 1 , Cr  3 d 5 4 s 1 , Cu  3 d 10 4 s 1
(b) Aufbau’s principle
(c) Pauli’s exclusion principle 152. Number of orbitats in h sub-shell is [BHU 2003]

(d) Heisenberg’s uncertainty principle (a) 11 (b) 15

145. Which of the following has maximum energy (c) 17 (d) 19
3s 3p 3d [AIIMS 2002] 153. Electronic configuration
1 s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 3 d 5 , 4 s 1 represents [CPMT 2003]
(a)
(a) Ground state (b) Excited state
3s 3p 3d (c) Anionic state (d) All of these

(b)

3s 3p 3d

3s 3p 3d
 Structure of atom 69
154. Which of the following sets is possible for 162. The electronic configuration of element with
quantum numbers atomic number 24 is [Pb. CET 2004]
[RPET 2003] (a) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 4 ,4 s 2
(a) n  4, l  3, m  2, s  0
(b) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10
1 (c) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6
(b) n  4 , l  4 , m  2, s  
2
(d) 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 5 4 s 1
1
(c) n  4 , l  4 , m  2, s   163. The maximum number of electrons in p -orbital
2
with n  5, m  1 is [Pb. CET 2003]
1
(d) n  4 , l  3, m  2, s   (a) 6 (b) 2
2
155. For principle quantum number n  4 the total (c) 14 (d) 10
number of orbitals having l  3 [AIIMS 2004] 164. Number of two electron can have the same values
(a) 3 (b) 7 of …… quantum numbers [UPSEAT 2004]

(c) 5 (d) 9 (a) One (b) Two

156. The number of 2 p electrons having spin quantum (c) Three (d) Four
number s  1 / 2 are [KCET 2004] 165. The number of orbitals present in the shell with
n  4 is
(a) 6 (b) 0
[UPSEAT 2004]
(c) 2 (d) 3
(a) 16 (b) 8
157. Which of the following sets of quantum numbers (c) 18 (d) 32
is correct for an electron in 4 f orbital[AIEEE 2004]
166. Which of the following electronic configuration is
1 not possible
(a) n  4 , l  3, m  1, s  
2 [MHCET 2003]
1 (a) 1s 2 s2 2
(b) 1s ,2 s 2 p 6
2 2
(b) n  4 , l  4 , m  4 , s  
2
(c) [ Ar ] 3 d 10 ,4 s 2 4 p 2 (d) 1s 2 ,2 s 2 2 p 2 ,3 s 1
1
(c) n  4 , l  3, m  4 , s   167. p x orbital can accommodate
2
1 [MNR 1990; IIT 1983; MADT Bihar 1995; BCECE 2005]
(d) n  3, l  2, m  2, s  
2 (a) 4 electrons
158. Consider the ground state of (Z  24 ) . The (b) 6 electrons
numbers of electrons with the azimuthal quantum (c) 2 electrons with parallel spins
numbers, l  1 and 2 are, respectively (d) 2 [AIEEE 2004]
electrons with opposite spins
(a) 16 and 4 (b) 12 and 5 168. The maximum number of electrons that can be
(c) 12 and 4 (d) 16 and 5 accommodated in ' f ' sub shell is
159. The four quantum numbers of the valence [CPMT 1983, 84; MP PET/PMT 1988; BITS 1988]
electron of potassium are [DPMT
(a) 22004] (b) 8
1 1 (c) 32 (d) 14
(a) 4, 1, 0 and (b) 4, 0, 1 and
2 2
169. The number of electrons which can be
1 1 accommodated in an orbital is[DPMT 1981; AFMC 1988]
(c) 4, 0, 0 and  (d) 4, 1, 1 and
2 2 (a) One (b) Two
160. Which of the following electronic configuration is (c) Three (d) Four
not possible according to Hund’s rule [Kerala PMT 2004]
170. The number of electrons in the atom which has
(a) 1s 2 2 s 2 (b) 1 s 2 2 s 1 20 protons in the nucleus[CPMT 1981, 93; CBSE PMT 1989]
(c) 1s 2 2 s 2 2 p 1x 2 p 1y 2 p 1x (d) 1s 2 2 s 2 2 p x2 (a) 20 (b) 10
(c) 30 (d) 40
(e) 1s 2 2 s 2 2 p x2 2 p 1y 2 p 1z
171. The maximum number of electrons accommodated
161. The ground state term symbol for an electronic in 5 f orbitals are [MP PET 1996]
state is governed by [UPSEAT 2004]
(a) 5 (b) 10
(a) Heisenberg’s principle
(c) 14 (d) 18
(b) Hund’s rule
172. The maximum number of electrons in an atom
(c) Aufbau principle with l  2 and n  3 is [MP PET/PMT 1998]
(d) Pauli exclusion principle
 70 Structure of atom
(a) 2 (b) 6 (c) 2 (d) 3
(c) 12 (d) 10 184. The number of unpaired electrons in a chromic
173. The configuration 1s 2 2 s 2 2 p 5 3 s 1 shows[AIIMS 1997] ion Cr 3  (atomic number = 24) is[MNR 1986; CPMT 1992]
(a) 6 (b) 4
(a) Ground state of fluorine atom
(c) 3 (d) 1
(b) Excited state of fluorine atom
10 0
(c) Excited state of neon atom 185. 3d 4s electronic configuration exhibits by

(d) Excited state of ion O 2 (a) Zn (b) Cu  
(c) Cd   (d) Hg  
174. For sodium atom the number of electrons with
m  0 will be 186. Which
[RPMT of the following metal ions will have
1999]
(a) 2 (b) 7 maximum number of unpaired electrons[CPMT 1996]
(c) 9 (d) 8 (a) Fe 2 (b) CO 2
2
175. The number of electrons that can be (c) Ni (d) Mn 2
accommodated in dz 2 orbital is 187. Which of the
[Kurukshetra CEEmetal
2002] ion will have highest number
(a) 10 (b) 1 of unpaired electrons

(c) 4 (d) 2 (a) Cu  (b) Fe 2 

176. Number of unpaired electrons in 1s 2 2 s 2 2 p 3 is (c) Fe 3  (d) Co 2 

188. The maximum number of unpaired electron can be
[CPMT 1982; MP PMT 1987; BHU 1987;
present in d orbitals are
CBSE PMT 1990; CET Pune 1998; AIIMS 2000] (a) 1 (b) 3
(a) 2 (b) 0 (c) 5 (d) 7
(c) 3 (d) 1 189. The molecule having one unpaired electron is
177. Total number of unpaired electrons in an atom of (a) NO (b) CO
atomic number 29 is [CPMT 1984, 93] (c) CN  (d) O 2
(a) 1 (b) 3 190. A filled or half-filled set of p or d -orbitals is
(c) 4 (d) 2 spherically symmetric. Point out the species
178. The number of unpaired electrons in 1s 2 , 2 s 2 2 p 4 is which has spherical symmetry
[NCERT 1984; CPMT 1991; MP PMT 1996, 2002] (a) Na (b) C
(a) 4 (b) 2 (c) Cl  (d) Fe
(c) 0 (d) 1 191. The atom of the element having atomic number 14
179. The maximum number of electrons that can be should have [AMU 1984]
accommodated in a 3 d subshell is (a) One unpaired electron (b)Two unpaired electrons
(a) 2 (b) 10 (c) Three unpaired electrons(d)Four unpaired electrons
(c) 6 (d) 14 192. An atom has 2 electrons in K shell, 8 electrons in
180. The maximum number of electrons which each L shell and 6 electrons in M shell. The number
sub-shell can occupy is [Pb. CET 1989] of s -electrons present in that element is[CPMT 1989]
(a) 2n 2 (b) 2n (a) 6 (b) 5
(c) 2(2l  1) (d) (2l  1) (c) 7 (d) 10
193. The number of unpaired electrons in carbon atom
181. Number of unpaired electrons in the ground state
in excited state is [MNR 1987]
of beryllium atom is
(a) One (b) Two
(a) 2 (b) 1
(c) Three (d) Four
(c) 0 (d) All the above
194. Maximum number of electrons present in ' N '
182. How many unpaired electrons are present in Ni 2  shell is
cation (atomic number = 28) [IIT 1981; MNR 1984;
[EAMCET 1984]
MP PMT 1995; Kerala PMT 2003]
(a) 18 (b) 32
(a) 0 (b) 2
(c) 2 (d) 8
(c) 4 (d) 6
195. The number of d electrons in Fe 2 (atomic
183. The number of unpaired electrons in an O2
number of Fe  26 ) is not equal to that of the[MNR 1993]
molecule is (a) p -electrons in Ne (At. No.= 10)
[MNR 1983]
(b) s -electrons in Mg (At. No.= 12)
(a) 0 (b) 1
 Structure of atom 71
(c) d -electrons in Fe (b) The second principal energy level can have four
(d) p -electrons in Cl  (At. No. of Cl = 17) sub-energy levels and contains a maximum of
eight electrons
196. A transition metal X has a configuration [ Ar]3 d 4 (c) The M energy level can have maximum of 32
in its  3 oxidation state. Its atomic number is[EAMCETelectrons
1990]
(a) 25 (b) 26 (d) The 4 s sub-energy level is at a higher energy
(c) 22 (d) 19 than the 3 d sub-energy level
197. The total number of electrons present in all the 207. The statements [AIIMS 1982]
p -orbitals of bromine are [MP(i)PET
In 1994]
filling a group of orbitals of equal energy, it
(a) Five (b) Eighteen is energetically preferable to assign electrons
to empty orbitals rather than pair them into a
(c) Seventeen (d) Thirty five
particular orbital.
198. Which of the following has the maximum number
(ii) When two electrons are
of unpaired electrons [IIT 1996]
placed in two different orbitals, energy is
(a) Mg 2  (b) Ti 3  lower if the spins are parallel.
(c) V 3  (d) Fe 2  are valid for
199. Which of the following has more unpaired d - (a) Aufbau principle
electrons (b) Hund's rule
[CBSE PMT 1999] (c) Pauli's exclusion principle
(a) Zn  (b) Fe 2  (d) Uncertainty principle
3  208. According to Aufbau's principle, which of the
(c) N (d) Cu
three 4 d, 5 p and 5 s will be filled with electrons
200. Maximum electrons in a d -orbital are [CPMT 1999]
first [MADT Bihar 1984]
(a) 2 (b) 10
(a) 4 d
(c) 6 (d) 14
(b) 5 p
201. The number of unpaired electrons in Fe 3  (Z  26 )
(c) 5 s
are
(d) 4 d and 5 s will be filled simultaneously
[KCET 2000]
209. The energy of an electron of 2 p y orbital is[AMU 1984]
(a) 5 (b) 6
(c) 3 (d) 4 (a) Greater than that of 2 p x orbital
202. How many unpaired electrons are present in (b) Less than that of 2 p x orbital
cobalt [Co] metal [RPMT 2002] (c) Equal to that of 2 s orbital
(a) 2 (b) 3 (d) Same as that of 2 p z orbital
(c) 4 (d) 7
210. Which of the following principles/rules limits the
203. The number of unpaired electrons in nitrogen is maximum number of electrons in an orbital to
[Pb. CET 2002] two[CBSE PMT 1989]
(a) 1 (b) 3 (a) Aufbau principle
(c) 2 (d) None of these (b) Pauli's exclusion principle
204. Which of the following has the least energy (c) Hund's rule of maximum multiplicity
(a) 2 p (b) 3 p (d) Heisenberg's uncertainty principle
(c) 2 s (d) 4 d 211. The electrons would go to lower energy levels
205. Pauli's exclusion principle states that[CPMT 1983, 84] first and then to higher energy levels according to
(a) Nucleus of an atom contains no negative which of the following
charge [BHU 1990; MP PMT 1993]
(b) Electrons move in circular orbits around the (a) Aufbau principle
nucleus (b) Pauli's exclusion principle
(c) Electrons occupy orbitals of lowest energy (c) Hund's rule of maximum multiplicity
(d) All the four quantum numbers of two (d) Heisenberg's uncertainty principle
electrons in an atom cannot be equal 212. Energy of atomic orbitals in a particular shell is in
206. For the energy levels in an atom, which one of the the order
following statements is correct [AIIMS 1983] [AFMC 1990]
(a) There are seven principal electron energy (a) s  p  d  f (b) s  p  d  f
levels (c) p  d  f  s (d) f  d  s  p
213. Aufbau principle is not satisfied by [MP PMT 1997]
 72 Structure of atom
(a) Cr and Cl (b) Cu and Ag h
(c) 2 (d) Zero
(c) Cr and Mg (d) Cu and Na 2
214. Which of the following explains the sequence of 225. The maximum number of electrons present in an
filling the electrons in different shells[AIIMS 1998; BHU 1999]orbit l  3 , is [Pb. PMT 2004]
(a) Hund's rule (b) Octet rule (a) 6 (b) 8
(c) Aufbau principle (d) All of these (c) 10 (d) 14
215. Aufbau principle is obeyed in which of the 226. Number of unpaired electrons in Mn 4  is[DPMT 2005]
following electronic configurations [AFMC 1999] (a) 3 (b) 5
(a) 1s 2 2 s 2 2 p 6 (b) 1s 2 3 p 3 3 s 2 (c) 6 (d) 4
227. Which of the following sequence is correct as per
(c) 1s 2 3 s 2 3 p 6 (d) 1s 2 2 s 2 3 s 2 Aufbau principle [DPMT 2005]
216. Following Hund’s rule which element contains six (a) 3 s  3 d  4 s  4 p (b) 1s  2 p  4 s  3 d
unpaired electron [RPET 2000] (c) 2 s  5 s  4 p  5 d (d) 2 s  2 p  3d  3 p
(a) Fe (b) Co
228. Electronic configuration of deuterium atom is
(c) Ni (d) Cr [J&K CET 2005]
217. Electron enters the sub-shell for which (n  l) (a) 1s 1
(b) 2s 2

value is minimum. This is enunciated as

(c) 2s 1 (d) 1s 2
[RPMT 2000]
(a) Hund’s rule
(b) Aufbau principle
(c) Heisenberg uncertainty principle
(d) Pauli’s exclusion principle
218. The atomic orbitals are progressively filled in
order of increasing energy. This principle is called
as 1. Which of the following atoms and ions are
[MP PET 2001] isoelectronic i.e. have the same number of
(a) Hund’s rule (b) Aufbau principle electrons with the neon atom
(c) Exclusion principle (d) de-Broglie rule [NCERT 1978]
219. The correct order of increasing energy of atomic (a) F  (b) Oxygen atom
orbitals is
(c) Mg (d) N 
[MP PET 2002]
(a) 5 p  4 f  6 s  5 d (b) 5 p  6 s  4 f  5 d 2. Atoms consists of protons, neutrons and
electrons. If the mass of neutrons and electrons
(c) 4 f  5 p  5 d  6 s (d) 5 p  5 d  4 f  6 s were made half and two times respectively to
220. The orbital with maximum energy is [CPMT 2002] their actual masses, then the atomic mass of 6 C 12
(a) 3d (b) 5p
(a) Will remain approximately the same
(c) 4s (d) 6d
(b) Will become approximately two times
221. p-orbitals of an atom in presence of magnetic
field are (c) Will remain approximately half
[Pb. PMT 2002] (d) Will be reduced by 25%
(a) Two fold degenerate (b) Non degenerate 3. The increasing order (lowest first) for the values
(c) Three fold degenerate (d) None of these of e / m (charge/mass) for [
222. Orbital angular momentum for a d-electron is[MP PET 2003] (a) e, p, n,  (b) n, p, e, 
6h 6h (c) n, p,  , e (d) n,  , p, e
(a) (b)
2 2 4. The electronic configuration of a dipositive metal
(c)
12 h
(d)
12 h M 2  is 2, 8, 14 and its atomic weight is 56 a.m.u.
2 2 The number of neutrons in its nuclei would be
223. Number of nodal centres for 2s orbital [RPET 2003] [MNR 1984, 89; Kerala PMT 1999]
(a) 1 (b) 0 (a) 30 (b) 32
(c) 4 (d) 3
(c) 34 (d) 42
224. The orbital angular momentum of an electron in
2 s -orbital is 5. [MP
The
PETratio
2004]of the energy of a photon of 2000 Å
1 h h wavelength radiation to that of 4000 Å radiation is
(a) (b)
2 2 2 [IIT 1986; DCE 2000; JIPMER 2000]
(a) 1/4 (b) 4
 Structure of atom 73
(c) 1/2 (d) 2 15. The ionization energy of hydrogen atom is
6. Discovery of the nucleus of an atom was due to 13 .6 eV . The energy required to excite the
the experiment carried out by[CPMT 1983; MP PET 1983] electron in a hydrogen atom from the ground
(a) Bohr (b) Mosley state to the first excited state is (Avogadro’s
constant = 6.022 × 1023) [BHU 1999]
(c) Rutherford (d) Thomson
7. In a Bohr's model of atom when an electron jumps (a) 1.69  10 20 J (b) 1 .69  10 23 J
from n  1 to n  3 , how much energy will be (c) 1 .69  10 23 J (d) 1 .69  10 25 J
emitted or absorbed [CBSE PMT 1996]
16. The energy required to dislodge electron from
(a) 2.15  10 11 erg (b) 0.1911  10 10 erg excited isolated H-atom, IE1  13 .6 eV is [DCE 2000]
(c) 2.389  10 12 erg (d) 0.239  10 10 erg (a)  13 .6 eV (b)  13 .6 eV
8. The nucleus of an atom can be assumed to be
(c)  13 .6 and  3.4 eV (d)  3.4 eV
spherical. The radius of the nucleus of mass
number A is given by 1.25  10 13  A 1 / 3 cm Radius 17. The number of nodal planes in a p x is
of atom is one Å . If the mass number is 64, then [IIT Screening 2000]
the fraction of the atomic volume that is occupied (a) One (b) Two
by the nucleus is [NCERT 1983]
(c) Three (d) Zero
(a) 1 .0  10 3 (b) 5.0  10 5
18. The third line in Balmer series corresponds to an
(c) 2.5  10 2 (d) 1 .25  10 13 electronic transition between which Bohr’s orbits
9. The energy of an electron in the first Bohr orbit of in hydrogen
H atom is 13 . 6 eV . The possible energy value(s) [MP PMT 2001]
of the excited state(s) for electrons in Bohr orbits
(a) 5  3 (b) 5  2
to hydrogen is(are)
[IIT 1998; Orissa JEE 2005] (c) 4  3 (d) 4  2
(a) 3 . 4 eV (b) 4 . 2 eV 19. Which of the following has maximum number of
unpaired electron (atomic number of Fe 26)[MP PMT 2001]
(c) 6 . 8 eV (d) 6 . 8 eV
10. The energy of the electron in the first orbit of (a) Fe (b) Fe (II)
 20
He is  871 .6  10 J . The energy of the electron (c) Fe (III) (d) Fe (IV)
in the first orbit of hydrogen would be[Roorkee Qualifying 20. The frequency of one of the lines in Paschen
1998]
(a)  871 .6  10 20 J (b)  435 .8  10 20 J series of hydrogen atom is 2 .340  10 11 Hz . The
quantum number n 2 which produces this
(c)  217 .9  10 20 J (d)  108 .9  10 20 J
transition is [DPMT 2001]
11. The total number of valence electrons in 4.2 gm of
(a) 6 (b) 5
N 3 ion is ( N A is the Avogadro's number)[CBSE PMT 1994]
(c) 4 (d) 3
(a) 1.6 N A (b) 3.2 N A
21. Which of the following electron transition in a
(c) 2.1 N A (d) 4.2 N A hydrogen atom will require the largest amount of
energy
12. The Bohr orbit radius for the hydrogen atom
[UPSEAT 1999, 2000, 01]
(n  1) is approximately 0 .530 Å . The radius for the
first excited state (n  2) orbit is[CBSE PMT 1998; BHU 1999] (a) From n  1 to n  2 (b) From n  2 to n  3
(c) From n   to n  1 (d) From n  3 to n  5
(a) 0 .13 Å (b) 1 .06 Å
22. In Bohr series of lines of hydrogen spectrum, the
(c) 4.77 Å (d) 2 .12 Å third line from the red end corresponds to which
14 1
13. The frequency of a wave of light is 12  10 s . The one of the following inter-orbit jumps of the
wave number associated with this light is[Pb. PMT 1999] electron for Bohr orbits in an atom of hydrogen
(a) 5  10 7 m (b) 4  10 8 cm 1 (a) 3  2 (b) 5  2

(c) 2  10 7
m 1
(d) 4  10 cm
4 1 (c) 4  1 (d) 2  5

14. The series limit for Balmer series of H-spectra is 23. The value of Planck’s constant is 6.63  10 34 Js . The
[AMU (Engg.) 1999] velocity of light is 3 . 0  10 8 ms 1 . Which value is
(a) 3800 (b) 4200 closest to the wavelength in nanometres of a
(c) 3646 (d) 4000 quantum of light with frequency of 8  10 15 s 1
(a) 3  10 7 (b) 2  10 25
(c) 5  10 18 (d) 4  10 1
 74 Structure of atom
24. As electron moves away from the nucleus, its 6. Assertion : Two electrons in an atom can have
potential energy [UPSEAT 2003] the same values of four quantum
(a) Increases (b) Decreases numbers.
(c) Remains constant (d) None of these Reason : Two electrons in an atom can be
present in the same shell, sub-shell
and orbital and have the same spin[AIIMS 20
7. Assertion : The value of n for a line in Balmer
series of hydrogen spectrum having
the highest wave length is 4 and 6.
Reason : For Balmer series of hydrogen
spectrum, the value n1  2 and
Read the assertion and reason carefully to mark the
correct option out of the options given below : n2  3, 4, 5.
(a) If both assertion and reason are true and the [AIIMS 1992]
reason is the correct explanation of the assertion. 8. Assertion : Absorption spectrum conists of
(b) If both assertion and reason are true but reason is some bright lines separated by dark
not the correct explanation of the assertion. spaces.
(c) If assertion is true but reason is false.
Reason : Emission spectrum consists of dark
(d) If the assertion and reason both are false.
lines.
(e) If assertion is false but reason is true.
[AIIMS 2002]
1. Assertion : The position of an electron can be 9. Assertion : A resonance hybrid is always more
determined exactly with the help of stable than any of its canonical
an electron microscope. structures.
Reason : The product of uncertainty in the Reason : This stability is due to
measurement of its momentum and delocalization of electrons.[AIIMS 1999]
the uncertainty in the measurement 10. Assertion : Cathode rays do not travel in
of the position cannot be less than a straight lines.
finite limit.
Reason : Cathode rays penetrate through
[NDA 1999] thick sheets [AIIMS 1996]
2. Assertion : A spectral line will be seen for a 11. Assertion : Electrons revolving around the
2 p x  2 p y transition. nucleus do not fall into the nucleus
Reason : Energy is released in the form of because of centrifugal force.
wave of light when the electron Reason : Revolving electrons are planetary
drops from 2 p x  2 p y orbital.[AIIMS 1996] electrons.
[AIIMS 1994]
3. Assertion : The cation energy of an electron is
largely determined by its principal 12. Assertion : Threshold frequency is a
quantum number. characteristic for a metal.
Reason : Threshold frequency is a maximum
Reason : The principal quantum number n is
frequency required for the ejection
a measure of the most probable
of electron from the metal surface.
distance of finding the electron
around the nucleus. 13. Assertion : The radius of the first orbit of
[AIIMS 1996]
hydrogen atom is 0.529Å.
30 Reason : Radius for each circular orbit
4. Assertion : Nuclide Al 13 is less stable than
(rn )  0.529Å (n 2 / Z) , where n  1,2,3
40
Ca 20
and Z  atomic number.
Reason : Nuclides having odd number of 14. Assertion : 3d z 2 orbital is spherically
protons and neutrons are generally
symmetrical.
unstable
Reason : 3d z 2 orbital is the only d -orbital
[IIT 1998]
5. Assertion : The atoms of different elements which is spherical in shape.
having same mass number but 15. Assertion : Spin quantum number can have the
different atomic number are known value +1/2 or –1/2.
as isobars Reason : (+) sign here signifies the wave
Reason : The sum of protons and neutrons, in function.
the isobars is always different[AIIMS 2000]
 Structure of atom 75
16. Assertion : Total number of orbitals associated 21 a 22 d 23 c 24 b 25 d
with principal quantum number
26 c 27 b 28 d 29 c 30 a
n  3 is 6.
31 b 32 d 33 b 34 c 35 c
Reason : Number of orbitals in a shell equals
to 2n . 36 a 37 b 38 a 39 d 40 c
17. Assertion : Energy of the orbitals increases as 41 c
1s  2 s  2 p  3 s  3 p  3 d  4 s  4 p
 4 d  4 f  ...... Atomic number, Mass number, Atomic species
Reason : Energy of the electron depends
completely on principal quantum 1 b 2 a 3 b 4 b 5 a
number. 6 a 7 c 8 b 9 c 10 b
18. Assertion : Splitting of the spectral lines in the 11 b 12 c 13 b 14 c 15 c
presence of magnetic field is known
16 c 17 c 18 a 19 c 20 a
as stark effect.
Reason : Line spectrum is simplest for 21 c 22 b 23 c 24 d 25 b
hydrogen atom. 26 b 27 a 28 a 29 c 30 b
19. Assertion : Thomson’s atomic model is known 31 c 32 d 33 d 34 c 35 c
as ‘raisin pudding’ model.
36 c 37 c 38 b 39 d 40 c
Reason : The atom is visualized as a pudding
of positive charge with electrons 41 b 42 c 43 a 44 c 45 b
(raisins) embedded in it. 46 c 47 d 48 a 49 c 50 c
20. Assertion : Atomic orbital in an atom is
51 a 52 c 53 b 54 a 55 c
designated by n, l, ml and m s .
56 a 57 d 58 c 59 a 60 a
Reason : These are helpful in designating
electron present in an orbital. 61 d 62 b 63 a 64 c 65 b
21. Assertion : The transition of electrons n3  n2 66 a 67 c 68 a 69 d 70 d
in H atom will emit greater energy 71 c 72 a 73 b 74 d
than n4  n3 .
Reason : n 3 and n 2 are closer to nucleus tan Atomic models and Planck's quantum theory
n4 .
1 c 2 a 3 b 4 b 5 d
22. Assertion : Cathode rays are a stream of  -
particles. 6 b 7 c 8 b 9 c 10 a

Reason : They are generated under high 11 b 12 a 13 d 14 b 15 b

pressure and high voltage. 16 c 17 a 18 c 19 a 20 d
23. Assertion : In case of isoelectronic ions the 21 d 22 c 23 d 24 d 25 c
ionic size increases with the 26 a 27 c 28 b 29 c 30 a
increase in atomic number.
31 b 32 c 33 d 34 b 35 b
Reason : The greater the attraction of
36 a 37 c 38 c 39 c 40 a
nucleus, greater is the ionic radius.
41 c 42 d 43 d 44 a 45 d
46 b 47 a 48 c 49 d 50 a
51 a 52 c 53 d 54 c 55 b
56 b 57 b 58 a 59 b 60 c
61 c 62 b 63 c 64 c 65 b
66 b 67 c 68 a 69 b 70 d
71 a 72 d 73 a 74 c 75 d
Discovery and Properties of anode, cathode rays 76 b 77 a 78 a 79 c 80 a
neutron and Nuclear structure 81 a

1 d 2 a 3 c 4 c 5 b
Dual nature of electron
6 a 7 b 8 a 9 d 10 c
11 b 12 d 13 b 14 a 15 b 1 c 2 a 3 a 4 b 5 c
16 b 17 c 18 c 19 c 20 b 6 b 7 d 8 a 9 d 10 d
 76 Structure of atom
11 c 12 c 13 b 14 b 15 b 151 d 152 a 153 a 154 d 155 b
16 c 17 c 18 c 19 b 20 a 156 d 157 a 158 b 159 c 160 d
21 d 161 c 162 d 163 b 164 c 165 a
166 d 167 d 168 d 169 b 170 a
Uncertainty principle and Schrodinger wave 171 c 172 d 173 c 174 b 175 d
equation 176 c 177 a 178 b 179 b 180 c
181 c 182 b 183 c 184 c 185 a
1 b 2 b 3 a 4 c 5 c
186 d 187 c 188 c 189 a 190 c
6 c 7 b 8 d 9 d 10 a
191 b 192 a 193 d 194 b 195 d
11 a 12 c 13 a 14 b 15 d
196 a 197 c 198 d 199 b 200 b
16 b 17 a 18 c 19 c 20 b
201 a 202 b 203 b 204 c 205 d

Quantum number, Electronic configuration 206 b 207 b 208 c 209 d 210 b

and Shape of orbitals 211 a 212 a 213 b 214 c 215 a
216 d 217 b 218 b 219 b 220 d
1 c 2 a 3 b 4 d 5 c
221 b 222 b 223 a 224 d 225 d
6 c 7 c 8 a 9 a 10 a
226 a 227 b 228 a
11 c 12 c 13 a 14 a 15 d
16 c 17 c 18 d 19 b 20 c Critical Thinking Questions
21 c 22 a 23 c 24 d 25 c
1 a 2 d 3 d 4 a 5 d
26 c 27 b 28 d 29 e 30 b
6 c 7 b 8 d 9 a 10 c
31 d 32 a 33 c 34 d 35 d
11 a 12 d 13 d 14 c 15 b
36 c 37 b 38 b 39 d 40 c
16 d 17 a 18 b 19 c 20 b
41 d 42 c 43 c 44 a 45 a 21 a 22 a 23 d 24 a
46 a 47 b 48 c 49 c 50 b
51 c 52 b 53 b 54 b 55 c
Assertion & Reason
56 c 57 b 58 e 59 c 60 c
1 d 2 d 3 a 4 a 5 c
61 d 62 d 63 d 64 c 65 b
6 d 7 e 8 d 9 a 10 e
66 d 67 c 68 d 69 c 70 b
11 b 12 c 13 a 14 d 15 c
71 a 72 c 73 c 74 c 75 a
16 d 17 c 18 e 19 a 20 e
76 c 77 c 78 c 79 d 80 d
21 b 22 d 23 d
81 b 82 c 83 a 84 a 85 b
86 c 87 a 88 b 89 c 90 b
91 d 92 a 93 b 94 b 95 d
96 d 97 a 98 a 99 d 100 c
101 b 102 d 103 a 104 c 105 d
106 a 107 c 108 d 109 a 110 d
111 d 112 b 113 c 114 b 115 b Discovery and Properties of anode, cathode rays
116 a 117 c 118 b 119 a 120 a neutron and Nuclear structure
121 d 122 b 123 b 124 b 125 d
1. (d) Neutrons and protons in the nucleus and
126 d 127 b 128 c 129 a 130 b electrons in the extranuclear region.
131 a 132 c 133 d 134 b 135 a 2. (a) It consists of proton and neutron and these
136 a 137 c 138 c 139 c 140 c are also known as nucleones.

141 c 142 d 143 c 144 c 145 b 3. (c) Radius of nucleus ~ 10 15 m .

146 d 147 a 148 c 149 b 150 c 4. (c) Positive ions are formed from the neutral
atom by the loss of electrons.
 Structure of atom 77
5. (b) The -ray particle constitute electrons.
6. (a) James Chadwick discovered neutron (0 n1 ) .
7. (b) Charge/mass for
2 1 1
n  0,   , p  and e 
4 1 1 / 1837
9. (d) The density of neutrons is of the order 10 11 kg / cc.
10. (c) This is because chargeless particles do not
undergo any deflection in electric or magnetic
field.
11. (b) Neutron and proton found in nucleus.
13. (b) Cathode rays are made up of negatively
charged particles (electrons) which are
deflected by both the electric and magnetic
fields.
15. (b) Mass of neutron is greater than that of proton,
meson and electron.
Mass of neutron = mass of proton + mass of
electron
16. (b) Proton is 1837 (approx 1800) times heavier
1
than an electron. Penetration power 
mass
4
18. (c) Nucleus of helium is 2 He mean 2 neutrons
and 2 protons.
19. (c) Proton is the nucleus of H  atom ( H  atom
devoid of its electron).
20. (b) Cathode rays are made up of negatively
charged particles (electrons, e  )
26. (c) Size of nucleus is measured in Fermi (1 Fermi
 10 15 m) .
27. (b) A molecule of an element is a incorrect
statement. The correct statement is “an
element of a molecule”.
 Structure of atom 75
29. (c) Proton is represented by p having charge +1 CO  6  8  14 and CN   6  7  1  14 .
discovered in 1988 by Goldstein. 9. (c) Mass of an atom is due to nucleus (neutron +
31. (b) The nature of anode rays depends upon the proton).
nature of residual gas. 10. (b) Atomic number is defined as the number of
32. (d) H  (proton) will have very large hydration protons in the nucleus.
energy due to its very small ionic size 11. (b) X 56 A  P  N  Z  N  E  N
26
1
Hydration energy  N  A  E  56  26  30
Size
12. (c) Most probable radius = a0 / Z
33. (b) Mass of a proton  1.673  10 24 g where a0 = 52.9 pm. For helium ion, Z = 2.
 Mass of one mole of proton 52 .9
rmp = = 26.45 pm.
 9 .1  10 24  6 .02  10 23  10 . 07  10 1  1 . 008 g 2
Mass of a electron  9.1  10 28 g 13. (b) Four unpaired electron are present in the
2
Fe 2  ion Fe 26  [ Ar ] 3 d 6 ,4 s 0
 Mass of one mole of electron
 9 .1  10 28  6 .02  10 23  54 .78  10 5 g  0 .55 mg . 14. (c) Na  has 10 electron and Li  has 2 electron so
these are different number of electron from
35. (c) One mole of electron = 6.023 × 1023 electron each other.
Mass of one electron = 9.1 × 10–28 gm 16. (c) P15  2, 8, 5
Mass of one mole of electrons
17. (c) 8O  1s 2 2 s 2 2 p 4
= 6.023 × 10 23  9.1  10 28 gm = 5.48  10 4 gm
18. (a) Br 80  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 10 4 s 2 4 p 5
= 5 . 48  10 4  1000 mg = 0.548 gm  0.55 mg . 35

A  80 , Z  35 , N  ?
36. (a) Charge on proton  1 unit, charge on  particle
= + 2 units, 2 : 1. N  A  Z  80  35  45
37. (b) m p / me ~ 1837 ~ 1.8  10 3 . atomic number (Proton) is 35 and no. of
neutron is 45.
38. (a) Splitting of signals is caused by protons
attached to adjacent carbon provided these 19. (c) 16 O   have more electrons than neutron
8
are not equivalent to the absorbing proton. p  8, e  10 , n  8 .
39. (d) Nucleus consists of proton and neutron both
20. (a) A 12 and X 13 both are isotopes but have
are called as nucleon. 6 6

different no. of neutrons.

40. (c) Positron (1e 0 ) has the same mass as that of
A12 , For A have p  6, e  6 and n  6 and
an electron (1e 0 ) . 6

1 6 X 13 , For B have p  6, e  6 and n  7

41. (c) Electron time lighter than proton so
1837 21. (c) P  20, mass no. (A) = 40
their mass ratio will be 1 : 1837
N  A–P = 40  20  20

Atomic number, Mass number, Atomic species P  N  20 .

22. (b) Electrons in Na   11  1  10
1. (b) The number of electrons in an atom is equal to Electrons in Mg 2   12  2  10
its atomic number i.e. number of protons.
40
2. (a) No. of protons = Atomic no. = 25 and no. of 23. (c) 20 Ca has 20 proton, 20 neutron.
neutron = 55 – 25 = 30. 24. (d) CH 3  6  3  1  8 e  ,
3. (b) No. of neutrons = mass number – no. of
protons. = W – N. H 3 O   3  8  1  10 e  ,

4. (b) 30 Zn 70 , Zn 2  has No. of Neutrons = 70 – 30 = NH 3  7  3  10 e  , CH 3  6  3  1  10 e 

40. 25. (b)  CONH 2  6  8  7  2  1 (from other atom to
5. (a) Na  and Ne are isoelectronic which contain 10 form covalent bond) = 24.
electrons. 26. (b) Complete E.C.  [ Ar]18 3d 10 4 s 2 4 p 6 .
6. (a) One molecule of CO2 have 22 electrons.
Hence no. of e   no. of protons  36  Z .

7. (c) Cl and Cl differs in number of electrons. Cl
28. (a) K   1s 2 2 s 2 2 p 6 3 s 2 3 p 6
has 17 e  while Cl  has 18 e  .
Cl   1s 2 2 s 2 2 p 6 3 s 2 3 p 6 .
8. (b) CO and CN  are isoelectronic.
29. (c) Mass no.  At. Wt.
 76 Structure of atom
Mass no. = no. of protons + no. of neutrons
At. no. = no. of protons. 56. (a) Bromine consists of outer most electronic
30. (b) N 2O  14  8  22 configuration [ Ar ] 3 d 10 4 s 2 4 p 5 .

CO2  6  16  22 . 57. (d) Na   1 s 2 2 s 2 2 p 6

31. (c) Neutron in 12

6 C  6 , , Neutrons in 28
14 Si  14 Mg++  1 s 2 2 s 2 2 p 6
Ratio = 6 : 14 = 3 : 7. O 2   1s 2 2 s 2 2 p 6
33. (d) N 7  1s 2 s 2 p2 2 3

Cl   1 s 2 2 s 2 2 p 6 3 s 2 3 p 6
N   1s 2 2 s 2 2 p 2
60. (a) Ar1840 = atomic number 18 and no. of Neutron
C  1s 2 s 2 p .
2 2 2
in case of Ar22
34. (c) O  C  O, linear structure 180 o angle Neutron = Atomic mass – Atomic number
Cl  Hg  Cl , linear structure 180 o
angle.  40  18  22
  61. (d) Nucleus of tritium contain [ H 13 ]
35. (c) H  1s and He  1s .2 2

36. (c) In the nucleus of an atom only proton and p 1 , e 1 , n  2

neutrons are present. 62. (b) N 3, F and Na  (These three ions have
63 
37. (c) Cu 29 Number of neutrons = atomic mass – e  10 , hence they are isoelectronic)
atomic number = 63 – 29 = 34. 63. (a) NO 3 and CO 32  consist of same electron and
38. (b) 21 Protons and 24 Neutrons are present in show same isostructural.
nucleus and element is Sc.
64. (c) Atomic number of chlorine 17 and in Cl  ion
40. (c) 7 X 14 , n  14  7  7 total no. of electron =18.
42. (c) Cl  have 17 proton, 18 neutron and 18 65. (b) Tritium (H 13 ) has one proton and two neutron.
electron.
67. (c) X 35  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3 d 10 4 s 2 4 p 5
43. (a) Number of unpaired electrons in inert gas is
zero because they have full filled orbitals. Total no. of e  is all p–orbitals  6  6  5  17 .
44. (c) Electrons and Protons are same in neutral atom. 68. (a) Since its nucleus contain 9 proton so its.
48. (d) No. of proton and no. of electron = 18 [ Ar1836 ] atomic number is 9 and its electronic
configuration is 2, 7. So it require one more
and No. of neutron = 20 electron to complete its octet. Hence its
Mass number = P + N = 18  20  38 . valency is 1.
(d) K2 S formed by K  and S 2  ion. We know that
231
49. (c) In Xe 89 number of protons and electrons is 69.
89 and No. of neutrons = A – Z = 231 – 89 = atomic number of K is 19 and in K  ion its
142. atomic number would be 18 similarly atomic
51. (a) NO 2 and O 3 are isostere. The number of number of S is 16 and in form S 2  ion its
atoms in these ( 3) and number of electrons atomic number would be 18 so the K  and
(24 ) are same. S 2  are isoelectronic with each other in K2 S .
52. (c) Number of electrons in nitrogen = 7 and 70. (d) 20 Ca  2, 8, 8, 2
number of electron is oxygen = 8 we know 2
Ca  2, 8, 8
that formula of nitrate ion is NO 3 we also
Hence, Ca 2  has 8 electrons each in outermost
know that number of electron
and penultimate shell.
= (1 × Number of electrons in nitrogen)
71. (c) Atomic no. of C = 6 so the number of protons
+ (3 × number of electrons in oxygen) + 1 in the nucleus = 6
= (1 × 7) + (3 × 8) + 1 = 32. 72. (a) No. of P  Z  7; No. of electrons in
Molecular mass 256
53. (b) Atomicity =   8  S8 . N 3   7  3  10 .
Atomic mass 32 2
73. (b) Heavy hydrogen is 1 D .Number of neutrons =
54. (a) In case of N 3  , p  7 and c  10
1
55. (c) Chlorine Cl17  [Ne ] 74. (d) Atomic number is always whole number.
3s2 3p5
Atomic models and Planck's quantum theory

Three electron
pair
 Structure of atom 77
2. (a) The central part consisting whole of the 46. (b) Generally electron moving in orbits according
positive charge and most of the mass caused to Bohr‘s principle.
by nucleus, is extremely small in size 47. (a) According to the planck’s law that energy of a
compared to the size of the atom. photon is directly proportional to its
3. (b) Electrons in an atom occupy the extra nuclear frequency i.e. E  h
region. 49. (d) Bohr’s radius of the hydrogen atom
4. (b) According to the Bohr model atoms or ions n 2  0.529Å
contain one electron. r  ; where z = Atomic number,
z
5. (d) The nucleus occupies much smaller volume
n = Number of orbitals
compared to the volume of the atom.
(c) -particles pass through because most part of 2.172  10 18  2.172  10 18
7. 51. (a) E   2

the atom is empty. n 22
19
8. (b) An electron jumps from L to K shell energy is  5 .42  10 J .
released. hc hc
52. (c) E  or  
9. (c) Neutron is a chargeless particles, so it does  E
not deflected by electric or magnetic field. 6.64  10 34  3  10 8
10. (a) Energy is always absorbed or emitted in   6 .64  10 8 Å
3  10 8
whole number or multiples of quantum.
53. (d) rn  r1  n 2
11. (b) Both He and Li  contain 2 electrons each.
r3  0 . 53  3 2  0.53  9  4.77 Å
18. (c) During the experimental verification of de-
Broglie equation, Davisson and Germer 54. (c) According to Rutherford an atom consists of
confirmed wave nature of electron. nucleus which is small in size but carries the
19. (a) Increases due to absorption of energy and it entire mass (P+ N ).
shows absorption spectra. 55. (b) Wavelength of spectral line emitted is
1
20. (d) Rutherford -Scattering experiment. inversely proportional to energy   .
21. (d) It represents Heisenberg’s uncertainty E
principle. 1 1 1
56. (b) E  ; E1  ; E2 
 8000 16000
E 22 4 1 E 328
23. (d) 4  2   ; E4  2   82 kJ / mol . E1 16000
E2 4 16 4 4 4   2  E1  2 E2
E2 8000
3  10 8 c
27. (c) When c     than   
 1.5  10 2 m c3  10 8 ms 1
 2  10 6 58. (a)     5.0  10 14 Hz .
 600  10  9 m
28. (b) According to quantum theory of radiation, a
13 .6 13 .6 13 .6
hot body emits radiant energy not 59. (b) E  eV    3 .40 eV
continuously but discontinuously in the form n2 22 4
of small packets of energy called quanta or r2 (2)2
65. (b) Bohr radius   2  4.
photons. r1 (1)
h 6.6  10 34 1
30. (a) p    3  10 23 kgms 1 1 1  1 1 
 2.2  10 11 66. (b) v   R  2  2   109678     82258 .5
  n1 n 2  1 4 
n 2h2
34. (b) Bohr’s radius  . Which is a positive   1 .21567  10 5 cm or   12 .1567  10 6 cm
4 2 me 2 z
quantity.  12 . 1567  10 8 m
40. (a) Gold used by Rutherford in scatting
c 3  10 8
experiment. v   24 .66  10 14 Hz .
 12 .567  10 8
 1 1 
41. (c) E  E3  E2  13 . 6  2  2   1 . 9 eV 67. (c) We know that  
h
;  m
h
 (2) (3)  mv m
42. (d) R  R 0 ( 1 .4  10 13 cm )  A 1 / 3 The velocity of photon (v) = 3  10 8 m sec 1
q 1q  1   1.54  10 8 cm  1.54  10 10 meter
43. (d)        9 . 6  10 7  4 . 8  10 7 C kg 1
 m  2  m  p 2 6 .626  10 34 Js
m 
44. (a) According to Hydrogen spectrum series. 1 .54  10 10 m  3  10 8 m sec 1
45. (d) The electron can move only in these circular  1 .4285  10 32 kg .
orbits where the angular momentum is a
68. (a) The spliting of spectral line by the magnetic
h
whole number multiple of or it is field is called Zeeman effect.
2
69. (b) r  n 2 (excited state n  2 )
quantised. r  4a0
 78 Structure of atom
70. (d) rn  n 2 : A n  n 4 79. (c) Positive charge of an atom is present in
nucleus.
A2 n 24 2 4
16
    16 : 1 81. (a) For n4  n1 , greater transition, greater the
A1 n14 1 4
1
energy difference, lesser will be the
4  2 mr 2 wavelength.
71. (a) It will take
nh
n2
Dual nature of electron
72. (d) rH  0.529 Å
z h h
For hydrogen ; n  1 and z  1 therefore 1. (c) According to de-Broglie equation   or
mv p
rH  0 . 529 Å
h
or .
For Be 3  : Z  4 and n  2 Therefore mc
0.529  2 2 4.
h
(b)   or
h h
de-Broglie equation.
rBe 3    0.529 Å . p mv
or
mc
4
2
13 . 6 Z eff 5. (c) Emission spectra of different  accounts for
73. (a) E ionisation  E   En  eV quantisation of energy.
n2
6. (b) According to de-Broglie equation
 13 .6 Z 2 13 .6 Z 2  h h h
=  2
   , p  mv ,   ,  
 n 2 n12  mv p mc

13 . 6  1 2 13 . 6  1 2  h 
E  h   ; h  13 .6  0.85 7. (d) According to de-Broglie    .
(1)2 (4 )2  mv 
h 6 .63  10 34
 h  6 .625  10 34 8. (a)     6 . 63  10  33 m
13 .6  0 .85
mv 10  3  100
  1 .6  10 19 = 3.08  10 15 s 1 . h 1
6 .625  10 34 9. (d)   . For same velocity   .
mv m
1 1 1 
74. (c)  R 2  2  SO 2 molecule has least wavelength because
  1
n n 
2 
their molecular mass is high.
1 1 1  1  h
 1 .097  10 m  2  2  7
10. (d) de-Broglie equation is   .
 1   p
   91  10 9 m 11. (c) Formula for de-Broglie wavelength is
9
We know 10  1 nm So   91nm h h 1 2 eV
 or    eV  mv 2 or  
75. (d) r  n 2 p mv 2 m
For Ist orbit   1 h 6 . 62  10 34
 
For IIIrd orbit =   3  9 2
2meV 2  9 . 1  10  31  2 . 8  10  23
So it will 9  .
  9.28  10 8 meter .
76. (b) Bohr suggest a formulae to calculate the
h
radius and energy of each orbit and gave the 12. (c)   , p  mv
following formulae p
n2h2 h 6 . 62  10 34
rn   
4 kme Z
2 4
mv 9 . 1  10  31  1 . 2  10 5
Where except n 2 , all other unit are constant so   6.626  10 9 m .
rn  n 2 .
13. (b) Mass of the particle (m )  10 6 kg and velocity
 E0
77. (a) Energy of an electron E  of the particle (v)  10 ms 1
n2
For energy level (n  2) h 6 . 63  10 34
   6 . 63  10  29 m
13 .6 13 .6 mv 10  6  10
E   3.4 eV .
(2) 2 4 15. (b) According to de–Broglie
78. (a) Energy of ground stage (E0 ) = 13 . 6 eV and h 6 . 62  10 20 erg . sec
 
mv 2
energy level = 5  5  10 4 cm / sec
13 .6 13 .6 13 .6 6 . 023  10 23
E5  2
eV  2
=  0 .54 eV .
n 5 25
 Structure of atom 79
6 .62  10 27  6 .023  10 23 h 6 . 62  10 34
 cm  4  10 8 cm  4 Å . x    5.27  10 30 m .
2  5  10 4 p  4 1  10  5  4  3 .14
13. (a) Uncertainty of moving bullet velocity
h 6 .625  10 34
16. (c)     10  30 m . h 6.625  10 34
mv
0 .2 k g 
5 v  
4  m  v 4  3.14  .01  10 5
60  60 ms 1
 5 . 2  10 28 m/sec .
17. (c) From de Broglie equation
h
h 6.62  10 34 14. (b) x .p  This equation shows Heisenberg’s
 = = 1.32  10 35 m . 4
mv 0.5  100
uncertainty principle. According to this
18. (c) Dual nature of particle was proposed by de- principle the product of uncertainty in
broglie who gave the following equation for position and momentum of particle is greater
the wavelength. h
than equal to .

h 4
mv 15. (d) Spin quantum number does not related with
19. (b) One percent of the speed of light is Schrodinger equation because they always
 1  show 1 / 2 , 1 / 2 value.
1 1
v   (3 . 00  10 ms ) = 3.00  10 ms
8 6
h
 100  h
16. (b) According to x  m  v  ; v 
4 x  m  4
Momentum of the electron (p ) = m 
= (9 . 11  10 31 kg ) (3 . 00  10 6 ms 1 ) 6 . 6  10 34
 5
 2 . 1  10  29 m / s
10  0 . 25  3 . 14  4
= 2 .73  10 24 kg ms 1 h
17. (a) Uncertainity in position x 
The de-broglie wavelength of this electron is 4   p
h 6 . 626  10 34 6 . 63  10 34
    5 .28  10 30 m .
p 2 . 73  10  24 kgms 1 4  3 . 14  (1  10 5 )
  2.424  10 10 m . 18. (c) Given that mass of electron  9.1  10 31 kg
20. (a) We know that the correct
relationship Planck’s constant  6 . 63  10 34 kg m 2 s 1
h
between wavelength and momentum is   . h h
p By using x  p  ; x  v  m 
4 4
Which is given by de-Broglie.
where :  x = uncertainity in position
21. (d) De-broglie equation applies to all the material
object in motion.  v = uncertainity in velocity
h
x  v 
Uncertainty principle and Schrodinger wave 4  m
equation 6.63  10 34
  5 .8  10 5 m 2 s 1 .
4  3.14  9.1  10 31
1. (b) The uncertainty principle was enunciated by
Heisenberg. Quantum number, Electronic configuration
2. (b) According to uncertainty principle, the and Shape of orbitals
product of uncertainties of the position and
momentum, is x  p  h / 4 . 3. (b) The shape of an orbital is given by azimuthal
h quantum number 'l' .
5. (c) x  p  is not the correct relation. But
4
5. (c) Hund’s rule states that pairing of electrons in
correct Heisenberg’s uncertainty equation is the orbitals of a subshell (orbitals of equal
h
x  p  . energy) starts when each of them is singly
4 filled.
7. (b) According to the Heisenberg’s uncertainty
6. (c) 1s 2 , 2 s 2 , 2 p 6 represents a noble gas electronic
principle momentum and exact position of an
electron can not be determined simultaneously. configuration.
h 7. (c) The electronic configuration of Ag in ground
8. (d) x. p  , if  x  0 then p   .
4 state is [Kr ] 4 d 10 5 s 1 .
h 8. (a) n, l and m are related to size, shape and
12. (c) According to x  p 
4 orientation respectively.
 80 Structure of atom
9. (a) Electronic configuration of Rb(37 ) is 35. (d) No. of electrons  2n 2 hence no. of orbital
2n 2
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2 4 p 6 5 s 1   n2 .
2
So for the valence shell electron (5 s 1 )
36. (c) If n  3 then l  0 to n  1 & m  l to  l
1
n  5, l  0 , m  0, s   37. (b) Na11  2, 8, 1  1 s 2 , 2 s 2 2 p 6 , 3 s 1
2
n  3, l  0, m  0, s  1 / 2
10. (a) 3d subshell filled with 5 electrons (half-filled)
is more stable than that filled with 4 38. (b) Hund’s rule states that pairing of electrons in
electrons. 1, 4 s electrons jumps into 3 d the orbitals of a subshell (orbitals of equal
subshell for more sability. energy) starts when each of them is singly
filled.
11. (c) In 2p – orbital, 2 denotes principal quantum
number (n) and p denotes azimuthal quantum 39. (d) As a result of attraction, some energy is
number (l  1) . released. So at infinite distance from the
nucleus energy of any electron will be
12. (c) Electronic configuration of H  is 1s 2 . It has 2 maximum. For bringing electrons from  to
electrons in extra nuclear space. the orbital of any atom some work has to be
13. (a) The electronic configuration must be 1 s 2 2 s 1 . done be electrons hence it bill loose its energy
for doing that work.
Hence, the element is lithium (z  3).
40. (c) This space is called nodal space where there is
14. (a) Principal quantum no. tells about the size of no possibility of oressene of electrons.
the orbital.
41. (d) For s orbital l  0 m  0 .
15. (d) An element has the electronic configuration
1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 2 , (Si ) . It’s valency electrons 42. (c) For M th shell, n  3; so maximum no. of
are four. electrons in M th shell  2n 2  2  3 2  18 .
16. (c) The magnetic quantum number specifies 43. (c) m  l to  l including zero.
orientation of orbitals. 44. (a) Number of radial nodes = (n  l  1)
17. (c) If l  2, m  3. (e to e ) . For 3s: n = 3, l = 0
18. (d) If n  3 then l  0, 1, 2 but not 3. (Number of radial node = 2)

20. (c) Atomic number of Cu is 29  ( Ar ) 4 s 1 3 d 10 . For 2p: n =2, l = 1

(Number of radial node = 0)
21. (c) The shape of 2 p orbital is dumb-bell.
45. (a) It consists only s orbital which is circular.
22. (a) When the value of n  2 , then l  1 and the
46. (a) Hund’s rule states that pairing of electrons in
value of m  1, 0,  1 i.e. 3 values.
the orbitals of a subshell (orbitals of equal
23. (c) Cr 24  ( Ar ) 3 d 5 4 s 1 electronic configuration energy) starts when each of them is singly
filled.
because half filled orbital are more stable than
other orbitals. 47. (b) If value of l is 2 then m  2,  1, 0,  1,  2 .
m  l to  l including zero.
24. (d) Kr has zero valency because it contains 8
electrons in outermost shell. (5 values of magnetic quantum number)
25. (c) 2 electron in the valence shell of calcium 48. (c) s, p, d orbitals present in Fe
Ca 20  (2, 8, 8, 2) . Fe 26  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 2 3 d 6
27. (b) Value of l  1 means the orbital is p (dumb- 50. (b) According to Aufbau rule.
bell shape).
51. (c) 3d subshell filled with 5 electrons (half-filled)
28. (d) Cr has Ar  4 s 1 3 d 5 electronic configuration is more stable than that filled with 4
because half filled orbital are more stable than electrons. 1, 4 s electrons jumps into 3 d
other orbitals. subshell for more sability.
31. (d) The two electrons will have opposite spins.
52. (b) K 19  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 1
33. (c) If m = –3, then l = 3, for this value n must be
4. for 4 s 1 electrons.
34. (d) No. of electrons  2n 2 hence no. of orbital n  4, l  0, m  0 and s  
1
.
2n 2 2
  n2 .
2
 Structure of atom 81
54. (b) 3d subshell filled with 5 electrons (half-filled) m  3,  2,  1, 0,  1,  2,  3 . m  l to l
is more stable than that filled with 4 including zero.
electrons. 1, 4 s electrons jumps into 3 d
80. (d) m  1 is not possible for s orbital (l  0).
subshell for more sability.
55. (c) It has 3 orbitals p x , p y , p z . 84. (a) Both 2p and 3p-orbitals have dumb-bell shape.
85. (b) 3d subshell filled with 5 electrons (half-filled)
57. (b) If l  2 then it must be d orbital which can is more stable than that filled with 4
have 10 electrons. electrons. 1, 4 s electrons jumps into 3 d
59. (c) for d orbital l  2 . subshell for more sability.
60. (c) m  l to  l including zero.
86. (c) The shape of 2 p orbital is dumb-bell.
61. (d) When n  3 shell, the orbitals are n 2  3 2  9 .
87. (a) 25 Mn  [ Ar ] 3 d 5 4 s 2 -2 Mn 2   [ Ar ] 3 d 5 4 s 0
No. of electrons  2n 2 electrons
89. (c) For p-orbital, l  1 means dumb-bell shape.
2n 2
Hence no. of orbital   n2 . 91. (d) l  3 means f subshell maximum number of e–
2
in f subshell = 14.
62. (d) Configuration of Ne = 1s 2 2 s 2 2 p 6
93. (b) As per Aufbau principle.
F  = 1s 2 2 s 2 2 p 6 94. (b) l  0 is s, l = 1is p and l  2 is d and so on
hence s p d may be used in state of no..
Na  = 1 s 2 2 s 2 2 p 6
1
Mg   = 1s 2 2 s 2 2 p 6 95. (d) For 4 d , n  4 , l  2, m  2,1,0,1,2, s   .
2
Cl  = 1 s 2 2 s 2 2 p 6 3 s 2 3 p 6 . 96. (d) m cannot be greater than l ( 0, 1).
63. (d) Unh 106  [Rn ] 5 f 14 5
, 6d , 7 s 1
97. (a) For n  1, l  0.
64. (c) K  and Ca   have the same electronic 99. (d) Na 11  1s 2 2 s 2 p 6 3 s 2
configuration (1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 )
1
65. (b) For s-orbital, l  0 . n  3, l  0, m  0 and s   .
2
66. (d) 3s1 is valency electrons of Na for this 102. (d) According to Aufbau’s rule.
1
n  3, l  0, m  0, s  105. (d) 2 p x , 2 p y , 2 p z sets of orbital is degenerate.
2
67. (c) 7 N  1s 2 ,2 s 2 2 p1x , 2 p1y , 2 p1z . Hund’s rule states that 106. (a) Mg12 have 1s 2 2 s 2 2 p 6 3 s 2 electronic
pairing of electrons in the orbitals of a configuration
subshell (orbitals of equal energy) starts 1
when each of them is singly filled. n  3, l  0, m  0, s   .
2
68. (d) (4) and (5) belong to d -orbital which are of
107. (c) The principle quantum number n  3 . Then
same energy.
azimuthal quantum number l  3 and number
69. (c) Atomic no. 17 is of chlorine. of orbitals  n 2  3 2  9 . 3 and 9
70. (b) The s-orbital has spherical shape due to its
108. (d) 29 Cu  [ Ar ] 3 d 10 4 s 1 , Cu 2   [ Ar ] 3 d 9 .4 s 0 .
non- directional nature.
71. (a) According to the Aufbau’s principle the new Ground state of Cu 29  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s1
electron will enter in those orbital which have Cu 2   1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 .
least energy. So here 4 p -orbital has least
energy then the others. 110. (d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3d 6 it shows electronic
72. (c) According to Aufbau’s principle. configuration of Iron.
111. (d) Orbitals are 4 s, 3 s, 3 p and 3 d . Out of these 3d
73. (c) 1s 2 2 s 2 2 p 6 ,3 s 2 3 p 6 ,4 s 2 3 d 6  2, 8 , 14 , 2 .
has highest energy.
74. (c) Ground state of Cu 29  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s1
113. (c) For the n  2 energy level orbitals of all kinds
Cu 2   1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 9 . are possible 2 n , 2 2  4 .
76. (c) No. of electrons in 3 rd shell = 2n 2 = 2 (3 ) 2  18
114. (b) n  2 than no. of orbitals  n 2 , 2 2  4
77. (c) F9  1 s 2 s 2 p
2 2 5
118. (b) For both A & B electrons s  1 / 2 & 1 / 2
respectively, n  3, l  0, m  0
78. (c) When l  3 then
 82 Structure of atom
119. (a) According to Aufbau’s rule. 152. (a) s p d f g h
120. (a) Possible number of subshells would be (6s, 5p, l=0 1 2 3 4 5
4d). Number of orbitals  5  2  1  11
121. (d) For f orbital l  3 . 153. (a) It is the ground state configuration of
chromium.
123. (b) 4d-orbital have highest energy in given data.
155. (b) n  4  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 3 d 10 , 4 s 2 , 4 p 6 , 4 d 10 , 4 f 14
125. (d) If m  3, l  3 and n  4 .
So l  (n  1)  4  1  3 which is f orbit contain 7
127. (b) N 714  1s 2 2 s 2 2 p 1x 2 p 1y 2 p 1z . orbital.
128. (c) m can't be greater than l. 156. (d) 2p have contain maximum 6 electron out of
which there are 3 are of + 1/2 spin and 3 are
130. (b) n  1 and m  1 not possible for s-orbitals.
of – 1/2 spin
131. (a) Fe 26  [ Ar ] 3 d 6 4 s 2  
   +1/2 –1/2
3
Fe  [ Ar ] 3 d 4 s .
5 0

132. (c) Maximum number of electron 157. (a) For 4f orbital electron, n  4
 2n 2 (where n  4 )  2  4 2  32 . l  3 (Because 0, 1, 2, 3)

133. (d) When 2p orbital is completely filled then s, p, d, f

electron enter in the 3s. The capacity of 2p m = + 3, + 2, +1, 0, – 1, – 2, – 3
orbital containing e  is 6. So 1 s 2 , 2 s 2 2 p 2 3 s 1 is s = +1/2
a wrong electronic configuration the write is
158. (b) 24 Cr  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 3 d 5 , 4 s1
1s 2 2 s 2 2 p 3 . l 1 l 1 l  2
134. (b) This electronic configuration is Cr (chromium (We know that for p the value of l  1 and for
element) in the ground state d , l  2)
 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 5 4 s 1 For l  1 total number of electron = 12

137. (c) No. of electron are same (18) in Cl  and Ar . For l  2 total number of electron = 5.

138. (c) For s-subshell l  0 then should be m  0 . 159. (c) Atomic number of potassium is 19 and hence
electronic configuration will be
139. (c) 19th electron of chromium is 4 s1 1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 4 s1
1
n  4 , l  0, m  0, s  
2 Hence for 4 s 1 electron value of Quantum
number are
140. (c) The value of m is – l to l including zero so for l
= 3, m would be –3, –2, –1, 0, +1, +2, +3. Principal quantum number n  4
141. (c) l  1 is for p orbital. Azimuthal quantum number l  0
Magnetic quantum number m  0
142. (d) Magnetic quantum number of sodium ( 3 s1 )
final electron is m = 0. Spin quantum number s  1 / 2

143. (c) Generally azimuthal quantum number defines 160. (d) According to Hund's rule electron first fill in
angular momentum. unpaired form in vacant orbital then fill in
paired form to stabilized the molecule by
146. (d) m  (2l  1) for d orbital l  2 m  (2  2  1)  5 .
which 1s 2 , 2 s 2 , 2 p x2 is not possible. According to
147. (a) The atomic number of chlorine is 17 its Hund's rule. Because 2 p x , py , p z have the same
configuration is 1s 2 2 s 2 2 p 6 3 s 2 3 p 5
energy level so electron first fill in unpaired
148. (c) n l m1 m2 form not in paired form so it should be
1s 2 , 2 s 2 , 2 p1x ,2 p1y .
3 2 1 0
This set (c) is not possible because spin 161. (c) It is governed by Aufbau principle.
1 162. (d) The electronic configuration of atomic number
quantum number values   .
2
24  1 s 2 , 2 s 2 , 2 p 6 , 3 s 2 ,3 p 6 ,3 d 5 , 4 s 1
2 2 6
149. (b) The ground state of neon is 1s 2 s 2 p on
163. (b) The maximum number of electron in any
excitation an electron from 2 p jumps to 3 s orbital is 2.
orbital. The excited neon configuration is
164. (c) According to pauli principle 2 electron does
1s 2 2 s 2 2 p 5 3 s 1 . not have the same value of all four quantum
 Structure of atom 83
number. They have maximum same value are
3.
187. (c) Fe 3  ion will have five (maximum) unpaired
165. (a) Number of orbitals  n  4  16 . 2 2
electrons.
166. (d) We know from the Aufbau principle, that 2p 190. (c) Due to full filled d-orbital Cl  has spherical
orbital will be filled before 3s orbital. symmetry.
Therefore, the electronic configuration 191. (b) Atomic number 14 leaving 2 unpaired electron
1 s 2 , 2 s 2 , 2 p 2 , 3 s 1 is not possible.
14 Si  1s 2 2 s 2 2 p 6 3 s 2 3 p 2
167. (d) Each orbital may have two electrons with
opposite spin.
168. (d) Maximum no. of electrons in a subshell 3p
1s 2s 2p 3s
 2(2l  1) for f-subshell, l = 3 so 14 electrons
accommodated in f -subshell.
192. (a) Shell = K, L, M = 1s 2 2 s 2 2 p 6 3 s 2 3 p 4
169. (b) Each orbital has atleast two electron.
Hence the number of s electron is 6 in that
170. (a) Nucleus of 20 protons atom having 20 element.
electrons.
193. (d) C 6  1s 2 , 2 s 2 2 p 2 (Ground state)
174. (b) For m  0 , electron must be in s-orbital.
176. (c) In this type of electronic configuration the  1s 2 2 s1 2 Px1 2 p1y 2 p1z (Excited state)
number of unpaired electrons are 3. In excited state no. of unpaired electron is 4.
194. (b) Max. no. of electrons in N-shell n  4 
=3
1s 2s 2p  2n 2  2  4 2  32 .
177. (a) Atomic number of Cu is 29 so number of
195. (d) 26 Fe  [ Ar ] 3 d 6 , 4 s 2
unpaired electrons is 1
4 s1 3d 10
Fe 2   [ Ar ] 3 d 6 , 4 s 0
Cu  (Ar ) Number of d-electrons = 6

1s 2 2s 2 2p4 17 Cl  [ Ne ] 3 s 2 , 3 p 5
178. (b) O8  Cl   [ Ne ] 3 s 2 , 3 p 6
Unpaired electron Number of p-electrons = 6.
181. (c) Be 4  1s , 2 s = (Ground state)
2 2
196. (a) Electrons in the atom  18  4  3  25 i.e.
Z  25 .
Number of unpaired electrons in the ground
state of Beryllium atom is zero. 197. (c) The atomic number of bromine is 35 and the
electronic configuration of Br is
182. (b) Two unpaired electrons are present in
Br 35  1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 3 d 10 , 4 s 2 , 4 p 5
Ni   (z  28 ) cation
total electron present in p-orbitals of Br is –

Ni 28  [ Ar ]
2 p 6  3 p 6  4 p 5  17 .
3d8 4s0
198. (d) Fe 2  has 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 6 configuration
183. (c) O 2  1 s 2 s 2 p 3 s 3 p
2 2 6 2 4
with 4 unpaired electron.
3s 2 3p4 199. (b) Fe 2  [ Ar ] 3 d 6 4 s 0

=4
2 Unpaired electrons

184. (c) Cr 24  ( Ar ) 3 d 5 4 s 1 but Cr 243   ( Ar ) 3 d 3 4 s 0 Fe 2  consist of maximum 4 unpaired

electrons.
185. (a) Zn 30  [ Ar ] 3 d 10 4 s 2
201. (a) Fe 3  (z  26 )

Zn  [ Ar ] 3 d 10
4s 0
Fe 3   [ Ar ] 3 d 5 4 s 0
2
186. (d) Mn ion will have five (maximum) unpaired
=5
electrons
3d 4s
[Ar]
Total no. of unpaired electron=5
3d 5 4
s
 84 Structure of atom
202. (b) Co 27  [ Ar ] 3 d 7 4 s 2   l(l  1)
h
;  2 (2  1)
h
2 2
3d 7
h h
  2 (2  1) ;  6 .
2 2

3 unpaired electron are present in cobalt 223. (a) Number of nodal centre for 2 s orbitals
metal. ( n  1)  2  1  1 .
203. (b) According to Hund's rule, the pairing of 224. (d) Since s-orbital have l  0
electrons will not occur in any orbital of a h
subshell unit and unless, all the available of it Angular momentum = l (l  1)  =
2
have one electron each.
h
Electronic configuration of 0 0 .
2
N 14  1 s 2 , 2 s 2 , 2 p x 2 p y 2 p z
1 1 1
7 225. (d) Azimuthal quantum number (l) = 3 shows the
presence of f orbit, which contain seven
Hence it has 3 unpaired electron in 2p-orbital.
orbitals and each orbital have 2 electrons.
204. (c) 2 s orbital have minimum energy and generally Hence 7  2  14 electrons.
electron filling increases order of energy
227. (b) According to Aufbau principle.
according to the Aufbau’s principle.
205. (d) According to Pauli’s exclusion principle no 228. (a) Atomic number of deuterium = 1; 1 D 2  1s1
two electrons in the same atom can have all
the set of four quantum numbers identical. Critical Thinking Questions
206. (b) The second principal shell contains four
orbitals viz 2 s, 2 p x , 2 p y and 2 p z . 1. (a) F  have the same number of electrons with
the neon atom.
207. (b) Follow Hund’s multiplicity rules.
2. (d) No change by doubling mass of electrons
208. (c) According to the Aufbau’s principle, electron however by reducing mass of neutron to half
will be first enters in those orbital which have total atomic mass becomes 6  3 instead of
least energy. So decreasing order of energy is 6  6 . Thus reduced by 25%.
5 p  4 d  5 s.
e 0
3. (d) for (i) neutron   0
210. (b) No two electrons in an atom can have m 1
identical set of all the four quantum numbers. 2
(ii)   particle   0 .5
212. (a) In particular shell, the energy of atomic 4
orbital increases with the value of l .
1
(iii) Proton  1
214. (c) Aufbau principle explains the sequence of 1
filling of orbitals in increasing order of
1
energy. (iv) electron   1837 .
1 / 1837
215. (a) According to Aufbau principle electron are
filling increasing order of energy. Therefore 4. (a) Metal is 56 M 2  (2, 8 , 14 ) than n  A  Z
the electronic configuration 1 s 2 2 s 2 2 p 6 obeys  56  26  30 .
Aufbau principle. c 1
5. (d) E  hv  h i.e. E 
216. (d) Electronic configuration of the Cr24 is  
[ Ar ] 4 s1 3 d 5 or E1  4000
 2   2.
E2 1 2000
=6
6. (c) Rutherford discovered nucleus.
3d 4s
7. (b) According to Bohr’s model E  E1  E3
217. (b) According to the Aufbau principle electron
filling minimum to higher energy level. 2.179  10 11
 2.179  10 11 
219. (b) According to Aufbau principle electron are 9
filled in various atomic orbital in the 8
  2 .179  10 11  1 .91  10 11  0.191  10 10 erg
increasing order of energy 9
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d Since electron is going from n  1 to n  3
< 5p < 6s < 4f < 5d < 6p < 7s. hence energy is absorbed.
220. (d) According to Aufbau’s rule. 8. (d) Radius of nucleus  1 .25  10 13  A1 / 3 cm
222. (b) We know that for d-electron l  2 .
 Structure of atom 85
 1 . 25  10 13  64 1 / 3  5  10 13 cm 1 1 
21. (a) E   2  2 
Radius of atom = 1 Å  10 8 cm .  n 2 n1 
c 3  10 8
Volume of nucleus (4 / 3) (5  10 13 )3 23. (d)     3.75  10 8
 v 8  10 15
Volume of atom (4 / 3) (10  8 )3
 3.75  10 8  10 9 nm  4  10 1 nm .
 1 . 25  10 13 .
9. (a) Values of energy in the excited state Assertion & Reason
13 .6 13 .6
  2 eV   3 .4 eV in which 1. (d) The assertion is false but the reason is true
n 4
n  2, 3, 4 etc. exact position and exact momentum of an
electron can never be determined as according
10. (c) E1 He 
 E1 H  z2 to Hesenberg’s uncertainity principle even
with the help of electron microscope because
 871 . 6  10 20  E1 H  4 when e  beam of electron microscope strikes
E1 H  217 .9  10 20 J the target e  of atom, the impact causes the
change in velocity of e  thus attempt to locate
11. (a) 42g of N 3 ions have 16 N A valence electrons the e  changes ultimately, the momentum &
4.2g of N 3 ion have 
16 N A
 4 .2  1 .6 N A . position of e  .
42 h
x .p   0 .57 ergs sec/ gm.
12. (d) Ist excited state means n  2 4

r  r0  2 2  0 .53  4  2 . 12 Å
2. (d) Both assertion and reason are false. 2 p x and
2 p y orbitals are degenerate orbitals, i.e., they
13. (d) Frequency   12  10 14 s 1 and velocity of light
are of equal energy and hence no possibility of
c  3  10 10 cm s 1 . We know that the wave transition of electron.
v 12  10 14 3. (a) We know that principal quantum number
number     4  10 4 cm 1
c 3  10 10 represent the main energy level or energy
shell. Since each energy level is associated
14. (c) The last line in any series is called series
with a definite amount of energy, this
limit. Series limit for Balmer series is 3646 Å.
quantum number determines to a large extent
13 .6 13 .6 te energy of an electron. It also determines
15. (b) E    3 .4 eV
n2 4 the average distance of an electron around the
We know that energy required for excitation nucleus. Therefore both Assertion and Reason
E  E 2  E1  3.4  (13 .6)  10 .2 eV are true and the Reason is a correct
explanation of the Assertion.
Therefore energy required for excitation of 4. (a) It is observed that a nucleus which is made up
10 .2
electron per atom   1.69  10  23 J of even number of nucleons (No. of n & p ) is
6 .02  10 23 more stable than nuclie which consist of odd
17. (a) The number of nodal plane are present in a p x number of nucleons. If number of neutron or
is one or no. of nodal place = l proton is equal to some numbers i.e., 2,8, 20,
50, 82 or 126 (which are called magic
for p x orbital l = 1
numbers), then these passes extra stability.
5. (c) The assertion that the isobars are the atoms of
x different elements having same mass number
but different atomic number, is correct but
Nodal plane reason is false because atomic mass is sum of
18. (b) In Balmer series of hydrogen atomic spectrum number of neutron and protons which should
which electronic transition causes third line be same for isobars.
O  L , n2  5  n1  2 6. (d) We know from the Pauli exclusion principle,
that two electrons in the same atom can not
1 1 1  have same value of all four quantum numbers.
20. (b)    RH  2  2 
  n1 n 2  This means each electron in an atom has only
one set of values for n, l, m and s . Therefore
1 1 1 
  R H  2  2   n 2  3 for Paschen series. both the Assertion and Reason are false.
  3 n 2 
7. (e) We know that the line in Balmer series of
hydrogen spectrum the highest wavelenght or
 86 Structure of atom
lowest energy is between n1  2 and n2  3 . And
for Balmer series of hydrogen spectrum, the
value of n1  2 and n 2  3,4,5 . Therefore the
Assertion is false but the Reason is true.
8. (d) We know that Absorption spectrum is
produced when white light is passed through
a substance and transmitted light is analysed
by a spectrograph. The dark spaces
corresponds to the light radiation absorbed by
the substance. And emission spectrum is
produced by analysing the radiant energy
emitted by an excited substance by a
spectrograph. Thus discontinuous spectra
consisting of a series of sharp lines and
separated by dark bands are obtained.
Therefore both the Assertion and Reason are
false.
9. (a) We know that a resonance hybrid or the
actual molecule is always more stable than
any of its canonical structures which is also
called hypothetical or imaginary structures.
This stability is due to delocalization of
electrons and is measured in terms of
resonance energy or delocalization energy, it
is defined as the difference in internal energy
of the resonance hybrid and the most stable
canonical structure. Therefore both the
Assertion and Reason are true and the Reason
is a correct explantion of the Assertion.
10. (e) We know that cathode rays cast shadows of
solid objects placed in their path. During
experiment performed on these rays,
fluorescene (flash of light) is observed in the
region, outside the shadow. This shows that
cathode rays travel in straight lines. We also
known that cathode rays penetrate through a
thin sheet of metals but are stopped by thick
sheets. Therefore both Assertion and Reason
are false.
11. (b) We know that electrons are revolving around
the nucleus at high speed in circular paths.
The centrifugal force (which arises due to
rotation of electrons) acting outwards,
balances the electrostatic force of attraction
(which arises due to attraction between
electrons and nucleus). This prevent the
electron from falling into the nucleus. We also
know that Rutherford’s model of atom is
comparable to the “solar system”. The
nucleeus represent the sun whereas revolving
electrons represent the planets revolving
around the sun. Thus revolving electron are
also called planetary electrons. Therefore both
Assertion and Reason are true but Reason is
not a correct explanation of Assertion.
12. (c) Assertion is true but Reason is false.
Threshold frequency is a minimum frequency
required for the emission of electrons from
the metal surface.
13. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
n2h2 n2
Radius, r   0.529 Å. rn also
4e 2 mZ Z
increases indicating a greater separation
between the orbit and the nucleus.
14. (d) Both assertion and Reason are false. Only s -
orbital is spherically symmertrical. Shape of
different d orbitals is as below.
15. (c) Assertion is true but reason is false. Spin
angular momentum of the electron, a vector
quantity, can have two orientations
(represented by + and – sign) relative to a
chosen axis. These two orientation are
distinguished by the spin quantum number m s
1 1
equals to  or  . These are called the two
2 2
spin states of the electron and are normaly
represented by the two arrows  (spin up)
and  (spin down) respectively.
16. (d) Both assertion and reason are false. Total
number of orbitals associated with Principal
quantum number n  3 is 9. One 3 s orbital +
three 3 p orbital + five 3 d orbitals. 
Therefore there are a total number of nine
orbitals. Number of orbitals in a shell equals
to n 2 .
17. (c) Assertion is true but reason is false. The order
1s  2 s  2 p  3 s  3 p  3 d  .... is true for the
energy of an electron in a hydrogen atom and
is solely determined by Principal quantum
number. For multielectron system energy also
depends on azimuthal quantum number. The
stability of an electron in a multi electron
atom is the net result of the attraction
between the electron and the uncleus and the
repulsion between the electron and the rest of
the electron present. Energies of different
subshell (azimuthal quantum number) present
within the same principal shell are found to
be in order of s  p  d  f .
18. (e) Assertion is false but reason is true. Splitting
of the spectral lines in the presence of a
magnetic field is known as Zeeman effect or in
electric field it is known as stark effect. The
splitting of spectral lines is due to different
orientations which the orbitals can have in the
presence of magnetic field.
19. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
20. (e) Assertion is false but reason is true. Atomic
orbital is designated by n, l and m l while state
of an electron in an atom is specified by four
quantum numbrs n, l, ml and m s .
21. (b) Both assertion and reason are true but reason
is not the correct explanation of assertion.
 Structure of atom 87
The difference between the energies of
adjacent energy levels decreases as we move
away from the nucleus. Thus in H atom
E2  E1  E3  E2  E4  E3 ......
22. (d) Both assertion and reason are false. Cathode
rays are stream of electrons. They are
generated through gases at low pressure and
high voltage.
23. (d) Both assertion and reason are false. In case of
isoelectronic, i.e., ions, having the same
number of electrons and different nuclear
charge, the size decreases with increase in
atomic number.
Ion At. No. No. of electrons Ionic
radii
Na+ 11 10 0.95Å
Mg2+ 12 10 0.65Å
Al3+ 13 10 0.50Å
 86 Structure of atom

1. The correct set of quantum numbers for the (c) Electron < hydrogen < helium < neon
unpaired electron of chlorine atom is [IIT 1989;
(d) NeonMP<PET 2004] < helium < electron
hydrogen
n l m 7. From the given sets of quantum numbers the one
(a) 2 1 0 that is inconsistent with the theory is [

(b) 2 1 1 (a) n  3; l  2; m  3; s  1 / 2

(c) 3 1 1 (b) n  4; l  3; m  3; s  1 / 2
(d) 3 0 0
(c) n  2; l  1; m  0l s  1 / 2
2. The orbital diagram in which the Aufbau's
(d) n  4; l  3; m  2; s  1 / 2
principle is violated is [IIT 1988; AMU 1999]

2s 2px 2 py 2 pz 8. The uncertainty in the position of an electron (

mass = 9 . 1  10 28 g) moving with a velocity of
(a)   
3 . 0  10 4 cm s 1 accurate upto 0.001% will be
(b)    
h
(Use in the uncertainty expression, where
(c)     4
(d)     h  6.626  10 27 erg  s ) [CBSE PMT 1995]

3. The mass of neutron is nearly (a) 1 . 92 cm (b) 7.68 cm

[MNR 1988; UPSEAT 1999, 2000, 02] (c) 5.76 cm (d) 3 . 84 cm
(a) 10 23 k g (b) 10 24 kg 9. The orbital angular momentum of an electron in
s orbital is
(c) 10 26 k g (d) 10 27 k g
[IIT 1996; AIEEE 2003; MP PET 2004]
4. Which electronic level would allow the hydrogen
1 h
atom to absorb a photon but not to emit a photon (a)  . (b) Zero
2 2
[IIT 1984; CPMT 1997]
h h
(a) 3 s (b) 2 p (c) (d) 2.
2 2
(c) 2 s (d) 1 s 10. Values of the four quantum numbers for the last
5. Which of the following is not correct for electron electron in the atom are n  4, l  1, m  1 and
distribution in the ground state [AIIMS 1982] s  1 / 2 . Atomic number of the atom will be
4s 3d (a) 22 (b) 32
(a) Co (Ar )       (c) 33 (d) 36
(b) Ni(Ar )       11. The atomic weight of an element is 39. The
number of neutrons in its nucleus is one more
(c) Cu (Ar )      
than the number of protons. The number of
(d) Zn(Ar )       protons, neutrons and electrons respectively in its
6. If electron, hydrogen, helium and neon nuclei are atom would be [MP PMT 1997]

all moving with the velocity of light, then the (a) 19, 20, 19 (b) 19, 19, 20
wavelengths associated with these particles are in (c) 20, 19, 19 (d) 20, 19, 20
the order [MP PET 1993]
12. The electrons identified by quantum numbers n
(a) Electron > hydrogen > helium > neon and l (i) n  4, l  1 (ii) n  4, l  0 (iii) n  3, l  2
(b) Electron > helium > hydrogen > neon
 Structure of atom 87

(iv) n  3, l  1 can be placed in order of increasing (a) p xy , d x 2 y 2 (b) d xy , d zx

energy from the lowest to highest, as [IIT 1999]
(c) p xy , d zx (d) d z 2 , d x 2 y 2
(a) (iv) < (ii) < (iii) <(i)
(b) (ii) < (iv) < (i) < (iii) 17. The number of atoms in 0.004 g of magnesium
(c) (i) < (iii) < (ii) < (iv) are
[AFMC 2000]
(d) (iii) < (i) < (iv) < (ii)
13. Ground state electronic configuration of nitrogen (a) 4  10 20 (b) 8  10 20
atom can be represented by (c)
[IIT 10 20
1999] (d) 6.02  10 20
(a)      18. Which of the following have the same number of
unpaired electrons in ‘d’ orbitals [

(b)      (a) Cr (b) Mn

(c) Fe3+ (d) Co3+
(c)      19. The quantum numbers + 1/2 and – 1/2 for the
electron spin represent [IIT Screening 2001]
(d)      (a) Rotation of the electron in clockwise and
anticlockwise direction respectively
14. Which of the following statements (s) is (are) (b) Rotation of the electron in anticlockwise and
correct clockwise direction respectively
[IIT 1998] (c) Magnetic moment of the electron pointing up
and down respectively
(a) The electronic configuration of Cr is
[ Ar ] 3 d 5 4 s 1 (Atomic no. of Cr  24 ) (d) Two quantum mechanical spin states which
have no classical analogue
(b) The magnetic quantum number may have a 20. The de-Broglie wavelength of a tennis ball of mass
negative value 60 g moving with a velocity of 10 metres per
(c) In silver atom, 23 electrons have a spin of one second is approximately [AIEEE 2003]
type and 24 of the opposite type (Atomic no. (a) 10 33 metres (b) 10 31 metres
of Ag  47 )
(c) 10 16 metres (d) 10 25 metres
(d) The oxidation state of nitrogen in HN 3 is  3
21. Which of the following are isoelectronic and
15. The position of both an electron and a helium isostructural NO 3 , CO 32  , ClO 3 , SO 3 [IIT Screening 2003]
atom is known within 1 .0 nm and the momentum
of the electron is known within 50  10 26 kg ms 1 . (a) NO 3 , CO 32  (b) SO 3 , NO 3

The minimum uncertainty in the measurement of (c) ClO 3 , CO 32  (d) CO 32  , SO 3

the momentum of the helium atom is
22. The total number of electrons present in all the s-
[CBSE PMT 1998; AIIMS 2001]
orbitals, all the p-orbitals and all the d-orbitals of
(a) 50 kg ms 1 (b) 60 kg ms 1 cesium ion are respectively [
(a) 8, 26, 10 (b) 10, 24, 20
(c) 80  10 26 kg ms 1 (d) 50  10 26 kg ms 1 (c) 8, 22, 24 (d) 12, 20, 22
16. Which of the following pair of orbitals posses two
nodal planes [RPMT 2000]
 88 Structure of atom

(SET -2)

1. (c) Electronic configuration of Cl is 11. 39

(a) K 19 , P  19 , E  19 , N  20
2
3s 3p
12. (a) (i) 4 p (ii) 4 s (iii) 3d (iv) 3 p order of increasing energy is
3 p  4 s  3 d  4 p.
[ Ne ] 3 s 2 3 p 5 or [Ne ] 2
3 p 2 x 3p y 3 p 1 z
13. (a,d) According to Hund’s principle.
14. (a,b,c) The oxidation state of nitrogen in
So for the unpaired electron (3 p 1z ) : 1
HN 3 is  .
1 3
n  3, l  1, m  1, S  
2 1
HN 3 : 1  3 x  0  3 x  1 or x 
2. (b) According to Aufbau principle the orbitals of 3
lower energy (2s) should be fully filled before
the filling of orbital of higher energy starts. 15. (d) The product of uncertainties in the position
and the momentum of a sub atomic particle
3. (d) Mass of neutron  1.675  10 27 kg.
 h/4 . Since  x is same for electron and
4. (d) 1s-orbital is of lowest energy. Absorption of
helium so p must be same for both the
photon can raise the electron in higher energy
state but emission is not possible. particle i.e. 50  10 26 kg ms 1 (given).
5. (c) The correct electronic configuration 16. (b) d xy and d zx has two modal planes.
Cu29  [ Ar], 4 s1 3d 10
17. (c) No. of atoms in magnesium
0 .004
=  6 .023  10 23 =1020
1 24
6. (a)   , m e  m H  m He  m Ne .
m 18. (a,b,c) Cr , Mn and Fe 3  have 5 unpaired
7. (a) When l  2, m  3 . electron in d-orbitals.
24 Cr  3 d 5 4 s1  5
8. (a) p  m  v
25 Mn  3 d 5 4 s 2  5
0 .001
p  9 .1  10  28  3 .0  10 4  Fe 3   3d 5 4 s 0  5
100 26

19. (a,d) Both statement are correct.

P  2.73  10 24
h 6.63  10 34
27 20. (a)     10  33 m
h 6 .626  10 mv 60  10  3  10
Hence x  
p  4 2 .73  10  28  4  3 . 14 21. (a) NO 3 and CO 32  consist of same electron and
x  1.92 cm. show same isostructural.
22. (b) (Cs 35 )  1s 2 , 2 s 2 , 2 p 6 ,3 s 2 ,3 p 6 ,3 d 10 ,4 s 2
9. (b) For 2s orbital, l = 0; azimuthal quantum
number is not show angular momentum for 4 p 6 ,4 d 10 ,5 s 2 ,5 p 6 ,6 s1
the 2 s orbitals.
Cs   1s 2 , 2 s 2 ,2 p 6 , 3 s 2 ,3 p 6 ,3 d 10 , 4 s 2 ,
h
Angular momentum  l(l  1) 0. 4 p 6 ,4 d 10 , 5 s 2 ,5 p 6
2
Total no. of e  in s-orbitals  10
10. (d) Atomic number is 36 and element is Kr .
 Structure of atom 89

Total no. of e  in p-ortbitals  24 Total no. of e  in d-ortbitals  20 .

***
 Chemical Bonding 89

Chapter

3
Chemical Bonding

Atoms of different elements excepting noble gases acid) and electrons rich
donot have complete octet so they combine with other molecule or ion (Lewis
atoms to form chemical bond. The force which holds the base)
atoms or ions together within the molecule is called a H and electronegative Hydrogen
chemical bond and the process of their combination is element (F, N,O)
called Chemical Bonding. It depends on the valency of Electrovalent bond
atoms.
An electrovalent bond is formed when a metal
Cause and Modes of chemical combination atom transfers one or more electrons to a non-metal
Chemical bonding takes place due to acquire a atom.
state of minimum energy and maximum stability and to  
 
      
convert atoms into molecule to acquire stable Na   Cl    Na   Cl   or Na  Cl 
configuration of the nearest noble gas. We divide atoms       
into three classes, Some other examples are: MgCl2, CaCl2, MgO,
(1) Electropositive elements which give up one or Na2S, CaH2, AlF3, NaH, KH, K2O , KI, RbCl, NaBr, CaH2
more electrons easily. They have low ionisation etc.
potentials.
(1) Conditions for formation of electrovalent
(2) Electronegative elements, which can gain bond
electrons. They have higher value of electronegativity. (i) The atom which changes into cation (+ ive ion)
(3) Elements which have little tendency to lose or should possess 1, 2 or 3 valency electrons. The other
gain electrons. atom which changes into anion (–ve ion) should possess
5, 6 or 7 electrons in the valency shell.
Different types of bonds are formed from these
types of atoms. (ii) A high difference of electronegativity (about
2) of the two atoms is necessary for the formation of an
Atoms involved Type
electrovalent bond. Electrovalent bond is not possible
A+B Electrovalent between similar atoms.
B+B Covalent (iii) There must be overall decrease in energy i.e.,
A+A Metallic energy must be released. For this an atom should have
Electrons deficient Coordinate low value of Ionisation potential and the other atom
molecule or ion (Lewis should have high value of electron affinity.
 90 Chemical Bonding
(iv) Higher the lattice energy, greater will be the case
of forming an ionic compound. The amount of energy
released when free ions combine together to form one mole
of a crystal is called lattice energy (U). Lattice
K of solidification.
energy  ; r   r  is internuclear distance.
r  r

The energy changes involved in the formation of
ionic compounds from their constituent elements can
be studied with the help of a thermochemical cycle
called Born Haber cycle.
1 duplets (in case of elements having only one shell) is
Na (s) + Cl 2 (g)
2 H
H sub 1/2Hdiss.
Na (g) Cl
+IE – e– – EA (g)+e–
 
Na (g) + Cl (g )
(Born Haber
Cycle)
According to Hess's law of constant heat
summation, heat of formation of an ionic solid is net
resultant of the above changes.
1 
H f  H Subl.  H diss.  IE  EA  U
2  Cl   Cl *
(2) Characteristics of electrovalent compounds
(i) Electrovalent compounds are generally
crystalline is nature. The constituent ions are arranged
in a regular way in their lattice.
(ii) Electrovalent compounds possess high melting
and boiling points. Order of melting and boiling points
in halides of sodium and oxides of IInd group elements
is as,
NaF  NaCl  NaBr  NaI , MgO  CaO  BaO
(iii) Electrovalent compounds are hard and brittle
in nature.
(iv) Electrovalent solids do not conduct
electricity. While electrovalent compounds in the
molten state or in solution conduct electricity.
(v) Electrovalent compounds are fairly soluble in
polar solvents and insoluble in non-polar solvents.
(vi) The electrovalent bonds are non-rigid and
non-directional. Thus these compound do not show
space isomerism e.g. geometrical or optical isomerism.
(vii) Electrovalent compounds furnish ions in
solution. The chemical reaction of these compounds are
known as ionic reactions, which are fast.
   
K  Cl   Ag NO3  Ag Cl   K NO3
(Precipitat e )
(viii) Electrovalent compounds show
isomorphism.
(ix) Cooling curve of an ionic compound is not
smooth, it has two break points corresponding to time
(x) Ionic compounds show variable electrovalency
due to unstability of core and inert pair effect.
Covalent bond
Covalent bond was first proposed by Lewis in
1916. The bond formed between the two atoms by mutual
sharing of electrons so as to complete their octets or
called covalent bond or covalent linkage. A covalent
f
bond between two similar atoms is non-polar covalent
Na+Cl– (s) bond while it is polar between two different atom
(Crystal)
–U
having different electronegativities. Covalent bond may
be single, double or a triple bond. We explain covalent
(Lattice
energy) bond formation by Lewis octet rule.
Chlorine atom has seven electrons in the valency
shell. In the formation of chlorine molecule, each
chlorine atom contributes one electron and the pair of
electrons is shared between two atoms. both the atoms
acquire stable configuration of argon.
**  
   
*
  Cl * Cl  or Cl  Cl
 
** 
( 2, 8 , 7 ) ( 2, 8 , 7 )
( 2, 8 , 8 ) ( 2, 8 , 8 )
Some other examples are :
H 2 S , NH 3 , HCN , PCl3 , PH3,
C2 H 2 , H 2 , C2 H4 , SnCl4 , FeCl3 , BH 3 , graphite, BeCl 2 etc.
(1) Conditions for formation of covalent bond
(i) The combining atoms should be short
by 1, 2 or 3 electrons in the valency shell in comparison
to stable noble gas configuration.
(ii) Electronegativity difference between the two
atoms should be zero or very small.
(iii) The approach of the atoms towards one
another should be accompanied by decrease of energy.
(2) Characteristics of covalent compounds
(i) These exist as gases or liquids under the
normal conditions of temperature and pressure. Some
covalent compounds exist as soft solids.
(ii) Diamond, Carborandum (SiC), Silica (SiO2),
AlN etc. have giant three dimensional network
structures; therefore have exceptionally high melting
points otherwise these compounds have relatively low
melting and boiling points.
(iii) In general covalent substances are bad
  conductor of electricity. Polar covalent compounds like
HCl in solution conduct electricity. Graphite can
 Chemical Bonding 91
conduct electricity in solid state since electrons can violated. This singlet is represented as (⇁). Thus, PCl5
pass from one layer to the other. and SF6 have structures as,
(iv) These compounds are generally insoluble in
Cl Cl F F
polar solvent like water but soluble in non-polar
solvents like benzene etc. some covalent compounds Cl P Cl F S F
like alcohol, dissolve in water due to hydrogen bonding. F F
Cl
(v) The covalent bond is rigid and directional.
(5) Construction of structures for molecules
These compounds, thus show isomerism (structural and
and poly atomic ions : The following method is
space).
applicable to species in which the octet rule is not
(vi) Covalent substances show molecular violated.
reactions. The reaction rates are usually low.
(i) Determine the total number of valence
(vii) The number of electrons contributed by an electrons in all the atoms present, including the net
atom of the element for sharing with other atoms is charge on the species (n1).
called covalency of the element. Covalency = 8 –
(ii) Determine n2 = [2 × (number of H atoms) + 8
[Number of the group to which element belongs]. The
× (number of other atoms)].
variable covalency of an element is equal to the total
number of unpaired electrons in s, p and d-orbitals of its (iii) Determine the number of bonding electrons,
valency shell. n3, which equals n2 – n1. No. of bonds equals n3/2.
(iv) Determine the number of non-bonding
The element such as P, S, Cl, Br, I have vacant d-
electrons, n4, which equals n1 – n3. No. of lone pairs
orbitals in their valency shell. These elements show
equals n4/2.
variable covalency by increasing the number of
unpaired electrons under excited conditions. The (v) Knowing the central atom (you’ll need
electrons from paired orbitals get excited to vacant d- to know some chemistry here, math will not help!),
orbitals of the same shell. arrange and distribute other atoms and n3/2 bonds.
Then complete octets using n4/2 lone pairs.
Four elements, H, N, O and F do not possess d-
orbitals in their valency shell. Thus, such an excitation is (vi) Determine the ‘formal charge’ on each atom.
not possible and variable valency is not shown by these (vii) Formal Charge = [valence electrons in atom)
elements. This is reason that NCl3 exists while NCl5 does – (no. of bonds) – (no. of unshared electrons)]
not. (viii) Other aspects like resonance etc. can now be
(3) The Lewis theory : The tendency of atoms to incorporated.
achieve eight electrons in their outermost shell is Illustrative examples
known as lewis octet rule.
(i) CO 32  ; n1  4  (6  3)  2  24 [2 added for net
Lewis symbol for the representative elements are
given in the following table, charge]
1 2 13 14 15 16 17 n 2 = (2 × 0) + (8 × 4) = 32 (no. H atom, 4 other
Group IA IIA IIIA IVA VA VIA VIIA atoms (1’C’ and 3 ‘O’)
Lewis X X     
X X  X  X X  n 3 = 32 – 24 = 8, hence 8/2 = 4 bonds
symbo    

l n 4 = 24 – 8 = 16, hence 8 lone pairs.
(4) Failure of octet rule : There are several
Since carbon is the central atom, 3 oxygen atoms
stable molecules known in which the octet rule is
are to be arranged around it, thus,
violated i.e., atoms in these molecules have number of
electrons in the valency shell either short of octet or O
|
more than octet. O  C  O , but total bonds are equal to 4.
BeF2 , BF3 , AlH3 are electron- deficients (Octet O
|
incomplete) hence are Lewis acid. Hence, we get O  C  O . Now, arrange lone pairs
In PCl5 , P has 10 electrons in valency shell while ..
.O :
in SF6 , S has 12 electrons in valence shell. Sugden . | ..
to complete octet : O  C  O :
introduced singlet linkage in which one electron is ..
donated (Instead of one pair of electrons) to the
(ii) CO 2 ; n1 = 4 + (6 × 2 ) = 16
electron deficient atom so that octet rule is not
n2 = (2 × 0) + (8 × 3) = 24
 92 Chemical Bonding
n3 = 24 – 16 = 8, hence 4 bonds Dipole moment is measured in “Debye” (D) unit.
n4 = 16 – 8 = 8, hence 4 lone-pairs 1 D  10 18 esu cm = 3 .33  10 30 coulomb metre (In S.I.
Since C is the central atom, the two oxygen atoms unit).
Dipole moment is indicated by an arrow having a
are around to be arranged it thus the structure would
symbol ( ) pointing towards the negative end.
be; O – C – O, but total no. of bonds = 4
Dipole moment has both magnitude and direction and
Thus, O = C = O. After arrangement of lone
.. ..
therefore it is a vector quantity.
pairs to complete octets, we get, : O  C  O : and thus Symmetrical polyatomic molecules are not polar
.. .. so they do not have any value of dipole moment.
final structure is : O  C  O : H
F
Co-ordinate covalent or Dative bond
This is a special type of covalent bond where the O C O C
B H H
shared pair of electrons are contributed by one species F F
only but shared by both. The atom which contributes H
the electrons is called the donor (Lewis base) while the  = 0 due to symmetry
other which only shares the electron pair is known as Unsymmetrical polyatomic molecules always
acceptor (Lewis acid). This bond is usually represented have net value of dipole moment, thus such molecules
are polar in nature. H2O, CH3Cl, NH3, etc are polar
by an arrow ( ) pointing from donor to the acceptor
molecules as they have some positive values of dipole
atom. moments. Cl
BF3 molecule, boron is short of two electrons. So
to complete its octet, it shares the lone pair of nitrogen O N C
in ammonia forming a dative bond.
H H H H H H
Water
   

F 
H 
F   = 1.84D H H
H     H F
            | |
Ammonia Methyl
H * N **  B 
 F

 H 
* N 
 B 
 F   H  N  B  F  = 1.46D chloride
          | |
 
  = 1.86D
H  F  H 
F  H F
 

 

  0 due to unsymmetry
Formation of a co- (1) Dipole moment is an important factor in
ordinate
bond between NH3 and
determining the geometry of molecules.
Examples : CO, N2BFO,
3 H2O2, N2O3, N2O4, N2O5, HNO3, Table : 3.1 Molecular geometry and dipole moment
NO 3 , SO2, SO3, H2SO4, SO 42  , SO 22  , H 3 PO4 , H4 P2O7 ,

General Molecular geometry Dipole Example
H3 PO3 , Al2Cl6 (Anhydrous), O3 , SO 2Cl2 , SOCl 2 , HIO3 , HClO4 , formul moment
a
HClO 3 , CH 3 NC , N 2 H 5 , CH 3 NO 2 , NH 4 , [Cu ( NH 3 )4 ]2  etc.
AX Linear May be HF, HCl
Characteristics of co-ordinate covalent non
compound zero
(1) Their melting and boiling points are higher AX 2 Linear Zero CO2 ,CS 2
than purely covalent compounds and lower than purely Bent or V-shape Non H 2O, NO2
ionic compounds. zero
(2) These are sparingly soluble in polar solvent AX 3 Triangular planar Zero BF3
like water but readily soluble in non-polar solvents. Pyramidal Non NH 3 , PCl3
(3) Like covalent compounds, these are also bad T-shape zero
ClF3
conductors of electricity. Their solutions or fused Non
masses do not allow the passage to electricity. zero
(4) The bond is rigid and directional. Thus, AX 4 Tetrahedral Zero CH 4 ,CCl4
coordinate compounds show isomerism. Square planar Zero XeF4
See saw Non
Dipole moment zero
SF4 ,TeCl 4

“The product of magnitude of negative or positive AX 5 Trigonal Zero PCl5

charge (q) and the distance (d) between the centres of bipyramidal Non BrCl5
positive and negative charges is called dipole moment”. Square pyramidal zero
 = Electric charge  bond length AX 6 Octahedral Zero SF6
As q is in the order of 10–10 esu and d is in the Distorted Non XeF6
order of 10–8 cm,  is in the order of 10–18 esu cm. octahedral zero
 Chemical Bonding 93
AX 7 Pentagonal Zero IF7 (5) Greater is the overlapping, lesser will be the
bipyramidal bond length, more will be attraction and more will be
(2) Every ionic compound having some percentage bond energy and the stability of bond will also be high.
of covalent character according to Fajan's rule. The (6) The extent of overlapping depends upon:
percentage of ionic character in compound having some
Nature of orbitals involved in overlapping, and nature
covalent character can be calculated by the following
of overlapping.
equation.
(7) More closer the valence shells are to the
Observed 
The % ionic character   100 . nucleus, more will be the overlapping and the bond
Theoretical 
energy will also be high.
(3) The trans isomer usually possesses either zero
(8) Between two sub shells of same energy level,
dipole moment or very low value in comparison to cis–
form the sub shell more directionally concentrated shows
more overlapping. Bond energy : 2 s  2 s < 2 s  2 p <
H  C  Cl H  C  Cl
|| || 2p  2p
H  C  Cl Cl  C  H
(9) s -orbitals are spherically symmetrical and
Fajan’s rule thus show only head on overlapping. On the other hand,
The magnitude of polarization or increased p -orbitals are directionally concentrated and thus
covalent character depends upon a number of factors. show either head on overlapping or lateral
These factors are, overlapping.Overlapping of different type gives sigma
() and pi () bond.
(1) Small size of cation : Smaller size of cation
greater is its polarizing power i.e. greater will be the Sigma () bond Pi () bond
covalent nature of the bond.
It results from the end to It result from the
(2) Large size of anion : Larger the size of anion end overlapping of two s- sidewise (lateral)
greater is its polarizing power i.e. greater will be the orbitals or two p-orbitals overlapping of two p-
covalent nature of the bond. or one s and one p- orbitals.
(3) Large charge on either of the two ions : As orbital.
the charge on the ion increases, the electrostatic Stronger Less strong
attraction of the cation for the outer electrons of the
Bond energy 80 kcals Bond energy 65 kcals
anion also increases with the result its ability for
forming the covalent bond increases. More stable Less stable
(4) Electronic configuration of the cation : For Less reactive More reactive
the two ions of the same size and charge, one with a Can exist independently Always exist along with a
pseudo noble gas configuration (i.e. 18 electrons in the -bond
outermost shell) will be more polarizing than a cation The electron cloud is The electron cloud is
with noble gas configuration (i.e., 8 electron in outer symmetrical about the above and below the
most shell). internuclear axis. plane of internuclear
Valence bond theory or VBT axis.

It was developed by Heitler and London in 1927 Hybridization

and modified by Pauling and Slater in 1931.
The concept of hybridization was introduced by
(1) To form a covalent bond, two atoms must
Pauling and Slater. Hybridization is defined as the
come close to each other so that orbitals of one
intermixing of dissimilar orbitals of the same atom but
overlaps with the other.
having slightly different energies to form same number
(2) Orbitals having unpaired electrons of anti spin of new orbitals of equal energies and identical shapes.
overlaps with each other. The new orbitals so formed are known as hybrid
(3) After overlapping a new localized bond orbital orbitals.
is formed which has maximum probability of finding
Characteristics of hybridization
electrons.
(1) Only orbitals of almost similar energies and
(4) Covalent bond is formed due to electrostatic
belonging to the same atom or ion undergoes
attraction between radii and the accumulated electrons
hybridization.
cloud and by attraction between spins of anti spin
electrons.
 94 Chemical Bonding
(2) Hybridization takes place only in orbitals, properties of the molecule. The actual structure is in
electrons are not involved in it. between of all these contributing structures and is
called resonance hybrid and the different individual
(3) The number of hybrid orbitals produced is
structures are called resonating structures or
equal to the number of pure orbitals, mixed during
canonical forms. This phenomenon is called
hybridization.
resonance.
(4) In the excited state, the number of unpaired
To illustrate this, consider a molecule of ozone
electrons must correspond to the oxidation state of the O3 . Its structure can be written as
central atom in the molecule. .. .. ..
O O
.. O
(5) Both half filled orbitals or fully filled orbitals
. . . .. ..
.O . . .
.
of equivalent energy can involve in hybridization. .O . .O. . .. . O
.. .O.. . ..
O
(a) (b ) (c )
(6) Hybrid orbitals form only sigma bonds.
As a resonance hybrid of above two structures (a)
(7) Orbitals involved in  bond formation do not
and (b. For simplicity, ozone may be represented by
participate in hybridization. structure (c), which shows the resonance hybrid having
(8) Hybridization never takes place in an isolated equal bonds between single and double.
atom but it occurs only at the time of bond formation. Resonance is shown by benzene, toluene, O3,
(9) The hybrid orbitals are distributed in space as allenes (>C = C = C<), CO, CO2, CO 3 , SO3, NO, NO2
apart as possible resulting in a definite geometry of while it is not shown by H2O2, H2O, NH3, CH4, SiO2.
molecule. As a result of resonance, the bond lengths of
(10) Hybridized orbitals provide efficient single and double bond in a molecule become equal e.g.
overlapping than overlapping by pure s, p and d- O–O bond lengths in ozone or C–O bond lengths in
orbitals. CO 32 – ion.
(11) Hybridized orbitals possess lower energy. The resonance hybrid has lower energy and hence
How to determine type of hybridization : The greater stability than any of the contributing structures.
structure of any molecule can be predicted on the basis Greater is the number of canonical forms especially
of hybridization which in turn can be known by the with nearly same energy, greater is the stability of the
following general formulation, molecule.

1 Difference between the energy of resonance

H  (V  M  C  A) hybrid and that of the most stable of the resonating
2
structures (having least energy) is called resonance
Where H = Number of orbitals involved in energy. Thus,
hybridization viz. 2, 3, 4, 5, 6 and 7, hence nature of Resonance energy = Energy of resonance hybrid –
hybridization will be sp, sp2, sp3, sp3d, sp3d2, sp3d3 Energy of the most stable of resonating structure.
respectively.
In the case of molecules or ions having resonance,
V = Number electrons in valence shell of the the bond order changes and is calculated as follows,
central atom,
Total no. of bonds between two atoms in all the structures
M = Number of monovalent atom Bond order 
Total no. of resonating structures
C = Charge on cation,
A = Charge on anion In benzene 

Resonance
double bond  single bond 2  1
The phenomenon of resonance was put forward Bond order    1.5
by Heisenberg to explain the properties of certain 2 2
molecules.
In carbonate ion
In case of certain molecules, a single Lewis
structure cannot explain all the properties of the
molecule. The molecule is then supposed to have many
structures, each of which can explain most of the
properties of the molecule but none can explain all the
 Chemical Bonding 95
O O O (iii) Greater the number of lone pairs of electrons
| || | present on the bonded atoms, greater is the repulsion
C  C  C between the atoms and hence less is the bond
// \ / \ / \\

O O dissociation energy.
O O 
O O
(iv) The bond energy increases as the hybrid
2 11
Bond order   1 .33 orbitals have greater amount of s orbital contribution.
3
Thus, bond energy decreases in the following order,
Bond characteristics sp  sp 2  sp 3
(1) Bond length (v) Greater the electronegativity difference, greater
“The average distance between the centre of the is the bond polarity and hence greater will be the bond
nuclei of the two bonded atoms is called bond length”. strength i.e., bond energy, H  F  H  Cl  H  Br  H  I ,

It is expressed in terms of Angstrom (1 Å = (vi) Among halogens Cl – Cl > F – F > Br – Br > I –

10 12 I, (Decreasing order of bond energy) Resonance
10 m) or picometer (1pm = 10 m).
increases bond energy.
In an ionic compound, the bond length is the sum
of their ionic radii ( d  r  r ) and in a covalent (3) Bond angle

compound, it is the sum of their covalent radii (e.g., for In case of molecules made up of three or more
HCl, d  rH  rCl ). atoms, the average angle between the bonded orbitals
(i.e., between the two covalent bonds) is known as bond
Factors affecting bond length
angle .
(i) The bond length increases with increase in the
Factors affecting bond angle
size of the atoms. For example, bond length of H  X
are in the order, HI  HBr  HCl  HF . (i) Repulsion between atoms or groups attached to
the central atom may increase or decrease the bond
(ii) The bond length decreases with the
angle.
multiplicity of the bond. Thus, bond length of carbon–
carbon bonds are in the order, C  C  C  C  C – C . (ii) In hybridisation as the s character of the s
hybrid bond increases, the bond angle increases.
(iii) As an s-orbital is smaller in size, greater the
s-character shorter is the hybrid orbital and hence
Bond type sp3 sp2 sp
shorter is the bond length.
Bond angle 109º28 120° 180°
For example, sp 3 C – H  sp 2 C – H  sp C – H

(iv) Polar bond length is usually smaller than the (iii) By increasing lone pair of electron, bond angle
theoretical non-polar bond length. decreases approximately by 2.5%.
(2) Bond energy CH4 NH3 H2O
“The amount of energy required to break one
Bond angle 109º 107o 105o
mole of bonds of a particular type so as to separate
them into gaseous atoms is called bond dissociation
(iv) If the electronegativity of the central atom
energy or simply bond energy”. Greater is the bond
decreases, bond angle decreases.
energy, stronger is the bond. Bond energy is usually
expressed in kJ mol –1 . H 2O  H 2S  H 2 Se  H 2 Te
Bond angle 104 . 5 o 92 . 2 o 91 . 2 o 89 . 5 o
Factors affecting bond energy
In case the central atom remains the same, bond
(i) Greater the size of the atom, greater is the
angle increases with the decrease in electronegativity
bond length and less is the bond dissociation energy i.e.
of the surrounding atom.
less is the bond strength.
(ii) For the bond between the two similar atoms, PCl 3 PBr 3 PI 3 , AsCl 3 AsBr 3 AsI 3
Bond angle 100 o 101 . 5 o 102 o 98 .4 o 100 . 5 o 101 o
greater is the multiplicity of the bond, greater is the
bond dissociation energy. Valence shell electron pair repulsion theory (VSEPR )
 96 Chemical Bonding
The basic concept of the theory was suggested by
Sidgwick and Powell (1940). It provides useful idea for
predicting shapes and geometries of molecules. The
concept tells that, the arrangement of bonds around the
central atom depends upon the repulsion’s operating
between electron pairs(bonded or non bonded) around
the central atom. Gillespie and Nyholm developed this
concept as VSEPR theory.
The main postulates of VSEPR theory are
(1) For polyatomic molecules containing 3 or more
atoms, one of the atoms is called the central atom to
which other atoms are linked.
(2) The geometry of a molecule depends upon the
total number of valence shell electron pairs (bonded or
not bonded) present around the central atom and their
repulsion due to relative sizes and shapes.
(3) If the central atom is surrounded by bond
pairs only. It gives the symmetrical shape to the
molecule.
(4) If the central atom is surrounded by lone pairs
(lp) as well as bond pairs (bp) of e  then the molecule
has a distorted geometry.
(5) The relative order of repulsion between electron
pairs is as follows : lp – lp > lp – bp > bp – bp.
A lone pair is concentrated around the central atom
while a bond pair is pulled out between two bonded
atoms. As such repulsion becomes greater when a lone
pair is involved.

Table : 3.2 Geometry of Molecules/Ions having bond pair as well as lone pair of electrons
Type No. of No. of
of bond lone pairs Hybridi- Expected Actual
Bond angle Examples
mole- pairs of of zation geometry geometry
cule electron electrons
V-shape,
Trigonal
AX 3 2 1 sp 2 < 120o Bent, SO2, SnCl2, NO2–
planar
Angular
Tetrahedra V-shape, H2O, H2S, SCl2, OF2, NH2–,
AX 4 2 2 sp 3 < 109o 28
l Angular ClO2–
Tetrahedra NH3, NF3 , PCl3, PH3, AsH3,
AX 4 3 1 sp 3 < 109o 28 Pyramidal
l ClO3– , H3O+
Trigonal Irregular
AX 5 4 1 sp 3 d < 109o 28 bipyramida tetrahedro SF4, SCl4, TeCl4
l n
Trigonal
AX 5 3 2 sp 3 d 90o bipyramida T-shaped ICl3, IF3, ClF3
l
Trigonal
AX 5 2 3 sp 3 d 180o bipyramida Linear XeF2, I3–, ICl2–
l
Square
AX 6 5 1 sp 3 d 2 < 90o Octahedral ICl5, BrF5, IF5
pyramidal
Square
AX 6 4 2 sp 3 d 2 – Octahedral XeF4, ICl4–
planar
Pentagonal Distorted
AX7 6 1 sp 3 d 3 – XeF6
pyramidal octahedral

Molecular orbital theory or MOT
Molecular orbital theory was given by Hund and
Mulliken in 1932.
The main ideas of this theory are,
(1) When two atomic orbitals combine or overlap,
they lose their identity and form new orbitals. The new
orbitals thus formed are called molecular orbitals.
(2) Molecular orbitals are the energy states of a
molecule in which the electrons of the molecule are
filled just as atomic orbitals are the energy states of an
atom in which the electrons of the atom are filled.
(3) In terms of probability distribution, a
molecular orbital gives the electron probability
distribution around a group of nuclei just as an atomic
orbital gives the electron probability distribution
around the single nucleus.
 Chemical Bonding 97
(4) Only those atomic orbitals can combine to Increasing energy (for electrons >
form molecular orbitals which have comparable 14)
energies and proper orientation. (b)  1s,  *1s,  2 s,  * 2 s,  2 py ,  2 p x ,
(5) The number of molecular orbitals formed is
equal to the number of combining atomic orbitals.  * 2pz
(6) When two atomic orbitals combine, they form Increasing energy (for electrons
two new orbitals called bonding molecular orbital and  14)
antibonding molecular orbital. (12) Number of bonds between two atoms is
(7) The bonding molecular orbital has lower called bond order and is given by
energy and hence greater stability than the
 N  NA 
corresponding antibonding molecular orbital. Bond order   B 
 2 
(8) The bonding molecular orbitals are
where N B  number of electrons in bonding MO.
represented by  ,  etc, whereas the corresponding
antibonding molecular orbitals are represented by N A  number of electrons in antibonding
 * ,  * etc. MO.
For a stable molecule/ion, N B  N A
(9) The shapes of the molecular orbitals formed
depend upon the type of combining atomic orbitals. (13) Bond order  Stability of molecule 
1
(10) The filling of molecular orbitals in a Dissociation energy  .
molecule takes place in accordance with Aufbau Bond length
principle, Pauli's exclusion principle and Hund's (14) If all the electrons in a molecule are paired
rule. The general order of increasing energy among the then the substance is a diamagnetic on the other hand
molecular orbitals formed by the elements of second if there are unpaired electrons in the molecule, then
period and hydrogen and their general electronic the substance is paramagnetic. More the number of
configurations are given below. unpaired electron in the molecule greater is the
(11) Electrons are filled in the increasing energy paramagnetism of the substance.
of the MO which is in order

(a)  1s,  *1s,  2 s,  * 2 s,  2 p x ,  2 py  * 2 py ,  * 2 p x

 2 pz ,  * 2 p z

*(2pz *(2pz
) )
2p
 (2py  (2px
* * 2p 2p
*(2py *(2px 2p
) ) ) )
 
(2py) (2px)

Increasing energy
Increasing energy

(2pz)
  
(2pz) (2py) (2px)
2s *(2s) 2s 2s *(2s) 2s

 (2s)  (2s)

1s *(1s) 1s 1s *(1s) 1s

 (1s)  (1s)
Atomi Molecular Atomi Atomi Molecular Atomi
c orbitals c c orbitals c
orbita orbita orbita orbita
Molecular
ls orbital energy level diagram
ls Molecular ls
orbital energy level diagram obtained by the
ls
(Applicable for elements with Z > 7) overlap of 2s and 2pz atomic orbitals after mixing
(Applicable for elements with Z < 7)
 98 Chemical Bonding

Hydrogen bonding (1) Dissociation : In aqueous solution, hydrogen

In 1920, Latimer and Rodebush introduced the fluoride dissociates and gives the difluoride ion (HF2 )
idea of “hydrogen bond”. instead of fluoride ion (F  ) . This is due to H-bonding in
For the formation of H-bonding the molecule HF. This explains the existence of KHF2 . H-bond formed
should contain an atom of high electronegativity such
is usually longer than the covalent bond present in the
as F, O or N bonded to hydrogen atom and the size of
the electronegative atom should be quite small. molecule (e.g. in H2O, O–H bond = 0.99 Å but H-
bond = 1.77 Å).
Types of hydrogen bonding
(1) Intermolecular hydrogen bond : (2) Association : The molecules of carboxylic
Intermolecular hydrogen bond is formed between two acids exist as dimers because of the hydrogen bonding.
different molecules of the same or different substances. The molecular masses of such compounds are found to
(i) Hydrogen bond between the molecules of be double than those calculated from their simple
hydrogen fluoride. formulae. For example, molecular mass of acetic acid is
found to be 120.
(ii) Hydrogen bond in alcohol and water
molecules (3) High melting and boiling point : The
compounds having hydrogen bonding show abnormally
(2) Intramolecular hydrogen bond (Chelation)
high melting and boiling points.
Intramolecular hydrogen bond is formed between
The high melting points and boiling points of the
the hydrogen atom and the highly electronegative atom
compounds (H 2 O, HF and NH 3 ) containing hydrogen
(F, O or N) present in the same molecule.
Intramolecular hydrogen bond results in the cyclisation bonds is due to the fact that some extra energy is needed
of the molecules and prevents their association. to break these bonds.
Consequently, the effect of intramolecular hydrogen (4) Solubility : The compound which can form
bond on the physical properties is negligible. hydrogen bonds with the covalent molecules are soluble
For example : Intramolecular hydrogen bonds are in such solvents. For example, lower alcohols are
present in molecules such as o-nitrophenol, o- soluble in water because of the hydrogen bonding which
nitrobenzoic acid, etc. can take place between water and alcohol molecules as
shown below,
O H
|| |      
O C C H  O .......... ...... H  O .......... ..... H  O
H O
O
H C2 H 5 H C2 H 5
O O
N N H The intermolecular hydrogen bonding increases
O
|| || Salicyldehyde solubility of the compound in water while, the
O O (o-hydroxy
Ortho nitrophenol benzaldehyde) intramolecular hydrogen bonding decreases.
Ortho nitrobenzoic acid

O H – O …… H – O – H
The extent of both intramolecular and H
intermolecular hydrogen bonding depends on
temperature. N O ON=O
Effects of hydrogen bonding
||
O
o- Nitrophenol p- Nitrophenol
Hydrogen bond helps in explaining the abnormal
Due to chelation, – OH – OH group available to
physical properties in several cases. Some of the group is not available to form hydrogen bond with
properties affected by H-bond are given below, form hydrogen bond with water, hence it is
water hence it is sparingly completely soluble in
soluble in water. water.
 Chemical Bonding 99
(5) As the compounds involving hydrogen bonding water becomes much more than the decrease in volume
between different molecules (intermolecular hydrogen due to breaking of H-bonds. Thus, after 277 K , there
bonding) have higher boiling points, so they are less is net increase of volume on heating which means
volatile. decrease in density. Hence density of water is maximum
277 K .
(6) The substances which contain hydrogen
bonding have higher viscosity and high surface tension.

(7) Explanation of lower density of ice than

water and maximum density of water at 277K : In
case of solid ice, the hydrogen bonding gives rise to a
cage like structure of water molecules as shown in
following figure. As a matter of fact, each water
molecule is linked tetrahedrally to four other water
molecules. Due to this structure ice has lower density
than water at 273 K. That is why ice floats on water. On
heating, the hydrogen bonds start collapsing, obviously
the molecules are not so closely packed as they are in
the liquid state and thus the molecules start coming
together resulting in the decrease of volume and hence
increase of density. This goes on upto 277K. After 277
K, the increase in volume due to expansion of the liquid

0.90 Å
H
1.77 Å
(99 pm)
O (177 pm)
H H H
Vacant spaces
O O

H H H H

O O

H H H H
O O
H H H H
O O
H H

Cage like structure of H2O in the ice

 98 Chemical Bonding
polymerised into the molecular species
H 2 F2 , H 3 F3 , H 4 F4 , H 5 F5 and H 6 F6 .

 Hydrogen bonding is strongest when the bonded

structure is stabilised by resonance.

 A chemical bond is expected to be formed when  Critical temperature of water is higher than that
of O 2 because H 2 O molecule has dipole moment.
the energy of the aggregate formed is about 40 kJ
mole–1 lower than the separate particles.

 Formation of a chemical bond is always an

exothermic process.

 Lattice energies of bi-bivalent solids > bi-

univalent solids > uni-univalent solids. For
example, lattice energy of
Electrovalent bonding
Mg 2  O 2  (3932 kJ mole 1
)  Ca 2  (F  )2 (2581 kJ mole 1
) 1. Which forms a crystal of NaCl
  1 [CPMT 1972; NCERT 1976; DPMT 1996]
Li F (1034 kJ mole ).
(a) NaCl molecules (b) Na  and Cl  ions
 When co-ordination number increases, the (c) Na and Cl atoms (d) None of the above
coulombic forces of attraction increases and 2. When sodium and chlorine reacts then [NCERT 1973]
hence stability increases. (a) Energy is released and ionic bond is formed
(b) Energy is released and a covalent bond is
 Ionic solids have negative vapour pressure. formed
 As a general rule, atomic crystals are formed by (c) Energy is absorbed and ionic bond is formed
the lighter elements of the middle columns of the (d) Energy is absorbed and covalent bond is
formed
periodic table.
3. Which one is least ionic in the following
 FeCl3 is more covalent than FeCl2 because compounds
[CPMT 1976; BHU 1998]
polarising power of Fe 3  is more than that of
(a) AgCl (b) KCl
Fe 2  . Similarly SnCl 4 is more covalent than
(c) BaCl2 (d) CaCl2
SnCl 2 .
4. The electronic configuration of four elements L,
P, Q and R are given in brackets
 Boron forms the maximum number of electron
deficient compounds than any other elements in
  
L 1s 2 , 2 s 2 2 p 4 ; Q 1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 5 
the periodic table. P 1s , 2 s
2 2
2 p , 3 s ; R 1s , 2 s
6 1 2 2
2 p6 , 3s2 
The formulae of ionic compounds that can be
 Roughly each lone pair decreases the bond angle
formed between these elements are [NCERT 1983]
by 2.5°.
(a) L2 P, RL, PQ and R2Q (b) LP, RL, PQ and RQ
 Greater the number of the lone pairs at the two (c) P2 L, RL, PQ and RQ2 (d) LP, R2 L, P2Q and RQ
bonding atoms, greater is the repulsion between
5. Electrovalent compound's [MP PMT 1984]
them and weaker is the bond. (a) Melting points are low
 The actual number of s- and p-electrons present (b) Boiling points are low
in the outermost shell of the element is called (c) Conduct current in fused state
(d) Insoluble in polar solvent
maximum covalency of that atom.
6. A electrovalent compound is made up of
 The hydrogen bonds are tetrahedral in their [CPMT 1978, 81; MNR 1979]
directions and not planar. (a) Electrically charged molecules
(b) Neutral molecules
 The hydrogen bond is stronger in HF and persists (c) Neutral atoms
even in vapour state. Such bonds account for the (d) Electrically charged atoms or group of atoms
fact that gaseous hydrogen fluoride is largely 7. Electrovalent bond formation depends on
 Chemical Bonding 99
(a) Ionization energy (b) Electron affinity (c) Sodium loses electron and chlorine accepts
(c) Lattice energy (d) All the three above electron
8. In the following which substance will have (d) Sodium accepts electron and chlorine loses
highest boiling point [NCERT 1973; MP PMT 1990] electron
(a) He (b) CsF 17. Which of the following is an electrovalent linkage
(c) NH 3 (d) CHCl 3 [CPMT 1974; DPMT 1984, 91; AFMC 1988]
9. An atom of sodium loses one electron and chlorine (a) CH4 (b) MgCl2
atom accepts one electron. This result the (c) SiCl4 (d) BF3
formation of sodium chloride molecule. This type
18. Electrovalent compounds do not have [CPMT 1991]
of molecule will be
(a) High M.P. and Low B.P. (b)High dielectric constant
[MP PMT 1987]
(c) High M.P. and High B.P. (d) High polarity
(a) Coordinate (b) Covalent
19. Many ionic crystals dissolve in water because
(c) Electrovalent (d) Matallic bond
[NCERT 1982]
10. Formula of a metallic oxide is MO . The formula (a) Water is an amphiprotic solvent
of its phosphate will be [CPMT 1986, 93]
(b) Water is a high boiling liquid
(a) M 2 PO4 2 (b) M PO4 
(c) The process is accompanied by a positive heat
(c) M 2 PO4 (d) M3 PO4 2 of solution
11. From the following which group of elements (d) Water decreases the interionic attraction in
easily forms cation the crystal
(a) F, Cl, Br (b) Li, Na, K lattice due to solvation
20. The electronic structure of four elements A, B, C,
(c) O, S , Se (d) N , P, As
D are
12. Which type of compounds show high melting and
(A) 1s 2 (B) 1s 2 , 2 s 2 2 p 2
boiling points [CPMT 1996]
(a) Electrovalent compounds (C) 1s 2 , 2 s 2 2 p 5 (D) 1s 2 , 2 s 2 2 p 6
(b) Covalent compounds The tendency to form electrovalent bond is largest
(c) Coordinate compounds in
(d) All the three types of compounds have equal [MNR 1987, 95]
melting and boiling points (a) A (b) B
13. Lattice energy of an ionic compound depends (c) C (d) D
upon 21. Chloride of metal is MCl2 . The formula of its
[AIEEE 2005]
phosphate will be [CPMT 1979]
(a) Charge on the ion only
(a) M 2 PO4 (b) M 3 PO4 2
(b) Size of the ion only
(c) M 2 PO4 3 (d) MPO4
(c) Packing of ions only
(d) Charge on the ion and size of the ion 22. The phosphate of a metal has the formula MPO4 .
14. In the given bonds which one is most ionic The formula of its nitrate will be
[EAMCET 1980] (a) MNO 3 (b) M 2 NO3 2
(a) Cs  Cl (b) Al  Cl
(c) M NO3 2 (d) M NO3 3
(c) C  Cl (d) H  Cl
15. Element x is strongly electropositive and y is 23. In the transition of Zn atoms to Zn   ions there is
a decrease in the [CPMT 1972]
strongly electronegative. Both element are
univalent, the compounds formed from their (a) Number of valency electrons
combination will be [IIT 1980] (b) Atomic weight
(a) x  y  (b) x  y  (c) Atomic number
(d) Equivalent weight
(c) x  y (d) x  y
24. Phosphate of a metal M has the formula
M 3 PO4 2 . The formula for its sulphate would be
16. In the formation of NaCl from Na and Cl [CPMT 1985]
(a) Sodium and chlorine both give electrons
[CPMT 1973; MP PMT 1996]
(b) Sodium and chlorine both accept electrons
(a) MSO 4 (b) M SO 4 2
 100 Chemical Bonding
(c) M 2 SO 4 3 (d) M 3 SO 4 2 (d) Atoms of sodium and chlorine
25. The molecular formula of chloride of a metal M is 33. The phosphate of a metal has the formula MHPO4 .
MCl3 . The formula of its carbonate would be[CPMT 1987] The formula of its chloride would be
(b) M 2 CO3 3
[NCERT 1974; CPMT 1977]
(a) MCO 3
(a) MCl (b) MCl2
(c) M 2 CO 3 (d) M CO3 2
(c) MCl3 (d) M 2 Cl3
26. Sodium chloride easily dissolves in water. This is
34. A number of ionic compounds e.g.
because
AgCl, CaF2 , BaSO 4 are insoluble in water. This is
[NCERT 1972; BHU 1973]
(a) It is a covalent compound because [NCERT 1984]
(a) Ionic compounds do not dissolve in water
(b) Salt reacts with water
(b) Water has a high dielectric constant
(c) It is a white substance
(c) Water is not a good ionizing solvent
(d) Its ions are easily solvated
(d) These molecules have exceptionally high
27. When NaCl is dissolved in water the sodium ion
alternative forces in the lattice
becomes
35. What is the nature of chemical bonding between
[NCERT 1974; CPMT 1989; MP PMT 1999]
Cs and F
(a) Oxidized (b) Reduced [MP PMT 1987; CPMT 1976]
(c) Hydrolysed (d) Hydrated (a) Covalent (b) Ionic
28. Solid NaCl is a bad conductor of electricity since (c) Coordinate (d) Metallic
[AFMC 1980] 36. Which one of the following compound is ionic
(a) In solid NaCl there are no ions [MNR 1985]
(b) Solid NaCl is covalent (a) KCl (b) CH 4
(c) In solid NaCl there is no motion of ions (c) Diamond (d) H 2
(d) In solid NaCl there are no electrons 37. Which of the following compound has
29. Favourable conditions for electrovalency are electrovalent linkage
(a) Low charge on ions, large cation, small anion [CPMT 1983, 84, 93]
(b) High charge on ions, small cation, large anion (a) CH 3 Cl (b) NaCl
(c) High charge on ions, large cation, small anion
(c) CH 4 (d) Cl 2
(d) Low charge on ions, small cation, large anion
38. An ionic compound is generally a [MADT Bihar 1981]
30. The sulphate of a metal has the formula
M 2 SO 4 3 . The formula for its phosphate will be (a) Good electrolyte (b) Weak electrolyte
(c) Non-electrolyte (d) Neutral
[DPMT 1982; CPMT 1972; MP PMT 1995]
(a) M HPO 4 2 (b) M 3 PO4 2
39. What metals combine with non-metals, the metal
atom tends to [AMU 1982]
(c) M 2 PO4 3 (d) MPO4
(a) Lose electrons
31. Ionic bonds are usually formed by combination of (b) Gain electrons
elements with [CBSE PMT 1993; MP PMT 1994]
(c) Remain electrically neutral
(a) High ionisation potential and low electron
(d) None of these
affinity
40. Chemical formula for calcium pyrophosphate is
(b) Low ionisation potential and high electron
Ca 2 P2 O7 . The formula for ferric pyrophosphate
affinity
(c) High ionisation potential and high electron will be [NCERT 1977]
affinity (a) Fe 3 (P2 O7 )3 (b) Fe 4 P4 O14
(d) Low ionisation potential and low electron (c) Fe 4 (P2 O7 )3 (d) Fe 3 PO4
affinity
41. Among the bonds formed by a chlorine atom with
32. Molten sodium chloride conducts electricity due
atoms of hydrogen, chlorine, sodium and carbon,
to the presence of [IIT 1981]
the strongest bond is formed between [EAMCET 1988; MP P
(a) Free electrons
(a) H  Cl (b) Cl  Cl
(b) Free ions
(c) Na  Cl (d) C  Cl
(c) Free molecules
 Chemical Bonding 101
42. Which of the following is least soluble [CPMT 1989] (c) XCl (d) X 2 Cl
(a) BeF2 (b) SrF2 53. Two element have electronegativity of 1.2 and
(c) CaF2 (d) MgF2 3.0. Bond formed between them would be[CPMT 1982; DCE
(a) Ionic (b) Polar covalent
43. Which of the following halides has maximum
melting point (c) Co-ordinate (d) Metallic
(a) NaCl (b) NaBr 54. Which of the following is least ionic [MP PET 2002]
(c) NaI (d) NaF (a) C 2 H 5 Cl (b) KCl
44. The high melting point and insolubility in organic (c) BaCl2 (d) C 6 H 5 N  H 3 Cl 
solvents of sulphanilic acid are due to its ......
55. Which type of bonding exists in Li 2 O and CaF2
structure. [IIT 1994]
respectively [RPET 2000]
(a) Simple ionic (b) Bipolar ionic
(a) Ionic, ionic (b) Ionic, covalent
(c) Cubic (d) Hexagonal
(c) Covalent, ionic (d) Coordinate, ionic
45. Out of the following, which compound will have
electrovalent bonding 56. An atom with atomic number 20 is most likely to
combine chemically with the atom whose atomic
(a) Ammonia (b) Water
number is
(c) Calcium chloride (d) Chloromethane
[BHU 2000]
46. The force which holds atoms together in an
(a) 11 (b) 14
electrovalent bond is
(c) 16 (d) 10
(a) Vander Waal's force
57. Bond formed in crystal by anion and cation is
(b) Dipole attraction force
[CBSE PMT 2000]
(c) Electrostatic force of attraction
(a) Ionic (b) Metallic
(d) All the above
(c) Covalent (d) Dipole
47. The main reaction during electrovalent bond
58. Atoms or group of atoms which are electrically
formation is
charged are known [UPSEAT 2001]
(a) Redox reaction (b) Substitution reaction
(a) Anions (b) Cations
(c) Addition reaction (d) Elimination reaction
(c) Ions (d) Atoms
48. Electrovalent compounds are [CPMT 1996]
59. Which one is the strongest bond [Pb. PMT 2001]
(a) Good conductor of electricity
(a) Br – F (b) F – F
(b) Polar in nature
(c) Cl – F (d) Br – Cl
(c) Low M.P. and low B.P.
60. The interionic attraction depends on interaction
(d) Easily available
of
49. Ionic compounds do not have [RPMT 1997]
[Kerala CET (Med.) 2002]
(a) Hard and brittle nature (a) Solute-Solute (b) Solvent-Solvent
(b) High melting and boiling point (c) The charges (d) Molecular properties
(c) Directional properties 61. Which of the following compounds is ionic
(d) Soluble in polar solvents [UPSEAT 2002]
50. Highest melting point would be of [RPMT 1999]
(a) KI (b) CH 4
(a) He (b) CsCl
(c) Diamond (d) H 2
(c) NH 3 (d) CHCl 3
62. Which of the following pairs of species has same
51. What is the effect of more electronegative atom electronic configuration [UPSEAT 2002]
on the strength of ionic bond [AMU 1999]
(a) Zn 2  and Ni 2  (b) Co 3 and Ni 4 
(a) Decreases (b) Increases
(c) Co 2  and Ni 2  (d) Ti 4  and V 3 
(c) Decreases slowly (d) Remains the same
63. The energy that opposes dissolution of a solvent is
52. An element X with the electronic configuration
[CPMT 2002]
1s 2 , 2 s 2 2 p 6 , 3 s 2 would be expected to form the
(a) Hydration energy (b) Lattice energy
chloride with the formula [JIPMER 2000]
(c) Internal energy (d) Bond energy
(a) XCl 3 (b) XCl 2
64. Which of the following has highest melting point
 102 Chemical Bonding
[RPET 2003] (c) LiBr (d) LiI
(a) BeCl 2 (b) MgCl2 6. The nature of bonding in graphite is
[DPMT 1986; CPMT 1986]
(c) CaCl2 (d) BaCl2
(a) Covalent (b) Ionic
65. Which of the following statements is not true for (c) Metallic (d) Coordinate
ionic compounds [RPET 2003] 7. Which of the following substances has giant
(a) High melting point covalent structure [DPMT 1985, 86; NCERT 1975]
(b) Least lattice energy (a) Iodine crystal (b) Solid CO2
(c) Least solubility in organic compounds (c) Silica (d) White phosphorus
(d) Soluble in water 8. With which of the given pairs CO2 resembles[BHU 2005]
66. Electrolytes are compound containing[MADT Bihar 1981] (a) HgCl2, C2H2 (b) HgCl2, SnCl4
(a) Electrovalent bond (b) Covalent bond (c) C2H2, NO2 (d) N2O and NO2
(c) Coordinate bond (d) Hydrogen bond 9. The electron pair which forms a bond between
67. Which of the following hydrides are ionic[Roorkee 1999] two similar non-metallic atoms will be [IIT 1986]
(a) Dissimilar shared between the two
(a) CaH2 (b) BaH 2
(b) By complete transfer from one atom to other
(c) SrH 2 (d) BeH 2 (c) In a similar spin condition
68. Which of the following conduct electricity in the (d) Equally shared in between the two
fused state 10. For the formation of covalent bond, the difference
[Roorkee 2000] in the value of electronegativities should be[EAMCET 1982]
(a) BeCl 2 (b) MgCl2 (a) Equal to or less than 1.7 (b) More than 1.7
(c) 1.7 or more (d) None of these
(c) SrCl 2 (d) BaCl2
11. Which type of bond is formed between similar
atoms
Covalent bonding (a) Ionic (b) Covalent
(c) Coordinate (d) Metallic
1. The valency of sulphur in sulphuric acid is [NCERT 1974]
12. Covalent compounds are generally ...... in water
(a) 2 (b) 4 [CPMT 1987]
(c) 6 (d) 8 (a) Soluble (b) Insoluble
2. The number of electrons involved in the bond (c) Dissociated (d) Hydrolysed
formation of N 2 molecule 13. Which one is the electron deficient compound[AIIMS 1982]
[IIT 1980; CPMT 1983, 84, 85; CBSE PMT 1992]
(a) ICl (b) NH 3

(a) 2 (b) 4 (c) BCl3 (d) PCl3

(c) 6 (d) 10 14. Which among the following elements has the
3. The electronic configuration of four elements are tendency to form covalent compounds
given in brackets (a) Ba (b) Be

  
L 1s 2 , 2 s 2 2 p1 ; M 1s 2 , 2 s 2 2 p 5  (c) Mg (d) Ca
15. Silicon has 4 electrons in the outermost orbit. In
Q 1s , 2 s
2 2
 
2 p 6 , 3 s1 ; R 1 s 2 , 2 s 2 2 p 2  forming the bonds [EAMCET 1981]
The element that would most readily form a (a) It gains electrons (b) It loses electrons
diatomic molecule is (c) It shares electrons (d) None of these
[NCERT 1983] 16. Which of the following occurs when two hydrogen
(a) Q (b) M atoms bond with each others
(c) R (d) L (a) Potential energy is lowered
4. In covalency [CPMT 1974, 76, 78, 81; AFMC 1982] (b) Kinetic energy is lowered
(a) Electrons are transferred (c) Electronic motion ceases
(b) Electrons are equally shared
(d) Energy is absorbed
(c) The electron of one atom are shared between
17. A bond with maximum covalent character
two atoms
between non-metallic elements is formed[NCERT 1982]
(d) None of the above
5. Which compound is highest covalent (a) Between identical atoms
(a) LiCl (b) LiF (b) Between chemically similar atoms
 Chemical Bonding 103
(c) Between atoms of widely different 26. The correct sequence of increasing covalent
electronegativities character is represented by [CBSE PMT 2005]
(d) Between atoms of the same size (a) LiCl  NaCl  BeCl 2 (b) BeCl 2  NaCl  LiCl
18. Amongst the following covalent bonding is found (c) NaCl  LiCl  BeCl 2 (d) BeCl 2  LiCl  NaCl
in
27. Bond energy of covalent O  H bond in water is
[CPMT 1973]
[EAMCET 1982]
(a) Sodium chloride (b) Magnesium chloride
(a) Greater than bond energy of H  bond
(c) Water (d) Brass
(b) Equal to bond energy of H  bond
19. Indicate the nature of bonding in diamond
(c) Less than bond energy of H  bond
[EAMCET 1980; BHU 1996; KCET 2000]
(d) None of these
(a) Covalent (b) Ionic
28. Solid CH 4 is [DPMT 1983]
(c) Coordinate (d) Hydrogen
20. Octet rule is not valid for the molecule (a) Molecular solid (b) Ionic solid
[IIT 1979; MP PMT 1995] (c) Pseudo solid (d) Does not exist
(a) CO2 (b) H 2 O 29. A covalent bond is likely to be formed between
two elements which [MP PMT 1987]
(c) CO (d) O 2
(a) Have similar electronegativities
21. Which of the following compounds are covalent
(b) Have low ionization energies
[IIT 1980; MLNR 1982]
(c) Have low melting points
(a) H 2 (b) CaO
(d) Form ions with a small charge
(c) KCl (d) Na2 S 30. The bond between two identical non-metal atoms
22. Indicate the nature of bonding in CCl4 and CaH2 has a pair of electrons [CPMT 1986]

[NCERT 1973] (a) Unequally shared between the two

(a) Covalent in CCl4 and electrovalent in CaH2 (b) Transferred fully from one atom to another
(c) With identical spins
(b) Electrovalent in both CCl4 and CaH2
(d) Equally shared between them
(c) Covalent in both CCl4 and CaH2
31. The valency of phosphorus in H 3 PO4 is[DPMT 1984]
(d) Electrovalent in CCl4 and covalent in CaH2
(a) 2 (b) 5
23. If the atomic number of element X is 7, the best (c) 4 (d) 1
electron dot symbol for the element is [NCERT 1973; CPMT 2003]
32. Which of the following substances has covalent
(a) X . (b) . X . bonding
. .. [AMU 1985]
(c) . X : (d) : X .
. .. (a) Germanium (b) Sodium chloride
24. Which is the most covalent [AFMC 1982] (c) Solid neon (d) Copper
(a) C  O (b) C  Br 33. The covalency of nitrogen in HNO 3 is [CPMT 1987]
(c) C  S (d) C  F (a) 0 (b) 3
25. The covalent compound HCl has the ionic (c) 4 (d) 5
character as
34. Hydrogen chloride molecule contains a[CPMT 1984]
[EAMCET 1980]
(a) Covalent bond (b) Double bond
(a) The electronegativity of hydrogen is greater
than that of chlorine (c) Coordinate bond (d) Electrovalent bond
(b) The electronegativity of hydrogen is equal to 35. As compared to covalent compounds,
that of chlorine electrovalent compounds generally have
(c) The electronegativity of chlorine is greater [CPMT 1990, 94; MP PMT 1997]
than that of hydrogen (a) Low melting points and low boiling points
(d) Hydrogen and chlorine are gases (b) Low melting points and high boiling points
 104 Chemical Bonding
(c) High melting points and low boiling points 44. The electronic configuration of a metal M is
(d) High melting points and high boiling points 1 s 2 , 2 s 2 2 p 6 , 3 s 1 . The formula of its oxides will be
36. The interatomic distances in H2 and Cl 2 [MP PET/PMT 1998]

molecules are 74 and 198 pm respectively. The (a) MO (b) M 2 O

bond length of HCl is (c) M 2 O3 (d) MO2
[MP PET 1993]
45. Which of the following statements regarding
(a) 272 pm (b) 136 pm covalent bond is not true [MP PET/PMT 1998]
(c) 124 pm (d) 248 pm (a) The electrons are shared between atoms
37. On analysis, a certain compound was found to (b) The bond is non-directional
contain iodine and oxygen in the ratio of 254 gm (c) The strength of the bond depends upon the
of iodine and 80 gm of oxygen. The atomic mass extent of overlapping
(d) The bond formed may or may not be polar
of iodine is 127 and that of oxygen is 16. Which of
46. If the electronic configuration of M  2, 8, 3 and
the following is the formula of the compound [CPMT 1981]
that of A  2, 8, 7, the formula of the compound is
(a) IO (b) I 2 O
[Bihar MEE 1996]
(c) I5 O 2 (d) I 2 O 5
(a) M 2 A 3 (b) MA2
38. Ionic and covalent bonds are present in
(c) M 2 A (d) MA3
[CBSE PMT 1990; MNR 1990; KCET 2000; UPSEAT 2001]
(e) M 3 A
(a) CCl4 (b) CaCl2
47. The table shown below gives the bond
(c) NH 4 Cl (d) H 2 O dissociation energies (Ediss) for single covalent
39. Highest covalent character is found in[EAMCET 1992] bonds of carbon (C) atoms with element
(a) CaF2 (b) CaCl2 A, B, C and D. Which element has the smallest
atoms [CBSE PMT 1994]
(c) CaBr2 (d) CaI2
1
Bond E diss (kJ mol )
40. Among the following which property is commonly
exhibited by a covalent compound [MP PET 1994] CA 240
(a) High solubility in water CB 328
(b) High electrical conductance C C 276
CD 485
(c) Low boiling point
(a) A (b) B
(d) High melting point
(c) C (d) D
41. Atoms in the water molecule are linked by[MP PAT 1996]
48. If a molecule X 2 has a triple bond, then X will
(a) Electrovalent bond
have the electronic configuration [CET Pune 1998]
(b) Covalent bond
(a) 1 s 2 2 s 2 2 p 5 (b) 1 s 2 2 s 2 2 p 3
(c) Coordinate covalent bond
(d) Odd electron bond (c) 1s 2 2 s 1 (d) 1 s 2 2 s 2 2 p 1
42. Which is the correct electron dot structure of 49. Which of the following compounds does not
N 2 O molecule follow the octet rule for electron distribution[CET Pune 199
(a) PCl5 (b) PCl3
[MP PET 1996]
.. .. (c) H 2 O (d) PH 3
(a) : N  N  O (b) : N  N   O : 
.. .. 50. The valency of A3 and B  2, then the
compound is
.. .. .. ..
(c) N  N  O (d) :N  N  O : [Bihar MEE 1997]
.. .. ..
(a) A 2 B3 (b) A3 B 2
43. A covalent bond between two atoms is formed by (c) A3 B3 (d) A 2 B 2
which of the following [MP PMT 1996]
(e) None of these
(a) Electron nuclear attraction
51. The number of electrons shared by each
(b) Electron sharing outermost shell of N 2 is [AFMC 1998]
(c) Electron transfer
(a) 2 (b) 3
(d) Electrostatic attraction (c) 4 (d) 5
 Chemical Bonding 105
52. Which of the following substances when dissolved (a) Two (b) Three
in water will give a solution that does not conduct (c) Four (d) Six
electricity
61. The acid having O  O bond is
[JIPMER 1999]
[IIT JEE Screening 2004]
(a) Hydrogen chloride (b) Potassium hydroxide
(a) H 2 S 2 O 3 (b) H 2 S 2 O6
(c) Sodium acetate (d) Urea
53. Which of the following atoms has minimum (c) H 2 S 2 O8 (d) H 2 S 4 O6
covalent radius
62. The following salt shows maximum covalent
[DPMT 2000]
character
(a) B (b) C
[UPSEAT 2004]
(c) N (d) Si
(a) AlCl3 (b) MgCl2
54. Boron form covalent compound due to[Pb. PMT 2000]
(c) CsCl (d) LaCl3
(a) Small size (b) Higher ionization
energy 63. Which type of bond is present in H 2 S molecule
(c) Lower ionization energy (d) Both (a) and (b) [MHCET 2003; Pb CET 2001]
55. Two elements X and Y have following electron (a) Ionic bond (b) Covalent bond
configurations (c) Co-ordinate (d) All of three
64. H 2 S is more acidic than H 2 O , due to [BVP 2004]
X  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 2
(a) O is more electronegative than S
and Y  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 (b) O  H bond is stronger than S  H bond
The compound formed by combination of X and Y (c) O  H bond is weaker than S  H bond
is (d) None of these
[DPMT 2001] 65. Which of the following has covalent bond
[AFMC 1988; DCE 2004]
(a) XY 5 (b) X 2 Y 5
(a) Na2 S (b) AlCl3
(c) X 5 Y 3 (d) XY 2 (c) NaH (d) MgCl2
56. Covalent compounds have low melting point 66. The following element forms a molecule with
because eight its own weight atoms [MHCET 2004]
[KCET 2002] (a) Si (b) S
(a) Covalent bond is less exothermic (c) Cl (d) P
(b) Covalent molecules have definite shape 67. In H 2O2 , the two oxygen atoms have
(c) Covalent bond is weaker than ionic bond (a) Electrovalent bond (b) Covalent bond
(d) Covalent molecules are held by weak Vander (c) Coordinate bond (d) No bond
Waal’s force of attraction 68. Carbon has a valency of 2 in CO and 4 in CO2 and

57. p and n-type of semiconductors are formed due to CH 4 . Its valency in acetylene C 2 H 2  is[NCERT 1971]
[UPSEAT 2002] (a) 1 (b) 2
(a) Covalent bonds (b) Metallic bonds (c) 3 (d) 4
69. Number of electrons in the valence orbit of
(c) Ionic bonds (d) Co-ordinate bond
nitrogen in an ammonia molecule are [MH CET 2004]
58. Which of the following is Lewis acid [RPET 2003]
(a) 8 (b) 5
(a) BF3 (b) NH 3 (c) 6 (d) 7
(c) PH 3 (d) SO 2 70. Hydrogen atoms are held together to form
2
hydrogen molecules by [AMU 1982]
59. Among the species : CO 2 , CH 3 COO  , CO, CO3 , (a) Hydrogen bond (b) Ionic bond
HCHO which has the weakest carbon- oxygen (c) Covalent bond (d) Dative bond
bond 71. Strongest bond is [AFMC 1987]
[Kerala PMT 2004] (a) C  C (b) C  H
(a) CO2 (b) CH 3 COO  (c) C  N (d) C  O
72. The major binding force of diamond, silicon and
(c) CO (d) CO3 2  quartz is
[Kerala CET (Med.) 2002]
(e) HCHO
(a) Electrostatic force (b) Electrical attraction
60. Valency of sulphur in Na2 S 2 O3 is [DPMT 1984]
 106 Chemical Bonding
(c) Co-valent bond force (d) Non-covalent bond (b) Electrons of one atom are shared with two
force atoms
73. Multiple covalent bonds exist in a molecule of[NCERT 1973] (c) Hydrogen bond is formed
(a) H 2 (b) F2 (d) None of the above
(c) C 2 H 4 (d) N 2 7. Which of the following contains a coordinate
covalent bond
74. Which of the following does not obey the octet
[MNR 1990; IIT 1986]
rule
(a) N 2 O 5 (b) BaCl2
[EAMCET 1993]
(a) CO (b) NH 3 (c) HCl (d) H 2 O

(c) H 2 O (d) PCl5 8. A coordinate bond is formed when an atom in a

molecule has [
75. Which of the following statements is correct for
(a) Electric charge on it
covalent bond [BHU 1997]
(b) All its valency electrons shared
(a) Electrons are shared between two atoms
(c) A single unshared electron
(b) It may be polar or non-polar
(d) One or more unshared electron pair
(c) Direction is non-polar
9. Which has a coordinate bond [RPMT 1997]
(d) Valency electrons are attracted
76. Among CaH2 , NH3 , NaH and B2 H 6 , which are (a) SO 32  (b) CH 4
covalent hydride [Orissa JEE 2005] (c) CO2 (d) NH 3
(a) NH3 and B2 H6 (b) NaH and CaH 2 10. The compound containing co-ordinate bond is
(c) NaH and NH 3 (d) CaH2 and B2 H 6 [AFMC 1999; Pb. CET 2002]
(a) O 3 (b) SO 3
Co-ordinate or Dative bonding
(c) H 2 SO 4 (d) All of these
1. Which species has the maximum number of lone 11. The number of dative bonds in sulphuric acid
pair of electrons on the central atom? [IIT 2005] molecules is
(a) [ClO3] (b) XeF4 [MP PET 2002]
(c) SF4 (d) [I3] (a) 0 (b) 1
2. A simple example of a coordinate covalent bond is (c) 2 (d) 4
exhibited by 12. [NCERT
Which1984]
of the following compounds has coordinate
(a) C 2 H 2 (b) H 2 SO 4 (dative) bond [RPET 2003]
(a) CH 3 NC (b) CH 3 OH
(c) NH 3 (d) HCl
(c) CH 3 Cl (d) NH 3
3. The bond that exists between NH 3 and BF3 is
called 13. The structure of orthophosphoric acid is[KCET 2003]
[AFMC 1982; MP PMT 1985; MNR 1994; O
H
KCET 2000; MP PET 2001; UPSEAT 2001]  |
(a) H  O  P  O  H (b) O  P  O  H
(a) Electrovalent (b) Covalent | |

(c) Coordinate (d) Hydrogen O O

| |
4. Which of the following does not have a coordinate H H
bond
O
[MADT Bihar 1984] H
| 
(a) SO 2 (b) HNO 3 (c) O  P  O  H (d) H  O  P  O
|
(c) H 2 SO 3 (d) HNO 2 H
5. Coordinate covalent compounds are formed by 14. What is the nature of the bond between B and O in
[CPMT 1990, 94] (C 2 H 5 )2 OBH 3 [Orissa JEE 2003]
(a) Transfer of electrons (b) Sharing of electrons
(a) Covalent (b) Co-ordinate covalent
(c) Donation of electrons (d)None of these process
(c) Ionic bond (d) Banana shaped bond
6. In the coordinate valency [CPMT 1989]
15. Sulphuric acid provides a example of
(a) Electrons are equally shared by the atoms
[Kerala CET (Med.) 2002]
(a) Co-ordinate bonds
 Chemical Bonding 107
(b) Non-covalent compound [IIT 1982, 83; MP PMT 1985, 91;
EAMCET 1988; AMU 1999]
(c) Covalent and co-ordinate bond
(a) Its planar structure
(d) Non-covalent ion
(b) Its regular tetrahedral structure
Dipole moment (c) Similar sizes of carbon and chlorine atoms
(d) Similar electron affinities of carbon and
1. Which molecules has zero dipole moment chlorine
[AIIMS 1980, 82, 91; Roorkee 2000; MH CET 2001] 11. The molecule which has the largest dipole
(a) H 2O (b) CO2 moment amongst the following [MNR 1983]
(c) HF (d) HBr (a) CH 4 (b) CHCl 3
2. In the following which one have zero dipole (c) CCl4 (d) CHI 3
moment
12. Positive dipole moment is present in
[DPMT 1985]
[MNR 1986; MP PET 2000]
(a) BF3 (b) CCl4
(a) CCl4 (b) C6 H 6
(c) BeCl 2 (d) All of these
(c) BF3 (d) HF
3. Which molecule has the largest dipole moment
13. The polarity of a covalent bond between two
[CPMT 1991]
atoms depends upon [AMU 1982]
(a) HCl (b) HI
(a) Atomic size (b) Electronegativity
(c) HBr (d) HF
(c) Ionic size (d) None of the above
4. The unequal sharing of bonded pair of electrons
14. Pick out the molecule which has zero dipole
between two atoms in a molecule causes[EAMCET 1986]
moment
(a) Dipole [CPMT 1989; EAMCET 1993; MP PMT 1999]
(b) Radical formation (a) NH 3 (b) H 2 O
(c) Covalent bond
(c) BCl 3 (d) SO 2
(d) Decomposition of molecule
15. Zero dipole moment is present in[DPMT 1986; IIT 1987]
5. Which of the following will show least dipole
character (a) NH 3 (b) H 2 O

[NCERT 1975; Kurukshetra CEE 1998] (c) cis 1, 2-dichloroethene (d)trans 1, 2-dichloroethene
(a) Water (b) Ethanol 16. Which of the following is the most polar[AFMC 1988]

(c) Ethane (d) Ether (a) CCl4 (b) CHCl 3

6. Which of the following molecules will show dipole (c) CH 3 OH (d) CH 3 Cl

moment 17. Which one has minimum (nearly zero) dipole
[NCERT 1972, 74; DPMT 1985] moment
(a) Methane (b) Carbon tetrachloride [IIT Screening 1994; CBSE PMT 1996]
(c) Chloroform (d) Carbon dioxide (a) Butene-1 (b) cis butene-2
7. Which of the following compounds possesses the (c) trans butene-2 (d) 2-methyl-1-propene
18.
dipole moment[NCERT 1978; EAMCET 1983; MP PMT 1995] Which one of the following is having zero dipole
(a) Water (b) Boron trifluoride moment
[RPMT 1997; EAMCET 1988; MNR 1991]
(c) Benzene (d) Carbon tetrachloride
(a) CCl4 (b) CH 3 Cl
8. Which bond angle  would result in the maximum
dipole moment for the triatomic molecule YXY [AIIMS 1980] (c) CH 3 F (d) CHCl 3

(a)   90 o
(b)   120 o 19. Which of the following molecules does not possess
a permanent dipole moment [CBSE PMT 1994]
(c)   150 o (d)   180 o
(a) H 2 S (b) SO 2
9. Which of the following would have a permanent
dipole moment [CBSE PMT 2005] (c) CS 2 (d) SO 3
(a) BF3 (b) SiF4 20. Which of the following has zero dipole moment
[CPMT 1997; AFMC 1998; CBSE PMT 2001]
(c) SF4 (d) XeF4
(a) CH 2 Cl 2 (b) CH 4
10. Carbon tetrachloride has no net dipole moment
(c) NH 3 (d) PH 3
because of
 108 Chemical Bonding
21. Fluorine is more electronegative than either (c) CH 4 (d) HI
boron or phosphorus. What conclusion can be
31. Which of the following has no dipole moment
drawn from the fact that BF3 has no dipole
[DCE 2002]
moment but PF3 does
(a) CO2 (b) SO 3
[Pb. PMT 1998]
(a) BF3 is not spherically symmetrical but PF3 is (c) O 3 (d) H 2 O

(b) BF3 molecule must be linear 32. Which of the following is non-polar [DCE 2002]

(c) The atomic radius of P is larger than the (a) PCl5 (b) PCl3
atomic radius of B (c) SF6 (d) IF7
(d) The BF3 molecule must be planar triangular
33. Identify the non-polar molecule in the set of
22. Which molecule does not show zero dipole compounds given : HCl, HF, H 2 , HBr [UPSEAT 2004]
moment
(a) H 2 (b) HCl
[RPET 1997, 99]
(a) BF3 (b) NH 3 (c) HF, HBr (d) HBr
(c) CCl4 (d) CH 4 34. Dipole moment is shown by [IIT 1986]
30 (a) 1, 4-dichlorobenzene
23. The dipole moment of HBr is 1 . 6  10 cm and
interatomic spacing is 1Å. The % ionic character (b) cis 1, 2-dichloroethene
of HBr is (c) trans 1, 2-dichloroethene
[MP PMT 2000]
(d) trans 1, 2-dichloro-2-pentene
(a) 7 (b) 10
35. If HCl molecule is completely polarized, so
(c) 15 (d) 27
expected value of dipole moment is 6.12D (deby),
24. Non-polar solvent is [RPET 2000]
but experimental value of dipole moment is 1.03D.
(a) Dimethyl sulphoxide (b) Carbon tetrachloride Calculate the percentage ionic character [Kerala CET 2005]
(c) Ammonia (d) Ethyl alcohol
(a) 17 (b) 83
25. Which shows the least dipole moment
(c) 50 (d) Zero
[UPSEAT 2001; DPMT 1982]
(a) CCl4 (b) CHCl 3 (e) 90

(c) CH 3 CH 2 OH (d) CH 3 COCH 3 Polarisation and Fajan's rule

26. Which molecule has zero dipole moment[UPSEAT 2001]
(a) H 2 O (b) AgI 1. BF3 and NF3 both molecules are covalent, but BF3
(c) PbSO 4 (d) HBr is non-polar and NF3 is polar. Its reason is
27. The dipole moment is zero for the molecule [CPMT 1989; NCERT 1980]
[IIT 1989; MP PMT 2002] (a) In uncombined state boron is metal and
(a) Ammonia (b) Boron trifluoride nitrogen is gas
(c) Sulphur dioxide (d) Water (b) B  F bond has no dipole moment whereas
28. N 2 is less reactive than CN  due to [UPSEAT 2003] N  F bond has dipole moment
(a) Presence of more electrons in orbitals (c) The size of boron atom is smaller than
(b) Absence of dipole moment nitrogen
(c) Difference in spin quantum no (d) BF3 is planar whereas NF3 is pyramidal
(d) None of these 2. Which one is polar molecule among the following
10
29. In a polar molecule, the ionic charge is 4 . 8  10 (a) CO2 (b) CCl4
e.s.u. If the inter ionic distance is one Å unit, then
the dipole moment is [MH CET 2003]
(c) H 2 O (d) CH 4

(a) 41.8 debye (b) 4.18 debye 3. If the electron pair forming a bond between two
(c) 4.8 debye (d) 0.48 debye atoms A and B is not in the centre, then the bond
is [AIIMS 1984]
30. Which of the following is a polar compound
[Pb. CET 2000]
(a) Single bond (b) Polar bond

(a) HCl (b) H 2 Se (c) Non-polar bond (d)  bond

 Chemical Bonding 109
4. Which of the following liquids is not deflected by (c) CH 2 Cl 2 (d) CH 2  CH 2
a non-uniform electrostatic field 13. Which[NCERT
of the1978]
following have both polar and non-
(a) Water (b) Chloroform polar bonds [AIIMS 1997]
(c) Nitrobenzene (d) Hexane (a) C 2 H 6 (b) NH 4 Cl
5. Which of the following is non-polar [EAMCET 1983] (c) HCl (d) AlCl3
(a) H 2 S (b) NaCl 14. Which of the following has a high polarising
(c) Cl 2 (d) H 2 SO 4 power
[CET Pune 1998]
6. Polarization is the distortion of the shape of an
(a) Mg 2  (b) Al 3 
anion by an adjacently placed cation. Which of the

following statements is correct (c) Na
[NCERT 1982] (d) Ca 2 
(a) Maximum polarization is brought about by a 15. Maximum covalent character is associated with
cation of high charge the compound [RPMT 1999]

(b) Minimum polarization is brought about by a (a) NaI (b) MgI2

cation of (c) AlCl3 (d) AlI3
low radius 16. Polarisibility of halide ions increases in the order
(c) A large cation is likely to bring about a large [DCE 1999]
   
degree of polarization (a) F , I , Br , Cl (b) Cl , Br , I , F 
  

(d) A small anion is likely to undergo a large

(c) I  , Br  , Cl  , F  (d) F  , Cl  , Br  , I 
degree of polarization
7. The bonds between P atoms and Cl atoms in 17. According to Fajan’s rule, covalent bond is
favoured by
PCl5 are likely to be [MP PMT 1987]
[AIIMS 1999]
(a) Ionic with no covalent character (a) Large cation and small anion
(b) Covalent with some ionic character (b) Large cation and large anion
(c) Covalent with no ionic character (c) Small cation and large anion
(d) Ionic with some metallic character (d) Small cation and small anion
8. Two electrons of one atom A and two electrons of 18. Which of the following statements is correct[AMU 1999]
another atom B are utilized to form a compound (a) SF4 is polar and non-reactive
AB. This is an example of [MNR 1981]
(b) SF6 is non-polar and very reactive
(a) Polar covalent bond (b) Non-polar covalent
bond (c) SF6 is a strong fluorinating agent
(c) Polar bond (d) Dative bond (d) SF4 is prepared by fluorinating SCl 2 with NaF
9. In which of the following molecule is the covalent 19. Choose the correct statement [RPMT 2000]
bond most polar [AMU 1985; MP PET (a) Amino polarisation is more pronounced by
2001] highly charged cation
(a) HI (b) HBr (b) Small cation has minimum capacity to polarise
(c) HCl (d) H 2 an anion.
10. Amongst ClF3 , BF3 and NH 3 molecules the one (c) Small anion has maximum polarizability
with non-planar geometry is [MP PMT 1999] (d) None of these
(a) ClF3 (b) NH 3 20. The ICl molecule is [DPMT 2001]
(a) Purely electrovalent
(c) BF3 (d) None of these
(b) Purely covalent
11. Which of the following possesses highest melting (c) Polar with negative end on iodine
point (d) Polar with negative end on chlorine
[CPMT 1999] 21. Which of the following is a polar compound[AIIMS 2001]
(a) Chlorobenzene (b) o-dichlorobenzene (a) HF (b) HCl
(c) m-dichlorobenzene (d) p-dichlorobenzene (c) HNO3 (d) H 2 SO 4
12. The polar molecule among the following is 22. Which of the following has zero dipole moment
[Orissa JEE 1997] [MP PMT 2002]
(a) CCl4 (b) CO2 (a) ClF (b) PCl3
 110 Chemical Bonding
(c) SiF4 (d) CFCl3 4. The number and type of bonds between two
23. Which of the following compounds has least carbon atoms in calcium carbide are [AIEEE 2005]
dipole moment (a) One sigma, one pi (b) One sigma, two pi
[RPET 2003] (c) Two sigma, one pi (d) Two singma, two pi
(a) PH 3 (b) CHCl 3 5. In a double bond connecting two atoms, there is a
sharing of
(c) NH 3 (d) BF3
[CPMT 1977, 80, 81; NCERT 1975;
24. Pauling’s electronegativity values for elements Bihar MEE 1980; MP PET 1999]
are useful in predicting [UPSEAT 2004]
(a) 2 electrons (b) 1 electron
(a) Polarity of bonds in molecules
(c) 4 electrons (d) All electrons
(b) Position of elements in electrochemical series
6. Strongest bond is [DPMT 1990]
(c) Co-ordination number (a) C  C (b) C  C
(d) Dipole moment of various molecules (c) C  C (d) All are equally strong
25. Amongst LiCl, RbCl, BeCl 2 and MgCl2 the 7.  bond is formed [JIPMER 2002]
compounds with the greatest and the least ionic (a) By overlapping of atomic orbitals on the axis
character, respectively, are [UPSEAT 2002] of nuclei
(a) LiCl and RbCl (b) RbCl and BeCl 2 (b) By mutual sharing of pi electron
(c) RbCl and MgCl2 (d) MgCl2 and BeCl 2 (c) By sidewise overlapping of half filled p-
26. Bond polarity of diatomic molecule is because of orbitals
[UPSEAT 2002] (d) By overlapping of s-orbitals with p-orbitals
(a) Difference in electron affinities of the two 8. The double bond between the two carbon atoms in
atoms ethylene consists of [NCERT 1981; EAMCET 1979]
(b) Difference in electronegativities of the two (a) Two sigma bonds at right angles to each other
atoms (b) One sigma bond and one pi bond
(c) Difference in ionisation potential (c) Two pi bonds at right angles to each other
(d) All of these (d) Two pi bonds at an angle of 60 o to each other
9. In the series ethane, ethylene and acetylene, the
Overlaping-  and - bonds C  H bond energy is [NCERT 1977]
(a) The same in all the three compounds
1. Triple bond in ethyne is formed from
(b) Greatest in ethane
[MP PMT 1990; NCERT 1979; EAMCET 1978; AMU 1985;
(c) Greatest in ethylene
CPMT 1988; MADT Bihar 1982; MH CET 2000]
(d) Greatest in acetylene
(a) Three sigma bonds
10. In a sigma bond
(b) Three pi bonds
(a) Sidewise as well as end to end overlap of
(c) One sigma and two pi bonds
orbitals take place
(d) Two sigma and one pi bond
(b) Sidewise overlap of orbitals takes place
2. The bond in the formation of fluorine molecule
(c) End to end overlap of orbitals takes place
will be
(d) None of the above
[MP PMT 1987]
11. The number of sigma and pi bonds in 1-butene-3-
(a) Due to s  s overlapping
yne are
(b) Due to s  p overlapping
[IIT 1989]
(c) Due to p  p overlapping (a) 5 sigma and 5 pi (b) 7 sigma and 3 pi
(d) Due to hybridization (c) 8 sigma and 2 pi (d) 6 sigma and 4 pi
3. Which type of overlapping results the formation 12. The most acidic compound among the following is
of a  bond [MP PET 1993]
[DPMT 1981] (a) CH 3 CH 2 OH (b) C6 H 5 OH
(a) Axial overlapping of s  s orbitals (c) CH 3 COOH (d) CH 3 CH 2 CH 2 OH
(b) Lateral overlapping of p  p orbitals 13. Which of the following is not correct[CBSE PMT 1990]
(c) Axial overlapping of p  p orbitals (a) A sigma bond is weaker than  bond
(d) Axial overlapping of s  p orbitals (b) A sigma bond is stronger than  bond
 Chemical Bonding 111
(c) A double bond is stronger than a single bond [MP PMT 1984; IIT 1982, 88; EAMCET 1993;
(d) A double bond is shorter than a single bond CBSE PMT 1992; MP PET 1995; RPMT 1997]
14. Strongest bond formed, when atomic orbitals (a) NO2 (b) ClO2
(a) Maximum overlap (b) Minimum overlap (c) CO2 (d) H 2S
(c) Overlapping not done (d) None of them
5. Which of the following molecules has trigonal
15. The p  p orbital overlapping is present in the planer geometry [CBSE PMT 2005]
following molecule [MP PET 1994] (a) IF3 (b) PCl3
(a) Hydrogen (b) Hydrogen bromide
(c) NH 3 (d) BF3
(c) Hydrogen chloride (d) Chlorine
16. In N 2 molecule, the atoms are bonded by 6. A sp 3 hybridized orbital contains
[MP PET 1996; UPSEAT 2001] [DPMT 1984; BHU 1985; CPMT 1976]

(a) One , Two  (b) One , One  (a)

1
s  character (b)
1
s  character
(c) Two , One  (d) Three  bonds 4 2
17. In which of following there exists a p  d (c)
2
s  character (d)
3
s  character
bonding 3 4
[AFMC 2001] 7. Structure of ammonia is
(a) Diamond (b) Graphite [MP PMT 1987, 89, 91; CPMT 1975, 82;

(c) Dimethyl amine (d) Trisilylamine RPMT 1999; JIPMER 2002]

18. Number of bonds in SO 2 [DCE 2001] (a) Trigonal (b) Tetrahedral

(c) Pyramidal (d) Trigonal pyramidal
(a) Two  and two 
8. The bond angle in ethylene is [CPMT 1987]
(b) Two  and one 
o o
(c) Two , two  and one lone pair (a) 180 (b) 120
(d) None of these (c) 109 o
(d) 90 o
19. Which of the following has p  d bonding[CBSE 2002]
9. Compound formed by sp 3 d hybridization will have
(a) NO 3 (b) CO 32 structure
[BHU 1982; RPMT 1999]
(c) BO 33 (d) SO 2
3
(a) Planar (b) Pyramidal
20. Number of sigma bonds in P4 O10 is [AIEEE 2002]
(c) Angular (d) Trigonal bipyramidal
(a) 6 (b) 7 10. Which of the following formula does not correctly
(c) 17 (d) 16 represent the bonding capacity of the atom
involved
Hybridisation [CBSE PMT 1990]

1. Which molecule is not linear [CPMT 1994]  H 

 |  F F
(a) BeF2 (b) BeH 2 (a)  H  P  H  (b)
 |  O
(c) CO2 (d) H 2O  H 
2. The bond angle in water molecule is nearly or O O
Directed bonds in water forms an angle of (c) O  N (d) H  C  C
[NCERT 1980; EAMCET 1981; MNR 1983, 85; OH OH
AIIMS 1982; CPMT 1989; MP PET 1994, 96;
11. Which of the following statement is not correct
MP PET/PMT 1998]
[AIIMS 1983]
(a) 120 o (b) 180 o
(a) Hybridization is the mixing of atomic orbitals
(c) 109 o 28 ' (d) 104 o 30 ' prior to their combining into molecular
3. The central atom in a molecule is in sp 2 hybrid orbitals
state. The shape of molecule will be [MP PMT 1987; (b) sp 2 hybrid orbitals are formed from two
CBSE PMT 1989]
p atomic orbitals and one s atomic orbital
(a) Pyramidal (b) Tetrahedral
(c) Octahedral (d) Trigonal planar (c) d 2 sp 3 hybrid orbitals are directed towards the

4. Which molecule is linear corners of a regular octahedron

 112 Chemical Bonding
(d) dsp 3 hybrid orbitals are all at 90 o to one (a) sp (b) sp 2
another (c) sp 3 (d) sp 2 d
12. The mode of hybridisation of carbon in CO2 is[CPMT 1991]
23. Shape of methane molecule is [MNR 1983]
(a) sp (b) sp 2 (a) Tetrahedral (b) Pyramidal
(c) sp 3 (d) None of these (c) Octahedral (d) Square planer
24. Which one amongst the following possesses an sp
13. In which of the following the central atom does
hybridized carbon in its structure [CBSE PMT 1989]
not use sp 3 hybrid orbitals in its bonding[MNR 1992]
(a) CH 2  C.Cl  CH  CH 2
(a) BeF3  (b) OH 3
(b) C.Cl 2  C.Cl 2

(c) NH 2 (d) NF3 (c) CH 2  C  CH 2
14. XeF2 involves hybridisation [DPMT 1990] (d) CH 2  CH  CH  CH 2
3 3
(a) sp (b) sp d 25. Which of the following is the correct electronic
formula of chlorine molecule [
(c) sp 3 d 2 (d) None of these
.. .. .. ..
15. Which of the following hybridisation results in (a) : Cl : Cl : (b) : Cl  : : Cl  :
.. .. .. ..
non-planar orbitals [CBSE PMT 1991]
.. .. .. ..
(a) sp 3 (b) dsp 2 (c) : Cl : Cl : (d) : Cl : : Cl :

(c) sp 2 (d) sp
26. In XeF4 hybridization is
16. Octahedral molecular shape exists in ..........
hybridisation (a) sp 3 d 2 (b) sp 3
[DPMT 1990] (c) sp 3 d (d) sp 2 d
(a) sp 3 d (b) sp 3 d 2 27. In HCHO , ' C' has hybridization [AIIMS 1987]
3 3
(c) sp d (d) None of these (a) sp (b) sp 2
17. The electronic structure of molecule OF2 is a
(c) sp 3 (d) All the above
hybrid of
28. Which has the shortest C  C bond length
(a) sp (b) sp 2
[NCERT 1982; CPMT 1989]
(c) sp 3 (d) sd 3 (a) C 2 H 5 OH (b) C 2 H 6
3
18. Percentage of s-character in sp hybrid orbital is (c) C 2 H 2 (d) C 2 H 4
(a) 25 (b) 50 29. The hybridization of Ag in the linear complex
(c) 66 (d) 75 Ag NH 3 2  is [CPMT 1985; BHU
19. Shape of XeF4 molecule is 1981]
[BHU 1987; AFMC 1992; CET Pune 1998; (a) dsp 2 (b) sp
Roorkee Qualifying 1998; DCE 2002]
(c) sp 2 (d) sp 3
(a) Linear (b) Pyramidal
(c) Tetrahedral (d) Square planar 30. Experiment shows that H 2 O has a dipole moment

20. For which of the following hybridisation the bond while CO2 has not. Point out the structures which
angle is maximum [CBSE PMT 1991] best illustrate these facts [DPMT 1984; NCERT 1983; CPM
2 O
(a) sp (b) sp
(a) (b) O  C  O ; H  O  H
3 2 O  C  O; H H
(c) sp (d) dsp
(c) C (d) O H
21. The C  H bond distance is the longest in[MNR 1990] ;H–H– || |

(a) C 2 H 2 (b) C 2 H 4 O O O C O ; O  H

(c) C 2 H 4 Br2 (d) C6 H 6 31. Which species do not have sp 3 hybridization

[DPMT 1985]
22. The nature of hybridization in CH 2 Cl  CH 2 Cl for
(a) Ammonia (b) Methane
carbon is
 Chemical Bonding 113
(c) Water (d) Carbon dioxide H
32. As compared to pure atomic orbitals, hybrid (a) OO
orbitals have H
(a) Low energy (b) Same energy (b) H  O  O  H (straight line)
(c) High energy (d) None of these H'
33. The compound 1, 2-butadiene has (c) OO
[IIT 1983; MP PMT 1996] H
(a) Only sp hybridized carbon atoms
Where H  O  O  O  O  H '  101 .5 o and all the
(b) Only sp 2 hybridized carbon atoms four atoms are in the same plane
(c) Both sp and sp 2 hybridized carbon atoms H'
(d) sp, sp 2 3
and sp hybridized carbon atoms (d) OO
H
34. The number of unpaired electrons in O 2 molecule
is Where H  O  O  O  O  H '  97 o and the
[MNR 1983; Kerala PET 2002] angle between H  O  O plane and O  O  H '
(a) 0 (b) 1 plane is 101 o
(c) 2 (d) 3 42. Number of shared electrons in between carbon-
35. In the following molecule, the two carbon atoms carbon atoms in ethylene molecule is
marked by asterisk (*) possess the following type (a) 2 (b) 4
of hybridized orbitals H 3 C  C  C  CH 3 [NCERT 1984]
* * (c) 6 (d) 3
43. The structural formula of a compound is
(a) sp 3 orbital (b) sp 2 orbital
CH 3  CH  C  CH 2 . The type of hybridization at
(c) sp orbital (d) s orbital
the four carbons from left to right are [
36. The bond angle in carbon tetrachloride is
(a) sp 2 , sp, sp 2 , sp 3 (b) sp 2 , sp 3 , sp 2 , sp
approximately
[MNR 1981; MP PMT 1987] (c) sp 3 , sp 2 , sp, sp 2 (d) sp 3 , sp 2 , sp 2 , sp 2
o o
(a) 90 (b) 109 44. Acetate ion contains [AMU 1983]
o
(c) 120 (d) 180 o (a) One C, O single bond and one C, O double
37. When two pairs of electrons are shared, bond is bond
[MNR 1979] (b) Two C, O single bonds
(a) Single covalent bond (b) Double covalent bond (c) Two C, O double bonds
(c) Dative bond (d) Triple bond
(d) None of the above
38. The nature of hybridization in the NH 3 molecule
45. The two carbon atoms in acetylene are
is
[AMU 1984; MADT Bihar 1982]
[EAMCET 1982]
3
(a) sp hybridized (b) sp 2 hybridized
(a) sp (b) sp 2
(c) sp hybridized (d) Unhybridized
(c) sp 3 (d) sp 3 d
46. Among the following compounds which is planar
39. Which one of the following compounds has bond in shape
angle as nearly 90 o [MP PMT 1985] [AMU 1992]
(a) NH 3 (b) H 2 S (a) Methane (b) Acetylene
(c) H 2 O (d) CH 4 (c) Benzene (d) Isobutene
40. In ethene, the bond angle(s) is/are 47. In methane the bond angle is [AMU 1983]
o
[CPMT 1976; AMU 1984; MP PMT 1985] (a) 180 (b)
o o o o
(a) 109 28 ' (b) 120 (c) 120 (d) 109
o 2
(c) 180 (d) Different 48. The angle between sp orbitals in ethylene is
41. Structure formula of H 2 O 2 is [CPMT 1993] [BHU 1987, 95; AMU 1985]
o
(a) 90 (b) 120 o
 114 Chemical Bonding
(c) 180 o (d) 109 . 5 o (c) Two centre bond (d) None of the above
49. The species in which the central atom uses 59. In the compound CH 3 OCl, which type of orbitals
sp 2 hybrid orbitals in its bonding is [IIT 1988] have been used by the circled carbon in bond
formation
(a) PH 3 (b) NH 3
[MP PET 1994]
(c) H 3 C  (d) SbH 3 (a) sp 3
(b) sp 2

50. Carbon atoms in diamond are bonded to each (c) sp (d) p

other in a configuration [CPMT 1981]
60. The correct order of the O  O bond length in
(a) Tetrahedral (b) Planar O 2 , H 2 O 2 and O 3 is [CBSE PMT 1995]
(c) Linear (d) Octahedral
(a) O2  O3  H 2 O2 (b) O3  H 2 O2  O2
51. Which of the following molecules can central
(c) H O  O3  O2 (d) O2  H 2 O2  O3
atom said to adopt sp 2 hybridization [CBSE PMT 1989; MP PET 1994]2 2
61. The structure of PF5 molecule is
(a) BeF2 (b) BCl 3
[AFMC 1995; JIPMER 2001]
(c) C 2 H 2 (d) NH 3
(a) Tetrahedral (b) Trigonal bipyramidal
52. In Cu NH3 4  SO4 , ; Cu has following hybridization (c) Square planar (d) Pentagonal
[AIIMS 1988; UPSEAT 2001] bipyramidal
(a) dsp 2 (b) sp 3 62. Which of the following hybridisation has
2 3 2 maximum s-characters [MP PET 1995]
(c) sp (d) sp d
(a) sp 3 (b) sp 2
53. The hybridization of carbon atoms in C  C single
bond of HC  C  CH  CH 2 is (c) sp[IIT 1991; MP PET 1995]
(d) None of these
63. The PCl5 molecule is a result of the hybridisation
(a) sp 3  sp 3 (b) sp 2  sp 3
of
(c) sp  sp 2 (d) sp 3  sp
[MP PET 1995; DCE 2000; MP PMT 2002]
54. The compound in which C * uses sp 3 hybrids for (a) sp d 2 2
(b) sp 3 d
bond formation is [IIT 1989]
(c) spd 3 (d) sp 2 d 3
 
(a) HCOOH (b) ( NH 2 )2 CO 64. Hybridisation involves [MP PMT 1996]
  (a) Addition of an electron pair
(c) ( NH 3 )3 COH HgCl2 (d) CH 3 CHO
(b) Mixing up of atomic orbitals
55. In diborane, the H  B  H bond angle is 120 o . The (c) Removal of an electron pair
hybridization of boron is likely to be (d) Separation of orbitals
[BHU 1981; CBSE PMT 1999]
65. The geometry of sulphur trioxide molecule is
(a) sp (b) sp 2 (a) Tetrahedral (b) Trigonal planar
(c) sp 3 (d) dsp 2 (c) Pyramidal (d) Square planar
56. The number of shared pairs of electrons in 66. The shapes of BCl 3 , PCl3 and ICl3 molecules are all
propane is (a) Triangular (b) Pyramidal
[BHU 1981] (c) T  shaped (d) All above are
(a) 2 (b) 4 incorrect
(c) 6 (d) 10 67. In benzene molecule all C  C bond lengths are
57. s-character in sp hybridised orbitals are equal because
(a) All carbon atoms are equivalent
1 1
(a) (b)
3 2 (b) All carbon atoms are sp 2 hybridised
1 2 (c) All C  C bonds in benzene, have same order
(c) (d)
4 3 (d) All C  C bonds are single covalent bond
58. The two types of bonds present in B2 H 6 are 68. Which one is false in the following statements
covalent and [MP PET 1997]
[IIT 1994] (a) Each carbon in ethylene is in sp 2
(a) Three centre bond (b) Hydrogen bond hybridisation
 Chemical Bonding 115
(b) Each carbon in acetylene is in sp 3 79. Which one of the following statements is true for
hybridisation ammonium ion [
(a) All bonds are ionic
(c) Each carbon in benzene is in sp 2
hybridisation (b) All bonds are coordinate covalent
(c) H atoms are situated at the corners of a
(d) Each carbon in ethane is in sp 3 hybridisation
square
69. Out of the following hybrid orbitals, the one
(d) H atoms are situated at the corners of a
which forms the bond at angle 120 o , is [MP PMT 1997]
tetrahedron
(a) d 2 sp 3 (b) sp 3 80. The bond angle in sp 2 hybridisation is [RPMT 1997]
(c) sp 2 (d) sp
(a) 180 o (b) 120 o
70. As the p  character increases, the bond angle in
(c) 90 o (d) 109 o 2'
hybrid orbitals formed by s and atomic orbitals[MP PMT 1997]
81. The correct order towards bond angle is[RPMT 1997]
(a) Decreases (b) Increases
(a) sp  sp 2  sp 3
(c) Doubles (d) Remains unchanged
71. sp 3 hybridization leads to which shape of the (b) sp 2  sp  sp 3
molecule (c) sp 3  sp 2  sp
[MP PET/PMT 1998]
(d) Bond angle does not depend on hybridisation
(a) Tetrahedron (b) Octahedron
82. The geometry and the type of hybrid orbital
(c) Linear (d) Plane triangle present about the central atom in BF3 is[IIT 1998; BHU 200
72. Which of the following will be octahedral[MP PET 1999]
(a) Linear, sp (b) Trigonal planar, sp 2
(a) SF6 (b) BF4 
(c) Tetrahedral, sp 3 (d) Pyramidal, sp 3
(c) PCl5 (d) BO 33 
83. In graphite, electrons are [CBSE PMT 1997]
73. The hybrid orbitals used by central atoms in
(a) Localised on every third C atom
BeCl 2 , BCl 3 and CCl4 molecules are respectively[MP PMT 1999]
(b) Present in antibonding orbital
(a) sp 2 , sp 3 and sp (b) sp , sp 2 and sp 3 (c) Localised on each C atom
(c) sp 3 , sp and sp 2 (d) sp 2 , sp and sp 3 (d) Spread out between the structure
74. The structure of H 2 O 2 is[CBSE PMT 1999; AFMC 2003] 84. The ammonium ion is [CET Pune 1998]
(a) Tetrahedral (b) Trigonal pyramidal
(a) Planar (b) Non-planar
(c) Spherical (d) Linear (c) Square planar (d) Square pyramidal

75. Which of the following is isoelectronic as well as 85. In sp hybridisation, shape is [Bihar MEE 1997]
has same structure as that of N 2 O [CPMT 1999] (a) Angular (b) Tetrahedral
(a) N 3 H (b) H 2 O (c) Bipyramidal (d) Linear

(c) NO 2 (d) CO2 (e) None of these

86. When the hybridisation state of carbon atom
76. CCl4 has the hybridisation [DPMT 1996]
changes from sp 3 to sp 2 to sp , the angle between
3 2
(a) sp d (b) dsp the hybridised orbitals
(c) sp (d) sp 3 [AIIMS 1998]

77. Compound having planar symmetry is [DPMT 1996] (a) Decreases gradually (b) Increases gradually
(a) H 2 SO 4 (b) H 2 O (c) Decreases considerably (d) All of these
(c) HNO 3 (d) CCl4 87. The structure and hybridisation of Si(CH 3 )4 is

78. Which of the following compounds is not linear [CBSE PMT 1996]
[CPMT 1996] (a) Bent, sp (b) Trigonal, sp 2
(a) SnCl 2 (b) HCl
(c) Octahedral, sp 3 d (d) Tetrahedral, sp 3
(c) CO2 (d) HgCl2
88. The type of hybridisation of boron in diborane is
 116 Chemical Bonding
[BHU 1999] (a) 1.15, 1.22 and 1.10 Å (b) 1.22, 1.15 and 1.10 Å
2
(a) sp - hybridisation (b) sp - hybridisation (c) 1.10, 1.15 and 1.22 Å (d) 1.15, 1.10 and 1.22 Å
3 3 2
(c) sp - hybridisation (d) sp d - hybridisation 99. Shape of BF3 molecule is [CPMT 2000; Pb. CET

89. Which compound does not possess linear 2002]

geometry (a) Linear (b) Planar
[RPET 1999] (c) Tetrahedral (d) Square pyramidal
(a) CH 2  CH 2 (b) HC  CH 2
100. In the complex [SbF 5 ] , sp 3 d hybridization is
(c) BeCl 2 (d) CO2 present. Geometry of the complex is[Pb. PMT 2000]
90. Which of the following molecule does not show (a) Square (b) Square pyramidal
tetrahedral shape [RPET 1999] (c) Square bipyramidal (d) Tetrahedral
(a) CCl4 (b) SiCl4 101. The bond angle is minimum in
[Pb. PMT 2001; MP PET 2003; UPSEAT 2004]
(c) SF4 (d) CF4
(a) H 2 Te (b) H 2 Se
91. Pyramidal shape would be of [RPET 1999]
(c) H 2 O (d) H 2 S
(a) NO 3 (b) H 2 O
102. The correct order of hybridization of the central
(c) H 3 O  (d) NH 4 atom in the following species NH 3 [PtCl 4 ]2  , PCl 5
92. What is the correct mode of hybridization of the and BCl 3 is
central atom in the following compounds : [IIT Screening 2001; BHU 2005]

NO 2 , SF4 , PF6 (a) dsp , dsp , sp and sp 3 (b) sp 3 , dsp 2 , dsp 3 , sp 2
2 3 2

[AMU 1999] (c) dsp 2 , sp 2 , sp 3 , dsp 3 (d) dsp 2 , sp 3 , sp 2 , dsp 3

2 3 2 3 3 3 2 3 2
(a) sp , sp , d sp (b) sp , sp d , sp d 103. Which of the following pairs has same structure[BHU 2001
3
(c) sp, sp d , sp d 3 2
(d) sp, sp , sp 2 3 (a) PH 3 and BCl 3 (b) SO 2 and NH 3

93. The hybridization in PF3 is [DCE 2000] (c) PCl5 and SF6 (d) NH 4 and SO 42 

(a) sp 3 (b) sp 2 104. The smallest bond angle is found in [AIIMS 2001]
(a) IF7 (b) CH 4
(c) dsp 3 (d) d 2 sp 3
(c) BeF2 (d) BF3
94. Which of the following molecule is linear[MP PMT 2000]
105. Which of the following is not linear [DCE 2001]
(a) SO 2 (b) NO 2
(a) CO2 (b) ClO2
(c) NO 2 (d) SCl 2 (c) I3 (d) None of these
3 2
95. The geometry of the molecule with sp d 106. Which of the following is not tetrahedral[MP PMT 2001]
hybridised central atom is [NCERT 1981; AFMC 1982; RPMT 2000]
(a) SCl 4 (b) SO 42 
(a) Square planar (b) Trigonal bipyramidal
(c) Ni(CO)4 (d) NiCl 42 
(c) Octahedral (d) Square pyramidal
107. As the s-character of hybridisation orbital
96. The bond angle in PH 3 is [RPMT 2000]
increases, the bond angle [BHU 2002; RPMT 2002]
(a) Much less than NH 3 (a) Increases (b) Decreases
(b) Equal to that of NH 3 (c) Becomes zero (d) Does not change
108. The shape of IF7 molecule is
(c) Much greater than NH 3
[AFMC 2002; MHCET 2003]
(d) Slightly greater than NH 3 (a) Octahedral (b) Pentagonal
97. Which of the following has tetrahedral structure bipyramidal
[CPMT 2000] (c) Trigonal bipyramidal (d) Tetrahedral

(a) CO 3 (b) NH  109. A completely filled d orbital (d 10 ) [UPSEAT 2002]

4
(a) Spherically symmetrical
(c) K 4 [Fe(CN )6 ] (d) None of these
(b) Has octahedral symmetry
98. The single, double and triple bond lengths of (c) Has tetrahedral symmetry
carbon in carbon dioxide are respectively[AIIMS 2000] (d) Depends on the atom
 Chemical Bonding 117
110. Which has sp 3 hybridization of central atom (a) H – H bond in H 2 (b) C – C bond in CH4
[UPSEAT 2002] (c) N  N bond in N 2 (d) O  O bond in O 2
(a) PCl3 (b) SO 3
(e) C – C bond in ethane
(c) BF3 (d) NO 3 120. The percentage s-character of the hybrid orbitals
111. In which of the following species is the in methane, ethene and ethyne are respectively[KCET 2003
interatomic bond angle is 109 o 28  [AIEEE 2002] (a) 25, 33, 50 (b) 25, 50, 75

(a) NH 3 , (BF4 )1 (b) ( NH 4 ) , BF 3 (c) 50, 75, 100 (d) 10, 20, 40
121. Arrange the hydra-acids of halogens in increasing
(c) NH 3 , BF4 (d) ( NH 2 )1 , BF3
order of acidity [Orissa JEE 2003]
112. A square planar complex is formed by (a) HF  HCl  HBr  HI (b) HI  HBr  HCl  HF
hybridisation of which atomic orbitals[AIEEE 2002]
(c) HF  HBr  HI  HCl (d) HF  HI  HBr  HCl
(a) s, p x , p y , d yz (b) s, p x , p y , d x 2 y 2
122. Which one has sp  hybridisation
2
[MP PMT 2004]
(c) s, p x , p y , d z 2 (d) s, p y , p z , d xy
(a) CO2 (b) N 2 O
113. In benzene, all the six C – C bonds have the same (c) SO 2 (d) CO
length because of [MP PET 2002]
123. Among the following compounds the one that is
(a) Tautomerism (b) sp 2 hybridisation polar and has central atom with
(c) Isomerism (d) Inductive effect sp 2  hybridization is
114. The bond energies of H  H and Cl – Cl are 430 kJ [MP PMT 2004; IIT 1997]
mol 1 and 242 kJ mol 1 respectively, H t for HCl (a) H 2CO3 (b) BF3
is 91 kJ mol-1. The bond energy of HCl will be [MP PET 2003] (c) SiF (d) HClO2
4
(a) 427 kJ (b) 766 kJ
124. The molecule which is pyramid shape is
(c) 285 kJ (d) 245 kJ [MP PMT 2004; EAMCET 1985; IIT 1989]
115. Which of the following has dsp 2 hybridization (a) PCl3 (b) CO 32 
[MP PET 2003]
(c) SO 3 (d) NO 3
2
(a) NiCl 4 (b) SCl 4
125. Which of the following has a linear structure[MP PMT 2004
(c) NH 4 (d) PtCl 42  (a) CCl4 (b) C2 H 2
116. Which one of the following is a planar molecule (c) SO 2 (d) C2 H 4
[EAMCET 2003]
126. In a regular octahedral molecule, MX 6 , the
(a) NH 3 (b) H 3 O  number X  M  X bonds at 180° is[CBSE PMT 2004]
(c) BCl 3 (d) PCl3 (a) Six (b) Four
117. Which one of the following is a correct set with (c) Three (d) Two
127. sp 3 d 2 hybrid orbitals are
respect to molecule, hybridisation and shape[EAMCET 2003] [MP PET 2004]
2
(a) BeCl 2 , sp , linear (a) Linear bipyramidal (b) Pentagonal
(c) Trigonal bipyramidal (d) Octahedral
(b) BeCl 2 , sp 2 , triangular planar
128. In an octahedral structure, the pair of d orbitals
(c) BCl 3 , sp 2 , triangular planar involved in d 2 sp 3 hybridization is

(d) BCl 3 , sp 3 , tetrahedral (a) d x 2 , d xz (b) d xy , d yz

118. Which of the following compounds doesn’t have (c) d x 2  y 2 , d z 2 (d) d xz , d x 2  y 2

linear structure [RPET 1997, 2003]
129. The correct order of bond angles (smallest first)
(a) CO2 (b) SO 2 in H 2 S , NH 3 , BF3 and SiH4 is [AIEEE 2004]
(c) BeCl 2 (d) C 2 H 2 (a) H 2 S  NH 3  SiH4  BF3
119. Which of the following bonds require the largest (b) NH 3  H 2 S  SiH4  BF3
amount of bond energy to dissociate the atom (c) H 2 S  SiH4  NH 3  BF3
concerned
(d) H 2 S  NH 3  BF3  SiH4
[UPSEAT 2003]
 118 Chemical Bonding
130. Which one of the following has the regular (a) sp 3 d (b) sp 3
tetrahedral structure [AIEEE 2004]
(c) sp 3 d 2 (d) sp 2
(a) BF4 (b) SF4
139. Which of the following molecules has pyramidal
(c) XeF4 (d) Ni(CN )4 2  shape
(Atomic no. : B  5, S  16 , Ni  28 , Xe  54 ) [DCE 2004; J&K CET 2005]

131. The states of hybridazation of boron and oxygen (a) PCl3 (b) SO 3
atoms in boric acid (H 3 BO3 ) are respectively [AIEEE 2004] (c) CO 32  (d) NO 3
(a) sp 3 and sp 2 (b) sp 2 and sp 3 140. The hybrdization of IF7 is [Pb. CET 2001]
2 2 3 3
(c) sp and sp (d) sp and sp (a) sp 3 d 3 (b) sp 2 d
132. The hybridisation in BF3 molecule is [Pb. PMT 2004]
(c) d 2 sp 3 (d) sp 3
2
(a) sp (b) sp
141. In which compound, the hydrogen bonding is the
(c) sp 3 (d) sp 3 d strongest in its liquid phase [Pb. CET 2001]

133. Among the compounds, BF3 , NCl3 , H 2 S , SF4 and (a) HF (b) HI
BeCl 2 , identify the ones in which the central atom (c) CH 4 (d) PH3
has the same type of hybridisation [Kerala of
142. Geometry PMT ammonia
2004] molecule and the
(a) BF3 and NCl3 (b) H 2 S and BeCl 2 hybridization of nitrogen involved in it are[MH CET 2004]
(a) sp 3 -hybridization and tetrahedral geometry
(c) BF3 , NCl3 and H 2 S (d) SF4 and BeCl 2
(b) sp 3 -hybridization and distorted tetrahedral
(e) NCl3 and H 2 S
geometry
134. The molecule of CO2 has 180° bond angle. It can (c) sp 2 -hybridization and triangular geometry
be explanid on the basis of [AFMC 2004]of these
(d) None
3 2 143. Be in BeCl 2 undergoes [MH CET 2004]
(a) sp hybridisation (b) sp hybridisation
(a) Diagonal hybridization
(c) sp hybridisation (d) d 2 sp 3 hybridisation
(b) Trigonal hybridization
135. sp 3 hybridisation is found in (c) Tetrahedral hybridization
[Pb. CET 2003; Orissa JEE 2005] (d) No hybridization
(a) CO 32  (b) BF3 144. Which of the following is non-linear molecule[DCE 2003]
(a) CO3 (b) CO2
(c) NO 3 (d) NH 3
(c) CS 2 (d) BeCl 2
136. Which set hydridisation is correct for the 145. The trigonal bipyramidal geometry results from
following compounds [Pb. CET 2003]
the hybridisation [UPSEAT 2004]
NO2 , SF4 PF6 (a) dsp 3 or sp 3 d (b) dsp 2 or sp 2 d

(a) sp , sp 2 , sp 3 (c) d 2 sp 3 or sp 3 d 2 (d) d 3 sp 2 or d 2 sp 3

(b) sp , sp 3 d , sp 3 d 2 146. The valency of carbon is four. On what principle it

can be explained in a better way
(c) sp 2 , sp 3 , d 2 sp 3 (a) Resonance (b) Hybridization
(d) sp , 3 3
sp d , 2 3
sp d 2 (c) Electron transfer (d) None of the above
147. Hybridization is due to the overlapping of
137. The state of hybridisation of B in BCl3 is
[MADT Bihar 1983]
[Pb. CET 2000; BHU 2004] (a) Orbitals of different energy levels
(a) sp (b) sp 2 (b) Orbitals of different energy content
(c) Orbitals of same energy content
(c) sp 3 (d) sp 2 d 2
(d) None of the above
138. The hybrid state of sulphur in SO 3 molecule is[DCE 2004]
148. If a molecule MX 3 has zero dipole moment, the
sigma bonding orbital used by M are
 Chemical Bonding 119
[IIT 1981; MP PMT 1994; Kerala PMT 2004] 7. The enolic form of acetone contains
(a) sp d  hybrid
3
(b) sp  hybrid [IIT 1990; Bihar MEE 1997]

(c) sp d  hybrid
3 2
(d) sp  hybrid
2 (a) 9 sigma bonds, 1 pi bond and 2 lone pairs
149. The linear structure is assumed by [IIT 1991] (b) 8 sigma bonds, 2 pi bonds and 2 lone pairs
 (c) 10 sigma bonds, 1 pi bond and 1 lone pair
(a) SnCl 2 (b) NCO

(c) CS 2 (d) NO  (d) 9 sigma bonds, 2 pi bonds and 1 lone pair

2
8. Point out incorrect statement about resonance
150. Hybridisation of central atom in NF3 is [Orissa JEE 2005]
[MP PET 1997]
(a) sp 3 (b) sp
(a) Resonance structures should have equal
(c) sp 2 (d) dsp 2 energy
151. The pair having similar geometry is [J&K CET 2005] (b) In resonance structures, the constituent atoms
(a) PCl3 , NH3 (b) BeCl2 , H 2O should be in the same position
(c) CH 4 , CCl4 (d) IF5 , PF5 (c) In resonance structures, there should not be
3 the same number of electron pairs
152. The d-orbital involved in sp d hybridisation is
[J&K CET 2005] (d) Resonance structures should differ only in the
(a) d x 2  y 2 (b) d xy location of electrons around the constituent
atoms
(c) d z 2 (d) d zx
9. The number of possible resonance structures for
`

Resonance CO 32  is
[MP PMT 2000]
1. Which one in the following is not the resonance (a) 2 (b) 3
structure of CO2 (c) 6 (d) 9
(a) O  C  O (b) 
O  C  O 10. Resonance hybrid of nitrate ion is [RPET 2000]
1/ 2 1/ 2 2 / 3
(c) 
O  C  O (d) O  C  O (a) O ........
N ........
O (b) O ........
N ........O 2 / 3
 
2. Which of the following molecule contains one pair  
of non-bonding electrons O 1/ 2 O 2 / 3
(a) CH 4 (b) NH 3 1/ 3

(c) O ........N ........O 1/3 (d) 2 / 3
O ...... N ......
O2 / 3
 
(c) H 2 O (d) HF
 
3. Resonance is due to[NCERT 1981; Kurukshetra CEE 1998] O 1/ 3 O 2 / 3
(a) Delocalization of sigma electrons 11. CO 32  anion has which of the following
(b) Delocalization of pi electrons characteristics
(c) Migration of H atoms [Roorkee 1999]
(d) Migration of protons (a) Bonds of unequal length
4. Resonating structures have different [AMU 1983] (b) sp 2 hybridization of C atom
(a) Atomic arrangements (b)Electronic arrangements (c) Resonance stabilization
(c) Functional groups (d) Alkyl groups (d) Same bond angles

5. In the cyanide ion, the formal negative charge is VSEPR Theory

on
[AMU 1984] 1. The structure of Cu H 2 O 4   ion is
(a) C [NCERT 1983; MP PMT 1983]
(b) N (a) Square planar (b) Tetrahedral
(c) Both C and N (c) Distorted rectangle (d) Octahedral
(d) Resonate between C and N 2. The bond angle in PH 3 would be expected to be
6. Which does not show resonance [CPMT 1990] close to
(a) Benzene (b) Aniline (a) 90 o (b) 105 o

(c) Ethyl amine (d) Toluene (c) 109 o (d) 120 o

 120 Chemical Bonding
3. In which molecule are all atoms coplanar[MP PMT 1994]
14. XeF2 molecule is [BHU 1982]
(a) CH 4 (b) BF3 (a) Linear (b) Triangular planar
(c) PF3 (d) NH 3 (c) Pyramidal (d) Square planar
4. Which has the least bond angle 15. [NCERT
Of the1973;
following sets which one does NOT contain
DPMT 1990; CBSE PMT 1990; UPSEAT 2003] isoelectronic species [AIEEE 2005]
(a) NH 3 (b) BeF2 (a) PO 43  , SO 42  , ClO 4 (b) CN  , N 2 , C 22 
(c) H 2 O (d) CH 4
(c) SO 32  , CO 32  , NO 3 (d) BO 33  , CO 32  , NO 3
5. In compound X , all the bond angles are exactly
16. A molecule which contains unpaired electrons is
109 o 28 ' , X is [CBSE PMT 1991]
[NCERT 1982]
(a) Chloromethane (b) Iodoform (a) Carbon monoxide (b) Molecular nitrogen
(c) Carbon tetrachloride (d) Chloroform
(c) Molecular oxygen (d) Hydrogen peroxide
6. The shape of SO 42  ion is 17. H 2 O is [MADT Bihar 1983]
[CPMT 1982; DPMT 1983, 84, 96; Bihar MEE 1997]
(a) A linear triatomic molecule
(a) Square planar (b) Tetrahedral
(b) A bent (angular) triatomic molecule
(c) Trigonal bipyramidal (d) Hexagonal
7. Which of the following molecules has one lone (c) Both of these
pair of electrons on the central atom (d) None of these
[EAMCET 1980; AMU 1982; MNR 1989] 18. Bond angle between two hybrid orbitals is 105 o .%
(a) H 2 O (b) NH 3 s-orbital character of hybrid orbital is [MP PMT 1986]
(c) CH 4 (d) PCl5 (a) Between 20  21 % (b) Between 19  20 %
8. Of the following compounds, the one having a (c) Between 21  22 % (d) Between 22  23 %
linear structure is[NCERT 1981; CPMT 1991; DPMT 1982; 19. The bond angle between H  O  H in ice is closest
MP PMT 1985; AIIMS 1996]
to
(a) NH 2 (b) CH 4
[CPMT 1989; UPSEAT 2002]
(c) C 2 H 2 (d) H 2 O o
(a) 120 28 ' (b) 60 o
9. XeF6 is
(c) 90 o (d) 105 o
(a) Octahedral (b) Distorted octahedral
20. Which of the following molecules does not have a
(c) Planar (d) Tetrahedral linear arrangement of atoms [
10. Which has maximum bond angle [CPMT 1993]
(a) H (b) C 2 H 2
2S
(a) CHF3 (c) BeH 2 (d) CO2
(b) CHCl 3 21. BCl 3 is a planar molecule while NCl 3 is
(c) CHBr3 pyramidal, because [CBSE PMT 1995]

(d) All have maximum bond angle (a) BCl 3 has no lone pair of electrons but NCl 3 has
11. Of the following species the one having a square a lone pair of electrons
planar structure is [NCERT 1981; MP PMT 1994] (b) B  Cl bond is more polar than N  Cl bond
(a) NH 4 (b) BF 4 (c) Nitrogen atom is smaller than boron atom
(d) N  Cl bond is more covalent than B  Cl bond
(c) XeF4 (d) SCl 4
22. The isoelectronic pair is [AIIMS 2005]
12. In which of the following is the angle between the (a) Cl 2 O, ICl 2 (b) ICl 2 ,ClO 2
two covalent bonds greatest
[NCERT 1975; AMU 1982; MNR 1987; (c) IF2 , I3 (d) ClO 2 , CIF2
IIT 1981; CPMT 1988; MP PMT 1994] 23. According to VSEPR theory, the most probable
(a) CO2 (b) CH 4 shape of the molecule having 4 electron pairs in
the outer shell of the central atom is
(c) NH 3 (d) H 2 O
(a) Linear (b) Tetrahedral
13. As the s-character of hybridized orbital decreases, (c) Hexahedral (d) Octahedral
the bond angle [DPMT 1986] 24. The molecular shapes of SF4 , CF4 and XeF4 are
(a) Decreases (b) Increases [AIEEE 2005]
(c) Does not change (d) Becomes zero
 Chemical Bonding 121
(a) The same with 2, 0 and 1 lone pairs of (a) NO 2 and BaO2 (b) KO2 and AlO 2
electrons on the central atom, respectively
(c) KO2 only (d) BaO2 only
(b) The same with 1, 1 and 1 lone pair of electrons
on the central atoms, respectively 34. True order of bond angle is [RPET 2003]

(c) Different with 0, 1 and 2 lone pairs of (a) H 2 O  H 2 S  H 2 Se  H 2 Te

electrons on the central atom, respectively (b) H 2 Te  H 2 Se  H 2 S  H 2 O
(d) Different with 1, 0 and 2 lone pairs of
(c) H 2 S  H 2 O  H 2 Se  H 2 Te
electrons on the central atom, respectively
25. Which of the following species is planar[JIPMER 1997] (d) H 2 O  H 2 S  H 2 Te  H 2 Se

(a) CO 2 
3 (b) NH 2
35. Which of the following has not a lone pair over
the central atom [Orissa JEE 2003]
(c) PCl3 (d) None of these
(a) NH 3 (b) PH 3
26. The shape of CH 3 species is [RPET 1999]
(c) BF3 (d) PCl3
(a) Tetrahedral (b) Square planar
36. In BrF3 molecule,the lone pairs occupy equatorial
(c) Trigonal planar (d) Linear
positions to minimize [CBSE PMT 2004]
27. Which of the following is the correct reducing
order of bond-angle [BHU 2000] (a) Lone pair- lone pair repuilsion and lone pair-
(a) NH 3  CH 4  C 2 H 2  H 2 O bond pair repulsion
(b) C 2 H 2  NH 3  H 2 O  CH 4 (b) Lone pair- lone pair repulsion only
(c) NH 3  H 2 O  CH 4  C 2 H 2 (c) Lone pair- bond pair repulsion only

(d) H 2 O  NH 3  CH 4  C 2 H 2 (d) Bond pair- bond pair repulsion only

28. Which compound has bond angle nearly to 90  37. H 2 O is dipolar, whereas BeF2 is not. It is because
[Pb. PMT 2001] [CBSE PMT 1989; 2004]
(a) H 2 O (b) H 2 S
(a) H 2 O is linear and BeF2 is angular
(c) NH 3 (d) CH 4
(b) H 2 O is angular and BeF2 is linear
29. A lone pair of electrons in an atom implies [KCET 2002]
(a) A pair of valence electrons not involved in (c) The electornegativity of F is greater than that
bonding of O

(b) A pair of electrons involved in bonding (d) H 2 O involves hydrogen bonding whereas

(c) A pair of electrons BeF2 is a discrete molecule

(d) A pair of valence electrons 38. Maximum bond angle is present in [BVP 2004]
o
30. The bond angle of water is 104 . 5 due to[CPMT 2002] (a) BCl3 (b) BBr3
(a) Repulsion between lone pair and bond pair (c) BF3 (d) Same for all
(b) sp 3 hybridization of O
39. The shape of a molecule of NH 3 , in which central
(c) Bonding of H 2 O
atoms contains lone pair of electron, is [MHCET 2003]
(d) Higher electronegativity of O (a) Tetrahedral (b) Planar trigonal
31. The correct sequence of decrease in the bond (c) Square planar (d) Pyramidal
angle of the following hybrides is [MP PET 2002] 40. The largest bond angle is in [DCE 2002; MNR 1984]
(a) NH 3  PH 3  AsH 3  SbH 3 (a) AsH 3 (b) NH 3
(b) NH 3  AsH 3  PH 3  SbH 3 (c) H 2 O (d) PH3
(c) SbH 3  AsH 3  PH 3  NH 3 41. The bond angle in ammonia molecule is[EAMCET 1980]
(d) PH 3  NH 3  AsH 3  SbH 3 (a) 91 o 8  (b) 93 o 3 '
o
32. Central atom of the following compound has one lone (c) 106 45 ' (d) 109 o 28 '
pair of electrons and three bond pairs of electrons[JIPMER42. Which of the following gives correct arrangement
2002]
(a) H 2 S (b) AlCl3 of compounds involved based on their bond
strength
(c) NH 3 (d) BF3
[BHU 2005]
33. Among KO 2 , AlO 2 , BaO 2 and NO 2 unpaired (a) HF > HCl > HBr > HI
electron is present in [MP PET 2003] (b) HI > HBr > HCl > HF
(c) HF > HBr > HCl > HI
 122 Chemical Bonding
(d) HCl > HF > HBr > HI (a) The difference between the number of
43. Which one has a pyramidal structure[CBSE PMT 1990] electrons in bonding and antibonding orbitals
(a) CH 4 (b) NH 3 (b) Total number of electrons in bonding and
antibonding orbitals
(c) H 2 O (d) CO2
(c) Twice the difference between the number of
44. Among the following the pair in which the two
electrons in bonding and antibonding
species are not isostructural is [CBSE PMT 2004]
electrons
(a) BH 4 and NH 4 (b) PF6 and SF6 (d) Half the difference between the number of
(c) SiF4 and SF4 (d) IO3 and XeO 3 electrons in bonding and antibonding
electrons
45. The maximum number of 90° angles between
9. Oxygen molecule is paramagnetic because
bond pair-bond pair of electrons is observed in [AIEEE 2004]
[NCERT 1984; IIT 1984]
(a) dsp 2 hybridization (b) sp 3 d hybridization (a) Bonding electrons are more than antibonding
(c) dsp 3 hybridization (d) sp 3 d 2 hybridization electrons
(b) Contains unpaired electrons
Molecular orbital theory (c) Bonding electrons are less than antibonding
electrons
1. Bond order is a concept in the molecular orbital (d) Bonding electrons are equal to antibonding
theory. It depends on the number of electrons in electrons
the bonding and antibonding orbitals. Which of 10. Which one is paramagnetic from the following
the following statements is true about it ? The [IIT 1989; CBSE PMT 1995]
bond order [AIIMS 1980] (a) O 2 (b) NO
(a) Can have a negative quantity 
(c) Both (a) and (b) (d) CN
(b) Has always an integral value
11. The bond order in N 2 ion is [Pb. CET 2004]
(c) Can assume any positive or integral or
fractional value including zero (a) 1 (b) 2
(d) Is a non zero quantity (c) 2.5 (d) 3
2. The bond order of NO molecule is [MP PET 1996] 12. Out of the following which has smallest bond
(a) 1 (b) 2 length
[RPMT 1997]
(c) 2.5 (d) 3
3. When two atomic orbitals combine they form (a) O 2 (b) O 2

(a) One molecular orbital (b)Two molecular orbital (c) O 2 (d) O 22 

(c) Three molecular orbital (d)Four molecular orbital13. Which of the following molecule is paramagnetic
4. Which of the following species is the least stable [CPMT 1980; RPET 1999;MP PMT 1999; RPMT 2000]

(a) O 2 (b) O 22 (a) Chlorine (b) Nitrogen

(c) Oxygen (d) Hydrogen
(c) O 21 (d) O 21 14. Which molecule has the highest bond order
5. The bond order is maximum in (a) N 2 (b) Li 2
[AIIMS 1983, 85; CBSE PMT 1994; MP PET 2002] (c) He 2 (d) O 2
(a) O 2 (b) O 21 15. The molecular electronic configuration of H 2 ion
(c) O 21 (d) O 22 is

6. Which of the following compounds of boron does (a)  1s 2

2

(b)  1s   x 1s 
2

not exist in the free form


(c)  1s   x 1s
2

1
(d)  1s 3
(a) BCl 3 (b) BF3
16. The paramagnetic nature of oxygen molecule is
(c) BBr3 (d) BH 3 best explained on the basis of
7. Molecular orbital theory was developed mainly by (a) Valence bond theory (b) Resonance
[BHU 1987; Pb. CET 2003] (c) Molecular orbital theory (d) Hybridization
17. In which case the bond length is minimum
(a) Pauling (b) Pauling and Slater
between carbon and nitrogen
(c) Mulliken (d) Thomson
(a) CH 3 NH 2 (b) C6 H 5 CH  NOH
8. The bond order of a molecule is given by[NCERT 1984]
 Chemical Bonding 123
(c) CH 3 CONH 2 (d) CH 3 CN (a) H 2 O (b) NO 2
18. Which one of the following species is diamagnetic (c) SO 2 (d) CO2
in nature
[AIEEE 2005] 28. The energy of a 2 p orbital except hydrogen atom
(a) He 2 (b) H2 is
[AMU 1983]
(c) H 2 (d) H 2
(a) Less than that of 2 s orbital
19. Which one of the following oxides is expected
(b) More than that of 2 s orbital
exhibit paramagnetic behaviour [CBSE PMT 2005]
(a) CO2 (b) SO 2 (c) Equal to that of 2 s orbital
(c) ClO2 (d) SiO2 (d) Double that of 2 s orbital

20. The bond order in N 2 molecule is 29. In the electronic structure of acetic acid, there are
[CBSE 1995; Pb. PMT 1999; MP PET 1997] [AMU 1983]
(a) 1 (b) 2 (a) 16 shared and 8 unshared electrons
(c) 3 (d) 4 (b) 8 shared and 16 unshared electrons
21. Which one is paramagnetic and has the bond (c) 12 shared and 12 unshared electrons
order 1/2
(d) 18 shared and 6 unshared electrons
[NCERT 1983]
(a) O 2 (b) N 2 30. Which of the following does not exist on the basis
of molecular orbital theory [AFMC 1990; MP PMT
(c) F2 (d) H 2
1996]
22. When two atoms of chlorine combine to form one
(a) H 2 (b) He 2
molecule of chlorine gas, the energy of the
molecule [AMU 1982] (c) He 2 (d) Li 2
(a) Greater than that of separate atoms 31. In P4 O10 , the number of oxygen atoms attached to
(b) Equal to that of separate atoms
each phosphorus atom is [IIT 1995]
(c) Lower than that of separate atoms
(d) None of the above statement is correct (a) 2 (b) 3
23. An atom of an element A has three electrons in its (c) 4 (d) 2.5
outermost shell and that of B has six electrons in 32. Of the following statements which one is correct
the outermost shell. The formula of the compound
(a) Oxygen and nitric oxide molecules are both
between these two will be
paramagnetic because both contain unpaired
[CPMT 1974, 84; RPMT 1999]
electrons
(a) A3 B4 (b) A 2 B3
(b) Oxygen and nitric oxide molecules are both
(c) A3 B 2 (d) A 2 B
diamagnetic because both contain no unpaired
24. The bond order of individual carbon-carbon bonds electrons
in benzene is [IIT 1980] (c) Oxygen is paramagnetic because it contains
(a) One (b) Two unpaired electrons, while nitric oxide is
(c) Between 1 and 2 (d) One and two diamagnetic because it contains no unpaired
alternately electrons
25. PCl5 exists but NCl 5 does not because
(d) Oxygen is diamagnetic because it contains no
[EAMCET 1977; MP PET/PMT 1988]
unpaired electrons, while nitric oxide is
(a) Nitrogen has no vacant d-orbitals
paramagnetic because it contains an unpaired
(b) NCl 5 is unstable
electron
(c) Nitrogen atom is much smaller
33. According to the molecular orbital theory, the
(d) Nitrogen is highly inert
bond order in C 2 molecule is
26. Paramagnetism is exhibited by molecules
[NCERT 1979; MP PET 2002] (a) 0 (b) 1
(a) Not attracted into a magnetic field (c) 2 (d) 3
(b) Containing only paired electrons 34. The molecular orbital configuration of a diatomic
(c) Carrying a positive charge molecule is
(d) Containing unpaired electrons
27. Which one of the following is paramagnetic[DPMT 1985]
 124 Chemical Bonding
  2 py2 (c) Paramagnetism (d) None of these
 1s 2  * 1s 2  2 s 2  * 2 s 2  2 p x2 
  2 pz
2
43. What is correct sequence of bond order [BHU 1997]

Its bond order is (a) O 2  O 2  O 2 (b) O 2  O 2  O 2

(a) 3 (b) 2.5 (c) O 2  O 2  O 2 (d) O 2  O 2  O 2
(c) 2 (d) 1
44. Which bond is strongest [RPMT 1997]
35. The difference in energy between the molecular
(a) F  F (b) Br  F
orbital formed and the combining atomic orbitals
(c) Cl  F (d) I  F
is called
45. Which of the following is not paramagnetic[AIIMS 1997]
(a) Bond energy (b) Activation energy
(c) Stabilization energy (d) Destabilization (a) S 2 (b) N 2 
energy (c) O 2 (d) NO
36. According to molecular orbital theory, the
46. Which one of the following molecules is
paramagnetism of O 2 molecule is due to presence
paramagnetic
of [MP PMT 1997]
[Pb. PMT 1998]
(a) Unpaired electrons in the bonding 
(a) CO2 (b) SO 2
molecular orbital
(c) NO (d) H 2 O
(b) Unpaired electrons in the antibonding
 molecular orbital 47. N 2 and O 2 are converted into monoanions N 2
(c) Unpaired electron in the bonding  molecular and O 2 respectively, which of the following
orbital statements is wrong
(d) Unpaired electrons in the antibonding [CBSE PMT 1997]
 molecular orbital (a) In N 2 , the N  N bond weakens
37. The bond order in O 2 is [MP PET 1999; BHU 2001] (b) In O 2 , the O  O bond order increases
(a) 2 (b) 2.5 (c) In O 2 , bond length increases
(c) 1.5 (d) 3 (d) N 2 becomes diamagnetic
38. Which of the following is paramagnetic[MP PET 1999] 48. With increasing bond order, stability of a bond

(a) O 2 (b) CN [CET Pune 1998]
(a) Remains unaltered (b) Decreases
(c) CO (d) NO 
(c) Increases (d) None of these
39. If N x is the number of bonding orbitals of an atom
49. Which is not paramagnetic [DCE 1999, 2000]
and N y is the number of antibonding orbitals,
(a) O 2 (b) O 2
then the molecule/atom will be stable if[DPMT 1996]
(c) O 22  (d) O 2
(a) N x  N y (b) N x  N y
50. The number of antibonding electron pairs in O 22 
(c) N x  N y (d) N x  N y
molecular ion on the basis of molecular orbital
40. Which of the following molecular orbitals has two theory is
nodal planes [KCET 1996] [Pb. PMT 2000]
(a)  2s (b)  2 p y (a) 4 (b) 3
(c) 2 (d) 5
(c)  * 2 p y (d)  * 2 p x
51. The bond order of He 2 molecule ion is
41. The number of nodal planes ' d ' orbital has[KCET 1996] [Pb. PMT 2000; Pb CET 2001]
(a) Zero (b) One (a) 1 (b) 2
(c) Two (d) Three 1 1
(c) (d)
42. Atomic number of an element is 26. The element 2 4
shows 52. Which one does not exhibit paramagnetism [DPMT 2000]
[CPMT 1996] (a) ClO2 (b) ClO 2
(a) Ferromagnetism (b) Diamagnetism (c) NO 2 (d) NO
 Chemical Bonding 125
53. In which of the following pairs the two molecules (d)  (1s)2  (1s)2  (2 s)2  (2 s)2  (2 p)2  (2 p)2
have identical bond order 64.[MP PMT 2000]
The paramagnetic property of the oxygen
(a) N 2 , O 22  (b) N 2 , O 2 molecule due to the presence of unpaired
(c) N 2 , O 2 (d) O 2 , N 2 electorns present in
[Kerala PMT 2004]
54. The bond order is not three for [MP PMT 2001]
(a) ( 2 p x )1 and ( * 2 p x )1
(a) N 2 (b) O 22 
(b) ( 2 p x )1 and ( 2 p y )1
(c) N 2 (d) NO 
(c) ( * 2 p y )1 and ( * 2 p z )1
55. In H 2 O2 molecule, the angle between the two O –
H planes is (d) ( * 2 p )1 and ( 2 p y )1
[CBSE PMT 2002]
y

(a) 90 o (b) 101 o (e) ( * 2 p z )1 and ( 2 p z )1

(c) 103 o (d) 105 o 65. In PO 43  ion, the formal charge on each oxygen
56. Which of the following molecule has highest bond atom and P  O bond order respectively are[DPMT 2004]
energy (a) 0.75 , 1.25 (b) 0.75 , 1.0
[AIIMS 2002]
(c) 0.75 , 0.6 (d) 3, 1.25
(a) F  F (b) C – C
(c) N – N (d) O – O 66. The bond order in CO 32  ion between C  O is
57. Which of the following species would be expected [Pb. PMT 2004]
paramagnetic [UPSEAT 2002] (a) Zero (b) 0.88
(a) Copper crystals (b) Cu  (c) 1.33 (d) 2

(c) Cu   (d) H 2 67. The bond order of O 2 is the same as in[CPMT 2004]

58. Which of the following is correct for N 2 triple (a) N 2 (b) CN 

bond (c) CO (d) NO 
[CPMT 2002] 68. Bond order of O 2 is [DPMT 2004]
(a) 3s (b) 1p, 2s
(a) 2 (b) 1.5
(c) 2p, 1s (d) 3p
(c) 3 (d) 3.5
59. In which of the following pairs molecules have
69. The total number of electron that takes part in
bond order three and are isoelectronics[MP PET 2003]
forming bonds in N 2 is [MP PET 2004]
(a) CN  , CO (b) NO  , CO 
(a) 2 (b) 4
(c) CN  , O 2 (d) CO, O 2 (c) 6 (d) 10
60. Which of the following is paramagnetic[MP PET 2003] 70. The bond length the species O 2 , O 2 and O 2 are in
(a) O 2 (b) CN  the order of [MP PET 2004]
(c) CO (d) N 2 (a) O 2  O2  O 2 (b) O 2  O 2  O2
61. How many bonding electron pairs are there in
(c) O 2  O 2  O 2 (d) O 2  O 2  O 2
white phosphorous [MP PET 2003]
(a) 6 (b) 12 71. According to molecular orbital theory which of
the following statement about the magnetic
(c) 4 (d) 8
ˆP character and bond order is correct regarding O 2 [IIT JEE
62. The atomicity of phosphorus is X and the PP
(a) Paramagnetic and bond order< O 2
bond angle in the molecule is Y. What are X and Y[EAMCET 2003]
(a) X = 4, Y = 90 o (b) X = 4, Y = 60 o (b) Paramagnetic and bond order> O 2
o o
(c) X = 3, Y = 120 (d) X = 2, Y = 180 (c) Dimagnetic and bond order< O 2
63. From elementary molecular orbital theory we can (d) Dimagnetic and bond order> O 2
give the electronic configuration of the singly
positive nitrogen molecular ion N 2 as 72. The bond order in NO is 2.5 while that in NO  is 3.
[UPSEAT 2003]
Which of the following statements is true for
(a)  (1s)2  (1s)2  (2 s)2  (2 s)2  (2 p)4  (2 p)1 these two species
(b)  (1s)2  (1s)2  (2 s)2  (2 s)2  (2 p)1 (2 p)3 [AIEEE 2004]

2  2 2 
(c)  (1s)  (1s)  (2 s)  (2 p)  (2 p)
2 4 (a) Bond length in NO is equal to that in NO
 126 Chemical Bonding
(b) Bond length in NO is greater than in NO  (e) H 2S

(c) Bond length in NO is greater than in NO Hydrogen bonding
(d) Bond length is unpredictable
73. Which of the following is diamagnetic [BVP 2004] 1. In the following which bond will be responsible
(a) Oxygen molecule (b) Boron molecule for maximun value of hydrogen bond
(a) O  H (b) N  H
(c) N 2 (d) None
(c) S  H (d) F  H
74. Bond energies in NO , NO  and NO  are such as 2. In which of the following hydrogen bond is
[Pb. CET 2004] present
(a) NO   NO  NO  (b) NO  NO   NO  (a) H 2 (b) Ice

(c) NO   NO  NO  (d) NO   NO   NO (c) Sulphur (d) Hydrocarbon

3. In the following which has highest boiling point
75. Which of the following is paramagnetic[UPSEAT 2004]
[MP PMT 1989; RPMT 1997]
(a) B 2 (b) C 2
(a) HI (b) HF
(c) N 2 (d) F2
(c) HBr (d) HCl
76. The paramagnetic molecule at ground state 4. Which contains hydrogen bond [
among the following is [UPSEAT 2004]
(a) HF (b) HCl
(a) H 2 (b) O 2
(c) HBr (d) HI
(c) N 2 (d) CO
5. Contrary to other hydrogen halides, hydrogen
77. Which has the highest bond energy [DCE 2002] fluoride is a liquid because[MP PMT 1990; AMU 1983; EAMC
(a) F2 (b) Cl 2
(a) Size of F atom is small
(c) Br2 (d) I 2
(b) HF is a weak acid
78. In O 2 , O 2 and O 22 molecular species, the total (c) HF molecule are hydrogen bonded
number of antibonding electrons respectively are[DCE 2003](d) Fluorine is highly reactive
(a) 7, 6, 8 (b) 1, 0, 2 6. In the following which species does not contain
(c) 6, 6, 6 (d) 8, 6, 8
sp 3 hybridization [DPMT 1985]
79. Which of the following is not paramagnetic[DCE 2002]
(a) NH 3 (b) CH4
(a) O 2 (b) O 22 
(c) H 2O (d) CO2
(c) O 22  (d) O 2
80. Which of the following species have maximum 7. As a result of sp hybridization, we get [IIT 1984]
number of unpaired electrons [AIIMS
(a) Two 1983]
mutual perpendicular orbitals
(a) O 2 (b) O 2
(b) Two orbitals at 180 o
(c) O 2 (d) O 22  (c) Four orbitals in tetrahedral directions
81. The correct order in which the O – O bond length (d) Three orbitals in the same plane
increases in the following is[BHU 2000; CBSE PMT 2005]
8. The reason for exceptionally high boiling point of
(a) H 2 O2  O2  O3 (b) O2  H 2 O2  O3
water is
(c) O2  O3  H 2 O2 (d) O3  H 2 O2  O2 [DPMT 1986; NCERT 1976; AMU 1984; EAMCET 1979;
82. Correct order of bond length is [Orissa JEE 2005] MP PMT 1993; AIIMS 1996; KCET 2001; CPMT 2003]
(a) CO 32   CO 2  CO (b) CO 2  CO  CO 32  (a) Its high specific heat
(c) CO  CO 2  CO 32  (d) None of these (b) Its high dielectric constant
83. Which of the following is paramagnetic[DPMT 2005] (c) Low ionization of water molecules
(a) N 2 (b) C2 (d) Hydrogen bonding in the molecules of water
(c) N 2 (d) O 22  9. Which concept best explains that o-nitrophenol is
84. Among the following molecules which one have more volatile than p-nitrophenol
smallest bond angle [Orissa JEE 2005] [AIIMS 1980, 82; Kurukshetra CEE 1998; MP PET
(a) NH 3 (b) PH3 2002]

(c) H 2O (d) H 2 Sc (a) Resonance (b) Hyperconjugation

(c) Hydrogen bonding (d) Steric hindrence
 Chemical Bonding 127
10. Which contains strongest H  bond 20. HCl is a gas but HF is a low boiling liquid. This is
[IIT 1986; MP PET 1997, 2003; UPSEAT 2001, 03] because
(a) O  H ..... S (b) S  H ..... O [NCERT 1984; MP PMT 2001]

(c) F  H ..... F (d) F  H ..... O (a) H  F bond is strong

11. Which of the following compound can form (b) H  F bond is weak
hydrogen bonds (c) Molecules aggregate because of hydrogen
[NCERT 1978; MP PMT 1997] bonding
(a) CH 4 (b) NaCl (d) HF is a weak acid
21. The relatively high boiling point of HF is due to
(c) CHCl 3 (d) H 2 O
[NCERT 1984]
12. Of the following hydrides which has the lowest
(a) Hydrogen bonding
boiling point
(b) Covalent bonding
[CBSE PMT 1987]
(c) Unshared electron pair on F
(a) NH 3 (b) PH 3
(d) Being a halogen acid
(c) SbH 3 (d) AsH 3
22. Water is liquid due to [MADT Bihar 1983]
13. The pairs of bases in DNA are held together by (a) Hydrogen bonding (b) Covalent bond
[NCERT 1978; DPMT 1985; CBSE PMT 1992] (c) Ionic bond (d) Vander Waals forces
(a) Hydrogen bonds (b) Ionic bonds 23. The maximum possible number of hydrogen bonds
(c) Phosphate groups (d) Deoxyribose groups in which an H 2 O molecule can participate is
14. Water has high heat of vaporisation due to[AFMC 1982] [MP PMT 1986; MNR 1991; IIT 1992;MP PET 1999]
(a) Covalent bonding (b) H  bonding (a) 1 (b) 2
(c) Ionic bonding (d) None of the above (c) 3 (d) 4
15. In which of the following compounds does 24. Hydrogen bonding is maximum in
hydrogen bonding occur [CBSE PMT 1989] [IIT 1987; MP PMT 1991; MP PET 1993, 2001;

(a) SiH 4 (b) LiH MNR 1995; CPMT 1999; KCET (Med.) 2002]
(a) Ethanol (b) Diethyl ether
(c) HI (d) NH 3
(c) Ethyl chloride (d) Triethyl amine
16. Which among the following compounds does not 25. The hydrogen bond is strongest in
show hydrogen bonding [MP PMT 1989]
[BHU 1987; CBSE PMT 1990, 92]
(a) Chloroform (b) Ethyl alcohol
(a) Water (b) Ammonia
(c) Acetic acid (d) Ethyl ether
(c) Hydrogen fluoride (d) Acetic acid
17. Acetic acid exists as dimer in benzene due to[CPMT 1982]
26. The high boiling point of ethanol (78 .2 o C)
(a) Condensation reaction
compared to dimethyl ether (23 .6 o C) , though both
(b) Hydrogen bonding
having the same molecular formulae C 6 H 6 O , is
(c) Presence of carboxyl group
due to [MP PMT 1993]
(d) Presence of hydrogen atom at   carbon
(a) Hydrogen bonding
18. Which one among the following does not have the (b) Ionic bonding
hydrogen bond [IIT 1983; MP PMT 1994;
(c) Coordinate covalent bonding
UPSEAT 2001]
(d) Resonance
(a) Phenol (b) Liquid NH 3 27. Methanol and ethanol are miscible in water due to
(c) Water (d) Liquid HCl [CPMT 1989]
19. The bond that determines the secondary structure (a) Covalent character
of a protein is [NCERT 1984; MP PET (b) Hydrogen bonding character
1996] (c) Oxygen bonding character
(a) Coordinate bond (b) Covalent bond (d) None of these
(c) Hydrogen bond (d) Ionic bond 28. B.P. of H 2 O (100 o C ) and H 2 S (42 o C ) explained by
 128 Chemical Bonding
(a) Vander Waal's forces (b) Covalent bond 37. Which of the following shows hydrogen bonding
(c) Hydrogen bond (d) Ionic bond [CPMT 2000]
29. Strength of hydrogen bond is intermediate (a) NH 3 (b) P
between
(c) As (d) Sb
[DPMT 1991]
38. The boiling point of a compound is raised by[DPMT 2001]
(a) Vander Waal and covalent
(a) Intramolecular hydrogen bonding
(b) Ionic and covalent
(b) Intermolecular hydrogen bonding
(c) Ionic and metallic
(c) Covalent bonding
(d) Metallic and covalent
(d) Ionic covalent
30. In which of the following compounds
intramolecular hydrogen bond is present[MP PET 1994]39. The boiling point of water is exceptionally high
because
(a) Ethyl alcohol (b) Water
[KCET 2001]
(c) Salicylaldehyde (d) Hydrogen sulphide
(a) Water molecule is linear
31. Hydrogen bonding is formed in compounds
containing hydrogen and [MP PET 1995] (b) Water molecule is not linear
(a) Highly electronegative atoms (c) There is covalent bond between H and O
(b) Highly electropositive atoms (d) Water molecules associate due to hydrogen
(c) Metal atoms with d-orbitals occupied bonding

(d) Metalloids 40. NH 3 has a much higher boiling point than PH 3

32. Which of the following compounds in liquid state because
does not have hydrogen bonding [MP PMT 1996] [UPSEAT 2002; MNR 1994]
(a) H 2 O (b) HF (a) NH 3 has a larger molecular weight

(c) NH 3 (d) C6 H 6 (b) NH 3 undergoes umbrella inversion

33. Compounds showing hydrogen bonding among (c) NH 3 forms hydrogen bond
HF, NH 3 , H 2 S and PH 3 are
(d) NH 3 contains ionic bonds whereas PH 3
(a) Only HF, NH 3 and PH 3 contains covalent bonds
(b) Only HF and NH 3 41. Which one has the highest boiling point[MP PET 2002]
(c) Only NH 3 , H 2 S and PH 3 (a) Acetone (b) Ethyl alcohol

(d) All the four (c) Diethyl ether (d) Chloroform

34. The high density of water compared to ice is due 42. Which of the following compounds has the highest
to boiling point [JIPMER 2002]

[CBSE PMT 1997; BHU 1999; AFMC 2001] (a) HCl (b) HBr
(a) Hydrogen bonding interactions (c) H 2 SO 4 (d) HNO 3
(b) Dipole-dipole interactions 43. Which of the following has minimum melting
(c) Dipole-induced dipole interactions point
(d) Induced dipole-induced dipole interactions [UPSEAT 2003]
35. Ethanol and dimethyl ether form a pair of (a) CsF (b) HCl
functional isomers. The boiling point of ethanol is (c) HF (d) LiF
higher than that of dimethyl ether due to the 44. Hydrogen bond energy is equal to [
presence of [AIIMS 1998]
(a) 3 – 7 cals (b) 30 – 70 cals
(a) Hydrogen bonding in ethanol
(c) 3 – 10 kcals (d) 30 – 70 kcals
(b) Hydrogen bonding in dimethyl ether
45. H 2 O is a liquid while H 2 S is gas due to[BHU 2003]
(c) CH 3 group in ethanol
(a) Covalent bonding
(d) CH 3 group in dimethyl ether
(b) Molecular attraction
36. Which of the following hydrogen bonds are
strongest in vapour phase (c) 1999]
[AMU H – bonding
(a) HF    HF (b) HF    HCl (d) H – bonding and molecular attraction
(c) HCl    HCl (d) HF    HI 46. H – bonding is maximum in [BHU 2003]
 Chemical Bonding 129
(a) C6 H 5 OH (b) C6 H 5 COOH (c) The lack of exchange of valency electrons

(c) CH 3 CH 2 OH (d) CH 3 COCH 3 (d) The exchange energy of mobile electrons

6. Which one of the following substances consists of
47. Select the compound from the following which small discrete molecules [CPMT 1987]
dissolves in water [IIT 1980]
(a) NaCl (b) Graphite
(a) CCl4 (b) CS 2 (c) Copper (d) Dry ice
(c) CHCl 3 (d) C2 H 5 OH 7. Which of the following does not apply to metallic
bond
48. When two ice cubes are pressed over each other,
[CBSE PMT 1989]
they unit to form one cube. Which of the following
(a) Overlapping valency orbitals
force is responsible for holding them together[NCERT 1978]
(b) Mobile valency electrons
(a) Vander Waal's forces
(c) Delocalized electrons
(b) Hydrogen bond formation
(d) Highly directed bonds
(c) Covalent attraction 8. In melting lattice, structure of solid [CPMT 1982]
(d) Dipole–dipole attraction (a) Remains unchanged (b) Changes
49. Which is the weakest among the following types (c) Becomes compact (d) None of the above
of bond 9. Which of the following has the highest melting
[NCERT 1979; MADT Bihar 1984] point
(a) Ionic bond (b) Metallic bond [CPMT 1994]
(a) Pb (b) Diamond
(c) Covalent bond (d) Hydrogen bond
(c) Fe (d) Na
50. H-bond is not present in [BCECE 2005]
10. In the formation of a molecule by an atom[AFMC 1995]
(a) Water (b) Glycerol
(a) Attractive forces operate
(c) Hydrogen fluoride (d) Hydrogen Sulphide
(b) Repulsive forces operate
(c) Both attractive and repulsive forces operate
Types of bonding and Forces in solid
(d) None of these

1. In a crystal cations and anions are held together 11. Which has weakest bond [RPMT 1997]

by (a) Diamond (b) Neon (Solid)

[EAMCET 1982] (c) KCl (d) Ice

12. Which of the following exhibits the weakest
(a) Electrons (b) Electrostatic forces
intermolecular forces [AIIMS 1999; BHU 2000]
(c) Nuclear forces (d) Covalent bonds (a) He (b) HCl
2. In the following metals which one has lowest (c) NH 3 (d) H 2 O
probable interatomic forces [MP PMT 1990]
13. Glycerol has strong intermolecular bonding
(a) Copper (b) Silver therefore it is
(c) Zinc (d) Mercury [RPET 2000]
3. In solid argon, the atoms are held together by (a) Sweet (b) Reactive
[NCERT 1981; MP PET 1995] (c) Explosive (d) Viscous
14. Among the following the weakest one is
(a) Ionic bonds (b) Hydrogen bonds
[Pb. PMT 2004; CPMT 2002]
(c) Vander Waals forces (d) Hydrophobic forces
(a) Metallic bond (b) Ionic bond
4. Which one is the highest melting halide[AIIMS 1980] (c) Van der Waal's force (d) Covalent bond
(a) NaCl (b) NaBr 15. Lattice energy of alkali metal chlorides follows
(c) NaF (d) NaI the order
5. The enhanced force of cohesion in metals is due to [DPMT 2004]

[NCERT 1972] (a) LiCl  NaCl  KCl  RbCl  CsCl

(a) The covalent linkages between atoms (b) CsCl  NaCl  KCl  RbCl  LiCl
(b) The electrovalent linkages between atoms (c) LiCl  CsCl  NaCl  KCl  RbCl
 130 Chemical Bonding
(d) NaCl  LiCl  KCl  RbCl  CsCl (c) 1, 2 and 3 (d) 1, 1 and 3
16. In the following which molecule or ion possesses 24. Covalent molecules are usually held in a crystal
electrovalent, covalent and co-ordinate bond at structure by
the same time [CPMT 1987] [MP PET 1995]
(a) HCl (b) NH 4 (a) Dipole-dipole attraction

(c) Cl  (d) H 2O2 (b) Electrostatic attraction

(c) Hydrogen bonds
17. Both ionic and covalent bond is present in the
following (d) Vander Waal's attraction
[MNR 1986; MP PMT 2004]
(a) CH4 (b) KCl

(c) SO 2 (d) NaOH

18. The formation of a chemical bond is accompanied

by
[MP PET 1995] 1. The values of electronegativity of atoms A and B
(a) Decrease in energy are 1.20 and 4.0 respectively. The percentage of
ionic character of A – B bond is
(b) Increase in energy
(a) 50 % (b) 43 %
(c) Neither increase nor decrease in energy
(c) 55.3 % (d) 72.24%
(d) None of these
19. Chemical bond implies [KCET 2002] 2. O 22  is the symbol of ….. ion [EAMCET 2003]

(a) Attraction (a) Oxide (b) Superoxide

(b) Repulsion (c) Peroxide (d) Monoxide
(c) Neither attraction nor repulsion 3. The number of electrons that are paired in oxygen
(d) Both (a) and (b) molecule is [

20. Which of the following statements is true[AIEEE 2002] (a) 7 (b) 8

(a) HF is less polar than HBr (c) 14 (d) 16
(b) Absolutely pure water does not contain any 4. When N 2 goes to N 2 , the N  N bond distance
ions
..... and when O 2 goes to O 2 , the O  O bond
(c) Chemical bond formation take place when
forces of attraction overcome the forces of distance .......
repulsion [IIT 1996]

(d) In covalency transference of electron takes (a) Decrease, increase (b) Increase, decrease
place (c) Increase, increase (d) None of these
21. Which of the following statements is true about 5. Which of the following contains a coordinate
Cu NH 3 4 SO 4 [CPMT 1988] covalent bond
(a) It has coordinate and covalent bonds [UPSEAT 2001]
(b) It has only coordinate bonds (a) N 2 H 5 (b) BaCl2
(c) It has only electrovalent bonds
(c) HCl (d) H 2 O
(d) It has electrovalent, covalent and coordinate
bonds 6. Which combination is best explained by the co-
ordinate covalent bond[JIPMER 2001; CBSE PMT 1990]
22. Blue vitriol has
(a) Ionic bond (b) Coordinate bond (a) H   H 2 O (b) Cl + Cl

(c) Hydrogen bond (d) All the above 1

(c) Mg  O2 (d) H 2  I2
23. The number of ionic, covalent and coordinate 2
bonds in NH 4 Cl are respectively [MP PMT 1999] 7. Arrange the following compounds in order of
(a) 1, 3 and 1 (b) 1, 3 and 2 increasing dipole moment.

(I) Toluene
(III)
(a) I  IV  II  III
(c) IV  I  III  II
8. The correct order of dipole moment is[Roorkee 1999]
(a) CH 4  NF3  NH 3  H 2 O
(b) NF3  CH 4  NH 3  H 2 O
(c) NH 3  NF3  CH 4  H 2 O
Chemical Bonding 131
(II) m  dichlorobenzene (a) 4 Cr  O bonds are equivalent
o  dichlorobenzene (IV) p (b)
dichlorobenzene
6 Cr  O bonds are equivalent
[IIT 1996]
(c) All Cr  O bonds are equivalent
(b) IV  I  II  III
(d) All Cr  O bonds are non-equivalent
(d) IV  II  I  III
16. Bond length of ethane (I), ethene (II), acetylene
(III) and benzene (IV) follows the order[CPMT 1999]
(a) I  II  III  IV (b) I  II  IV  III
(c) I  IV  II  III (d) III  IV  II  I
17. Hybridisation state of chlorine in ClF3 is [RPET 1999]

(d) H 2 O  NH 3  NF3  CH 4 (a) sp 3 (b) sp 3 d

9. Which of the following has the highest dipole (c) sp 3 d 2 (d) sp 3 d 3
moment 18. Molecular shapes of SF4 , CF4 and XeF4 are
[AIIMS 2002]
[IIT Screening 2000]
H CH 3
| |
(a) The same with 2, 0 and 1 lone pairs of
H
(a) CO (b) C  C electrons respectively
H | |
H (b) The same, with 1, 1 and 1 lone pairs of
CH 3
electrons respectively
CH 3 H Cl CH 3 (c) Different, with 0, 1 and 2 lone pairs of
| | | |
(c) C  C (d) C  C electrons respectively
| | | |
CH 3 H (d) Different, with 1, 0 and 2 lone pairs of
CH 3 Cl
electrons respectively
10. Which of the following arrangement of molecules
19. Structure of IF4 and hybridization of iodine in
is correct on the basis of their dipole moments [AIIMS 2002]
(a) BF3  NF3  NH 3 (b) NF3  BF3  NH 3 this structure are [UPSEAT 2001]
3
(c) NH 3  BF3  NF3 (d) NH 3  NF3  BF3 (a) sp d , Linear

11. The type of hybrid orbitals used by the chlorine (b) sp 3 d 2 , T-shaped
atom in ClO 2 is [IIT 1992] (c) sp 3 d , Irregular tetrahedral

(a) sp 3 (b) sp 2 (d) sp 3 d 2 , Octahedral

(c) sp (d) None of these 20. In which of the following the central atom does
12. Among the following species, identify the not use sp3 hybrid orbitals in its bonding[UPSEAT 2001, 02]

isostructural pairs, NF3 , NO 3 , BF 3 , H 3 O  , HN 3 [IIT 1996] (a) BeF 3 (b) OH 3

(c) NH 2 (d) NF3
(a) [ NF3 , NO 3 ] and [BF 3 , H 3 O  ]
21. The magnetic moment of K 3 [Fe(CN )6 ] is found to
(b) [NF3 , HN 3 ] and [ NO 3 , BF 3 ]
be 1.7 B.M. How many unpaired electron (s) is/are
(c) [ NF3 , H 3 O  ] and [ NO 3 , BF 3 ] present per molecule [Orissa JEE 2003]
(d) [ NF3 , H 3 O  ] and [HN 3 , BF3 ] (a) 1 (b) 2
(c) 3 (d) 4
13. In the compound CH2  CH  CH 2  CH2  C  CH,
22. N 2 and O 2 are converted into monocations N 2
the C2  C3 bond is of the type [IIT 1999]
and O 2 respectively. Which is wrong[CBSE PMT 1997]
(a) sp  sp 2
(b) sp  sp 3 3
(a) In N 2 , the N  N bond weakens
(c) sp  sp 3
(d) sp  sp 2 3
(b) In O 2 , the O  O bond order increases

14. The correct order of increasing C  O bond length (c) In O 2 , paramagnetism decreases
of CO , CO 32  , CO 2 is [IIT 1999] (d) N 2 becomes diamagnetic

(a) CO 32   CO 2  CO (b) CO 2  CO 32   CO 23. The common features among the species CN  , CO

and NO  are [IIT Screening 2001]
(c) CO  CO 32   CO 2 (d) CO  CO 2  CO 32  (a) Bond order three and isoelectronic
(b) Bond order three and weak field ligands
15. In the dichromate dianion [IIT 1999]
 132 Chemical Bonding
(c) Bond order two and -acceptors (d) If the assertion and reason both are false.
(d) Isoelectronic and weak field ligands (e) If assertion is false but reason is true.
24. The number of S – S bonds in sulphur trioxide
trimer S 3O9 is [IIT Screening 2001] 1. Assertion : Water is a good solvent for ionic
(a) Three (b) Two compounds but poor one for
(c) One (d) Zero covalent compounds.
25. Strongest intermolecular hydrogen bond is Reason : Hydration energy of ions releases
present in the following molecules pairs [IIT 1981;sufficient
DCE 2000] energy to overcome
(a) SiH 4 and SiF lattice energy and break hydrogen
bonds in water, while covalent
O
|| bonded compounds interact so
(b) CH 3  C  CH 3 and CHCl 3 weakly that even Vander Wall's
O O forces between molecules of
|| || covalent compounds cannot be
(c) H  C  OH and CH 3  C  OH
broken. [AIIMS 1996]
(d) H 2 O and H 2 O 2
2. Assertion : The atoms in a covalent molecule
26. A compound contains atoms X, Y , Z. The are said to share electrons, yet
oxidation number of X is  2, Y is + 5 and Z is some covalent molecules are polar.
2. Therefore, a possible formula of the Reason : In a polar covalent molecule, the
compound is [CPMT 1988] shared electrons spend more time
(b) X 2 YZ 3 2
on the average near one of the
(a) XYZ 2
atoms. [AIIMS 1996]
(c) X 3 YZ 4 2 (d) X 3 Y 4 Z 2 3. Assertion : Diborane is electron deficient
27. Bonds present in CuSO 4 .5 H 2 O is Reason
[IIT 1983; DCE: 2001]
There are no enough valence
electrons to form the expected
(a) Electrovalent and covalent
number of covalent bonds[AIIMS 2001]
(b) Electrovalent and coordinate
4. Assertion : A resonance hybrid is always more
(c) Electrovalent, covalent and coordinate stable than any of its canonical
(d) Covalent and coordinate structures
28. The ionization of hydrogen atom would give rise Reason : This stability is due to
to delocalization of electrons[AIIMS 1999]
[UPSEAT 2001] 5. Assertion : All F  S  F angle in SF4 greater
(a) Hybrid ion (b) Hydronium ion than 90° but less than 180°

(c) Proton (d) Hydroxyl ion Reason : The lone pair-bond pair repulsion is
weaker than bond pair-bond pair
29. Which can be described as a molecule with
repulsion
residual bonding capacity [JIPMER 2000]
[AIIMS 2004]
(a) BeCl 2 (b) NaCl 6. Assertion : The electronic structure of O 3 is
(c) CH 4 (d) N 2 O
O O
O
Reason : structure is not allowed
O O
because octet around cannot be
expanded.
[IIT 1998]
Read the assertion and reason carefully to mark the
correct option out of the options given below : 7. Assertion : Bond order can assume any value
(a) If both assertion and reason are true and the number including zero
reason is the correct explanation of the assertion. Reason : Higher the bond order, shorter is
(b) If both assertion and reason are true but reason is bond length and greater is bond
not the correct explanation of the assertion. energy
(c) If assertion is true but reason is false. [AIIMS 1999]
 Chemical Bonding 133
8. Assertion : Ortho nitrophenol molecules are electronegativity is the ability of an
associated due to the presence of element to attract electrons
intermolecular hydrogen bonding towards itself in a shared pair of
while paranitrophenol involves electrons.
intramolecular, hydrogen bonding Reason : Electron affinity is a relative
Reason : Ortho nitrophenol is more volatile number and electronegativity is
than the para nitrophenol[AIIMS 1999] experimentally measurable.
9. Assertion : Nitrogen molecule diamagnetic. 21. Assertion : Geometry of SF4 molecule can be
Reason : N2 molecule have unpaired termed as distorted tetrahedron, a
electrons. folded square or see saw.
10. Assertion : Ice is less dense than liquid water. Reason : Four fluorine atoms surround or
Reason : There are vacant spaces between form bond with sulphur molecule.
hydrogen bonded water molecules 22. Assertion : BF3 has greater dipole moment
in ice. than H 2 S .
11. Assertion : Water is liquid but H 2 S is a gas. Reason : Fluorine is more electronegative
Reason : Oxygen is paramagnetic. than sulphur.
12. Assertion : Iodine is more soluble in water then 23. Assertion : The bond between two identical
in carbon tetrachloride. nonmetal atoms has a pair of
Reason : Iodine is a polar compound. electrons with identical spin.
13. Assertion : o and p -nitrophenols can be Reason : Electrons are transferred fully from
separated by steam distillation. one atom to another.
Reason : o -nitrophenol have intramolecular 24. Assertion : B2 molecule is diamagnetic.
hydrogen bonding while p- Reason : The highest occupied molecular
nitrophenol exists as associated orbital is of  type. [AIIMS 2005]

molecules. 25. Assertion : The nearly tetrahedral arrangement

14. Assertion : The fluorine has lower reactivity. of the orbitals about the oxygen
Reason : FF bond has low bond atom allows each water molecule to
dissociation energy. form hydrogen bonds with as many
as four neighbouring water
15. Assertion :  is strong while  is a weak bond.
molecules.
Reason : Atoms rotate freely about  bond.
Reason : In ice each molecule forms four
16. Assertion : The crystal structure gets stabilized
hydrogen bonds as each molecule is
even though the sum of electron
fixed in the space.
gain enthalpy and ionization
26. Assertion : The bond order of helium is always
enthalpy is positive.
zero.
Reason : Energy is absorbed during the
formation of crystal lattice. Reason : The number of electrons in bonding
molecular orbital and antibonding
17. Assertion : Order of lattice energy for same
molecular orbital is equal.
halides are as LiX  NaX  KX .
Reason : Size of alkaline – earth metal
increases from Li to K .
18. Assertion : Born-Haber cycle is based on Hess’s
law.
Reason : Lattice enthalpy can be calculated
by Born- Haber cycle.
Electrovalent bonding
19. Assertion : Bond energy has order like
C C  C  C  C  C . 1 b 2 a 3 a 4 c 5 c
Reason : Bond energy increases with
6 d 7 d 8 b 9 c 10 d
increase in bond order.
11 b 12 a 13 d 14 a 15 a
20. Assertion : Electron affinity refers to an
isolated atom’s attraction for an 16 c 17 b 18 a 19 d 20 c
additional electron while 21 b 22 d 23 a 24 a 25 b
 134 Chemical Bonding
26 d 27 d 28 c 29 a 30 d
31 b 32 b 33 b 34 d 35 b 1 d 2 c 3 b 4 d 5 c

36 a 37 b 38 a 39 a 40 c 6 a 7 b 8 a 9 c 10 b

41 c 42 b 43 d 44 b 45 c 11 d 12 c 13 b 14 b 15 d

46 c 47 a 48 b 49 c 50 b 16 d 17 c 18 b 19 a 20 d

51 b 52 b 53 a 54 a 55 a 21 a 22 c 23 d 24 a 25 b

56 c 57 a 58 c 59 a 60 c 26 b

61 a 62 b 63 d 64 d 65 b
Overlaping -  and - bonds
66 a 67 abc 68 bd

1 c 2 c 3 b 4 b 5 c
Covalent bonding
6 c 7 c 8 b 9 d 10 c
1 c 2 c 3 B 4 b 5 d 11 b 12 c 13 a 14 a 15 d
6 a 7 c 8 a 9 d 10 a 16 a 17 d 18 c 19 d 20 d
11 b 12 b 13 c 14 b 15 c
16 a 17 a 18 c 19 a 20 b Hybridisation
21 a 22 a 23 c 24 c 25 c
1 d 2 d 3 d 4 c 5 d
26 c 27 a 28 a 29 a 30 d
6 a 7 c 8 b 9 d 10 d
31 b 32 a 33 d 34 a 35 d
11 d 12 a 13 a 14 b 15 a
36 b 37 d 38 c 39 d 40 c
16 b 17 c 18 a 19 d 20 b
41 b 42 b 43 b 44 b 45 b
21 c 22 c 23 a 24 c 25 a
46 d 47 d 48 b 49 a 50 a
26 a 27 b 28 c 29 b 30 a
51 b 52 d 53 c 54 d 55 d
31 d 32 a 33 d 34 c 35 c
56 d 57 a 58 a 59 d 60 a
36 b 37 b 38 c 39 b 40 b
61 c 62 a 63 b 64 b 65 b
41 d 42 b 43 c 44 a 45 c
66 b 67 b 68 d 69 b 70 c
46 c 47 d 48 b 49 c 50 a
71 c 72 c 73 cd 74 ad 75 ab
51 b 52 a 53 c 54 c 55 c
76 a
56 d 57 b 58 a 59 b 60 c
Co-ordinate or Dative bonding 61 b 62 c 63 b 64 b 65 b
66 a 67 c 68 b 69 c 70 a
1 d 2 b 3 c 4 d 5 c
71 a 72 a 73 b 74 b 75 d
6 b 7 a 8 d 9 a 10 d
76 d 77 c 78 a 79 d 80 b
11 c 12 a 13 a 14 b 15 c
81 c 82 b 83 d 84 a 85 d

Dipole moment 86 b 87 d 88 c 89 a 90 c
91 c 92 c 93 a 94 b 95 c
1 b 2 d 3 d 4 a 5 c 96 a 97 b 98 b 99 b 100 b
6 c 7 a 8 a 9 c 10 b 101 a 102 b 103 d 104 a 105 b
11 b 12 d 13 b 14 c 15 d 106 a 107 a 108 b 109 b 110 a
16 c 17 c 18 a 19 c 20 b 111 a 112 b 113 b 114 d 115 d
21 d 22 b 23 b 24 b 25 a 116 c 117 c 118 b 119 c 120 a
26 b 27 b 28 b 29 c 30 a 121 a 122 c 123 a 124 a 125 b
31 a 32 c 33 a 34 bd 35 a 126 c 127 d 128 c 129 c 130 a
131 b 132 b 133 e 134 c 135 d
Polarisation and Fajan’s rule 136 b 137 b 138 d 139 a 140 a
 Chemical Bonding 135
141 a 142 b 143 a 144 a 145 a 6 d 7 b 8 d 9 c 10 c
146 b 147 c 148 d 149 bcd 150 a 11 d 12 b 13 a 14 b 15 d
151 ac 152 a 16 d 17 b 18 d 19 c 20 c
21 a 22 a 23 d 24 a 25 c
Resonance 26 a 27 b 28 c 29 a 30 c
31 a 32 b 33 d 34 a 35 a
1 d 2 b 3 b 4 b 5 b
36 a 37 a 38 b 39 d 40 c
6 c 7 a 8 c 9 b 10 c
41 a 42 c 43 b 44 c 45 c
11 abcd
46 b 47 d 48 b 49 d 50 d

VSEPR Theory Types of bonding and Forces in solid

1 a 2 a 3 b 4 c 5 c 1 b 2 d 3 c 4 c 5 d
6 b 7 b 8 c 9 b 10 a 6 d 7 d 8 b 9 b 10 c
11 c 12 a 13 a 14 a 15 c 11 d 12 a 13 d 14 c 15 a
16 c 17 b 18 d 19 d 20 a 16 b 17 d 18 a 19 d 20 c
21 a 22 d 23 b 24 d 25 a 21 d 22 d 23 a 24 d
26 c 27 b 28 b 29 a 30 a
31 a 32 c 33 c 34 a 35 c Critical Thinking Question
36 b 37 b 38 d 39 d 40 b
41 c 42 a 43 b 44 c 45 d 1 d 2 c 3 c 4 b 5 a
6 a 7 b 8 a 9 a 10 d

Molecular orbital theory 11 a 12 c 13 d 14 d 15 b

16 c 17 b 18 d 19 c 20 a
1 a 2 c 3 b 4 b 5 c 21 a 22 d 23 a 24 d 25 c
6 d 7 c 8 b 9 c 10 b 26 c 27 c 28 c 29 a
11 c 12 b 13 c 14 a 15 c
16 c 17 d 18 b 19 c 20 c Assertion & Reason
21 d 22 c 23 b 24 c 25 a
1 a 2 a 3 a 4 a 5 c
26 d 27 b 28 b 29 a 30 c
6 b 7 b 8 e 9 c 10 a
31 c 32 a 33 c 34 a 35 c
11 b 12 d 13 a 14 e 15 c
36 d 37 b 38 a 39 a 40 c
16 c 17 c 18 b 19 a 20 c
41 c 42 a 43 b 44 a 45 a
21 b 22 e 23 d 24 d 25 a
46 c 47 b 48 c 49 c 50 a
26 a
51 c 52 b 53 a 54 a 55 a
56 c 57 c 58 c 59 a 60 a
61 a 62 b 63 a 64 c 65 a
66 c 67 a 68 a 69 c 70 a
71 b 72 b 73 d 74 c 75 a
76 b 77 b 78 a 79 c 80 a
81 c 82 a 83 c 84 d

Hydrogen bonding

1 d 2 b 3 b 4 a 5 c
 Chemical Bonding 133
18. (a) Electrovalent compounds generally have high
m.pt and high b.pt due to stronger coulombic
forces of attractions.
19. (d) Water is a polar solvent so it decreases the
interionic attraction in the crystal lattice due
to solvation.
Electrovalent bonding
20. (c) Element C has electronic structure 1s 2 , 2 s 2 2 p 5 ,
1. (b) NaCl is ionic crystal so it is formed by Na  it requires only one electron to complete its
and Cl  ions. octet and it will form anion so it will form
electrovalent bond.
2. (a) Bond formation is always exothermic.
21. (b) Since the chloride of a metal is MCl 2
Compounds of sodium are ionic.
3. (a) According to Fajan’s rule ionic character is therefore metal ‘M’ must be divalent i.e. M 2  .
less. As a result the formula of its phosphate is
M 3 (PO4 )2 .
4. (c) Valencies of L, Q, P and R is – 2, – 1, + 1 and +
2 respectively so they will form P2 L, RL, PQ 22. (d) In MPO4 the oxidation state of M is +3.

and RQ 2 . Hence, the formula of nitrate is M( NO3 )3 .

23. (a) Ion is formed by gaining or losing electrons.
5. (c) Electrovalent compounds are good conductor
To form cation electron are lost from the
of heat and electricity in molten state or in
aqueous solution. valency shell, so Zn atoms to Zn   ions there
is a decrease in the no. of valency electron.
7. (d) Electrovalent bond formation depends on
24. (a) M 3 (PO4 )2 means M is divalent so formula of
ionization energy of cation, electron affinity
of anion and on lattice energy. its sulphate is MSO 4 .

8. (b) Because CsF is electrovalent compound.
9. (c) NaCl is formed by electrovalent bonding.
10. (d) Valency of metal is + 2 by formula MO so its
phosphate would be M 3 (PO4 )2 because valency
of [PO4 ] is – 3.
11. (b) Li, Na and K are alkali metals with low
ionization energy and one electron in their
outermost shell so they will form cation
easily.
12. (a) Melting point and boiling point of
electrovalent compounds are high due to
strong electrostatic force of attraction
between the ions.
13. (d) The value of lattice energy depends on the
charges present on the two ions and distance
between them. It shell be high if charges are
high and ionic radii are small.
14. (a) Cs is more electropositive.
15. (a) X loses electron, Y gains it.
 
16. (c) Formation of NaCl occurs by Na ion and Cl ion .
17. (b) MgCl2 has electrovalent linkage because
magnesium is electropositive metal while
chlorine is electronegative.
25. (b) As the molecular formula of chloride of a
metal M is MCl3 , it is trivalent so formula of
its carbonate will be M 2 (CO3 )3 .
26. (d) Sodium chloride is electrovalent compound so
it dissolves in water which is a polar solvent.
27. (d) When sodium chloride is dissolved in water,
the sodium ion is hydrated.
30. (d) Yet the formula of sulphate of a metal (M) is
M 2 (SO 4 )3 , it is M 3  ion so formula of its
phosphate would be MPO4 .
32. (b) Molten sodium chloride conducts electricity
due to the presence of free ions.
33. (b) The phosphate of a metal has the formula
MHPO4 it means metal is divalent so its
chloride would be MCl2 .
34. (d)
35. (b) Cs is highly electropositive while F is highly
electronegative so they will form ionic bond.
37. (b) Na is highly electropositive while Cl is highly
electronegative so they will form ionic bond.
38. (a) Ionic compounds are good conductors of heat
and electricity so they are good electrolyte.
39. (a) Metal tends to lose electrons due to low
ionization energy.
40. (c) As the formula of calcium pyrophosphate is
Ca2 P2 O7 means valency of pyrophosphate
 134 Chemical Bonding
radical is – 4 so formula of ferric 67. (abc) CaH2 , BaH2 , SrH 2 are ionic hydride.
pyrophosphate is Fe4 P2 O7 3 . 68. (bcd) Generally are ionic
MgCl2 , SrCl 2 , BaCl2
41. (c) M  X bond is a strongest bond so between compounds so they conduct electricity in
Na  Cl is a strongest bond. fused state.
42. (b) The solubility order is :
BeF2  MgF2  CaF2  SrF2 so SrF2 is least Covalent bonding
soluble.
2. (c) In N2 molecule each Nitrogen atom
43. (d) NaF has maximum melting point, melting

point decreases of sodium halide with contribute 3 e so total no. of electron’s are 6.
increase in size of halide their bond energy 3. (b) Non-metals readily form diatomic molecules
get lower. by sharing of electrons. Element
44. (b) Sulphanilic acids have bipolar structure so M (1 s 2 2 s 2 2 p 5 ) has seven electrons in its
their melting point is high and insoluble in valence shell and thus needs one more
organic solvents. electron to complete its octet. Therefore, two
45. (c) CaCl2 will have electrovalent bonding because atoms share one electron each to form a
calcium is electropositive metal while chlorine diatomic molecule (M 2 )
is electronegative so they will combined with
.. .. .. ..
electrovalent bond. : M ..M :  : M : M :
47. (a) Electrovalent bond is formed by losing .. .. .. ..
electrons from one atom and gaining electron 5. (d) Covalent character depend on the size of
by other atom i.e. redox reaction. cation and anion.
48. (b) Electrovalent compound are polar in nature
6. (a) In graphite all carbon atoms are sp 2 -
because they are formed by ions.
hybridised and have covalent bond.
50. (b) CsCl has ionic bonding.
7. (c) Silica has tendency to form long chain
51. (b) As soon as the electronegativity increases,
covalent structure such as carbon so it has
ionic bond strength increases.
giant covalent structure.
52. (b) This X element is a second group element so
its chloride will be XCl2 .
8. (a) All have linear structure.
O = C = O, Cl – Hg – Cl, HC  CH
53. (a) When electronegativity difference is from 1.7
to 3.0. This bond is called as ionic bond. 9. (d) Similar atoms form covalent bond.
54. (a) Ethyl chloride is an organic compound so it 10. (a) Covalent bond forms when electronegativity
will be covalent. difference of two atom is equal to 1.7 or less
55. (a) Lithium oxide and calcium fluoride show ionic than 1.7
characters. 11. (b) Similar atoms form covalent bond.
57. (a) Generally cation and anion form ionic bond. 12. (b) Water is a polar solvent while covalent
58. (c) Those atoms which contain +ve and –ve sign compounds are non-polar so they usually
are known as ion. insoluble in water.
59. (a) Generally Br-F contain maximum 13. (c) BCl 3 is electron deficient compound because
electronegativity difference compare to other it has only ‘6’ electrons after forming bond.
compound. 14. (b) Due to its small size and 2 electrons in s-
61. (a) Due to greater electronegativity difference. orbital Be forms covalent compound.
3d 4s 18. (c) H 2 O will formed by covalent bonding.
3
62. (b) Co  3d 4 s ,
6 0
21. (a) Two identical atoms are joined with covalent
bond so H 2 will be covalent.
4s
23. (c) Element ‘X’ has atomic no. 7 so its electronic
Ni 4   3d 6 4 s 0 , configuration will be 2, 5. So its electron dot
64. (d) BaCl2 contain higher ionic character. .
symbol would be : X .
66. (a) Electrolytes are compound which get .
dissociated into their ion in water so it 24. (c) C-S will be most covalent. Covalent character
contains electrovalent bond. depend on the size of cation and anion.
 Chemical Bonding 135
25. (c) HCl has ionic character yet it has covalent 49. (a) PCl5 does not follow octet rule, it has 10
compound because electronegativity of electrons in its valence shell.
chlorine is greater than that of hydrogen. 50. (a) The compound will be A2 B3 (By criss cross
26. (c) Order of polarising power Be    Li   Na  rule).
Hence order of covalent character 51. (b) Each nitrogen share 3 electrons to form triple
BeCl 2  LiCl  NaCl . bond.
31. (b) Valency of phosphorus in H 3 PO4 is supposed 52. (d) Urea solution does not conduct electricity
‘x’ then 3  x  8  0 , x  5  0 , x  5 . because it is a covalent compound.
33. (d) (1)  x  3(2)  0  1  x  6  0  x  6  1  5 . 54. (d) Due to the small size and higher ionization
energy, boron forms covalent compound.
34. (a) HCl molecule has covalent bond.
58. (a) BF3 contain 6 electron so it is lewis acid.
35. (d) Electrovalent compounds have high melting
point and high boiling point. 59. (d) Among the given species. The bond
dissociation energy of C  O bond is minimum
36. (b) Middle length of H 2  74 pm
in case of CO 32  by which C  O bond become
74
Length of H   37 pm more weaker in CO 32  or the bond order of
2
Middle length of Cl2  198 pm CO 32  (1.33) is minimum so the bond become
weaker.
198
Length of Cl   99 pm 60. (a) Valency of Na2 S 2 O3 is supposed to be x, then
2
Bond length of HCl = Length of H + Length of 2  2 x  ( 6)  0 , 2 x  4  0 , x  2 .
Cl O O
|| ||
= 37 + 99 = 136 pm 61. (c) H  O  S  O  O  S  O  H (Marshall acid)
|| ||
254 O O
37. (d) Compound has 254 gm of I 2 means 2
127 62. (a) Among the given choice Al is least
80 electropositive therefore, the bond between Al
mole, while 80 gm O 2 means  5 mole so
16 and Cl will be least ionic or most covalent or
they will form compound I2 O5 . the difference in electronegativeity of two
38. (c) NH 4 Cl has covalent as well as ionic bond. atom is less than 1.8.
63. (b) Electronic configuration of
 H 
 |  16 S
32
 1s 2 ,2 s 2 ,2 p 6 ,3 s 2 ,3 p 4 . In the last orbit it has
H  N  H   Cl 
  only 6 electron. So it require 2 electron to
|
  complete its octet, therefore it share 2
 H 
electron with two hydrogen atom and forms 2
39. (d) Covalent character increases when we come
covalent bond with it.
down a group so CaI2 will have highest
64. (b) The acidity of hydrides of VI group elements
covalent character.
increase from top to bottom as the bond
41. (b) In water molecule three atom are linked by strength X  H decrease from top to bottom
covalent bond.
H 2 O  H 2 S  H 2 Se  H 2 Te
O
Structure is 65. (b) We know that Al 3 cation is smaller than Na 
H H
(because of greater nuclear change) According
..
42. (b) : N  N   O : or N  N  O. to Fajan's rule, small cation polarise anion
..
upto greater extent. Hence Al 3  polarise Cl 
44. (b) The electronic configuration of Na (Z  11) is
ion upto greater extent, therefore AlCl3 has
1 s 2 , 2 s 2 2 p 6 , 3 s 1 . The oxide of Na is Na2 O . covalent bond between Al and Cl atoms.
45. (b) Covalent bond is directional. 66. (b) Sulphur has the second highest catenation
47. (d) Bond dissociation energy decreases with property after carbon. Its molecule has eight
increase in size. So D is smallest. atom bonded together (i.e. S 8 )
48. (b) Molecule X is nitrogen because nitrogen 67. (b) H 2 O2 has open book structure.
molecule has triple bond. It’s configuration O
2 2 3 H
will be 1s , 2 s 2 p .
O
H
 136 Chemical Bonding
7. (a) Structure of N 2 O5 is O  N  O  N  O .
 
O O
69. (b) The electronic configuration of nitrogen is 9. (a) SO 32  has one coordinate bond.  O  S  O 


7 N  1s 2 ,2 s 2 ,2 p 3 O
10. (d) Co-ordinate bond is a special type of covalent
It has 5 electrons in valency shell, hence in
bond which is formed by sharing of electrons
ammonia molecule it complete its octet by between two atoms, where both the electrons
sharing of three electron with three H atom, of the shared pair are contributed by one
therefore it has 8 electrons in its valence shell atom. Since this type of sharing of electrons
in ammonia molecule exits in O3 , SO 3 and H 2 SO 4 . Therefore all
.. .. these contains coordinate bond.
H  N  H or H  N  H 
| 12. (a) CH 3 N  C contain dative bond.
.
 H 13. (a) H 3 PO4 is orthophosphoric acid.
H
O
71. (c) Multiple bonds have more bond energy so 
C  N will be the strongest. H O  PO  H
|
72. (c) Diamond, silicon and quartz molecule bounded O
|
by covalent bond.
H
73. (cd) C2 H 4 and N 2 has 15. (c) Sulphuric acid contain, covalent and co-
multiple bonds. ordinate bond.
74. (ad) CO has only 6 electrons
while PCl5 has 10 electrons after sharing so Dipole moment
both don’t follow octet rule.
1. (b) CO2 is a symmetrical molecule so its dipole
76. (a) Among these, NaH and CaH2 are ionic
moment is zero.
hydrides and B2 H 6 and NH 3 are covalent
2. (d) These all have zero dipole moment.
hydrides. 3. (d) HF has largest dipole moment because
electronegativity difference of both is high so it
Co-ordinate or Dative bonding is highly polar.
5. (c) Due to its symmetrical structure.
1. (d) 6. (c) Chloroform has 3 chlorine atom and one
– F F
hydrogen atom attached to the carbon so it is
Cl polarised and it will show dipole moment.
Xe
8. (a) The dipole moment of two dipoles inclined at
O an angle  is given by the equation
O F F
O
  X 2  Y 2  2 XY cos
F
cos 90   0 . Since the angle increases from
F
90  180 , the value of cos becomes more and
I more – ve and hence resultant decreases.
S F
Thus, dipole moment is maximum when
I   90  .
F 9. (c) Due to distorted tetrahedral geometry SF4 has
2. (b) H 2 SO 4 has co-ordinate covalent bond. permanent dipole moment F
F
O
 : S
H O  SO H F

F
O
3. (c) NH 3 has lone pair of electron while BF3 is 10. (b) CCl4 has no net dipole moment because of its
electron deficient compound so they form a regular tetrahedral structure.
co-ordinate bond. NF3  BF3
12. (d) H-F is polar due to difference of
4. (d) HNO 2 does not have co-ordinate bond. electronegativity of hydrogen and fluorine so
Structure is H  O  N  O . it shows positive dipole moment.
 Chemical Bonding 137
14. (c) BCl3 has zero dipole moment because of its 1 . 03
  100  16 . 83 %  17 %
trigonal planar geometry. 6 . 12

16. (c) Dipole moment of CH 3 OH is maximum in it. Polarisation and Fajan's rule
20. (b) CH 4 have regular tetrahedron so its dipole
1. (d) BF3 is planar while NF3 is pyramidal due to
moment is zero.
the presence of lone pair of electron on
22. (b) Ammonia have some dipole moment.
nitrogen in NF3 .
23. (b) Charge of e   1 .6  10 19
2. (c) H 2 O is a polar molecule due to
Dipole moment of HBr  1.6  10 30 electronegativity difference of hydrogen and
Inter atomic spacing  1 Å  1  10 10 m oxygen.
% of ionic character in 3. (b) When electronegativity difference is more
dipole moment of HBr  100 between two joined atoms then covalent bond
HBr  becomes polar and electron pair forming a
inter spacing distance q
bond don’t remain in the centre.
1.6  10 30
  100 4. (d) Hexane has symmetrical structure so does not
1.6  10 19  10 10 have polarity.
 10 30  10 29  100  10 1  100  0.1  100  10 % 5. (c) When two identical atoms form a bond, bond
25. (a) Carbon tetrachloride has a zero dipole is non-polar.
moment because of its regular tetrahedral 6. (a) According to Fajan’s rule, polarisation of
structure. anion is influenced by charge and size of
27. (b) BF3 has zero dipole moment. cation more is the charge on cation, more is
polarisation of anion.
29. (c) Given ionic charge  4.8  10 10 e.s.u. and ionic
8. (a) When two atoms shares two electrons it is an
distance  1 A  10 8 cm we know that dipole
example of covalent bond. This covalent bond
moment = ionic charge × ionic distance  4 .8  10 10  10 8 may be polar or may be non-polar depends on
 4 .8  10 8 e.s.u. per cm  4 . 8 debye. the electronegativity difference. In given
example formula is AB. So it is polar.
30. (a) Higher is the difference in electronegativity of
two covalently bonded atoms, higher is the 9. (c) HCl is most polar due to high electronegativity
polarity. In HCl there is high difference in the of Cl.
electronegativity of H and Cl atom so it is a 10. (b) NH 3 has sp 3 hybridised central atom so it is
polar compound.
non planar.
31. (a) Linear molecular has zero dipole moment CO2
11. (d) p-dichloro benzene have highest melting
has linear structure so it does not have the point.
dipole moment O  C  O .
13. (b) NH4 Cl has both types of bonds polar and non
32. (c) SF6 is symmetrical and hence non polar
polar
because its net dipole moment is zero.

33. (a) Polarity create due to the difference in  H 
 | 
electronegativity of both atom in a molecule H  N  H  Cl 
except H 2 all other molecule have the  |

 H 
different atom so they will have the polarity
while H 2 will be non polar. 14. (b) Greater the charge of cation more will be its
polarising power (according to Fajan’s rule).
34. (bd) cis isomer shows dipole moment
15. (d) AlI3 Aluminiumtriiodide shows covalent
while that of trans is zero or very low
value. Trans 1, 2 di-chloro-2-pentene will character. According to Fajan’s rule.
also show dipole moment due to 16. (d) As the size of anion increases, polarity
unsymmetry. character increases.
35. (a) % of ionic character 20. (d) Due to the electronegativity difference.
Experiment al value of dipole moment
= 21. (a) We know that greater the difference in
Expected value of dipole moment
electronegativity of two atoms forming a
 138 Chemical Bonding
covalent bond. More is its polar nature. In HF 20. (d) Structure of P4 O10 is
there is a much difference in the O
electronegatives of hydrogen and flourine.
P
Therefore (HF) is a polar compound.
O O
22. (c) Silicon tetrafloride has a centre of symmetry.
O
23. (d) BF3 have zero dipole moment. O P P O
O
25. (b) According to Fajan’s rule largest cation and
smallest anion form ionic bond. O O
26. (b) Polarity character is due to the difference in P

electronegativity of two atoms or molecule.

O
Overlaping-  and - bonds
Each phosphorus is attached to 4 oxygen
  atoms.
1. (c)
H– C– Hybridisation
C H

1. (d) H 2 O is not linear because oxygen is sp 3
2. (c) In fluorine molecule formation p-p orbitals
take part in bond formation. hybridised in H 2 O .
3. (b) -bond is formed by lateral overlapping of 2. (d) O
unhybridised p-p orbitals. 95.7 pm
(104.5)o
C
H H
4. (b) Ca 1 and 2
C 4. (c) CO2 has sp – hybridization and is linear.
5. (c) In a double bond connecting two atom sharing 1
of 4 electrons take place as in H 2 C  CH 2 . 5. (d) No. of e– pair  3  [3  3] =0
2
6. (c) C  C is a multiple bond so it is strongest. F
No. of e– pair  3 +0 120°
9. (d) As the bond order increases, C  H bond
F B 120°
energy also increases so it will be greatest in
acetylene because its B.O. is 3. 120° F
H H
| |
11. (b) H  C  C  C  C No. of atom bonded to the central atom  3
|
In case of 3, 3 geometry is Trigonal planar.
  H
6. (a) In sp 3 –hybridisation each sp 3 hybridised
16. (a) N N orbital has 1/4 s-character.
 8. (b) In ethylene both Carbon atoms are sp 2 -
17. (d) We know that trisilylamine is sp 2 –hybridized
hybridised so 120 o .
therefore p  d bonding is possible due to
9. (d) Structure of sp 3 d hybridized compound is
the availability of vacant d-orbitals with
silicon. Trigonal bipyramidal.
O
18. (c) ||
10. (d) In H  C  C  O  H the asterisked carbon has a
*
S
2, 2 bond and one lone pair. valency of 5 and hence this formula is not
.. .. correct.
:O :O
11. (d) dsp 3 hybrid orbitals have bond angles
.. ..
(d) : O  S  O : 5 atoms has 12 electrons in its
o o
19. 120 , 90 .
||

O: 13. (a) In BeF 3 , Be is not sp 3 –hybridised it is sp 2

..
outermost shell. One (S  O) bond will be (p- hybridised.
p)  bond while two (S  O) bond will be (p-d) 17. (c) In molecule OF2 oxygen is sp 3 hybridised.
 bond.
 Chemical Bonding 139
18. (a) In sp 3 hybrid orbitals s-character is 1/4th 46. (c) Benzene has all carbons sp 2 hybridised and
means 25%. planar in shape.
19. (d) XeF4 molecule has ‘Xe’ sp 3 d 2 hybridised and 47. (d) In methane C is sp 3 hybridized and bond
its shape is square planar. angle is 109 . o

20. (b) The bond angle is maximum for sp

H H H
hybridisation because two sp hybridised | | |
56. (d) H  C  C  C  H
orbitals lies at angle of 180 o . | | |

21. (c) C2 H 4 Br2 has all single bonds so C  H bond H H H

distance is the largest. There are 10 shared pairs of electrons.

23. (a) In methane molecule C is sp hybridised so its 3 58. (a) The diborane molecule has two types of B – H
shape will be tetrahedral. bond :
3 2 1 (i) B  H t – It is a normal covalent bond.
24. (c) In compound CH 2  C  CH 2 the second carbon
(ii) B  H b – It is a three centred bond.
sp-hybridised.
.. .. Hb
25. (a) : Cl   Cl : is the correct electronic formula of Ht Ht
.. ..
Cl2 molecule because each chlorine has 7 B B
Ht
electrons in its valence shell. Ht
Hb
26. (a) XeF4 has sp 3 d 2 hybridisation, its shape is
61. (b) PF5 involves sp 3 d hybridization and hence
square planar.
has trigonal bipyramidal structure.
27. (b) In HCHO, carbon is sp 2 hybridized
1
H 62. (c) s-character in sp   100  50 %
| 2
H  C2  O
sp 1
s-character in sp 2   100  33 .3 %
28. (c) Because of the triple bond, the carbon-carbon 3
bond distance in ethyne is shortest. 1
s-character in sp 3   100  25 %
29. (b) The hybridisation of Ag in complex 4
[ Ag ( NH 3 )2 ] will be sp because it is a Linear Hence, maximum s-character is found in sp-
complex. hybridisation.
30. (a) Structure of CO2 is linear O  C  O while 63. (b) The molecule of PCl5 has sp 3 d hybridisation,
O structure is trigonal bipyramidal.
that of H 2 O is i.e. bent structure so
H H 64. (b) Merging (mixing) of dissimilar orbitals of
in CO2 resultant dipole moment is zero while different energies to form new orbitals is
that of H 2 O has some value. known as hybridisation and the new orbital
formed are known as hybrid oribitals. They
31. (d) CO2 is not sp 3 hybridised, it is sp hybridised. have similar energy.
32. (a) As compare to pure atomic orbitals, hybrid 65. (b) In SO 3 sulphur is sp 2 hybridized so its shape
orbitals have low energy.
will be trigonal planar.
sp 2 sp sp 2 sp 3
33. (d) CH 2  C  CH – CH 3 1, 2-butadiene. 66. (a) These all are triangular with sp 2
hybridization.
36. (b) CCl4 is sp 3 hybridised so bond angle will be
67. (c) Bond length depends upon bond order and in
approximately 109 o .
benzene all C  C bonds have same bond
40. (b) Ethene has sp 2 hybridised carbon so bond order.
angles are 120 o . 68. (b) In C 2 H 2 each carbon has sp -hybridization
O H  C  C H
sp sp
44. (a) Acetate ion is CH 3 C i.e. one C  O
O 70. (a) As p-character increases the bond angle
decreases.
single bond and one C  O double bond.
 140 Chemical Bonding
1 NH 3  PH3  AsH 3  SbH 3  BiH3 .
In sp - p-character , bond angle - 180 o
2
97. (b) Generally NH 4 shows sp 3 hybridization.
2 2
In sp - p-character , bond angle - 120 o
3 98. (b) We know that single, double and triple bond
lengths of carbon in carbon dioxide are
3
In sp 3 - p-character , bond angle - 109 o 1 . 22 Å, 1 . 15 Å and 1.10Å respectively.
4
71. (a) sp 3 -hybridization called tetrahedral because 99. (b) It shows sp 2 –hybridization so it is planar.
it provides tetrahedral shape to the molecule. 101. (a) Bond angle of hydrides decreases down the
72. (a) S-atom in SF6 has sp d 3 2
hybridisation. So, the group.
structure of SF6 will be octahedral. 102. (b) Hybridization of N in NH 3 is sp 3 that of Pt in

74. (b) Structure of H 2 O2 is non-planar. It has open [PtCl 4 ]2  is dsp 2 that P in PCl5 is sp 3 d and
book structure. that of B in BCl3 is sp 2 .
75. (d) Structure of N 2 O is similar to CO2 both have
103. (d) NH 4 and SO 42  both show sp 3 –hybridization
linear structure.
and tetrahedral structure.
78. (a) SnCl 2 is V–shaped.
104. (a) It is shows sp 3 d 3 –hybridization. Hence the
 3
79. (d) In NH 4 nitrogen is sp hybridised so 4 bond angle is about 72 o .
hydrogen situated at the corners of a 107. (a) s-character increases with increase in bond
tetrahedron. angle.
81. (c) Increasing order of bond angle is
Hybridization s% Angle
sp 3  sp 2  sp .
109  120  180  sp 50 180 o
84. (a) NH 4 has sp 3 –hybridized nitrogen so its shape sp 2 33.3 120 o
is tetrahedral. sp 3 25 109 .28 o
86. (b) Bond angle increases with change in
sp 3 d 1 20 90 o and 120 o
hybridisation in following order sp 3  sp 2  sp .
108. (b) IF7 molecule show sp 3 d 3 –hybridization.
88. (c) In Diborane boron shows sp 3 –hybridization.
89. (a) Alkene does not show linear structure but it 110. (a) PCl3 contain three bonding and one lone pair
has planar structure due to sp 2 –hybridisation. electron. Hence shows sp 3 –hybridization.
90. (c) Generally SF4 consist of 10 electrons, 4 111. (a) Ammonia and (BF4 )1 shows sp 3 –
bonding electron pair and one lone pair of hybridization.
electron, hence it shows sp 3 d hybridization. 112. (b) For square planar geometry hybridization is
92. (c) Atom/Ion Hybridisation dsp 2 involving s, p x , p y and d x 2  orbital.
y2
NO 2 sp
113. (b) All carbon atoms of benzene consist of
SF4 sp 3 d with one lone pair of alternate single and double bond and show
electron sp 2 hybridization.
PF6 sp 3 d 2 116. (c) BCl3 molecule show sp 2 –hybridization and
93. (a) PF3 consist of three bonding pair electrons planar structure.
and one lone pair of electron hence it shows 117. (c) BCl3 Boron trichloride molecule show sp 2 –
sp 3 – hybridization. hybridization and trigonal planar structure.
118. (b) SO 2 molecule shows sp 2 –hybridization and
94. (b) NO 2 shows sp–hybridization. So its shape is
bent structure.
linear.
119. (c) Due to multiple bonding in N 2 molecule.
95. (c) Generally octahedral compound show sp 3 d 2 –
120. (a) % of s-character in
hybridization.
100 100
96. (a) In fifth group hydride bond angle decreases CH 4   25 , C 2 H 4   33 ,
3
( sp ) 4 2
( sp ) 3
from top to bottom
 Chemical Bonding 141
100 130. (a)
C2 H 2   50 2– F –
( sp ) 2 NC CN
121. (a) Acidic character increases when we come F
Ni B
down a group, so HI is the strongest acid.
F
122. (c) SO 2 has sp 2 hybridization have the V shape NC CN F
structure ( 120 ) due to 2 lone pair of electron Square planar Regular
over S atom. CO2 and N 2O have the sp tetrahedral
F F F F
hybridization.
123. (a) In H 2 CO3 and BF3 central atom are in F Xe
S
2
sp hybridization but in H 2 CO3 due to the
F F
ionic character of O  H bond it will be polar F
(High electronegativity of oxygen). See saw shaped Square planar
3
124. (a) Due to sp hybridization and presence of lone
pair of electron on p atom PCl3 are of 131. (b)
H
pyramidal shape like that of NH 3 . ··

··
O
125. (b) There is sp hybridization in C2 H 2 so it has the
linear structure. B
H sp2 H
126. (c) In octahedral molecule six hybrid orbitals ··
O ··
O sp3
3
directed towards the corner of a regular sp ·· ··
octahedron with a bond angle of 90°.
X
132. (b) In the formation of BF3 molecule, one s and
X X
2p orbital hybridise. Therefore it is sp 2
M
hybridization.
X X
133. (e) In NCl3 and H 2 S the central atom of both (N
X
according to this geometry, the number of and S) are in sp 3 hybridization state
X  M  X bond at 180° must be three. ·· ··
3 2
N ··
S
127. (d) sp d hybrid orbital have octahedral shape 92.5°
107 Cl
Cl H H
128. (c) In the formation of d 2 sp 3 hybrid orbitals two Cl °

(n  1)d orbitals of e.g., set [i.e., (n  1) dz 2 and while in BF3 and NCl3 central atoms are in
(n  1)dx  y orbitals] one ns and three np
2 2
sp 2 and sp 3 hybridization respectively. In H 2 S
[ np x , np y and np z ] orbitals combine together and BeCl 2 central atom are in sp 3 and sp 2
and form six d 2 sp 3 hybrid orbitals. hybridization In BF3 , NCl3 & H2S central
129. (c) The correct order of bond angle (Smallest atom are in sp 2 , sp 3 & sp 3 hybridization and
first) is in the central atom are in sp 3 and
H 2 S  NH 3  SiH4  BF3 sp hybridization.

92 .6  107   109 28 '  120  134. (c) Cground state  2 s 2 ,2 p x p y ; Cexcited state  2 s1 ,2 p x p y p z
1 1 1 1 1

H N
 2 s 2 ,2 p x p y p z
2 1 1
H
Oground state
H 107°
92.6° In the formation of CO2 molecule, hybridization
S H H
of orbitals of carbon occur only to a limited
H extent involving only one s and one p orbitals
F
there is thus sp hybridisation of valence shell
109°
120° 28' Si orbitals of the carbon atom resulting in the
B formation of two sp hybrid orbitals.
H H
F F
Oxygen atom in
H ground state
sp – p
 bonded p – p
Carbon atom in
excited state
sp – p p – p
 bonded
Oxygen atom in
ground state
 142 Chemical Bonding
142. (b) In the ammonia molecule N atom is
sp 3  hybridized but due to the presence of one
lone pair of e  (i.e. due to greater
L p  b p repulsion) it has distorted tetrahedral
(or pyramidal) geometry.
135. (d) In NH 3 , N undergoes sp 3 hybridization. Due to
N
the presence of one lone pair, it is pyramidal
in shape. H H H
136. (b) NO 2 SF 4 PF6
sp sp 3 d sp 3 d 2

137. (b) The configuration of  1s 2 ,2 s 2 2 p 1 143. (a) Be  1s 2 ,2 s 2 ,2 p 0

5B 4

B in ground state Be in ground state

1s 2s 2p 1s 2s 2p
B in excited state Be in excited state
1s 2s 2p
BeCl2
In BCl3 state
1s 2s 2p Cl Cl
Cl Cl Cl sp hybridisation
2 (Linear diagonal
sp hybridisation
hybridization)
138. (d) In SO 3 molecule, S atom remains sp 2 hybrid, 144. (a) Except CO3 other choice CO2 , CS 2 and BeCl 2
O
hence it has trigonal planar structure have sp  hybridization and shows the linear

S structure while CO3 have sp 3 hybridization

and show the non linear structure because
O O
sp 3 generate tetrahedral structure.
139. (a) In PCl3 molecule, phosphorous is
sp 3  hybridised but due to presence of lone 145. (a) dsp 3 or sp 3 d hybridization exhibit trigonal
pair of electron, it has pyramidal structure bipyramidal geometry e.g., PCl5

P Cl Cl
Cl Cl Cl sp3d2 (Trigonal
Cl P
140. (a) The electronic configuration of bipyramidal)
I  [ Xe ] 5 s 2 ,5 p 5 hence Cl Cl
5s 5p 5d
I in ground state
146. (b) Carbon has only two unpaired electrons by its
5s 5p 5d configuration but hybridization is a concept
I in excited state by which we can explain its valency 4.
147. (c) Hybridization is due to overlapping of orbitals
and I F7 in excited of same energy content.
state
F F F I F F F
148. (d) MX 3 show the sp 2 hybridization in which
sp3d3
3sp 2 hybridized orbital of M bonded by 3 X
IF7 shows sp 3 d 2 hybridization. So, its
from  bond and having the zero dipole
structure is pentagonal bipyramidal.
moment.
141. (a) Compound containing highly electronegative
element (F, O, N) attached to an 149. (bcd) SnCl 2 has V–shaped geometry.
electropositive element (H) show hydrogen
150. (a) NF3 is predominantly covalent in nature and
bonding. Fluorine (F) is highly electronegative
and has smaller size. So hydrogen fluoride has pyramidal structure (the central atom is
shows the strongest hydrogen bonding in the
liquid phase.
 Chemical Bonding 143
sp 3 hybridised) with a lone pair of electrons in 8. (c) C2 H 2 has linear structure because carbons
the fourth orbital. are sp-hybridised and lies at 180 o .
9. (b) XeF6 is distorted Octahedral. It has sp 3 d 3
151. (ac) PCl3 , NH 3  Pyramidal.
hybridisation with lone pair of electron on Xe,
CH 4 , CCl4  Tetrahedral. so its shape is distorted.
10. (a) 5s 5p 5d
152. (a) dsp 3 or sp 3 d : one s  three p  one d (d z 2 ) . 11. (c) Xe ground state

Resonance 5s 5p 5d
Xe double excitation
1. (d) Choice (a), (b), (c) are the resonance
5s 5p 5d
structures of CO2 .
2. (b) In NH 3 nitrogen has one lone pair of electron. XeF4

5. (b) In CN ion formal negative charge is on sp 3 d 2 - hybridization
nitrogen atom due to lone pair of electrons.
  12. (a) CO2 has bond angle 180 o .

 O H
| 13. (a) As the s-character of hybridized orbitals
7. (a) CH 3  C  CH 2 has 9, 1 and 2 lone pairs. decreases the bond angle also decreases
8. (c) In resonance structure there should be the In sp 3 hybridisation: s-character 1/4, bond
same number of electron pairs.
angle 109 o
9. (b) There are three resonance structure of CO 32 
In sp 2 hybridisation: s-character 1/3, bond
ion.
angle 120 o
O O O
In sp hybridisation: s-character 1/2, bond
C C C angle 180 o

O O O O 
O O 14. (a) XeF2 molecule is Linear because Xe is sp
(I) (II) (III) hybridised.
11. (abcd) It has all the characteristics. 15. (c) SO 42  has 42 electrons; CO 32  has 32 electrons;
NO 3 has 32 electrons.
VSEPR Theory
16. (c) Molecular oxygen contains unpaired electron
2. (a) The bond angle in PH3 would be expected to so it is paramagnetic (according to MOT).
17. (b) Structure of H 2 O is a bent structure due to
be close to 90 o . (The bond angle H  P  H in
PH3 is 93 o ) repulsion of lone pair of oxygen.
18. (d) Bond angle between two hybrid orbitals is
3. (b) In BF3 molecule Boron is sp 2 hybridised so its
105 o it means orbitals are sp 3 hybridised but
all atoms are co-planar.
4. (c) Due to lp  lp repulsions, bond angle in H 2 O is to lone pair repulsion bond angle get changed
from 109 o to 105 o . So its % of s-character is
lower (104 o .5 o ) than that in NH 3 (107 o ) and
between 22-23%.
CH 4 (109 o 2 8 ) . BeF2 on the other hand, has sp- 22. (d) Number of electrons in ClO2–
hybridization and hence has a bond angle of = 7 + 6 + 6 + 1 = 20
180 o . Number of electrons in ClF2+ = 7+7+7 –
5. (c) Compound is carbontetrachloride because
1=20.
CCl4 has sp 3 –hybridization 4 orbitals giving
23. (b) Central atom having four electron pairs will
regular tetrahedron geometry. In others the be of tetrahedral shape.
geometry is little distorted inspite of sp 3
F ..
hybridization due to different atoms on the F
F F F
vertices of tetrahedron.
C Xe
6. (b) SO 42  ion is tetrahedral since hybridization of 24. (d) .S.
F F F F F
S is sp 3 . F F ..
7. (b) NH 3 molecule has one lone pair of electrons
26. (c) It shows sp 2 –hybridization and show trigonal
on the central atom i.e. Nitrogen.
planar structure.
 144 Chemical Bonding
28. (b) H 2 S show bond angle nearly 90 o .  NH 3 has largest bond angle.

31. (a) Bond angle of hydrides is decreases top to 41. (c) In NH 3 , sp 3 -hybridization is present but bond
bottom in the group. NH 3  PH3  AsH 3  SbH 3 angle is 106 o 4 5  because Nitrogen has lone
32. (c) pair of electron according to VSEPR theory
due to bp-lp repulsion bond angle decreases
N Three bond pair and one lone pair of
from 109 o 45 ' to 106 o 4 5  .
electron.
42. (a) Bond strength decreases as the size of the
H H H halogen increases from F to I.
33. (c) Unpaired electrons are present in KO2 while 43. (b) NH 3 has pyramidal structure, yet nitrogen is
others have paired electron sp 3 hybridised. This is due to the presence of
NO 2 = 22 electrons ; BaO2 = 72 electrons lone pair of electron.
AlO2  30 electrons ; KO2  35 electrons 44. (c) SiF4 has symmetrical tetrahedral shape which

34. (a) Bond angle decreases from H 2 O to H 2 Te . is due to sp 3 hybridization of the central
35. (c) BF3 does not contain lone pair of electron. sulphur atom in its excited state
configuration. SF4 has distorted tetrahedral
36. (b) Bent T-shaped geometry or Sea- Saw geometry which arise due to
F in which both lone pairs sp 3 d hybridization of central sulphur atom and
..
occupy the equatorial due to the presence of lone pair of electron in
position of the trigonal one of the equatorial hybrid orbital.
Br F
bipyramidal here 45. (d)
.. (l p  l p ) repulsion = 0
F O
(l p  b p ) repulsion = 4 and O O

37. repulsion
(b) The overall value of the dipole =2 of a
moment
dsp2 sp3d sp3d2
polar molecule depends on its geometry and
hybridization hybridization hybridization
shape i.e., vectorial addition of dipole moment
(Four 90° (Six 90° angle (Twelve 90°
of the constituent bonds water has angular angles between between bond angle between
structure with bond angle 105° as it has dipole bond pair and pair and bond bond pair and
moment. However BeF2 is a linear molecule bond pair) pair) bond pair)
since dipole moment summation of all the Molecular orbital theory
bonds present in the molecule cancel each
other. No. of bonding e   No. of antibondin g e 
O F Be F 2. (c) B.O. 
2
H H
8 3 5
   2 .5 .
2 2
3. (b) One bonding M.O. and one anti-bonding M.O.
38. (d) BCl3 , BBr3 and BF3 , all of these have same
4. (b) O 22  is least stable.
structure i.e. trigonal planar
( sp 2 hybridization) Hence bond angle is same 5. (c) B.O. of O 2 is 2, B.O. of O 21 is 1.5, B.O. of O 21
for all of them (i.e., equal to 120°) is 2.5 and of O 22  is 1.
39. (d) We know that molecule of (NH 3 ) has
6. (d) Hydride of boron does not exist in BH 3 form.
maximum repulsion due to lone pair of
It is stable as its dimer di borane (B2 H 6 ) .
electron. Its shape is pyramidal and is
sp 3 hybridization. 10. (c) O 2 (2  8  1  17 ) has odd number of electrons
..
N and hence it is paramagnetic. All the
40. (b) :O : H
H 107° remaining molecules/ions, i.e.,
H 105° H
H CN  (6  7  1  14 ) diamagnetic
NO (7  8  15 ) has odd number of electrons and
.. ..
As hence it is paramagnetic.
P
H
H H H No. of N b  No. of N a 5
11. (c) B.O.    2 .5 .
H 2 2
H Less than 107°
12. (b) Bond order of O 2 is highest so its bond length
As the electronegativity of central atom
is smallest.
decreases bond angle is decreases
 Chemical Bonding 145
13. (c) Oxygen is paramagnetic due to the presence of Each phosphorus is attached to 4 oxygen atoms.
two unpaired electron : N  Na 84
33. (c) B.O. of carbon  b  2.
O 2   (1s) 2   (1s) 2  (2 s) 2   (2 s) 2 2 2
N  N a 10  4
 (2 p x )2  (2 p y )2  (2 p x )2   (2 p y )1   (2 p z )1 34. (a) B.O.  b  3.
2 2
17. (d) In CH 3 CN bond order between C and N is 3 so N  Na 8  3 5
its bond length is minimum. 37. (b) B.O.  b    2.5 .
2 2 2
18. (b) 38. (a) Electronic configuration of O2 is
He 2 H2 H 2 H 2
O2   (1s)2   (1s)2  (2 s)2   (2 s)2  (2 p x )2  (2 p y )2
 (1s)    
*  (2 p z )2   (2 p y )1   (2 p z )1
 (1s)  
The molecule has two unpaired electrons So,
1 1 1
B.O. 1 it is paramagnetic
2 2 2
(c)  2 p y has two nodal planes.
*
Magnetic 40.
P D P P
nature
42. (a) Element with atomic number 26 is Fe. It is a
(P = Paramagnetic, D = Diamagnetic) ferromagnetic.
19. (c) Due to unpaired e  ClO2 is paramagnetic. 43. (b) Correct Sequence of bond order is
O 2  O 2  O 22 
20. (c) The Bond order in N 2 molecule is 3, N  N
B.O – 2.5 2 1.5
Here, N b  2  4  2  8 and N a  2
44. (a) Due to small bond length.
 B.O.  ( 8  2) / 2  3. 45. (a) S 2 have all paired electrons so it is
1 diamagnetic.
21. (d) H 2 has the bond order , it has only one
2 46. (c) NO has 15 electrons.
electron so it will be paramagnetic. 47. (b) In the conversion of O 2 into O 2 bond order
22. (c) When bond forms between two atom then decreases.
their energy get lower than that of separate
49. (c) O 22  does not have any unpaired electron so it
atoms because bond formation is an
exothermic process. is diamagnetic.
23. (b) Valency of A is 3 while that of B is 2 so 50. (a) O 22  consist of four antibonding electron pair
according to Criss Cross rule the formula of [1s and 2s have two antibonding and 2 p x 2 p y
the compound between these two will be
have two antibonding electron pair].
A 2 B3 . 51. (c) The electron’s distribution in molecular orbitals
24. (c) Due to resonance bond order of C  C bonds is 1s 2 , 2 s 1
in benzene is between 1 and 2.
2 1 1
25. (a) Nitrogen does not have vacant ‘d’-orbitals so B.O.    0 .5 .
it can’t have +5 oxidation state i.e. the reason 2 2
PCl5 exists but NCl5 does not. 52. (b) ClO 2 has all paired electrons hence it does not
26. (d) Molecules having unpaired electrons show show paramagnetism.
paramagnetism. 1
53. (a) B.O.  [ N b  N a ]
27. (b) NO2 has unpaired electrons so it would be 2
1 6 1 6
paramagnetic. N 2  [10  4 ]   3 ; O 22   [10  4 ]   3 .
30. (c) Helium molecule does not exist as bond order 2 2 2 2
of He 2  0 .  1 1 5
54. (a) B.O. for N 2 = [ N b  N a ] = [9  4 ]   2 .5 .
31. (c) Structure of P4 O10 is 2 2 2
O 55. (a) H 2 O2 contain bond angle between two O  H
planes about 90 o .
P
56. (c) Nitrogen molecule has highest bond energy
O O
due to presence of triple bond.
O 57. (c) Cu 2   [ Ar18 ] 3 d 9 4 s 0 it has one unpaired
O P P O
O electron so it is paramagnetic.
59. (a) CN   14 electrons ; CO =14 electrons
O O 1 6
P B.O. = [10  4 ]   3 .
2 2

O
 146 Chemical Bonding

60. (a) B.O. =

1 5
[10  5]   2 .5 , paramagnetic Hence bond order 
1
N b  N a   1 [10  6]  2 .
2 2 2 2
P 69. (c) Nitrogen form triple bond N  N
61. (a) P P In which 6 electron take part.
P 70. (a) As bond order increase bond length decrease
the bond order of species are
64. (c) The paramagnetic property in oxygen came
number of bonding electron - Number of a.b. electron
through unpaired electron which can be 
2
explained by molecular orbital theory.
Antibondin
10  6
2px*
g For O 2  2 ;
2
10  5
O 2   2.5
2
2pz* 10  7
2py* O 2   1.5
2
So, bond order O 2  O 2  O 2 and bond length
Px Py Pz Px Py Pz
are O 2  O 2  O 2 .
71. (b) O2 :
 2py 2
 * 2py 1

 1s ,  1s ,  2 s ,  2 s ,  2 p x
2 * 2 2 * 2 2

 2pz 2  * 2pz1
2Px bonding 10  6
Bond order   2.0
2
So 2 unpaired of electron present in
(Two unpaired electrons in antibonding
 2 p y* and  2 p *z . molecular
Total number of bonds between atoms orbital)
65. (a) Bond order 
2  2 py  2 py
2 * 1
Total number of resonating structure O 2 :  1 s 2 ,  * 1 s 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x  2 *
 2 pz  2 pz
0
5
 1 .25 
4 10  5
Bond order   2.5
66. (c) We know that carbonate ion has following 2
resonating structures (One unpaired electron in antibonding
–
O O –
O molecular orbital so it is paramagnetic)
C=O  C – O–  C – O– 72. (b) Higher the bond order, shorter will be the
–
O –
O O bond length, thus NO  having the higher bond
order that is 3 as compared to NO having
Total number of bonds between atoms bond order 2 so NO  has shorter bond length.
Bond order 
Total number of resonating structure 73. (d) Oxygen molecule (O 2 ) boron molecule (B 2 ) and
1 1  2 4 N 2 ion, all of them have unpaired electron,
   1 .33 .
3 3 hence they all are paramagnetic.
67. (a) O 2 (15 e  )  K : K * ( 2 s) 2 ( * 2 s) 2 ( 2 p x ) 2 74. (c) Bond order of NO  , NO and NO  are
( 2 p y )2 ( 2 p z )2 ( * 2 p y )1 ( * 2 p z )0 3, 2.5 and 2 respectively, bond energy  bond
1 order
Hence, bond order  (10  5)  2 .5
2 75. (a) Paramagnetic property arise through unpaired
electron. B2 molecule have the unpaired
N 2 (13 e  )  KK ( 2 s) ( 2 s) ( 2 p x )
* 2 * 2 2

electron so it show paramagnetism.

( 2 p y ) ( 2 p z )1
2
B2   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x   2 p y
1 1

1
Hence, bond order  (9  4 )  2 .5 .
(2 unpaired electron)
2
C2   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x . 2 p y
2 2
68. (a) Electronic configuration of O 2 is (No unpaired electron)

O 2  ( 1s) ( 1s) ( 2 s) ( 2 s) ( 2 s) ( 2 p z )
2 * 2 2 * 2 * 2 2
N 2   1s  1s ,  2 s 2 * 2 s 2 ,  2 p x ,  2 p y  2 p z
2 * 2 2 2 2

( 2 p x2   2 p y2 ) ( * 2 p 1x   * 2 p 1y )
(No unpaired electron)
 Chemical Bonding 147
F2  s 2 ,  * 1s 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x ,  2 p y ,  2 p z ,
2 2 2
C2 : KK (2 s)2  * (2 s)2  (2 p x )2  (2 py )2 (diamagnetic)
(No unpaired electron)
N 2 : KK (2 s)2  * (2 s)2  (2 p x )2  (2 py )2  (2 p z )2
 * 2 py 2 , * 2 pz 2
(paramagnetic)
So only B2 exist unpaired electron and show
O22  : KK (2 s)  * (2 s)  (2 p z )  (2 p x )2  (2 py )2
2 2 2
the paramagnetism.
76. (b)  * (2 p x )2  * (2 py )2 (diamagnetic)
 2 py  * 2 py
2 1
84. (d) NH3  107 , PH3  93 , H 2O  104 .5
O2   1s ,  1s ,  2 s ,  2 s ,  2 p x
2 * 2 2 * 2 2
H 2 Se  91 , H 2 S  92 .5
 2 pz 2  * 2 pz 2
So two unpaired electron found in O 2 at Hydrogen bonding
ground stage by which it shows
paramagnetism. 1. (d) Hydrogen bonding will be maximum in F-H
77. (b) Due to greater electron affinity Cl2 has the bond due to greater electronegativity
highest bond energy. difference.
78. (a) Molecular orbital electronic configuration of 2. (b) Ice has hydrogen bonding.
these species are : 3. (b) H – F has highest boiling point because it has
O2 (17 e  )   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x ,  2 p y ,
2 2 hydrogen bonding.
6. (d) CO2 is sp-hybridised
 2 p z 2 ,  * 2 p y 2 * 2 p z 1
7. (b) sp-hybridization gives two orbitals at
O2 (16 e)   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x ,  2 p y , 180 o with Linear structure.
2 2

8. (d) Hydrogen bonding increases the boiling point

 2 p z 2 * 2 p y 1 * 2 p z 1
of compound.
O 22  (18 e )   1s 2 * 1s 2 ,  2 s 2 * 2 s 2 ,  2 p x ,  2 p y ,
2 2 9. (c) o-Nitrophenol has intramolecular hydrogen
bonding but p-Nitrophenol has intermolecular
 2 p z 2 * 2 p y 2 * 2 p z 2 hydrogen bonding so boiling point of p-
Hence number of antibonding electrons are Nitrophenol is more than o-Nitrophenol.
7,6,and 8 respectively. 10. (c) The strongest hydrogen bond is in hydrogen
79. (c) Species with unpaired electrons is fluoride because the power of hydrogen bond
paramagnetic O 2 has 2 unpaired electrons,  electronegativity of atom and
1
O 2 has one unpaired, O 22  has zero unpaired electronegativity 
atomic size
electrons, O 22  has one unpaired.
So fluorine has maximum electronegativity
80. (a) O 2 has 2 unpaired electron while O 2 and O 2 and minimum atomic size.
11. (d) H 2 O can form hydrogen bonds rest CH 4 and
has one each unpaired electrons while
CHCl 3 are organic compound having no
O 22  does not have any unpaired electron.
oxygen while NaCl has itself intraionic
81. (c) H  O  O  H , O  O  O , O  O
attraction in the molecule.
O O 12. (b) PH3 has the lowest boiling point because it
O O O O does not form Hydrogen bond.
Due to resonance in O 3 O  O bond length will 14. (b) Hydrogen bonding increases heat of
vaporisation.
be in b/w O  O and O  O .
15. (d) Only NH 3 forms H-bonds.
82. (a) From valency bond theory, bond order in CO,
  22. (a) Water molecule has hydrogen bonding so
i.e. : C  O : is 3, that of O  C  O is 2 while
molecules get dissociated so it is liquid.
that of CO 32  ion is 1.33. Since the bond length
23. (d) In case of water, five water molecules are
increases as the bond order decreases, i.e. attached together through four hydrogen
CO  CO 2  CO 32  . bonding.

83. (c) N 2 : KK (2 s)2  * (2 s)2  (2 p x )2  (2 py )2  (2 p z )2 25. (c) Hydrogen bond is strongest in hydrogen
fluoride.
(diamagnetic)
 148 Chemical Bonding
28. (c) Boiling point of H 2 O is more than that of 12. (a) Generally zero group elements are linked by
H 2 S because H 2 O forms hydrogen bonding the Vander Waal’s force. Hence these show
weakest intermolecular forces.
while H 2 S does not.
13. (d) Glycerol has a three OH group hence it is

O H viscous in nature.

30. (c) C O Interamolecular H-bonding.
14. (c) Vander waal's forces is the weakest force of
H attraction.
16. (b) NH 4 contain all three types of bond in its
31. (a) Hydrogen bond is formed when hydrogen is
attached with the atom which is highly 
 H 
electronegative and having small radius.  | 
structure  H  N  H 
34. (a) Water is dense than ice because of hydrogen  |

bonding interaction and structure of ice.  H 
35. (a) Ethanol have hydrogen bonding so its boiling 17. (d) In NaOH covalent bond is present in O  H
point is higher than its isomer dimethyl ether. bond while ionic bond is formed between OH 
36. (a) A compound having maximum electronegative and Na  .
element will form strong Hydrogen bond. 18. (a) Bond formation is an exothermic reaction so
37. (a) Due to electronegativity difference of N 2 and there is decrease in energy of product.
H 2 , NH 3 form hydrogen bond. 22. (d) Blue vitriol is CuSO 4 . 5 H 2 O and it has all
38. (b) Intermolecular hydrogen bonding compound types of bonds.
contain more b.p. compare to intramolecular 
 H 
hydrogen bonding compound.  | 
39. (d) Water molecule contain hydrogen bonding. 23. (a)  H  N  H  Cl 
 |

40. (c) It contain intermolecular hydrogen bonding.  H 
41. (b) Ethyl alcohol has a intermolecular hydrogen Ionic bond = 1, Covalent bond = 3
bond. Co-ordinate bond = 1.
43. (b) HCl contain weak covalent bond.
45. (c) Due to intermolecular hydrogen bonding Critical Thinking Questions
water molecules come close to each other and
exist in liquid state. 1. (d) We know that ionic characters
46. (b) Due to greater resonance stabilization.  16 [ E A  EB ]  3 .5  [ E A  EB ]2
47. (d) C2 H 5 OH will dissolve in water because it or ionic characters = 72.24%
forms hydrogen bond with water molecule. 3. (c) Configuration of O 2 molecule is
48. (b) In ice cube all molecules are held by inter
molecular hydrogen bond. [ (1s)2   (1s)2  (2 s)2  * (2 s)2  (2 p x )2  (2 p y )2
49. (d) Hydrogen bonding is developed due to inter  (2 p z )2   (2 p x )1   (2 p y )1 ]
atomic attraction so it is the weakest.
No. of pair are 7 so total no. of paired
Types of bonding and Forces in solid electrons are 14.
 
1. (b) In electrovalent crystal has cation and anion 6. (a) H  O :  H   H  O  H
| |
are attached by electrostatic forces. H H
2. (d) Mercury has very weak interatomic forces so 7. (b) The correct order of increasing dipole moment
it remains in liquid state. is
3. (c) The melting and boiling points of argon is low p-dichlorobenzene < Toluene < m-
hence, in solid argon atoms are held together dichlorobenzene < o-dichlorobenzene.
by weak Vander Waal’s forces. 8. (a) The dipole moment of CH4  0 D,
4. (c) NaF is the strongest ionic crystal so its
NF3  0.2 D, NH 3  1.47 D and H 2 O  1.85 D .
melting point would be highest.
Therefore the correct order of the dipole
9. (b) Diamond is the hardest substance it’s melting
moment is CH4  NF3  NH3  H2O .
point would be highest.
10. (c) Bond is formed by attractive and repulsive 10. (d) Ammonia molecule is more basic than
forces of both the atoms. nitrogen trifluoride and Boron trifluoride
 Chemical Bonding 149
because ammonia molecule easily gives lone 27. (c) CuSO 4 .5 H 2 O has electrovalent, covalent and
pair of electron. coordinate bonds.
 3
11. (a) Chlorine atom in ClO 2 is sp hybridised but  O 
its shape is angular. 2
   

Cu O  S  O . 5 H 2O .

12. (c) [ NF3 and H 3 O  ] are pyramidal while [ NO 3  
 O 
and BF3 ] are planar. Hence answer (c) is
correct. Assertion & Reason
13. (d) CH 2  CH  CH 2  CH 2  C  CH
sp 2 sp 3 1. (a) Solubility in water depends on hydration
hy bridised
energy and lattice energy.
 
14. (d) B.O. in CO i.e., : C  O : is 3, that of O  C  O 2. (a) Polarity in covalent bond developed due to
is 2 while that of CO 32  ion is 1.33. Since the shifting of electrons towards one of the
bonded atoms.
bond length increases as the bond order
5. (c) SiF4 have sp 3 hybridization & shape of
decreases i.e. CO  CO 2  CO 32  . Thus option
regular F
(d) is correct.
tetrahedral where
15. (b) Dichromate dianion has following structure
2
the bond angle of
 O O  109.5o
FS F are
   
O  Cr  O  Cr  O  found 109 . 5 o S
 
  which is greater F
 O O 
than 90 o but less F
6, Cr  O bonds are equivalent. F
17. (b) ClF3 is a [ AB3 ] type of molecule because it than 180 o .
consist of three bonding pair and two lone Repulsion sequence are
pair of electrons hence this compound shows Lp  Lp  Lp  Bp  Bp  Bp so assertion are true

sp 3 d hybridization. but the reason are false.

9. (c) N 2 molecule is diamagnetic. The diamagnetic
20. (a) BeF 3 does not show sp 3 –hybridization
character is due to the presence of paired
because this compound is not formed. electron N 2 molecule does not contain any
21. (a) K 3 [Fe(CN )6 ]
unpaired electron. Thus, assertion is coorect
Fe 26  4 s 2 3 d 6 but the reason is false.
10. (a) It is correct that during formation of Ice from
Fe 3   3 d 5 4 s 0
water there are vacant spaces between
hydrogen bonded molecules of Ice. Ice has a
= cage like structure. Due to this reason Ice is
      less dense than liquid water. hence both
assertion & reason are true & reason are the
correct explanation of assertion.
Unpaired electron d 2sp 3 –hybridization 11. (b) Water is liquid while H 2 S is gas because
oxygen is of small size & more electronegative
22. (d) N 2 has one unpaired electron so it would be
in comparision to sulphur. Hence water
paramagnetic. molecules exist as associated molecules to
23. (a) Each of the species has 14 electron so form liquid state due to hydrogen bonding
isoelectronic and shows bond order 3. H 2 S does not have hydrogen bonding & can’t
1 1 6 associated hence it is gas.
B.O.  [ N b  N a ]  [10  4 ]   3 .
2 2 2 12. (d) Iodine is more soluble in CCl4 than in H 2 O
24. (d) O O because iodine is non polar & thus it dissolve
O in CCl4 because like dissolves like.
S S
O O 13. (a) o & p -nitrophenols can be separated by
O
steam distillation because o -nitrophenol is
O S O
steam volatile. Here, both assertion & reason
are correct & reason is correct explanation of
O
assertion.
Trimer of SO 3 .
 150 Chemical Bonding
14. (e) Fluorine is highly reactive F  F bond has low 23. (d) Both assertion & reason are false because
bond dissociation energy. Here assertion is pairs of electron will have different spins.
false but reason is true. Electrons are equally shared between them.
15. (c) It is true that sigma ( ) bond is stronger than pi 24. (d) In B2, total number of electrons = 10
( ) bond but the reason that there is free
B2  (1s)2 *(1s2) (2s)2 *(2s)2 (2px)1
rotation of atoms is false.
(2py)1
16. (c) Energy is released in the formation of the
Presence of unpaired electron shows the
crystal lattice. It is qualitative measure of the
paramagnetic nature.
stability of an ionic compound so assertion is
true & reason are false. The highest occupied molecular orbital is of -
17. (c) Li, Na & K are alkali metals & not alkaline type.
earth metal so, size of alkali metal increases 25. (a) Both assertion & reason are true & reason is
So. Assertion is true & reason are false. the correct explanation of the assertion
because. At any given instant, at room
18. (b) Hess’s law states that the enthalpy of a
temperature each water molecules forms
reaction is the same, whether it takes place in
hydrogen bonds with other water molecules.
a single step or in more than one step. In born
The H 2 O molecules are in continuous motion.
haber cycle the formation of an cycle ionic
compound may occur either by direct So hydrogen bonds are constantly & rapidly
combination of the element or by a stepwise broken & formed. In Ice H 2 O molecules are
process involving vaporization of elements, however fixed in the space lattice.
conversion of the gaseous atoms into ions & 26. (a) Both assertion & reason are true & reason is
the combination of the gaseous ions to form the correct explanation of assertion, because
the ionic solid. helium molecule is formed by linking two
19. (a) With increase in bond order, bond length helium atoms. both have 1 s orbitals. These
decreases & hence bond energy increases so will combine to form two molecular orbitals
both assertion & reason are true & reason are  ( 1 s ) &  * ( 1 s ) four available electrons are
the correct explanation of assertion.
accommodated as  (1s)2 &  * (1s)2 .
20. (c) Electron affinity is experimentally measurable
while electronegativity is a relative number so
assertion is true but reason are false.
21. (b) Assertion & reason both are correct but reason
is not the correct explanation of assertion
sulphur has five electrons pairs whose
arrangement should be trigonal bipyramidal
according to VSEPR theory. Two structure are
possible
F
.. F | F
FS F :S
F | F
F
(a) (b)
Lone pair in the Lone pair in the
axial position (three equatorial position
l.p – b.p repulsion at (two L.p – b.p
22. 90o)BF has zero dipole
(e) repulsion)
moment because of its
3

structure.
F
F  B    0
F
H 2 S has two lone pairs on sulphur atom &
hence. It has irregular shape.
Thus it possess dipole moment. So assertion is
false but reason are true.
 Chemical Bonding 149

1. Nature of the bond formed between two elements (d) Covalent bond is stronger than ionic bond
depends on the 10. Which one of the following molecules has a
(a) Oxidation potential (b) Electronegativity coordinate bond [CPMT 1988, 94]
(c) Ionization potential (d) Electron affinity (a) NH 4 Cl (b) AlCl3
2. Two elements X and Y have following electronic (c) NaCl (d) Cl 2
configurations X  1s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 6 , 4 s 2 and 11. Co-ordinate bond is absent in [RPMT 2002]
Y  1 s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 5 . The expected compound (a) BH 4 (b) CO 32
formed by combination of X and Y is [BHU 1990]
(c) H 3 O  (d) NH 4 
(a) XY 2 (b) X 5 Y 2
12. The dipole moment of chlorobenzene is 1.73 D.
(c) X 2 Y 5 (d) XY 5
The dipole moment of p -dichlorobenzene is
3. Electricity do not pass through ionic compounds expected to be
(a) In solution (b) In solid state [CPMT 1991]
(c) In melted state (d) None of these (a) 3.46 D (b) 0.00 D
4. From the following which compound on heating (c) 1.73 D (d) 1.00 D
readily sublimes 13. Polarization of electrons in acrolein may be
(a) NaCl (b) MgCl2 written as
(c) BaCl2 (d) AlCl3 [IIT 1988]
  
   
5. Which one in the following contains ionic as well (a) C H 2  CH  C H  O (b) C H 2  CH  CH  O
as covalent bond [IIT 1979; CPMT 1983; DPMT 1983]
   
(a) CH4 (b) H 2 (c) C H 2  C H  CH  O (d) C H 2  CH  CH  O
(c) KCN (d) KCl 14. The order of dipole moments of the following
6. The solution of sugar in water contains molecules is
[NCERT 1972; MP PET 2000] [Roorkee 2000]

(a) Free atoms (a) CHCl 3  CH 2 Cl 2  CH 3 Cl  CCl 4

(b) Free molecules (b) CH 2 Cl 2  CH 3 Cl  CHCl 3  CCl 4
(c) Free ions (c) CH 3 Cl  CH 2 Cl 2  CHCl 3  CCl 4
(d) Free atoms and free molecules
(d) CH 2 Cl 2  CHCl 3  CH 3 Cl  CCl 4
7. In which of the following reactions, there is no
15. The electronegativity of C, H, O, N and S are 2.5,
change in the valency [NCERT 1974; CPMT 1971, 78]
(a) 4 KClO3  3 KClO4  KCl 2.1, 3.5, 3.0 and 2.5 respectively. Which of the
following bond is most polar [
(b) SO 2  2 H 2 S  2 H 2 O  3S
(a) O  H (b) S  H
(c) BaO2  H 2 SO 4  BaSO 4  H 2 O2
(c) N  H (d) C  H
(d) 2BaO  O2  2BaO2 16. Which of the following bond has the most polar
8. The octet rule is not followed in [BHU 1981] character
(a) F2 (b) NaF [DPMT 1982; CBSE PMT 1992; CPMT 1999]
(a) C  O (b) C  Br
(c) CaF2 (d) BF3
(c) C  S (d) C  F
9. Sodium chloride is an ionic compound whereas
17. The geometry of H 2 S and its dipole moment are[IIT 1999]
hydrogen chloride is a gas because [KCET 2002]
(a) Sodium is reactive (a) Angular and non-zero (b) Angular and zero
(b) Covalent bond is weaker than ionic bond (c) Linear and non-zero (d) Linear and zero
(c) Hydrogen chloride is a gas
 150 Chemical Bonding
18. How many  and  bonds are there in the (a) Planar triangle (b) Pyramidal
molecule of tetracyanoethylene (c) Tetrahedral (d) Square planar
N C CN 26. Which of the following halogens has the highest
CC
N C CN bond energy [CPMT 1988]
[NCERT 1980; MP PMT 1986, 95;Orissa JEE 1997] (a) F2 (b) Cl 2
(a) Nine  and nine  (b) Five  and nine  (c) Br2 (d) I 2
(c) Nine  and seven  (d) Five  and eight  27. What bond order does O 22  have [Pb. PMT 2001]
19. The shape of H 3 O  ion is [EAMCET 1993; CPMT
(a) 3 (b) 2
2001]
(c) 1 (d) 1/2
(a) Linear (b) Angular
28. In the process, O 2  O 22  e the electron lost is
(c) Trigonal planar (d) Triangular pyramidal
from
20. The hybridization in sulphur dioxide is[IIT 1986;
DPMT 1990] [Orissa JEE 2002]

(a) sp (b) sp 3 (a) Bonding -orbital (b) Antibonding -orbital

2
(c) 2 p z orbital (d) 2 p x orbital
(c) sp (d) dsp 2
29. The maximum number of hydrogen bonds formed
21. The number and type of bonds between two
by a water molecule in ice is
carbon atoms in CaC2 are [IIT 1996]
[MP PET 1993; AFMC 2002;UPSEAT 1999, 2001, 02]
(a) One sigma ( ) and one pi ( ) bonds
(a) 4 (b) 3
(b) One sigma ( ) and two pi ( ) bonds (c) 2 (d) 1
(c) One sigma ( ) and one and a half pi ( ) bonds 30. Hydrogen bonding is not present in
(d) One sigma ( ) bond [AIIMS 1998; MP PET/PMT 1998]
22. Which of the following resonating structures of (a) Glycerine
N 2 O is the most contributing [Roorkee Qualifying 1998] (b) Water
(a) N  N  O (b) N  N  O (c) Hydrogen sulphide
(c) N  N  O (d) N  N  O (d) Hydrogen fluoride
23. The hybridization of atomic orbitals of nitrogen in 31. The bonds in K 4 [Fe (CN )6 ] are [
  
NO , NO , and NH
2 3 4 are [IIT Screening
(a) All ionic2000]
(a) sp, sp 3 and sp 2 respectively (b) All covalent
(c) Ionic and covalent
(b) sp, sp 2 and sp 3 respectively
(d) Ionic, covalent and coordinate covalent
(c) sp 2 , sp and sp 3 respectively 32. In which of the following ionic, covalent and
2
(d) sp , sp 3
and sp respectively coordinate bonds are present
(a) Water
24. The molecule having one unpaired electron is
[IIT 1985; MP PMT 1989] (b) Ammonia
(a) NO (b) CO (c) Sodium cyanide
 (d) Potassium bromide
(c) CN (d) O 2

25. The geometry of ClO 3 , according to valence shell

electron pair repulsion (VSEPR) theory will be
[KCET 1996; MP PET 1997]
 Chemical Bonding 151

(SET -3)

1. (b) If the two elements have similar 16. (d) C  F bond has the most polar character due
electronegativities,the bond between them to difference of their electronegativity.
will be covalent, while a large difference in 17. (a) H 2 S has angular geometry and have some
electronegativities leads to an ionic bond. value of dipole moment.
2. (a) From electronic configuration valencies of X
N   C 
C 

N
and Y are + 2 and –1 respectively so formula  

of compound is XY 2 . 18. (a) C  C
 
  
3. (b) Ionic compounds can’t pass electricity in solid N 

C C 

N
state because they don’t have mobile ion in
solid state. 9 and 9 bonds.
4. (d) AlCl3 sublimes readily on heating. 19. (d) H 3 O  has sp 3 hybridization and its shape is
.. triangular pyramidal due to lone pair on
5. (c) Structure of KCN is [K  (C   N )] . oxygen.
6. (b) Sugar is an organic compound which is 20. (c) SO 2 molecule has sp 2 hybridisation.
covalently bonded so in water it remains as C
free molecules.
21. (b) In Ca two carbons are joined with 1 and 2
***
2 6 2 6
7. (c) In the reaction BaO2  H 2 SO 4  BaSO 4  H 2 O C
valency is not changing. bonds.
8. (d) BF3 does not have octet, it has only six 22. (a) In N 2 O molecule N  N  O structure is most
electrons so it is electron deficient compound. contributed.
9. (b) NaCl is a ionic compound because it consists 23. (b) The shape of NO 2 , NO 3 and NH 4 are linear
of more elelctronegativity difference compare trigonal planar and tetrahedral respectively.
to HCl. Thus the hybridization of atomic orbitals of
10. (a) NH 4 Cl has a coordinate bond besides covalent nitrogen in these species are sp, sp 2 and sp 3

 H  respectively.
 |  24. (a) NO has one unpaired electron with Nitrogen.
and ionic bonds  H  N  H  Cl 
..
 |

 H  : N :: O :
. ..
O ..


| 25. (b) O  Cl  O
11. (b) O  C  O has covalent bonds only. |

12. (b) Due to symmetry dipole moment of p-dichloro O

benzene is zero. 26. (b) Bond energy of Cl2 is highest among all
13. (d) halogen molecule. Bond energies of
14. (d) CCl4 has zero dipole moment because of F2 , Cl2 , Br2 , I2 are 37, 58, 46 and 36 Kcal mol 1
symmetric tetrahedral structure. CH 3 Cl has respectively.
slightly higher dipole moment which is equal 27. (c) O 22  have bond order one
to 1.86D. Now CH 3 Cl has less 1 2
B.O. [10  8 ]   1 .
electronegativity then CH 2 Cl2 . But CH 2 Cl2 2 2
has greater dipole moment than CHCl 3 . 28. (b) Electron lost from antibonding  orbital.
15. (a) More the difference in electronegativity of 29. (a) In ice each water molecule forms four
atoms. Bond between them will be more polar. hydrogen bond through which each water
 152 Chemical Bonding
molecule is tetrahedrally attached with other
water molecule.
H
O
H H H
O O
H H H H
O O
H H H H
O O
H H H H
O O
H H

30. (c) Hydrogen bonding is present in molecules

which have F, O, or N atoms.
31. (d) Structure of K 4 [Fe(CN )6 ] is
4
 
 CN 
 C  N 
  C  N
4K  Fe 
 
 C  N C  N 
CN
 
32. (c) Sodium cyanide contain ionic, covalent and
coordinate bond.
 152 Solution and Colligative properties

Chapter

4
Solution & Colligative properties

“A solution is a mixture in which substances are Liquid Solid Salt in water, sugar in water.
intermixed so intimately that they can not be observed Solid Gas Adsorption of gases over metals;
as separate components”. The dispersed phase or the hydrogen over palladium.
substance which is to be dissolved is called solute, Solid Liquid Mercury in zinc, mercury in gold,
CuSO4.5H2O.
while the dispersion medium in which the solute is
Solid Solid Homogeneous mixture of two or more
dispersed to get a homogenous mixture is called the metals (alloys), e.g., copper in gold,
solvent. zinc in copper.
Solubility Among these solutions the most significant type
of solutions are those which are in liquid phase and
“Solubility of a substance may be defined as the
may be categorised as, (1) Solid in liquid solutions,
amount of solute dissolved in 100gms of a solvent to
(2) Liquid in liquid solutions and (3) Gas in liquid
form a saturated solution at a given temperature”. A solutions.
saturated solution is a solution which contains at a
Methods of expressing concentration of solution
given temperature as much solute as it can hold in
presence of dissolveding solvent. Any solution may Concentration of solution is the amount of solute
contain less solute than would be necessary to saturate dissolved in a known amount of the solvent or solution.
it. Such a solution is known as unsaturated solution. The concentration of solution can be expressed in
When the solution contains more solute than would be various ways as discussed below,
necessary to saturate it then it is termed as (1) Percentage : It refers to the amount of the
supersaturated solution. solute per 100 parts of the solution. It can also be
called as parts per hundred (pph). It can be expressed
Kinds of solutions by any of following four methods,
All the three states of matter (gas, liquid or solid) (i) Weight to weight percent
may behave either as solvent or solute. Depending on Wt.of solute
% w/w   100
the state of solute or solvent, mainly there may be Wt.of solution
following nine types of binary solutions. Example : 10% Na 2 CO3 solution w/w means 10 g
Solvent Solute Example of Na 2 CO3 is dissolved in 100 g of the solution. (It
Gas Gas Mixture of gases, air. means 10 g Na 2 CO3 is dissolved in 90 g of H 2 O )
Gas Liquid Water vapours in air, mist.
Gas Solid Sublimation of a solid into a gas,
(ii) Weight to volume percent
smoke. Wt. of solute
% w/v   100
Liquid Gas CO2 gas dissolved in water (aerated Volume of solution
drinks). Example : 10% Na 2 CO3 (w/v) means 10 g Na 2 CO3
Liquid Liquid Mixture of miscible liquids, e.g.,
alcohol in water.
is dissolved in 100 cc of solution.
(iii) Volume to volume percent
 Solution and Colligative properties 153
Vol. of solute Wt. of solute per litre of solution
% v/v   100 (iii) N 
Vol. of solution g eq. wt. of solute
Example : 10% ethanol (v/v) means 10 cc of
Wt. of solute 1000
ethanol dissolved in 100 cc of solution. (iv) N  
g.eq. wt. of solute Vol. of solution in ml
(iv) Volume to weight percent
Percent of solute  10
Vol. of solute (v) N  ,
% v/w   100 g eq. wt. of solute
Wt.of solution
Example : 10% ethanol (v/w) means 10 cc of Strength in g l -1 of solution
(vi) N 
ethanol dissolved in 100 g of solution. g eq. wt. of solute

(2) Parts per million (ppm) and parts per Wt%  density  10
(vii) N 
billion (ppb) : When a solute is present in trace Eq. wt.
quantities, it is convenient to express the concentration
(viii) If volume V1 and normality N1 is so
in parts per million and parts per billion. It is the
changed that new normality and volume N 2 and V2
number of parts of solute per million (10 6 ) or per
then,
billion (10 9 ) parts of the solution. It is independent of
N 1 V1  N 2 V2 (Normality equation)
the temperature.
(ix) When two solutions of the same solute are
mass of solute component
ppm   10 6 mixed then normality of mixture (N ) is
Total mass of solution
N 1 V1  N 2 V2
mass of solute component N
ppb   10 9 V1  V2
Total mass of solution
(x) Vol. of water to be added i.e., (V2  V1 ) to get a
(3) Strength : The strength of solution is defined
solution of normality N 2 from V1 ml of normality N 1
as the amount of solute in grams present in one litre
(or dm 3 ) of the solution. It is expressed in g/litre or  N  N2 
V2  V1   1  V1

 N2 
3
(g / dm ) .

Mass of solute in grams (xi) If Wg of an acid is completely neutralised by

Strength 
Volume of solution in litres V ml of base of normality N
(4) Normality (N) : It is defined as the number of Wt. of acid VN

gram equivalents (equivalent weight in grams) of a g eq. wt. of acid 1000
solute present per litre of the solution. Unit of Wt. of base Vol. of acid  N of acid
normality is gram equivalents litre–1. Normality Similarly, 
g eq. wt. of base 1000
changes with temperature since it involves volume.
When a solution is diluted x times, its normality also (xii) When Va ml of acid of normality N a is mixed
decreases by x times. Solutions in term of normality with Vb ml of base of normality N b
generally expressed as, (a) If Va N a  Vb N b (Solution neutral)
N  Normal solution; 5 N  Penta normal, (b) If Va N a  Vb N b (Solution is acidic)
10 N  Deca normal; N / 2  semi normal (c) If Vb N b  Va N a (Solution is basic)
N / 10  Deci normal; N / 5  Penti normal (xiii) Normality of the acidic mixture
N / 100 or 0.01 N  centinormal, Va N a  Vb N b

(Va  Vb )
N / 1000 or 0.001= millinormal
(xiv) Normality of the basic mixture
Mathematically normality can be calculated by Vb N b  Va N a
following formulas, 
(Va  Vb )
Number of g.eq. of solute
(i) Normality ( N )  No. of meq * of solute
Volume of solution (l) (xv) N 
Vol. of solution in ml
Weight of solute in g. (* 1 equivalent = 1000 milliequivalent or
(ii) N 
g. eq. weight of solute  Volume of solution (l) meq.)
(5) Molarity (M) : Molarity of a solution is the
number of moles of the solute per litre of solution (or
 154 Solution and Colligative properties

number of millimoles per ml. of solution). Unit of (xi) Volume of water added to get a solution of
molarity is mol/litre or mol/dm3 For example, a molar molarity M 2 from V1 ml of molarity M1 is
(1 M ) solution of sugar means a solution containing 1
 M  M2 
mole of sugar (i.e., 342 g or 6.02  10 23 molecules of it) V2  V1   1  V1

 M2 
per litre of the solution. Solutions in term of molarity
generally expressed as, Relation between molarity and normality
1 M = Molar solution, 2 M = Molarity is two, Molecular mass
Normality of solution = molarity 
M Equivalent mass
or 0.5 M = Semimolar solution,
2 Normality  equivalent mass = molarity 
M molecular mass
or 0.1 M = Decimolar solution,
10 Molecular mass
For an acid, = Basicity
M Equivalent mass
or 0.01 M = Centimolar solution
100 So, Normality of acid = molarity  basicity.
M Molecular mass
or 0.001 M = Millimolar solution For a base, = Acidity
1000 Equivalent mass
 Molarity is most common way of representing So, Normality of base = Molarity  Acidity.
the concentration of solution.
(6) Molality (m) : It is the number of moles or
1
 Molarity is depend on temperature as, M  gram molecules of the solute per 1000 g of the solvent.
T Unit of molality is mol / kg . For example, a 0 .2 molal
 When a solution is diluted (x times), its molarity (0 .2m ) solution of glucose means a solution obtained by
also decreases (by x times)
dissolving 0.2 mole of glucose in 1000 gm of water.
Mathematically molarity can be calculated by
Molality (m) does not depend on temperature since it
following formulas,
involves measurement of weight of liquids. Molal
No. of moles of solute (n)
(i) M , solutions are less concentrated than molar solution.
Vol. of solution in litres
Mathematically molality can be calculated by
Wt. of solute (in gm) per litre of solution
(ii) M following formulas,
Mol. wt. of solute
Number of moles of the solute
Wt. of solute (in gm) 1000 (i) m   1000
(iii) M   Weight of the solvent in grams
Mol. wt. of solute Vol. of solution in ml .
No. of millimoles of solute Strength per 1000 grams of solvent
(iv) M  (ii) m 
Vol. of solution in ml Molecular mass of solute
Percent of solute  10 No. of gm moles of solute
(v) M  (iii) m 
Mol. wt. of solute Wt. of solvent in kg
Strength in gl-1 of solution Wt. of solute 1000
(vi) M  (iv) m  
Mol. wt. of solute Mol. wt. of solute Wt. of solvent in g
10  Sp. gr. of the solution  Wt.% of the solute
(vii) M  No. of millimoles of solute
Mol. wt. of the solute (v) m 
Wt. of solvent in g
(viii) If molarity and volume of solution are
changed from M1 , V1 to M 2 , V2 . Then, 10  solubility
(vi) m 
Mol. wt. of solute
M1 V1  M 2 V2 (Molarity equation)
1000  wt. % of solute (x )
(ix) In balanced chemical equation, if n1 moles of (vii) m 
(100  x )  mol. wt. of solute
reactant one react with n 2 moles of reactant two. Then,
(viii)
1000  Molarity
M 1 V1 M V m
 2 2 (1000  sp. gravity)  (Molarity  Mol. wt. of solute)
n1 n2
Relation between molarity (M) and molality
(x) If two solutions of the same solute are
(m)
mixed then molarity (M) of resulting solution.
M 1 V1  M 2 V2 Molarity
M Molality (m) =
Molarity  molecular mass
(V1  V2 ) Density 
1000
 Solution and Colligative properties 155
Molality  density m
Molarity (M)  XA 
Molality  molecular mass 55 .5  m
1
1000 (9) Mass fraction : Mass fraction of a component
(7) Formality (F) : Formality of a solution may in a solution is the mass of that component divided by
the total mass of the solution. For a solution containing
be defined as the number of gram formula masses of
w A gm of A and w B gm of B
the ionic solute dissolved per litre of the solution. It is
represented by F . Commonly, the term formality is wA
Mass fraction of A ; Mas fraction of
used to express the concentration of the ionic solids w A  wB
which do not exist as molecules but exist as network of wB
B
ions. A solution containing one gram formula mass of w A  wB
solute per litre of the solution has formality equal to It may be noted that molality, mole fraction, mass
one and is called formal solution. It may be mentioned fraction etc. are preferred to molarity, normality, etc.
here that the formality of a solution changes with because the former involve the weights of the solute
change in temperature. and solvent where as later involve volumes of
solutions. Temperature has no effect on weights but it
Formality
has significant effect on volumes.
Number of gram formula masses of solute
(F)= (10) Demal unit (D) : The concentrations are also
Volume of solution in litres expressed in “Demal unit”. One demal unit represents
Mass of ionic solute (g) one mole of solute present in one litre of solution at
=
(gm . formula mass of solute)  (Volume of solution (l)) 0o C .

W B (g ) W B (g)  1000
Colligative properties
Thus, F  or
GFM  V (l) GFM  V (ml ) Certain properties of dilute solutions containing
non-volatile solute do not depend upon the nature of
(8) Mole fraction (X) : Mole fraction may be
the solute dissolved but depend only upon the
defined as the ratio of number of moles of one
concentration i.e., the number of particles of the solute
component to the total number of moles of all the
present in the solution. Such properties are called
components (solvent and solute) present in the solution.
colligative properties. The four well known examples of
It is denoted by the letter X . It may be noted that the
the colligative properties are,
mole fraction is independent of the temperature. Mole
(1) Lowering of vapour pressure of the solvent.
fraction is dimensionless. Let us suppose that a solution
(2) Osmotic pressure of the solution.
contains the components A and B and suppose that
(3) Elevation in boiling point of the solvent.
WA g of A and WB g of B are present in it.
(4) Depression in freezing point of the solvent.
WA
Number of moles of A is given by, n A  and Since colligative properties depend upon the
MA number of solute particles present in the solution, the
WB simple case will be that when the solute is a non-
the number of moles of B is given by, n B 
MB electrolyte. In case the solute is an electrolyte, it may
where M A and M B are molecular masses of A split to a number of ions each of which acts as a
and B respectively. particle and thus will affect the value of the colligative
Total number of moles of A and B  n A  n B property.
nA Each colligative property is exactly related to
Mole fraction of A , X A 
n A  nB other, Relative lowering of vapour pressure, elevation
nB in boiling point and depression in freezing point are
Mole fraction of B , X B  directly proportional to osmotic pressure.
n A  nB
The sum of mole fractions of all the components in Lowering of vapour pressure
the solution is always one.
The pressure exerted by the vapours above the
nA nB
XA  XB   1. liquid surface in equilibrium with the liquid at a given
n A  nB n A  nB
temperature is called vapour pressure of the liquid. The
Thus, if we know the mole fraction of one vapour pressure of a liquid depends on,
component of a binary solution, the mole fraction of the
(1) Nature of liquid : Liquids, which have weak
other can be calculated.
intermolecular forces, are volatile and have greater
Relation between molality of solution (m) and
mole fraction of the solute (XA). vapour pressure. For example, dimethyl ether has
greater vapour pressure than ethyl alcohol.
 156 Solution and Colligative properties

(2) Temperature : Vapour pressure increases pressure of the pure solvent. It is determined by
with increase in temperature. This is due to the Ostwald-Walker method.
reason that with increase in temperature more Thus according to Raoult’s law,
molecules of the liquid can go into vapour phase.
w
(3) Purity of liquid : Pure liquid always has a p0  p n m
 
vapour pressure greater than its solution. p0 nN w W

Raoult’s law : When a non-volatile substance m M
is dissolved in a liquid, the vapour pressure of the where, p  Vapour pressure of the solution
liquid (solvent) is lowered. According to Raoult’s law
p 0  Vapour pressure of the pure solvent
(1887), at any given temperature the partial vapour
pressure (pA) of any component of a solution is equal n  Number of moles of the solute
to its mole fraction (XA) multiplied by the vapour N  Number of moles of the solvent
pressure of this component in the pure state ( p 0A ) . That w and m  weight and mol. wt. of solute
is, p A  p 0A  X A W and M  weight and mol. wt. of the solvent.
The vapour pressure of the solution (Ptotal) is the Limitations of Raoult’s law
sum of the partial pressures of the components, i.e., for  Raoult’s law is applicable only to very dilute
the solution of two volatile liquids with vapour solutions.
pressures p A and p B .  Raoult’s law is applicable to solutions
containing non-volatile solute only.
Ptotal  p A  p B  ( p 0A  X A )  ( p B0  XB)
 Raoult’s law is not applicable to solutes which
Alternatively, Raoult’s law may be stated as “the dissociate or associate in the particular
relative lowering of vapour pressure of a solution solution.
containing a non-volatile solute is equal to the mole
fraction of the solute in the solution.” Ideal and Non-Ideal solution
Relative lowering of vapour pressure is defined as
the ratio of lowering of vapour pressure to the vapour

Table: 4.1 Ideal and non-ideal solutions

Non-ideal solutions
Ideal solutions Positive deviation from Raoult's Negative deviation from Raoult's
law law

1. Obey Raoult's law at every 1. Do not obey Raoult's law. 1. Do not obey Raoult's law.
range of concentration.
2. H mix  0; neither heat is 2. H mix  0. Endothermic 2. H mix  0. Exothermic
evolved nor absorbed dissolution; heat is absorbed. dissolution; heat is evolved.
during dissolution.
3. Vmix  0; total volume of 3. Vmix  0. Volume is increased 3. Vmix  0. Volume is decreased
solution is equal to sum of after dissolution. during dissolution.
volumes of the components.

4. P  p A  p B  p 0A X A  p B0 X B i.e., 4. p A  p 0A X A ; p B  p B0 X B 4. p A  p 0A X A ; p B  p B0 X B

p A  p 0A X A : p B  p B0 X B  p A  p B  p 0A X A  p B0 X B  p A  p B  p 0A X A  p B0 X B

5. A  A, A  B, B  B interactions 5. A  B attractive force should be 5. A  B attractive force should be

should be same, i.e., 'A' and 'B' weaker than A  A and B  B greater than A  A and B  B
are identical in shape, size and attractive forces. 'A' and 'B' attractive forces. 'A' and 'B'
character. have different shape, size and have different shape, size and
character. character.
 Solution and Colligative properties 157
6. Escaping tendency of 'A' and 'B' 6. 'A' and 'B' escape easily 6. Escaping tendency of both
should be same in pure liquids showing higher vapour pressure components 'A' and 'B' is
and in the solution. than the expected value. lowered showing lower vapour
pressure than expected ideally.
Examples: Examples: Examples:
Dilute solutions; Acetone +ethanol Acetone + aniline;
benzene + toluene: acetone + CS 2 : acetone + chloroform;
n-hexane + n-heptane; water + methanol; CH3OH  CH3COOH ;
chlorobenzene + water + ethanol; H2O  HNO3
bromobenzene;
CCl4  toluene; chloroform + diethyl ether;
ethyl bromide + ethyl iodide;
CCl4  CHCl3 ; water + HCl;
n-butyl chloride + n-butyl
acetone + benzene; acetic acid + pyridine;
bromide
CCl4  CH 3OH ; chloroform + benzene

cyclohexane + ethanol

Graphical representation of ideal and non-ideal solutions

Ideal Positive deviation Negative deviation

solution Total vapour
p°A P=pA + pB p°A pressure p°A Total vapour
pressure
Vapour pressure

Vapour pressure

Vapour pressure
PA=p0A XA p°B p°B p°B

PB=p0B XB
Ideal
Ideal

XA = 1 Mole XA = 0 XA = 1 Mole XB = 1 XA = 1 Mole XA = 0

XB = 0 fraction XB = 1 XB = 0 fraction XA= 0 XB = 0 fraction XB = 1

Azeotropic mixture intermediate composition for which the vapour

pressure of the solution is minimum and hence, boiling
Azeotropes are defined as the mixtures of liquids point is maximum. At this composition the solution
which boil at constant temperature like a pure liquid distill`s at constant temperature without the change in
and possess same composition of components in liquid composition. This type of solutions are called maximum
as well as in vapour phase. Azeotropes are also called boiling azeotrope. e.g.,
constant boiling mixtures because whole of the H 2 O  HCl, H 2 O  HNO 3 , H 2 O  HClO4
azeotropes changes into vapour state at constant
temperature and their components can not be Osmosis and Osmotic pressure of the solution
separated by fractional distillation. Azeotropes are of
two types as described below, (1) Osmosis : The flow of solvent from pure
solvent or from solution of lower concentration into
(1) Minimum boiling azeotrope : For the
solution of higher concentration through a semi-
solutions with positive deviation there is an
permeable membrane is called Osmosis. Osmosis may
intermediate composition for which the vapour
be divided in following types,
pressure of the solution is maximum and hence, boiling
point is minimum. At this composition the solution (i) Exo-Osmosis : The outward osmotic flow of
distills at constant temperature without change in water from a cell containing an aqueous solution
composition. This type of solutions are called minimum through a semi-permeable membrane is called as Exo-
boiling azeotrope. e.g., osmosis. For example, egg (after removing hard shell)
placed in conc. NaCl solutions, will shrink due to exo-
H2O  C2 H5 OH , H2O  C2 H5 CH2OH
osmosis.
CHCl 3  C2 H 5 OH , (CH 3 )2 CO  CS 2 (ii) Endo-osmosis : The inward flow of water into
(2) Maximum boiling azeotrope : For the the cell containing an aqueous solution through a semi-
solutions with negative deviations there is an
 158 Solution and Colligative properties

permeable membrane is called as endo-osmosis. e.g., an  C .....(i)

egg placed in water swells up due to endo-osmosis. According to Gaylussac Van't Hoff law (at conc.
(iii) Reverse osmosis : If a pressure higher than temp.)
osmotic pressure is applied on the solution, the solvent
 T .....(ii)
will flow from the solution into the pure solvent
through the semi-permeable membrane. Since here the From equation (i) and (ii)
flow of solvent is in the reverse direction to that   CT ,   CRT (Van't Hoff equation)
observed in the usual osmosis, the process is called n  n w RT  w
reverse osmosis.   RT  C   ;    n  
V  V m V  m
Differences between osmosis and diffusion
Here, C = concentration of solution in moles per
Osmosis Diffusion
litre
In osmosis movement of In diffusion there is no role R = gas constant ; T = temperature
molecules takes place of semi-permeable
through a semi-permeable membrane.
n = number of moles of solute ; V = volume of
membrane.
solution
m = molecular weight of solute ; w = weight of
It involves movement of It involves passage of
solute
only solvent molecules from solvent as well as solute
one side to the other. molecules from one region (iii) Conditions for getting accurate value of
to the other. molecular mass are,
Osmosis is limited to Diffusion can take place in (a) The solute must be non-volatile.
solutions only. liquids, gases and solutions. (b) The solution must be dilute.
Osmosis can be stopped or Diffusion can neither be (c) The solute should not undergo dissociation or
reversed by applying stopped nor reversed association in the solution.
additional pressure on the (iv) Relation of osmotic pressure with different
solution side. colligative properties : Osmotic pressure is related to
(2) Osmotic pressure () relative lowering of vapour pressure, elevation of
boiling point and depression of freezing point
The osmotic pressure of a solution at a particular according to the following relations,
temperature may be defined as the excess hydrostatic
pressure that builds up when the solution is separated  Po  P  dRT dRT
(a)    A o A 
 M (b)   Tb 
from the solvent by a semi-permeable membrane. It is  PA  1000  Kb
denoted by .
dRT
or (c)   Tf 
1000  K f
Osmotic pressure may be defined as the excess
pressure which must be applied to a solution in order In the above relations,  = Osmotic pressure; d =
to prevent flow of solvent into the solution through the Density of solution at temperature T; R = Universal gas
semi-permeable membrane. constant; M = Mol. Mass of solute; K b = Molal elevation
or constant of solvent; K f = Molal depression
Osmotic pressure is the excess pressure which constant of solvent
must be applied to a given solution in order to increase
(v) Isotonic, Hypertonic and Hypotonic
its vapour pressure until it becomes equal to that of the
solution. solutions
(i) Measurements of osmotic pressure : (a) Isotonic or iso-osmotic solutions : Two
Following methods are used for the measurement of solutions of different substances having same osmotic
osmotic pressure, pressure at same temperature are known as isotonic
(a) Pfeffer’s method, (b) Morse and Frazer’s solutions.
method, (c) Berkeley and Hartley’s method, (d) For isotonic solutions, 1   2 Primary Condition
Townsend’s negative pressure method, (e) De Vries
…..(i)
plasmolytic method.
(ii) Determination of molecular mass of non- Also, C1  C2
volatile solute from osmotic pressure () : The osmotic n1 n2
pressure is a colligative property. For a given solvent or 
V1 V2 Secondary Conditions
the osmotic pressure depends only upon the molar
concentration of solute but does not depend upon its w1 w2
or 
nature. The following relation relates osmotic pressure m1 V1 m 2 V2
to the number of moles of the solute, …..(ii)
According to Boyle Van't Hoff law (at conc. temp.)

Eq. (ii) holds good only for those solutes which
neither possess the tendency to get associate nor
dissociate in solution, e.g.,
Urea and glucose are isotonic then, 1   2 and
C1  C2
Urea and NaCl are isotonic then, 1   2 but
(dissociat e)
C1  C2
Urea and Benzoic acid are isotonic then, 1   2 but
(associate )
C1  C2
(b) Hypertonic and hypotonic solution : The
solution which has more osmotic pressure than the
other solution is called as hypertonic solution and the
solution which has lesser osmotic pressure than the
other is called as hypotonic solution.
The flow of solvent is always from lower osmotic
pressure to higher osmotic pressure i.e. from hypotonic
to hypertonic solution.
Elevation in b.pt. of the solvent (Ebullioscopy)
Boiling point of a liquid may be defined as the
temperature at which its vapour pressure becomes
equal to atmospheric pressure, i.e., 760 mm. Since the
addition of a non-volatile solute lowers the vapour
pressure of the solvent, solution always has lower
vapour pressure than the solvent and hence it must be
heated to a higher temperature to make its vapour
pressure equal to atmospheric pressure with the result
the solution boils at a higher temperature than the pure
solvent. Thus sea water boils at a higher temperature
than distilled water. If Tb is the boiling point of the
solvent and T is the boiling point of the solution, the
difference in the boiling point (T or  Tb) is called the
elevation of boiling point.
T  Tb  Tb or T
Elevation in boiling point is determined by
Landsberger’s method and Cottrell’s method. Study of
elevation in boiling point of a liquid in which a non-
volatile solute is dissolved is called as ebullioscopy.
Important relations concerning elevation in
boiling point
(1) The elevation of boiling point is directly
proportional to the lowering of vapour pressure, i.e.,
Tb  p 0  p
(2) Tb  Kb  m
where Kb  molal elevation constant
ebullioscopic constant of the solvent; m  Molality of
the solution, i.e., number of moles of solute per 1000 g
of the solvent; Tb  Elevation in boiling point
Solution and Colligative properties 159
1000  K b  w 1000  K b  w
(3) Tb  or m 
m W Tb  W
where, K b is molal elevation constant and defined
as the elevation in b.pt. produced when 1 mole of the
solute is dissolved in 1 kg of the solvent.
w and W are the weights of solute and solvent
and m is the molecular weight of the solute.
0 . 002 (T0 )2
(4) Kb 
lV
where T0  Normal boiling point of the pure
solvent; lV  Latent heat of evaporation in cal / g of pure
solvent; K b for water is 0 . 52 deg  kg mol 1 .
Depression in f.pt. of the solvent (Cryoscopy)
Freezing point is the temperature at which the
liquid and the solid states of a substance are in
equilibrium with each other or it may be defined as the
temperature at which the liquid and the solid states of a
substance have the same vapour pressure. It is observed
that the freezing point of a solution is always less than
the freezing point of the pure solvent. Thus the freezing
point of sea water is low than that of pure water. The
depression in freezing point (T or Tf ) of a solvent
is the difference in the freezing point of the pure
solvent (Ts ) and the solution (Tsol. ) .
Ts  Tsol  Tf or T
NaCl or CaCl2 (anhydrous) are used to clear
snow on roads. They depress the freezing point of
water and thus reduce the temperature of the
formation of ice.
Depression in freezing point is determined by
Beckmann’s method and Rast’s camphor method. Study
of depression in freezing point of a liquid in which a
non-volatile solute is dissolved in it is called as
cryoscopy.
Important relations concerning depression in
freezing point.
(1) Depression in freezing point is directly
proportional to the lowering of vapour pressure.
Tf  p 0  p
(2) Tf  K f  m
where Kf  molal depression constant or
cryoscopic constant; m  Molality of the solution (i.e.,
no. of moles of solute per 1000 g of the solvent);
Tf  Depression in freezing point
or 1000  K f  w 1000  K f  w
(3) T f  or m 
m W T f  W
where Kf is molal depression constant and
defined as the depression in freezing point produced
 160 Solution and Colligative properties
when 1 mole of the solute is dissolved in 1kg of the
solvent. w and W are the weights of solute and solvent
and m is the molecular weight of the solute.
R(T0 )2 0 .002 (T0 )2
(4) K f   Molecular masses can be calculated by measuring
l f 1000 lf
where T0  Normal freezing point of the solvent;
l f  Latent heat of fusion/g of solvent; K f for water is
1 . 86 deg  kg mol 1
Colligative properties of electrolytes
The colligative properties of solutions, viz.
lowering of vapour pressure, osmotic pressure,
elevation in b.p. and depression in freezing point,
depend on the total number of solute particles present
in solution. Since the electrolytes ionise and give more
than one particle per formula unit in solution, the
colligative effect of an electrolyte solution is always
greater than that of a non-electrolyte of the same molar
concentration. All colligative properties are used for
calculating molecular masses of non-volatile solutes.
However osmotic pressure is the best colligative
property for determining molecular mass of a non-
volatile substance.
Colligative properties are depending on following
factory
(1) Colligative properties  Number of particles
 Number of molecules
(in case of non-electrolytes)
 Number of ions
(In case of electrolytes)
 Number of moles of
solute
 Mole fraction of solute
(2) For different solutes of same molar
concentration, the magnitude of the colligative
properties is more for that solution which gives more
number of particles on ionisation.
(3) For different solutions of same molar
concentration of different non-electrolyte solutes, the
magnitude of the colligative properties will be same for
all.
(4) For different molar concentrations of the
same solute, the magnitude of colligative properties is
more for the more concentrated solution.
(5) For solutions of different solutes but of same
percent strength, the magnitude of colligative property
is more for the solute with least molecular weight.
(6) For solutions of different solutes of the same
percent strength, the magnitude of colligative property
is more for that solute which gives more number of
particles, which can be known by the knowledge of
molecular weight and its ionisation behaviour.
Abnormal molecular masses
any of the colligative properties. The relation between
colligative properties and molecular mass of the solute
is based on following assumptions.
(1) The solution is dilute, so that Raoult’s law is
obeyed.
(2) The solute neither undergoes dissociation nor
association in solution.
In case of solutions where above assumptions are
not valid we find discrepencies between observed and
calculated values of colligative properties. These
anomalies are primarily due to
(i) Association of solute molecules.
(ii) Dissociation of solute molecules.
(i) Association of solute molecules : Certain
solutes in solution are found to associate. This
eventually leads to a decrease in the number of
molecular particles in the solutions. Thus, it results in a
decrease in the values of colligative properties.
1
Colligative property 
molecular mass of solute
therefore, higher values are obtained for
molecular masses than normal values for unassociated
molecules.
(ii) Dissociation of solute molecules : A number
of electrolytes dissociate in solution to give two or
more particles (ions). Therefore, the number of solute
particles, in solutions of such substances, is more than
the expected value. Accordingly, such solutions exhibit
higher values of colligative properties. Since colligative
properties are inversely proportional to molecular
masses, therefore, molecular masses of such substances
as calculated from colligative properties will be less
than their normal values.
Van’t Hoff’s factor (i) : In 1886, Van’t Hoff
introduced a factor ‘i’ called Van’t Hoff’s factor, to
express the extent of association or dissociation of
solutes in solution. It is ratio of the normal and
observed molecular masses of the solute, i.e.,
Normal molecular mass
i
Observed molecular mass
In case of association, observed molecular mass
being more than the normal, the factor i has a value
less than 1. But in case of dissociation, the Van’t Hoff’s
factor is more than 1 because the observed molecular
mass has a lesser value than the normal molecular
mass. In case there is no dissociation the value of ‘i’
becomes equal to one.
 Solution and Colligative properties 161
Since colligative properties are inversely
proportional to molecular masses, the Van’t Hoff’s
factor may also be written as,
Observed value of colligative property
i
Calculated value of colligative property
assuming no association or dissociation

No. of particl es after associatio n or dissociati on

i
No. of particl es before associatio n or dissociati on
Introduction of the Van’t Hoff factor modifies the
equations for the colligative properties as follows,
Relative lowering of vapour
Po  P
pressure  A o A  iX B
PA
Elevation of boiling point, Tb  ikbm
Depression in freezing point, Tf  ik f m

inRT
Osmotic pressure,   ;   iCRT
V
From the value of ‘i’, it is possible to calculate
degree of dissociation or degree of association of
substance.
Degree of dissociation () : It is defined as the
fraction of total molecules which dissociate into
simpler molecules or ions.
i1
 ; m= number of particles in solution
m 1
Degree of association () : It is defined as the
fraction of the total number of molecules which
associate or combine together resulting in the
formation of a bigger molecules.
i 1
 ; m = number of particles in solution.
1/m 1
 160 Solution and Colligative properties

 Semipermeable membrane of Cu2[Fe(CN )6 ] dose

not work in non aqueous solutions because it get
dissolved in non aqueous solvents.

 Osmotic coefficient (g) is the ratio of van’t Hoff

factor (i) to the no. of ions furnished by one
 A supersaturated solution is metastable. molecule of the electrolyte (N). i.e., g  i / N .
 Dissolution of gases in liquid is always
exothermic because S   ve (non favourable
factor) and in order to have G   ve
(spontaneous process), H has to be –ve.

 1 M aqueous solution is more concentrated than 1

m aqueous solution.
Solubility
 Substances having high V.P. (e.g., petrol)
1. The solubility of a gas in water depends on [MP PET 2002]
evaporate more quickly than substances having
(a) Nature of the gas (b) Temperature
low V.P. (e.g., motor oil).
(c) Pressure of the gas (d) All of the above
 Babo’s law : The lowering in vapour pressure of a 2. Which of the following is not correct for D2 O
solution caused by addition of an non-volatile [Orissa JEE 2002]
solute is called as Babo’s law. (a) Boiling point is higher than H 2 O
(b) D2 O reacts slowly than H 2 O
 Konowaloff’s rule : In case of a binary solution,
(c) Viscosity is higher than H 2 O at 25 o
at a fixed temperature, the vapour phase is
richer in that component whose addition causes (d) Solubility of NaCl in it is more than H 2 O
increase in total vapour pressure of the solution 3. The statement “ The mass of a gas dissolved in a
i.e., vapour phase is always richer in the more given mass of a solvent at any temperature is
proportional to the pressure of the gas above the
volatile component.
solvent” is [AMU 2002]
 When a non-volatile solute is added to the (a) Dalton’s Law of Partial Pressures
solvent, V.P. decrease, B.P. increase, F.P. (b) Law of Mass Action
decrease. (c) Henry’s Law
(d) None of these
 Ethylene glycol is commonly added to car radiators 4. Which is correct about Henry’s law [KCET 2002]
to depress the freezing point of water. It is known (a) The gas in contact with the liquid should
as antifreeze. behave as an ideal gas
(b) There should not be any chemical interaction
 NaCl or CaCl2 (anhydrous) are used to clear between the gas and liquid
snow on roads. It depresses the freezing point of (c) The pressure applied should be high
(d) All of these
water and reduce the temperature at which ice is
5. The statement “If 0.003 moles of a gas are
expected to be formed.
dissolved in 900 g of water under a pressure of 1
atmosphere, 0.006 moles will be dissolved under
 Plasmolysis : When a plant cell is placed in a
a pressure of 2 atmospheres”, illustrates[JIPMER 1999]
hypertonic solution, the fluid from the plant cell
(a) Dalton’s law of partial pressure
comes out and the cell shrinks. This phenomenon
(b) Graham’s law
is called plasmolysis and is due to osmosis.
(c) Raoult’s law
 Bursting of red blood cells when placed in water (d) Henry’s law
6. The solution of sugar in water contains [BHU 1973]
is due to osmosis.
(a) Free atoms (b) Free ions
 Gelatinous Cu2[Fe(CN )6 ] and gelatinous Ca3 (PO4 )2 (c) Free molecules (d) Free atom and
molecules
are artificial semipermeable membranes.
Method of expressing concentration of solution
 Solution and Colligative properties 161
(c) 0.99 (d) 9.9
1. 25 ml of 3.0 M HNO 3 are mixed with 75 ml of 12.
How much of NaOH is required to neutralise 1500
4.0 M HNO3 . If the volumes are additive, the cm 3 of 0.1 N HCl (At. wt. of Na =23) [KCET 2001]
(a) 4 g
molarity of the final mixture would be [DPMT 1986; MH CET 2001] (b) 6 g
(a) 3.25 M (b) 4.0 M (c) 40 g (d) 60 g
(c) 3.75 M (d) 3 . 50 M 13. If 5.85 g of NaCl (molecular weight 58.5) is
dissolved in water and the solution is made up to
2. The amount of anhydrous Na2CO3 present in 250 0.5 litre, the molarity of the solution will be[AMU 1999; Pb P
ml of 0.25 M solution is [DPMT 2001] (a) 0.2 (b) 0.4
(a) 6.225 g (b) 66.25 g (c) 1.0 (d) 0.1
(c) 6.0 g (d) 6.625 g 14. A mixture has 18g water and 414g ethanol. The
3. Dilute one litre 1 molar H 2 SO 4 solution by 5 litre mole fraction of water in mixture is (assume ideal
water, the normality of that solution is[DPMT 1983] behaviour of the mixture) [
(a) 0 . 2 N (b) 5 N (a) 0.1 (b) 0.4
(c) 0.7 (d) 0.9
(c) 10 N (d) 0.33 N
15. The number of molecules in 4.25 g of ammonia is
4. If 5.85 gms of NaCl are dissolved in 90 gms of approximately [CBSE PMT 2002]
water, the mole fraction of NaCl is
(a) 0.5  10 23
(b) 1.5  10 23
[CMC Vellore 1991; MP PMT 1994; AFMC 1998]
(a) 0.1 (b) 0.2 (c) 3.5  10 23 (d) 2 . 5  10 23
(c) 0.3 (d) 0.01 16. The largest number of molecules is in[Kurukshetra CEE 1998]
(e) 0.0196 (a) 25 g of CO2 (b) 46 g of C2 H 5 OH
5. The molarity of 0.006 mole of NaCl in 100 ml (c) 36 g of H 2 O (d) 54 g of N 2 O5
solution is
[Bihar MEE 1996]
17. If 1 M and 2.5 litre NaOH solution is mixed with
another 0.5 M and 3 litre NaOH solution, then
(a) 0.6 (b) 0.06
molarity of the resultant solution will be[CBSE PMT 2002]
(c) 0.006 (d) 0.066
(a) 1.0 M (b) 0.73 M
(e) None of these
(c) 0.80 M (d) 0.50 M
6. 9 . 8 g of H 2 SO 4 is present in 2 litres of a solution.
18. When a solute is present in trace quantities the
The molarity of the solution is[EAMCET 1991; MP PMT 2002]
following expression is used[Kerala CET (Med.) 2002]
(a) 0 . 1 M (b) 0 . 05 M
(a) Gram per million (b) Milligram percent
(c) 0 . 2 M (d) 0 . 01 M
(c) Microgram percent (d) Nano gram percent
7. What will be the molarity of a solution containing
5 g of sodium hydroxide in 250 ml solution (e) Parts per million
19. When the concentration is expressed as the
[MP PET 1999; BHU 1999; KCET 1999;
number of moles of a solute per litre of solution it
AIIMS 2000; Pb. CET 2000]
known as
(a) 0.5 (b) 1.0
[Kerala CET (Med.) 2002]
(c) 2.0 (d) 0.1
(a) Normality (b) Molarity
8. The normality of 0 . 3 M phosphorus acid (H 3 PO3 )
(c) Mole fraction (d) Mass percentage
is
(e) Molality
[IIT 1999; AIIMS 2000]
(a) 0.1 (b) 0.9 20. The normality of 2.3 M H 2 SO 4 solution is[KCET 2000]
(c) 0.3 (d) 0.6 (a) 2.3 N (b) 4.6 N
9. Which of the following has maximum number of (c) 0.46 N (d) 0.23 N
molecules 21. The molarity of a solution made by mixing 50ml
[CBSE PMT 2002] of conc. H 2 SO 4 (36N) with 50 ml of water is[MP PMT 2001
(a) 16 gm of O 2 (b) 16 gm of NO2
(a) 36 M (b) 18 M
(c) 7 gm of N 2 (d) 2 gm of H 2 (c) 9 M (d) 6 M
10. Molarity is expressed as[JIPMER 1991; CBSE PMT 1991] 22. 171 g of cane sugar (C12 H 22O11 ) is dissolved in 1
(a) Gram/litre (b) Moles/litre litre of water. The molarity of the solution is[MP PMT 2001
(c) Litre/mole (d) Moles/1000 gms (a) 2.0 M (b) 1.0 M
11. 20 ml of HCl solution requires 19 .85 ml of
(c) 0.5 M (d) 0.25 M
0.01 M NaOH solution for complete neutralization. 23. The volumes of 4 N HCl and 10 N HCl required to
The molarity of HCl solution is make[MP PMT 1999]
1 litre of 6 N HCl are [Kerala PMT 2004]
(a) 0.0099 (b) 0.099
 162 Solution and Colligative properties

(a) 0.75 litre of 10 N HCl and 0.25 litre of 4 N HCl 31. How many gram of HCl will be present in 150 ml
(b) 0.25 litre of 4 N HCl and 0.75 litre of 10 N HCl of its 0.52 M solution [RPET 1999]
(c) 0.67 litre of 4 N HCl and 0.33 litre of 10 N HCl (a) 2.84 gm (b) 5.70 gm
(d) 0.80 litre of 4 N HCl and 0.20 litre of 10 N (c) 8.50 gm (d) 3.65 gm
HCl 32. The number of moles present in 2 litre of 0.5 M
(e) 0.50 litre of 4 N HCl and 0.50 litre of 10 N HCl NaOH is
24. Which statement is true for solution of 0.020 M [MH CET 2001]
H 2 SO 4 (a) 0.5 (b) 0.1
[DPMT 2001] (c) 1 (d) 2
(a) 2 litre of the solution contains 0.020 mole of 33. 36g water and 828g ethyl alcohol form an ideal
SO 42  solution. The mole fraction of water in it, is[MP PMT 2003]
(a) 1.0 (b) 0.7
(b) 2 litre of the solution contains 0.080 mole of
H 3O  (c) 0.4 (d) 0.1
34. What will be the normality of a solution
(c) 1 litre of the solution contains 0.020 mole containing 4.9 g. H 3 PO4 dissolved in 500 ml
H 3O 
water [MP PMT 2003]
(d) None of these (a) 0.3 (b) 1.0
25. 10 litre solution of urea contains 240g urea. The (c) 3.0 (d) 0.1
active mass of urea will be [KCET 2000] 35. 3.0 molal NaOH solution has a density of 1.110
(a) 0.04 (b) 0.02 g/ml. The molarity of the solution is [BVP 2003]
(c) 0.4 (d) 0.2 (a) 3.0504 (b) 3.64
26. 5 ml of N HCl, 20 ml of N/2 H 2 SO 4 and 30 ml of N/3 (c) 3.05 (d) 2.9732
HNO3 are mixed together and volume made to one 36. Which of the following modes of expressing
litre. The normally of the resulting solution is [Kerala CET (Med.) 2003]
concentration is independent of temperature [
N N CBSE PMT 1992, 95; MP PMT 1992; AIIMS 1997, 2001]
(a) (b)
5 10 (a) Molarity (b) Molality
N N (c) Formality (d) Normality
(c) (d)
20 40 37. The molality of a solution is [MP PMT 1996]
N (a) Number of moles of solute per 1000 ml of the
(e)
25 solvent
27. The amount of K2 Cr2 O7 (eq. wt. 49.04) required (b) Number of moles of solute per 1000 gm of the
to prepare 100 ml of its 0.05 N solution is[JIPMER 2002]
solvent
(a) 2.9424 g (b) 0.4904 g (c) Number of moles of solute per 1000 ml of the
(c) 1.4712 g (d) 0.2452 g
solution
28. With increase of temperature, which of these
(d) Number of gram equivalents of solute per
changes
1000 ml of the solution
[AIEEE 2002]
(a) Molality 38. The number of molecules in 16 gm of methane is
(b) Weight fraction of solute [MP PET/PMT 1998]

(c) Fraction of solute present in water (a) 3.0  10 23 (b) 6 .02  10 23

(d) Mole fraction 16 16
(c)  10 23 (d)  10 23
29. 25ml of a solution of barium hydroxide on 6 .02 3.0
titration with a 0.1molar solution of hydrochloric 39. The number of moles of a solute in its solution is
acid gave a litre value of 35 ml. The molarity of 20 and total number of moles are 80. The mole
barium hydroxide solution was fraction of solute is
[AIEEE 2003] [MP PMT 1997]
(a) 0.07 (b) 0.14 (a) 2.5 (b) 0.25
(c) 0.28 (d) 0.35 (c) 1 (d) 0.75
30. 2.0 molar solution is obtained , when 0.5 mole 40. The normality of a solution of sodium hydroxide
solute is dissolved in [MP PMT 2003] 100 ml of which contains 4 grams of NaOH is[CMC Vellore
(a) 250 ml solvent (b) 250 g solvent (a) 0.1 (b) 40
(c) 250 ml solution (d) 1000 ml solvent (c) 1.0 (d) 0.4
 Solution and Colligative properties 163
41. Two solutions of a substance (non electrolyte) are 50. Conc. H 2 SO 4 has a density of 1.98 gm/ml and is
mixed in the following manner 480 ml of 1.5M 98% H 2 SO 4 by weight. Its normality is[MP PET 2002]
first solution + 520 mL of 1.2M second solution.
(a) 2 N (b) 19.8 N
What is the molarity of the final mixture [AIEEE 2005]
(c) 39.6 N (d) 98 N
(a) 1.20 M (b) 1.50 M
51. The mole fraction of the solute in one molal
(c) 1.344 M (d) 2.70 M
aqueous solution is [CBSE PMT 2005]
42. The normal amount of glucose in 100 ml of blood (a) 0.027 (b) 0.036
(8–12 hours after a meal) is [BHU 1981] (c) 0.018 (d) 0.009
(a) 8 mg (b) 80 mg N
52. With 63 gm of oxalic acid how many litres of
(c) 200 mg (d) 800 mg 10
solution can be prepared [RPET 1999]
43. Molar solution means 1 mole of solute present in
(a) 100 litre (b) 10 litre
[BCECE 2005]
(c) 1 litre (d) 1000 litre
(a) 1000g of solvent (b) 1 litre of solvent
53. Molarity of 0.2 N H 2 SO 4 is [KCET 2005]
(c) 1 litre of solution (d) 1000g of solution
(a) 0.2 (b) 0.4
44. What will be the molality of a solution having
18 g of glucose (mol. wt. = 180) dissolved in 500 g (c) 0.6 (d) 0.1
54. 10.6 grams of a substance of molecular weight 106
of water
was dissolved in 100 ml . 10 ml of this solution was
[MP PET/PMT 1998; CBSE PMT 2000; JIPMER 2001]
pipetted out into a 1000 ml flask and made up to the
(a) 1 m (b) 0.5 m mark with distilled water. The molarity of the
(c) 0.2 m (d) 2 m resulting solution is [EAMCET 1998]

45. A solution of Al2 (SO 4 )3 {d  1.253 gm / ml } contain (a) 1.0M (b) 10 2 M

22% salt by weight. The molarity, normality and (c) 10 3 M (d) 10 4 M
molality of the solution is 55.[MP
The
PETmole
2004] fraction of water in 20% aqueous
(a) 0.805 M, 4.83 N, 0.825 M solution of H 2 O2 is [EAMCET 1993]

(b) 0.825 M, 48.3 N, 0.805 M 77 68

(a) (b)
68 77
(c) 4.83 M, 4.83 N, 4.83 M
20 80
(d) None (c) (d)
80 20
46. Which of the following should be done in order to
56. Mole fraction (X ) of any solution is equal to
prepare 0.40 M NaCl starting with 100 ml of
No. of moles of solute
0.30 M NaCl (mol.wt. of NaCl  58 .5 ) [BIT 1992] (a)
Volume of solution in litre
(a) Add 0.585 g NaCl (b) Add 20 ml water No. of gram equivalent of solute
(b)
(c) Add 0.010 ml NaCl (d) Evaporate 10 ml Volume of solution in litre
water No. of moles of solute
(c)
47. Which of the following solutions has the highest Mass of solvent in kg
normality No. of moles of any constituent
(d)
[JIPMER 1991] Total no. of moles of all constituents
(a) 8 gm of KOH / litre (b) N phosphoric acid 57. When WB gm solute (molecular mass MB )
(c) 6 gm of NaOH / 100 ml (d) 0.5 M H 2 SO 4 dissolves in WA gm solvent. The molality M of the
48. What volume of 0.8 M solution contains 0.1 mole solution is
of the solute [AFMC 1984] WB MB WB 1000
(a)  (b) 
(a) 100 ml (b) 125 ml W A 1000 MB WA
(c) 500 ml (d) 62 .5 ml W A 1000 WA  M B
(c)  (d)
49. Hydrochloric acid solution A and B have WB MB WB  1000
concentration of 0 . 5 N and 0 . 1 N respectively. The 58. Normality (N ) of a solution is equal to
volumes of solutions A and B required to make No. of moles of solute
2 litres of 0 . 2 N HCl are (a)
Volume of solution in litre
[KCET 1993] No. of gram equivalent of solute
(a) 0.5 l of A  1.5 l of B (b)
Volume of solution in litre
(b) 1 .5 l of A  0 . 5 l of B No. of moles of solute
(c)
(c) 1 .0 l of A  1.0 l of B Mass of solvent in kg
(d) 0.75 l of A  1 .25 l of B (d) None of these
 164 Solution and Colligative properties

59. The volume strength of 1.5 N H 2 O2 solution is (a) Solubility product of CuS is equal to the ionic
[CBSE PMT 1997; BHU 2002] product of ZnS
(a) 4.8 (b) 5.2 (b) Solubility product of CuS is equal to the
(c) 8.8 (d) 8.4 solubility product of ZnS
60. How many gm of H 2 SO 4 is present in 0 .25 gm (c) Solubility product of CuS is lower than the
mole of H 2 SO 4 [CPMT 1990] solubility product of ZnS
(a) 24.5 (b) 2.45 (d) Solubility product of CuS is greater than the
(c) 0.25 (d) 0.245 solubility product of ZnS
61. 20 g of hydrogen is present in 5 litre vessel. The 71. The number of moles of solute per kg of a solvent
molar concentration of hydrogen is [DPMT 2000] is called its [DPMT 1983; IIT 1985; CPMT 1999]
(a) 4 (b) 1 (a) Molarity (b) Normality
(c) 3 (d) 2 (c) Molar fraction (d) Molality
62. To prepare a solution of concentration of 0.03 72. 1.0 gm of pure calcium carbonate was found to
g/ml of AgNO3 , what amount of AgNO3 should be require 50 ml of dilute HCl for complete reaction.
added in 60 ml of solution [AFMC 2005] The strength of the HCl solution is given by[CPMT 1986]
(a) 1.8 (b) 0.8 (a) 4 N (b) 2 N
(c) 0.18 (d) None of these (c) 0.4 N (d) 0.2 N
63. How many grams of dibasic acid (mol. wt. 200) 73. Molecular weight of glucose is 180. A solution of
should be present in 100 ml of its aqueous solution glucose which contains 18 gms per litre is[AFMC 1978]
to give decinormal strength[AIIMS 1992; CBSE PMT 1999; AFMC (a) 2 molal
1999; (b) 1 molal
KCET 2000; CPMT 2001] (c) 0.1 molal (d) 18 molal
(a) 1 g (b) 2 g 74. 0.5 M of H 2 SO 4 is diluted from 1 litre to 10 litre,
(c) 10 g (d) 20 g normality of resulting solution is [AFMC 2005]
64. The weight of pure NaOH required to prepare (a) 1 N (b) 0.1 N
250 cm 3 of 0 . 1 N solution is[KCET 1991; Kerala PMT 2004] (c) 10 N (d) 11 N
(a) 4 g (b) 1 g 75. If one mole of a substance is present in 1 kg of
(c) 2 g (d) 10 g solvent, then
65. If 20 ml of 0.4 N NaOH solution completely [CPMT 1996]
neutralises 40 ml of a dibasic acid. The molarity of (a) It shows molar concentration
the acid solution is (b) It shows molal concentration
[EAMCET 1987] (c) It shows normality
(a) 0 . 1 M (b) 0 . 2 M (d) It shows strength gm / gm
(c) 0 . 3 M (d) 0 . 4 M
76. The molality of 90% H2 SO4 solution is
66. Which of the following concentration factor is
affected by change in temperature [DCE 2002] [density=1.8 gm/ml] [MP PMT 2004]
(a) Molarity (b) Molality (a) 1.8 (b) 48.4
(c) Mole fraction (d) Weight fraction (c) 9.18 (d) 94.6
67. The distribution law is applied for the 77. The volume of water to be added to 100 cm 3 of 0.5 N
distribution of basic acid between [UPSEAT 2001] H 2 SO 4 to get decinormal concentration is [
(a) Water and ethyl alcohol 3 3
(a) 400 cm (b) 500 cm
(b) Water and amyl alcohol 3
(c) 450 cm (d) 100 cm 3
(c) Water and sulphuric acid
78. If 25 ml of 0.25 M NaCl solution is diluted with
(d) Water and liquor ammonia
water to a volume of 500ml the new
68. Which is heaviest [CBSE PMT 1991] concentration of the solution is
(a) 25 gm of mercury [UPSEAT 2000, 01]
(b) 2 moles of water (a) 0.167 M (b) 0.0125 M
(c) 2 moles of carbon dioxide (c) 0.833 M (d) 0.0167 M
(d) 4 gm atoms of oxygen 79. 10 grams of a solute is dissolved in 90 grams of a
69. The molarity of a solution of Na2 CO3 having solvent. Its mass percent in solution is
10 .6 g / 500 ml of solution is [AFMC 1992; DCE 2000] (a) 0.01 (b) 11.1
(a) 0 . 2 M (b) 2 M (c) 10 (d) 9
(c) 20 M (d) 0 . 02 M 80. What is the molality of a solution which contains

18 g of glucose (C6 H12O6 ) in 250 g of water [UPSEAT 2001]
70. On passing H 2 S gas through a solution of Cu
(a) 4.0 m (b) 0.4 m
and Zn 2 ions, CuS is precipitated first because[AMU 2001]
(c) 4.2 m (d) 0.8 m
 Solution and Colligative properties 165
81. Calculate the molality of 1 litre solution of 93% 92. The weight of H 2C2O4 . 2 H 2O required to prepare
H 2 SO 4 (weight/volume). The density of the 500 ml of 0 . 2 N solution is [EAMCET 1991]
solution is 1.84 g /ml [UPSEAT 2000] (a) 126 g (b) 12 .6 g
(a) 10.43 (b) 20.36 (c) 63 g (d) 6 .3 g
(c) 12.05 (d) 14.05
93. In a solution of 7.8 gm benzene C6 H 6 and 46 .0 gm
82. Volume of water needed to mix with 10 ml 10N
HNO 3 to get 0.1 N HNO 3 [UPSEAT 2003]
toluene (C6 H 5 CH 3 ) , the mole fraction of benzene
in this solution is [BHU 1981, 87]
(a) 1000 ml (b) 990 ml
(a) 1 / 6 (b) 1 / 5
(c) 1010 ml (d) 10 ml
83. The sum of the mole fraction of the components of (c) 1 / 2 (d) 1 / 3
a solution is 94. A solution contains 25 %H 2 O , 25 %C 2 H 5 OH and
(a) 0 (b) 1 50 % CH 3 COOH by mass. The mole fraction of
(c) 2 (d) 4 H 2 O would be
84. Increasing the temperature of an aqueous solution (a) 0.25 (b) 2.5
will cause
(c) 0.503 (d) 5.03
[IIT Screening 1993]
95. A 5 molar solution of H 2 SO 4 is diluted from 1 litre
(a) Decrease in molality (b) Decrease in molarity
(c) Decrease in mole fraction (d)Decrease in % w/w to 10 litres. What is the normality of the solution [AFMC 20
85. 1000 gms aqueous solution of CaCO3 contains 10 (a) 0.25 N (b) 1 N
(c) 2 N (d) 7 N
gms of carbonate. Concentration of the solution is[CPMT 1985]
96. Molarity of a solution containing 1g NaOH in
(a) 10 ppm (b) 100 ppm
(c) 1000 ppm (d) 10000 ppm 250 ml of solution is [EAMCET 1990]

86. 3.65 gms of HCl is dissolved in 16.2 gms of water. (a) 0 . 1 M (b) 1 M
The mole fraction of HCl in the resulting solution (c) 0.01 M (d) 0.001 M
is [EAMCET 2003]
97. What is molarity of a solution of HCl which
(a) 0.4 (b) 0.3 contains 49% by weight of solute and whose
(c) 0.2 (d) 0.1 specific gravity is 1.41
87. An aqueous solution of glucose is 10% in strength. [CPMT 2001; CBSE PMT 2001]
The volume in which 1 gm mole of it is dissolved (a) 15.25 (b) 16.75
will be (c) 18.92 (d) 20.08
[AIIMS 1992; Pb. CET 2004]
98. NaClO solution reacts with H 2 SO 3 as,
(a) 18 litre (b) 9 litre
NaClO  H 2 SO 3  NaCl  H 2 SO 4 . A solution of
(c) 0.9 litre (d) 1.8 litre
NaClO used in the above reaction contained 15g
88. The concentration of an aqueous solution of
of NaClO per litre. The normality of the solution
0.01 M CH3OH solution is very nearly equal to
would be [AMU 1999]
which of the following [BITS 1992]
(a) 0.8 (b) 0.6
(a) 0.01 % CH 3OH (b) 0.01m CH3OH
(c) 0.2 (d) 0.33
(c) x CH 3 OH  0.01 (d) 0.99 M H 2O
99. A solution contains 1 .2046  10 24 hydrochloric acid
(e) 0.01 N CH 3OH molecules in one dm 3 of the solution. The
89. When 1 .80 gm glucose dissolve in 90 gm of H 2 O , strength of the solution is [KCET 2004]

the mole fraction of glucose is [AFMC 2000] (a) 6 N (b) 2 N

(a) 0.00399 (b) 0.00199 (c) 4 N (d) 8 N
(c) 0.0199 (d) 0.998 1
100. 10 N and N solution is called
10
90. 6 .02  10 20 molecules of urea are present in 100 ml
of its solution. The concentration of urea solution (a) Decinormal and decanormal solution
is [AIEEE 2004] (b) Normal and decinormal solution
(a) 0.02 M (b) 0.01 M (c) Normal and decanormal solution
(c) 0.001 M (d) 0.1 M (d) Decanormal and decinormal solution
101. When 7.1gm Na 2 SO 4 (molecular mass 142)
(Avogadro constant, N A  6 .02  10 23 mol 1 )
dissolves in 100 ml H 2 O , the molarity of the
91. The number of moles of SO 2 Cl2 in 13 .5 gm is[CPMT 1994]
solution is
(a) 0.1 (b) 0.2 [CBSE PMT 1991; MP PET 1993, 95]
(c) 0.3 (d) 0.4 (a) 2.0 M (b) 1.0 M
 166 Solution and Colligative properties
(c) 0.5 M (d) 0.05 M 113. 10 ml of conc. H 2 SO 4 (18 molar) is diluted to 1
102. Molarity of 4% NaOH solution is [EAMCET 1987]
litre. The approximate strength of dilute acid could
(a) 0 . 1 M (b) 0 . 5 M be [JIPMER 1991]
(c) 0 . 01 M (d) 1 . 0 M (a) 0.18 N (b) 0.09 N
103. When 6 gm urea dissolve in 180 gm H 2 O . The mole (c) 0.36 N (d) 1800 N
fraction of urea is [CPMT 1988] 114. The normality of 10 lit. volume hydrogen peroxide is
10 10 . 1 [Kerala CET (Med.) 2003]
(a) (b)
10 . 1 10 (a) 0.176 (b) 3.52
10 . 1 0 .1 (c) 1.78 (d) 0.88
(c) (d) (e) 17.8
0 .1 10 . 1
104. The normality of 10% (weight/volume) acetic acid 115. Essential quantity of ammonium sulphate taken
is for preparation of 1 molar solution in 2 litres is
[CPMT 1983] (a) 132 gm (b) 264 gm
(a) 1 N (b) 10 N (c) 198 gm (d) 212 gm
(c) 1.7 N (d) 0.83 N 116. In a mixture of 1 gm H 2 and 8 gm O 2 , the mole
105. Unit of mole fraction is [BHU 1998, 2005]
fraction of hydrogen is [Orissa JEE 2002]
(a) Moles/litre (b) Moles/litre2
(a) 0.667 (b) 0.5
(c) Moles–litre (d) Dimensionless
(c) 0.33 (d) None of these
106. Normality of 2 M sulphuric acid is
[AIIMS 1991, 92; Pb. CET 2002] 117. A solution of CaCl2 is 0.5 mol / litre, then the moles
(a) 2 N (b) 4 N of chloride ion in 500 ml will be [MP PMT 1986]
(c) N / 2 (d) N / 4 (a) 0.25 (b) 0.50
107. Molar concentration (M ) of any solution = (c) 0.75 (d) 1.00
No. of moles of solute 118. What is the molarity of H 2 SO 4 solution, that has
(a)
Volume of solution in litre a density 1.84 gm/cc at 35 o C and contains solute
No. of gram equivalent of solute 98% by weight
(b)
Volume of solution in litre [AIIMS 2001]
No. of moles of solute (a] 4.18 M (b) 8.14 M
(c) (c) 18.4 M (d) 18 M
Mass of solvent in kg
119. A certain aqueous solution of FeCl3 (formula mass
No. of moles of any constituent
(d) =162) has a density of 1.1 g / ml and contains
Total no. of moles of all constituents
108. If 5 .0 gm of BaCl2 is present in 10 6 gm solution, 20 .0% FeCl3 . Molar concentration of this solution
the concentration is is [Pb. PMT 1998]
(a) 1 ppm (b) 5 ppm (a) 0.028 (b) 0.163
(c) 50 ppm (d) 1000 ppm (c) 1.27 (d) 1.47
109. 1 Molar solution contains [DPMT 2002]
120. If 0.50 mol of CaCl2 is mixed with 0.20 mol of
(a) 1000g of solute (b) 1000g of solvent Na3 PO4 , the maximum number of moles of
(c) 1 litre of solvent (d) 1 litre of solution Ca3 (PO4 )2 which can be formed, is
110. To neutralise completely 20 mL of 0.1 M aqueous (a) 0.70 (b) 0.50
solution of phosphorous acid (H 3 PO3 ), the volume (c) 0.20 (d) 0.10
of 0.1 M aqueous KOH solution required is 121.[AIEEE
An X2004]
molal solution of a compound in benzene
(a) 40 mL (b) 20 mL has mole fraction of solute equal to 0.2. The value
(c) 10 mL (d) 60 mL of X is
111. On dissolving 1 mole of each of the following [KCET 1996; DCE 2001]
acids in 1 litre water, the acid which does not give (a) 14 (b) 3.2
a solution of strength 1 N is (c)
[MP 4 1993]
PET (d) 2
(a) HCl (b) Perchloric acid 122. Molecular weight of urea is 60. A solution of urea
(c) HNO 3 (d) Phosphoric acid containing 6 g urea in one litre is [BHU 1996, 99]
112. How many grams of NaOH will be required to (a) 1 molar (b) 1.5 molar
neutralize 12.2 grams of benzoic acid[MP PMT 1999] (c) 0.1 molar (d) 0.01 molar
(a) 40 gms (b) 4 gms 123. The molar solution of sulphuric acid is equal to
(c) 16 gms (d) 12 .2 gms [MP PET 1999]
(a) N solution (b) 2 N solution
(c) N / 2 solution (d) 3 N solution
 Solution and Colligative properties 167
124. The weight of sodium carbonate required to 134. If we take 44 g of CO2 and 14 g of N 2 what will
prepare 500 ml of a semi- normal solution is [JIPMER 1999] be mole fraction of CO2 in the mixture[KCET 1990]
(a) 13.25 g (b) 26.5 g
(a) 1/5 (b) 1/3
(c) 53 g (d) 6.125 g
125. 200 ml of a solution contains 5.85 g dissolved (c) 2/3 (d) 1/4
135. What is the volume of 0.1 N HCl required to react
sodium chloride. The concentration of the
solution will be (Na  23 ; Cl  35 .5) [MP PMT 1999] completely with 1 .0 g of pure calcium carbonate
(a) 1 molar (b) 2 molar (Ca  40 , C  12 and O  16 ) [KCET 1998]
(c) 0.5 molar (d) 0.25 molar (a) 150 cm 3
(b) 250 cm 3

126. Molarity of a solution prepared by dissolving 75.5

(c) 200 cm 3 (d) 100 cm 3
g of pure KOH in 540 ml solution is [BHU 1999]
(a) 3.05 M (b) 1.35 M 136. The amount of NaOH in gms in 250 cm 3 of a
(c) 2.50 M (d) 4.50 M 0.100 M NaOH solution would be
127. Which one of the following is an extensive (a) 4 gm (b) 2 gm
property (c) 1 gm (d) 2.5 gm
[KCET 1998]
137. 4.0 gm of NaOH are contained in one decilitre of
(a) Molar volume (b) Molarity solution. Its molarity would be
(c) Number of moles (d) Mole fraction (a) 4 M (b) 2 M
128. Addition of conc. HCl to saturated BaCl2 solution
(c) 1 M (d) 1.5 M
precipitates BaCl2 ; because [AMU 2000]
138. When 90 gm of water is mixed with 300 gm of
(a) It follows from Le Chatelier’s principle acetic acid. The total number of moles will be
(b) Of common-ion effect (a) 5 (b) 10
(c) Ionic product (Ba  ), (Cl  ) remains constant in a (c) 15 (d) 20
saturated solution
139. A molal solution is one that contains one mole of a
(d) At constant temperature, the product (Ba 2 ), solute in
(Cl  )2 remains constant in a saturated [NCERT 1983; DPMT 1983; CPMT 1985; IIT 1986;
solution MP PMT 1987; EAMCET 1990; MP PET 1994, 99]
129. How much water is needed to dilute 10 ml of 10 N (a) 1000 gm of the solvent
hydrochloric acid to make it exactly decinormal
(b) One litre of the solvent
(0.1 N)
[EAMCET 1982] (c) One litre of the solution
(a) 990 ml (b) 1000 ml (d) 22.4 litres of the solution
(c) 1010 ml (d) 100 ml 140. What weight of ferrous ammonium sulphate is
130. The formula weight of H2 SO4 is 98. The weight of needed to prepare 100 ml of 0.1 normal solution
the acid in 400 ml of 0 . 1 M solution is[EAMCET 1987] (mol. wt. 392)
(a) 2.45 g (b) 3.92 g [CPMT 1983]

(c) 4.90 g (d) 9.8 g (a) 39.2 gm (b) 3.92 gm

(c) 1.96 gm (d) 19.6 gm
131. The molarity of pure water is
[CPMT 1974, 88, 90; CMC Vellore 1991; RPET 1999; 141. If 18 gm of glucose (C6 H12O6 ) is present in 1000
NCERT 1974, 76; MP PMT 1999; AMU 2002] gm of an aqueous solution of glucose, it is said to
(a) 55.6 (b) 5.56 be [CPMT 1986]
(c) 100 (d) 18 (a) 1 molal (b) 1.1 molal
132. The molarity of a 0.2 N Na2 CO3 solution will be (c) 0.5 molal (d) 0.1 molal
[MP PMT 1987; Pb. CET 2004] 142. The number of moles of KCl in 1000 ml of 3 molar
(a) 0.05 M (b) 0.2 M solution is [NCERT 1973]
(c) 0.1 M (d) 0.4 M
(a) 1 (b) 2
133. How many moles of water are present in 180 g of
(c) 3 (d) 1.5
water
[JIPMER 1991; DPMT 1982; Manipal MEE 1995] 143. The unit of molality is [Pb. CET 2003]

(a) 1 mole (b) 18 mole (a) Mole per litre (b) Mole per kilogram
(c) 10 mole (d) 100 mole (c) Per mole per litre (d) Mole litre
 168 Solution and Colligative properties
144. A solution contains 1 mole of water and 4 mole of (d) Nature of solvent only
ethanol. The mole fraction of water and ethanol 8. Which is not a colligative property
will be
[CPMT 1984; BHU 1982; Manipal MEE 1995]
(a) 0.2 water + 0.8 ethanol (a) Refractive index
(b) 0.4 water + 0.6 ethanol (b) Lowering of vapour pressure
(c) 0.6 water + 0.8 ethanol (c) Depression of freezing point
(d) 0.8 water + 0.2 ethanol (d) Elevation of boiling point
9. Which of the following is a colligative property
Colligative properties
[BHU 1990; NCERT 1983; MP PMT 1983; DPMT 1981, 83;
MP PET/PMT 1998; AIIMS 1999; Pb. CET 2000]
1. The magnitude of colligative properties in all
colloidal dispersions is ….than solution [AMU 1999] (a) Surface tension (b) Viscosity
(a) Lower (b) Higher (c) Osmotic pressure (d) Optical rotation
10. Colligative properties are used for the
(c) Both (d) None
determination of
2. Equimolar solutions in the same solvent have[AIEEE 2005] [Kerala CET (Engg.) 2002]
(a) Same boiling point but different freezing point (a) Molar Mass
(b) Same freezing point but different boiling point (b) Equivalent weight
(c) Same boiling and same freezing points (c) Arrangement of molecules
(d) Different boiling and different freezing points (d) Melting point and boiling point
3. Which of the following is a colligative property (d) Both (a) and (b)
[AFMC 1992; CBSE PMT 1992; MP PMT 1996, 2003] 11. What does not change on changing temperature
(a) Osmotic pressure (b) Boiling point [DCE 2001]

(c) Vapour pressure (d) Freezing point (a) Mole fraction (b) Normality

4. The colligative properties of a solution depend on (c) Molality (d) None of these
[CPMT 1984; MP PMT 1993; UPSEAT 2001; Kerala PMT 2002]
(a) Nature of solute particles present in it
Lowering of vapour pressure
(b) Nature of solvent used 1. Vapour pressure of CCl4 at 25 o C is 143 mm of
(c) Number of solute particles present in it Hg 0.5 gm of a non-volatile solute (mol. wt. = 65)
(d) Number of moles of solvent only is dissolved in 100 ml CCl4 . Find the vapour
5. Which of the following is not a colligative pressure of the solution (Density of
property CCl 4  1 . 58 g / cm )
2
[CBSE PMT 1998]
[BHU 1982; CPMT 1988; DPMT 1985; MP PET 1999]
(a) 141 .43 mm (b) 94 .39 mm
(a) Osmotic pressure
(c) 199 .34 mm (d) 143 .99 mm
(b) Elevation in B.P.
(c) Vapour pressure 2. For a solution of volatile liquids the partial
vapour pressure of each component in solution is
(d) Depression in freezing point directly proportional to
6. Which of the following is not a colligative (a) Molarity (b) Mole fraction
property
(c) Molality (d) Normality
[MP PET 2001; CPMT 2001; Pb. CET 2001] 3. “The relative lowering of the vapour pressure is
(a) Optical activity equal to the mole fraction of the solute.” This law
(b) Elevation in boiling point is called
(c) Osmotic pressure [MP PET 1997, 2001]
(a) Henry's law (b) Raoult's law
(d) Lowering of vapour pressure
(c) Ostwald's law (d) Arrhenius's law
7. Colligative properties of a solution depends upon
[MP PMT 1994, 2002]
4. The relative lowering of vapour pressure
produced by dissolving 71.5 g of a substance in
(a) Nature of both solvent and solute 1000 g of water is 0.00713. The molecular weight
(b) The relative number of solute and solvent of the substance will be
particles [DPMT 2001]
(c) Nature of solute only (a) 18.0 (b) 342
 Solution and Colligative properties 169
(c) 60 (d) 180 [EAMCET 1991; CBSE PMT 1991]
5. When mercuric iodide is added to the aqueous (a) Solute moleules and solvent molecules
solution of potassium iodide, the [IIT 1987] (b) Solute molecules and the total molecules in
(a) Freezing point is raised the solution
(b) Freezing point is lowered (c) Solvent molecules and the total molecules in
the solution
(c) Freezing point does not change
(d) Solvent molecules and the total number of
(d) Boiling point does not change ions of the solute
6. Vapour pressure of a solution is 13. 5cm 3 of acetone is added to 100 cm 3 of water, the
[EAMCET 1988; MP PET 1994]
vapour pressure of water over the solution
(a) Directly proportional to the mole fraction of (a) It will be equal to the vapour pressure of pure
the solvent water
(b) Inversely proportional to the mole fraction of (b) It will be less than the vapour pressure of
the solute pure water
(c) Inversely proportional to the mole fraction of (c) It will be greater than the vapour pressure of
the solvent pure water
(d) Directly proportional to the mole fraction of (d) It will be very large
the solute 14. At 300 K, when a solute is added to a solvent its
vapour pressure over the mercury reduces from
7. When a substance is dissolved in a solvent the
vapour pressure of the solvent is decreased. This 50 mm to 45 mm. The value of mole fraction of
results in solute will be
(a) 0.005 (b) 0.010
[NCERT 1981]
(c) 0.100 (d) 0.900
(a) An increase in the b.p. of the solution
15. A solution has a 1 : 4 mole ratio of pentane to
(b) A decrease in the b.p. of the solvent hexane. The vapour pressure of the pure
(c) The solution having a higher freezing point hydrocarbons at 20°C are 440 mmHg for pentane
than the solvent and 120 mmHg for hexane. The mole fraction of
(d) The solution having a lower osmotic pressure pentane in the vapour phase would be
than the solvent [CBSE PMT 2005]
(a) 0.549 (b) 0.200
8. If P o and P are the vapour pressure of a solvent
(c) 0.786 (d) 0.478
and its solution respectively and N 1 and N 2 are
16. Benzene and toluene form nearly ideal solutions.
the mole fractions of the solvent and solute At 20°C, the vapour pressure of benzene is 75 torr
respectively, then correct relation is and that of toluene is 22 torr. The parial vapour
(a) P  P o N 1 (b) P  P o N 2 pressure of benzene at 20°C for a solution
containing 78g of benzene and 46g of toluene in
(c) P o  P N 2 (d) P  P o ( N 1 / N 2 )
torr is [AIEEE 2005]
9. An aqueous solution of methanol in water has (a) 50 (b) 25
vapour pressure [MNR 1986] (c) 37.5 (d) 53.5
(a) Equal to that of water 17. The vapour pressure lowering caused by the
(b) Equal to that of methanol addition of 100 g of sucrose(molecular mass =
(c) More than that of water 342) to 1000 g of water if the vapour pressure of
(d) Less than that of water pure water at 25 o C is 23.8 mm Hg
[RPET 1999]
10. The pressure under which liquid and vapour can
coexist at equilibrium is called the (a) 1.25 mm Hg (b) 0.125 mm Hg
(a) Limiting vapour pressure (c) 1.15 mm Hg (d) 00.12 mm Hg
(b) Real vapour pressure 18. Which of the following is incorrect [J & K 2005]

(c) Normal vapour pressure (a) Relative lowering of vapour pressure is

independent
(d) Saturated vapour pressure
(b) The vapour pressure is a colligative property
11. Which solution will show the maximum vapour
(c) Vapour pressure of a solution is lower than
pressure at 300 K [DPMT 2001]
the vapour pressure of the solvent
(a) 1 M C 12 H 22O11 (b) 1 M CH 3 COOH
(d) The relative lowering of vapour pressure is
(c) 1 M NaCl2 (d) 1 M NaCl directly propertional to the original pressure
12. The relative lowering of the vapour pressure is 19. Among the following substances the lowest
equal to the ratio between the number of vapour pressure is exerted by
 170 Solution and Colligative properties

(a) Water (b) Mercury 27. An aqueous solution of glucose was prepared by
(c) Kerosene (d) Rectified spirit dissolving 18 g of glucose in 90 g of water. The
20. According to Raoult's law the relative lowering of relative lowering in vapour pressure is [KCET 2002]
vapour pressure of a solution of volatile substance (a) 0.02 (b) 1
is equal to (c) 20 (d) 180
[CBSE PMT 1995; BHU 2001]
28. “Relative lowering in vapour pressure of solution
(a) Mole fraction of the solvent containing non-volatile solute is directly
(b) Mole fraction of the solute proportional to mole fraction of solute”. Above
(c) Weight percentage of a solute statement is [AFMC 2004]
(d) Weight percentage of a solvent (a) Henry law (b) Dulong and Petit law
21. When a substance is dissolved in a solvent, the (c) Raoult's law (d) Le-Chatelier's
vapour pressure of the solvent is decreased. This principle
results in
[MP PMT 1983; NCERT 1981]
29. An ideal solution was obtained by mixing
methanol and ethanol. If the partial vapour
(a) An increase in the boiling point of the solution
pressure of methanol and ethanol are 2.619 kPa
(b) A decrease in the boiling point of solvent
and 4.556 kPa respectively, the composition of the
(c) The solution having a higher freezing point
than the solvent vapour (in terms of mole fraction) will be
(d) The solution having a lower osmotic pressure [Pb. PMT 1998]
than the solvent (a) 0.635 methanol, 0.365 ethanol
22. The vapour pressure of a liquid depends on (b) 0.365 methanol, 0.635 ethanol
(a) Temperature but not on volume (c) 0.574 methanol, 0.326 ethanol
(b) Volume but not on temperature (d) 0.173 methanol, 0.827 ethanol
(c) Temperature and volume
30. The vapour pressure of two liquids P and Q are 80
(d) Neither on temperature nor on volume
and 600 torr, respectively. The total vapour
23. Which one of the statements given below pressure of solution obtained by mixing 3 mole of
concerning properties of solutions, describes a P and 2 mole of Q would be
colligative effect [AIIMS 2003]
[CBSE PMT 2005]
(a) Boiling point of pure water decreases by the
(a) 140 torr (b) 20 torr
addition of ethanol
(b) Vapour pressure of pure water decreases by (c) 68 torr (d) 72 torr
the addition of nitric acid 31. The vapour pressure of benzene at a certain
(c) Vapour pressure of pure benzene decreases by temperature is 640 mm of Hg . A non-volatile and
the addition of naphthalene non-electrolyte solid weighing 2 . 175 g is added to
(d) Boiling point of pure benzene increases by the 39 . 08 g of benzene. The vapour pressure of the
addition solution is 600 mm of Hg . What is the molecular
of toluene weight of solid substance
24. The atmospheric pressure is sum of the [CBSE PMT 1999; AFMC 1999]
[Kerala CET (Med.) 2002]
(a) 49.50 (b) 59.6
(a) Pressure of the biomolecules
(c) 69.5 (d) 79.8
(b) Vapour pressure of atmospheric constituents
(c) Vapour pressure of chemicals and vapour 32. Which one of the following is the expression of
pressure of volatiles Raoult's law
(d) Pressure created on to atmospheric molecules p  ps n p p N
(a)  (b) s 
25. The vapour pressure of pure liquid A is 0.80 atm. p nN p N n
On mixing a non-volatile B to A, its vapour p  ps N ps  p N  n
(c)  (d) 
pressure becomes 0.6 atm. The mole fraction of B ps N n ps N
in the solution is [MP PET 2003]
p  vapour pressure of pure solvent
(a) 0.150 (b) 0.25
(c) 0.50 (d) 0.75 p s  vapour pressure of the solution
26. Lowering of vapour pressure is highest for [BHU 1997] n  number of moles of the solute
(a) Urea (b) 0 . 1 M glucose N  number of moles of the solvent
(c) 0.1 M MgSO4 (d) 0.1 M BaCl2 33. Which has maximum vapour pressure [DPMT 2001]
(a) HI (b) HBr
(c) HCl (d) HF
 Solution and Colligative properties 171
34. When a non-volatile solute is dissolved in a (d) The vapour pressure of the solution is equal to
solvent, the relative lowering of vapour pressure the mole fraction of solvent
is equal to 41. The vapour pressure of a solvent A is 0.80 atm
[BHU 1979; IIT 1983] When a non-volatile substance B is added to this
(a) Mole fraction of solute solvent its vapour pressure drops to 0.6 atm.
(b) Mole fraction of solvent What is mole fraction of B in solution
(c) Concentration of the solute in grams per litre (a) 0.25 (b) 0.50
(d) Concentration of the solute in grams 100 ml (c) 0.75 (d) 0.90
35. 60 gm of Urea (Mol. wt 60) was dissolved in 9.9 42. Determination of correct molecular mass from
moles, of water. If the vapour pressure of pure Raoult's law is applicable to
water is Po , the vapour pressure of solution is [DCE 2000] (a) An electrolyte in solution
(a) 0.10 Po (b) 1.10 Po (b) A non-electrolyte in a dilute solution
(c) A non-electrolyte in a concentrated solution
(c) 0.90 Po (d) 0.99 Po
(d) An electrolyte in a liquid solvent
36. The vapour pressure of water at 20 o C is 17.54 43. If two substances A and B have PA0 : PB0  1 : 2 and
mm. When 20g of a non-ionic, substance is
dissolved in 100g of water, the vapour pressure is have mole fraction in solution 1 : 2 then mole
lowered by 0.30 mm. What is the molecular fraction of A in vapours [DPMT 2005]
weight of the substances [UPSEAT 2001] (a) 0.33 (b) 0.25
(a) 210.2 (b) 206.88 (c) 0.52 (d) 0.2
(c) 215.2 (d) 200.8 44. A dry air is passed through the solution,
containing the 10 gm of solute and 90 gm of water
37. In an experiment, 1 g of a non-volatile solute was
and then it pass through pure water. There is the
dissolved in 100 g of acetone (mol. mass = 58) at
depression in weight of solution wt by 2.5 gm and
298K. The vapour pressure of the solution was
in weight of pure solvent by 0.05 gm. Calculate
found to be 192.5 mm Hg. The molecular weight of
the molecular weight of solute [Kerala CET 2005]
the solute is (vapour pressure of acetone = 195
mm Hg) (a) 50 (b) 180
[CPMT 2001; CBSE PMT 2001; Pb CET 2002] (c) 100 (d) 25
(a) 25.24 (b) 35.24 (e) 51
(c) 45.24 (d) 55.24
Ideal and Non-ideal solution
38. How many grams of CH 3 OH should be added to
water to prepare 150 ml solution of 2 M CH 3 OH [CBSE PMT
1. 1994]
Which of the following liquid pairs shows a
(a) 9.6 (b) 2.4 positive deviation from Raoult's law
[MP PET 1993; UPSEAT 2001; AIEEE 2004]
(c) 9 . 6  10 3 (d) 2 .4  10 3
(a) Water-nitric acid (b) Benzene-methanol
39. The vapour pressure of a solvent decreased by
10 mm of mercury, when a non-volatile solute was (c) Water-hydrochloric acid (d)Acetone-chloroform
added to the solvent. The mole fraction of the 2. Which one of the following is non-ideal solution
solute in the solution is 0.2. What should be the (a) Benzene + toluene
mole fraction of the solvent, if decrease in the
vapour pressure is to be 20 mm of mercury (b) n -hexane + n -heptane
(c) Ethyl bromide + ethyl iodide
[CBSE PMT 1998]
(a) 0.8 (b) 0.6 (d) CCl4  CHCl 3
(c) 0.4 (d) 0.2 3. A non ideal solution was prepared by mixing 30
40. For a dilute solution, Raoult's law states that ml chloroform and 50 ml acetone. The volume of
[CPMT 1987; BHU 1979; IIT 1985; MP PMT 2004;
mixture will be [Pb. CET 2003]

MNR 1988; AMU 2002] (a) > 80 ml (b) < 80 ml

(a) The lowering of vapour pressure is equal to (c) = 80 ml (d)  80 ml
mole fraction of solute 4. Which pair from the following will not form an
(b) The relative lowering of vapour pressure is ideal solution
equal to mole fraction of solute (a) CCl4  SiCl4 (b) H 2 O  C4 H 9 OH
(c) The relative lowering of vapour pressure is
(c) C2 H 5 Br  C2 H 5 I (d) C6 H14  C7 H16
proportional to the amount of solute in
solution 5. An ideal solution is that which [MP PMT 1996]
(a) Shows positive deviation from Raoult's law
 172 Solution and Colligative properties

(b) Shows negative deviation from Raoult's law 16. Formation of a solution from two components can
(c) Has no connection with Raoult's law be considered as [CBSE PMT 2003]
(i) Pure solvent  separated solvent molecules
(d) Obeys Raoult's law
H1
6. Which one of the following mixtures can be (ii) Pure solute  separated
separated into pure components by fractional solute molecules H2
distillation [CPMT 1987]
(iii) Separated solvent and
(a) Benzene – toluene (b) Water – ethyl alcohol solute molecules  solution H3
(c) Water – nitric acid (d) Water – hydrochloric Solution so formed will be ideal if
acid (a) H soln  H 3  H1  H 2
7. All form ideal solutions except[DPMT 1983; MP PET 1997] (b) H soln  H1  H 2  H 3
(a) C2 H 5 Br and C 2 H 5 I (b) C6 H 5 Cl and C6 H 5 Br (c) H soln  H1  H 2  H 3
(c) C6 H 6 and C6 H 5 CH 3 (d) C 2 H 5 I and C2 H 5 OH (d) H soln  H1  H 2  H 3
8. Which property is shown by an ideal solution 17. Identify the mixture that shows positive deviation
[MP PET 2002] from Raoult’s law [Kerala CET (Engg.) 2002]
(a) CHCl 3  (CH 3 )2 CO (b) (CH 3 )2 CO  C6 H 5 NH 2
(a) It follows Raoult's law (b) H mix  0
(c) CHCl 3  C6 H 6 (d) (CH 3 )2 CO  CS 2
(c) Vmix  0 (d) All of these
(e) C6 H 5 N  CH 3 COOH
9. When two liquid A and B are mixed then their
boiling points becomes greater than both of them. 18. When acetone is added to chloroform, then
What is the nature of this solution hydrogen bond is formed between them.These
(a) Ideal solution liquids show
(b) Positive deviation with non ideal solution (a) Positive deviation from Raoult's law
(c) Negative deviation with non ideal solution (b) Negative deviation from Raoult's law
(d) Normal solution (c) No deviation from Raoult's law
10. In mixture A and B components show –ve (d) Volume is slightly increased
deviation as 19. Which of the following is true when components
[AIEEE 2002] forming an ideal solution are mixed [AMU 2000]
(a) Vmix  0 (a) H m  Vm  0 (b) H m  Vm
(b) H mix  0 (c) Hm  Vm (d) H m  Vm  1
(c) A-B interaction is weaker than A-A and B-B 20. The liquid pair benzene-toluene shows[MP PET 1995]
interaction (a) Irregular deviation from Raoult's law
(d) A-B interaction is strong than A-A and B-B (b) Negative deviation from Raoult's law
interaction (c) Positive deviation from Raoult's law
11. In which case Raoult's law is not applicable (d) Practically no deviation from Raoult's law
(a) 1M NaCl (b) 1 M urea 21. The solution which shows negative or positive
(c) 1 M glucose (d) 1 M sucrose deviation by Raoult's law, is called
12. A solution that obeys Raoult's law is[EAMCET 1993] (a) Ideal solution (b) Real solution
(a) Normal (b) Molar (c) Non-ideal solution (d) Colloidal solution
(c) Ideal (d) Saturated 22. Which of the following does not show positive
13. An example of near ideal solution is deviation from Raoult’s law [
(a) n -heptane and n -hexane (a) Benzene-Chloroform
(b) CH 3 COOH  C5 H 5 N (b) Benzene-Acetone
(c) Benzene-Ethanol
(c) CHCl 3  (C 2 H 5 )2 O
(d) Benzene-Carbon tetrachloride
(d) H 2 O  HNO 3 23. Which of the following mixture shows positive
14. A mixture of liquid showing positive deviation in deviation by ideal behaviour
Raoult's law is (a) CHCl 3  (CH 3 )2 CO (b) C6 H 6  C6 H 5 CH 3
(a) (CH 3 )2 CO  C2 H 5 OH (b) (CH 3 )2 CO  CHCl 3 (c) H 2 O  HCl (d) CCl4  CHCl 3
(c) (C2 H 5 )2 O  CHCl 3 (d) (CH 3 )2 CO  C6 H 5 NH 2 24. Which property is not found in ideal solution
15. All form ideal solution except [UPSEAT 2001] (a) PA  PAo  X A (b) H mix  0
(a) C2 H 5 Br and C2 H 5 I (b) C2 H 5 Cl and C6 H 5 Br (c) Vmix  0 (d) All of these
(c) C6 H 6 and C6 H 5 CH 3 (d) C2 H 5 I and C2 H 5 OH
 Solution and Colligative properties 173
25. Which of the following is not correct for ideal (d) Azeotropic liquid mixture
solution 4. Azeotropic mixture are [CPMT 1982]
[JIPMER 1997]
(a) Constant temperature boiling mixtures
(a) S mix  0 (b) H mix  0
(b) Those which boils at different temperatures
(c) It obeys Raoult's law (d) Vmix  0
(c) Mixture of two solids
26. Which of the following does not show negative
(d) None of the above
deviation from Raoult’s law [MP PMT 2001]
(a) Acetone-Chloroform (b) Acetone-Benzene 5. A mixture of two completely miscible non-ideal
(c) Chloroform-Ether (d) Chloroform-Benzene liquids which distil as such without change in its
composition at a constant temperature as though
27. A mixture of benzene and toluene forms[MP PMT 1993]
it were a pure liquid. This mixture is known as
(a) An ideal solution (b) Non-ideal solution
(a) Binary liquid mixture (b)Azeotropic mixture
(c) Suspension (d) Emulsion
28. Which of the following is an ideal solution (c) Eutectic mixture (d) Ideal mixture
(a) Water + ethanol
(b) Chloroform + carbon tetrachloride Osmosis and Osmotic pressure of the solution
(c) Benzene + toluene
(d) Water + hydrochloric acid 1. If 3 gm of glucose (mol. wt. 180) is dissolved in
29. When ethanol mixes in cyclohexane; cyclohexane 60 gm of water at 15 o C . Then the osmotic
reduces the intermolecular forces between pressure of this solution will be
ethanol molecule. In this, liquid pair shows (a) 0.34 atm (b) 0.65 atm
(a) Positive deviation by Raoult's law (c) 6.57 atm (d) 5.57 atm
(b) Negative deviation by Raoult's law
2. The concentration in gms per litre of a solution of
(c) No deviation by Raoult's law
cane sugar (M  342 ) which is isotonic with a
(d) Decrease in volume
solution containing 6 gms of urea (M  60 ) per
30. Liquids A and B form an ideal solution[AIEEE 2003]
litre is
(a) The enthalpy of mixing is zero
(b) The entropy of mixing is zero [Orissa PMT 1989]
(c) The free energy of mixing is zero (a) 3.42 (b) 34.2
(d) The free energy as well as the entropy of (c) 5.7 (d) 19
mixing are each zero 3. Osmotic pressure is 0.0821 atm at temperature of
300 K . Find concentration in mole/litre [Roorkee 1990]
Azeotropic mixture
(a) 0.033 (b) 0.066
2
(c) 0 .33  10
o
1. The azeotropic mixture of water (b. p.100 C) and (d) 3
o o
HCl (b. p. 85 C ) boils at 108 . 5 C . When this mixture 4. Osmotic pressure of a solution containing 0.1
is distilled it is possible to obtain [IIT 1981] mole of solute per litre at 273 K is (in atm) [CPMT 1988]
(a) Pure HCl 0.1
(a)  0 .08205  273 (b) 0.1  1  0.08205  273
(b) Pure water 1
(c) Pure water as well as pure HCl 1 0 .1 273
(c)  0 .08205  273 (d) 
(d) Neither HCl nor H 2 O in their pure states 0.1 1 0 .08205
5. A solution contains non-volatile solute of
2. An azeotropic solution of two liquids has boiling
molecular mass M p . Which of the following can
point lower than either when it [NCERT 1978; IIT 1981]
(a) Shows a negative deviation from Raoult's law be used to calculate molecular mass of the solute
in terms of osmotic pressure (m = Mass of solute,
(b) Shows no deviation from Raoult's law V = Volume of solution and  = Osmotic pressure)
(c) Shows positive deviation from Raoult's law [CBSE PMT 2002]
(d) Is saturated m   m  RT
(a) Mp    VRT (b) Mp   
3. A liquid mixture boils without changing   V 
constituent is called
m   m 
[DPMT 1982; CPMT 1987] (c) Mp    (d) Mp    RT
 V  RT V
(a) Stable structure complex
6. The osmotic pressure of a 5% (wt/vol) solution of
(b) Binary liquid mixture
cane sugar at 150 o C is [AMU 1999]
(c) Zeotropic liquid mixture
(a) 2.45 atm (b) 5.078 atm
 174 Solution and Colligative properties

(c) 3.4 atm (d) 4 atm solution, what is its osmotic pressure (R = 0.082
7. The relationship between osmotic pressure at lit. atm. k 1 mol 1 ) at 273k
273 K when 10 g glucose (P1 ),10 g urea (P2 ) and [UPSEAT 2001]
10 g sucrose (P3 ) are dissolved in 250 ml of water (a) 6.02 atm (b) 4.92 atm
is [CBSE PMT 1996] (c) 4.04 atm (d) 5.32 atm
(a) P1  P2  P3 (b) P3  P1  P2 15. Blood has been found to be isotonic with[CPMT 1994]
(a) Normal saline solution
(c) P2  P1  P3 (d) P2  P3  P1
(b) Saturated NaCl solution
8. In osmosis [DPMT 1985] (c) Saturated KCl solution
(a) Solvent molecules move from higher (d) Saturated solution of a 1 : 1 mixture of NaCl
concentration to lower concentration and KCl
(b) Solvent molecules move from lower to higher 16. If 20 g of a solute was dissolved in 500 ml of
concentration water and osmotic pressure of the solution was
(c) Solute molecules move from higher to lower found to be 600 mm of Hg at 15 o C, then
concentration molecular weight of the solute is
(d) Solute molecules move from lower to higher [BHU 2004]
concentration (a) 1000 (b) 1200
9. Semipermeable membrane is that which permits (c) 1400 (d) 1800
the passage of[BHU 1979; CPMT 1977, 84, 90; MP PMT 1994]
17. The osmotic pressure of 0.4% urea solution is
(a) Solute molecules only 1.66 atm and. that of a solution of suger of 3.42
(b) Solvent molecules only % is 2.46 atm. When both the solution are mixed
then the osmotic pressure of the resultant
(c) Solute and solvent molecules both solution will be [MP PMT 1985]
(d) Neither solute nor solvent molecules (a) 1.64 atm (b) 2.46 atm
10. Two solutions A and B are separated by semi- (c) 2.06 atm (d) 0.82 atm
permeable membrane. If liquid flows form A to B 18. Blood is isotonic with [DCE 2000]
then [MH CET 2000]
(a) 0.16 M NaCl (b) Conc. NaCl
(a) A is less concentrated than B
(c) 50 % NaCl (d) 30 % NaCl
(b) A is more concentrated than B 19. Which inorganic precipitate acts as
(c) Both have same concentration semipermeable membrane or The chemical
(d) None of these composition of semipermeable membrane is[CPMT 1984, 9
11. A 5% solution of canesugar (mol. wt. =342) is (a) Calcium sulphate (b) Barium oxalate
isotonic with 1% solution of a substance X . The (c) Nickel phosphate (d) Copper ferrocyanide
molecular weight of X is 20.[CBSE
The PMT 1998]
osmotic pressure of 1 m solution at 27 o C is[CPMT 1999]
(a) 34.2 (b) 171.2
(a) 2.46 atm (b) 24.6 atm
(c) 68.4 (d) 136.8 (c) 1.21 atm (d) 12.1 atm
12. Which of the following colligative properties can 21. Osmotic pressure of a solution can be measured
provide molar mass of proteins (or polymers or quickly and accurately by[JIPMER 1991; CPMT 1983]
colloids) with greater precision [Kerala PMT 2004]
(a) Berkeley and Hartley's method
(a) Relative lowering of vapour pressure
(b) Morse's method
(b) Elevation of boiling point
(c) Pfeffer's method
(c) Depression in freezing point
(d) De Vries method
(d) Osmotic pressure
22. The solution in which the blood cells retain their
(e) Rast's method normal form are with regard to the blood[CBSE PMT 1991]
13. The average osmotic pressure of human blood is 7.8 (a) Isotonic (b) Isomotic
bar at 37 o C . What is the concentration of an (c) Hypertonic (d) Equinormal
aqueous NaCl solution that could be used in the
23. The osmotic pressure of a solution is given by the
blood stream [AIIMS 2004]
relation
(a) 0.16 mol / L (b) 0.32 mol / L [CPMT 1983, 84, 87, 93, 94]
(c) 0.60 mol / L (d) 0.45 mol / L RT CT
(a) P  (b) P 
14. A solution of sucrose(molar mass = 342 g/mol) is C R
prepared by dissolving 68.4 g of it per litre of the
 Solution and Colligative properties 175
RC P (a) 8.4 atm (b) 0.48atm
(c) P  (d)  RT
T C (c) 4.8 atm (d) 4.0 atm
24. The osmotic pressure of a solution is directly 33. Diffusion of solvent through a semi permeable
proportional to membrane is called [AFMC 2003]
(a) The molecular concentration of solute (a) Diffusion (b) Osmosis
(b) The absolute temperature at a given (c) Active absorption (d) Plasmolysis
concentration 34. Solutions having the same osmotic pressure under
(c) The lowering of vapour pressure a given set of conditions are known as[BHU 1979; EAMCET
(d) All of the above CPMT 1990; MP PMT 1999; AFMC 1999, 2001]
25. What would happen if a thin slice of sugar beet is (a) Hypertonic (b) Hypotonic
placed in a concentrated solution of NaCl [CMC Vellore 1986]
(c) Normal (d) Isotonic
(a) Sugar beet will lose water from its cells 35. At low concentrations, the statement that
(b) Sugar beet will absorb water from solution equimolal solutions under a given set of
(c) Sugar beet will neither absorb nor lose water experimental conditions have equal osmotic
(d) Sugar beet will dissolve in solution pressure is true for [EAMCET 1979; BHU 1979]
26. The osmotic pressure of a dilute solution is given (a) All solutions
by (b) Solutions of non-electrolytes only
[MP PMT 1987] (c) Solutions of electrolytes only
(a) P  Po x (b) V  nRT (d) None of these
36. Which one of the following would lose weight on
P Po  P
(c) P  Po N 2 (d)  exposure to atmosphere [NCERT 1975]
Po Po
(a) Concentrated H 2 SO 4
27. Which statement is wrong regarding osmotic
(b) Solid NaOH
pressure (P), volume (V) and temperature (T)[MP PMT 1985]
(c) A saturated solution of CO2
1
(a) P  if T is constant
V (d) Anhydrous sodium carbonate
(b) P  T if V is constant 37. The molecular weight of NaCl determined by
osmotic pressure method will be
(c) P  V if T is constant
(a) Same as theoritical value
(d) PV is constant if T is constant
(b) Higher than theoritical value
28. Isotonic solutions have [DPMT 1984; MP PMT 1986]
(c) Lower than theoritical value
(a) Equal temperature (b) Equal osmotic
(d) None of these
pressure
38. The osmotic pressure of solution increases, if
(c) Equal volume (d) Equal amount of
[CPMT 1985, 87, 91]
solute
(a) Temperature is decreased
29. Which of the following associated with isotonic
solutions is not correct [AMU 2002]
(b) Solution concentration is increased
(c) Number of solute molecules is increased
(a) They will have the same osmotic pressure
(d) Volume is increased
(b) They have the same weight concentrations
39. At the same temperature, following solution will
(c) Osmosis does not take place when the two
be isotonic
solutions are separated by a semipermeable
[MP PMT 1985]
membrane
(a) 3.24 gm of sucrose per litre of water and 0.18
(d) They will have the same vapour pressure
gm glucose per litre of water
30. Isotonic solution have the same
(b) 3.42 gm of sucrose per litre and 0.18 gm
[EAMCET 1979; JIPMER 1991, 2002; glucose in 0.1 litre water
AFMC 1995; MP PMT 2002]
(c) 3.24 gm of sucrose per litre of water and
(a) Density (b) Molar concentration 0.585 gm of sodium chloride per litre of water
(c) Normality (d) None of these (d) 3.42 gm of sucrose per litre of water and 1.17
31. A 0.6% solution of urea (molecular weight = 60) gm of sodium chloride per litre of water
would be isotonic with [NCERT 1982; DCE 2002] 40. The osmotic pressure of a decinormal solution of
(a) 0 . 1 M glucose (b) 0.1M KCl BaCl2 in water is
(c) 0.6% glucose solution (d) 0.6% KCl solution (a) Inversely proportional to its celsius
temperature
32. The value of osmotic pressure of a 0.2 M aqueous
solution at 293K is [AMU 2002]
 176 Solution and Colligative properties

(b) Inversely proportional to its absolute 48. If a 0 . 1 M solution of glucose (mol. wt. 180) and
temperature 0.1 molar solution of urea (mol. wt. 60) are placed
(c) Directly proportional to its celsius on the two sides of a semipermeable membrane to
temperature equal heights, then it will be correct to say [CBSE PMT 199
(d) Directly proportional to its absolute (a) There will be no net movement across the
temperature membrane
41. Blood cells will remain as such in [CPMT 2004] (b) Glucose will flow across the membrane into
(a) Hypertonic solution (b) Hypotonic solution urea solution
(c) Isotonic solution (d) None of these (c) Urea will flow across the membrane into
42. The osmotic pressure of a dilute solution is glucose solution
directly proportional to the [MP PMT
(d) 1987]will flow from urea solution into
Water
(a) Diffusion rate of the solute glucose solution
(b) Ionic concentration 49. At constant temperature, the osmotic pressure of
a solution
(c) Elevation of B.P.
[CPMT 1986]
(d) Flow of solvent from a concentrated to a
(a) Directly proportional to the concentration
dilute solution
(b) Inversely proportional to the concentration
43. The osmotic pressure in atmospheres of 10%
(c) Directly proportional to the square of the
solution of canesugar at 69 o C is [AFMC 1991]
concentration
(a) 724 (b) 824 (d) Directly proportional to the square root of the
(c) 8.21 (d) 7.21 concentration
44. Which of the following molecules would diffuse 50. The solution containing 4 . 0 gm of a polyvinyl
through a cell membrane [NCERT 1978] chloride polymer in 1 litre of dioxane was found
(a) Fructose (b) Glycogen to have an osmotic pressure 6 .0  10 4 atmosphere
(c) Haemoglobin (d) Catalase at 300 K , the value of R used is 0.082 litre
atmosphere mole 1k 1 . The molecular mass of the
45. Two solutions of KNO3 and CH 3 COOH are
polymer was found to be [NCERT 1978]
prepared separately. Molarity of both is 0.1 M and
(a) 3 .0  10 2 (b) 1.6  10 5
osmotic pressures are P1 and P2 respectively. The
(c) 5 . 6  10 4 (d) 6 . 4  10 2
correct relationship between the osmotic pressures
is [CPMT 1983, 84; Pb CET 2004] 51. Solvent molecules pass through the
semipermeable membrane is called
(a) P2  P1 (b) P1  P2
[CPMT 1983; MP PMT 1987; RPET 2000; DCE 2004]
P1 P2 (a) Electrolysis (b) Electrophoresis
(c) P1  P2 (d) 
P1  P2 P1  P2 (c) Cataphoresis (d) Osmosis
46. The osmotic pressure of a dilute solution of a 52. If molecular weight of compound is increased
non-volatile solute is [JIPMER 1999] then sensitivity is decreased in which of the
(a) Directly proportional to its temperature on following methods
the centigrade scale [DCE 2001]

(b) Inversely proportional to its temperature on (a) Elevation in boiling point(b) Viscosity
the Kelvin scale (c) Osmosis (d) Dialysis
(c) Directly proportional to its temperature on 53. If solubility of NaCl at 20 o C is 35 gm per 100
the Kelvin scale gm of water. Then on adding 50 gm of NaCl to
(d) Inversely proportional to its temperature on the same volume at same temperature the salt
the centigrade scale remains undissolved is
(a) 15 gm (b) 20 gm
47. Osmotic pressure of a urea solution at 10 o C is
500 mm . Osmotic pressure of the solution become (c) 50 gm (d) 35 gm
105.3 mm. When it is diluted and temperature 54. Which of the following associated with isotonic
solution is not correct
raised to 25 o C. The extent of dilution is [MP PET 2004]
(a) They will have the same osmotic pressure
(a) 6 Times (b) 5 Times
(b) They have the same weight concentration
(c) 7 Times (d) 4 Times
 Solution and Colligative properties 177
(c) Osmosis does not take place when the two 2. The molal elevation constant of water  0 .52 o C .
solutions are separated by a semipermeable The boiling point of 1.0 molal aqueous KCl
membrane solution (assuming complete dissociation of KCl ),
(d) They will have the same vapour pressure therefore, should be [BHU 1987]
55. If osmotic pressure of a solution is 2 atm at 273 K , (a) 100 . 52 o C (b) 101 .04 o C
then at 546 K , the osmotic pressure is (c) 99 .48 o C (d) 98 .96 o C
(a) 0.5 atm (b) 1 atm 3. The rise in the boiling point of a solution
(c) 2 atm (d) 4 atm containing 1.8 gram of glucose in 100 g of a
56. In osmosis reaction, the volume of solution solvent in 0 .1 o C . The molal elevation constant of
(a) Decreases slowly (b) Increases slowly the liquid is [CPMT 1999]
(c) Suddenly increases (d) No change (a) 0.01 K / m (b) 0.1 K / m
57. As a result of osmosis the volume of solution (c) 1 K / m (d) 10 K / m
[JIPMER 2000] 4. If 0.15 g of a solute dissolved in 15 g of solvent is
(a) Increases (c) Decreases boiled at a temperature higher by 0 .216 o C than
(c) Remains constant (d) Increases or that of the pure solvent. The molecular weight of
decreases the substance (molal elevation constant for the
58. A solution of urea contain 8.6 gm/litre (mol. wt. solvent is 2 .16 o C ) is
60.0). It is isotonic with a 5% solution of a non- [CBSE PMT 1999; BHU 1997]
volatile solute. The molecular weight of the solute (a) 1.01 (b) 10
will be [MP PMT 1986] (c) 10.1 (d) 100
(a) 348.9 (b) 34.89 5. Pressure cooker reduces cooking time for food
(c) 3489 (d) 861.2 because
59. One mole each of urea, glucose and sodium [MP PMT 1987; NCERT 1975; CPMT 1991; AIEEE 2003]
chloride were dissolved in one litre of water (a) Heat is more evenly distributed in the cooking
Equal osmotic pressure will be produced by space
solutions of [MH CET 1999] (b) Boiling point of water involved in cooking is
(a) Glucose and sodium chloride increased
(b) Urea and glucose (c) The higher pressure inside the cooker crushes
(c) Sodium chloride and urea the food material
(d) None of these (d) Cooking involves chemical changes helped by
60. Which of the following aqueous solutions produce a rise in temperature
the same osmotic pressure [Roorkee 1999]
6. Which of the following statements is correct for
(a) 0.1 M NaCl solution
the boiling point of solvent containing a dissolved
(b) 0.1 M glucose solution solid substance
(c) 0.6 g urea in 100 ml solution
[NCERT 1972, 74]
(d) 1.0 g of a non-electrolyte solute (X) in 50 ml
solution (Molar mass of X = 200) (a) Boiling point of the liquid is depressed
61. Which of the following aqueous solutions are (b) Boiling point of the liquid is elevated
isotonic (R  0 .082 atm K 1 mol 1 ) [Roorkee Qualifying 1998] (c) There is no effect on the boiling point
(a) 0.01 M glucose (d) The change depends upon the polarity of
(b) 0.01 M NaNO3 liquid
(c) 500 ml solution containing 0.3 g urea 7. When a substance is dissolved in a solvent, the
(d) 0.04 N HCl vapour pressure of solvent decreases. It brings[BHU 2004]
(a) A decrease in boiling point of solution
Elevation of boiling boint of the solvent (b) An increase in boiling point of the solution

1. The latent heat of vapourisation of water is (c) A decrease in freezing point of the solution
9700 Cal / mole and if the b.p. is 100 o C , (d) An increase in freezing point of the solution
ebullioscopic constant of water is 8. Elevation in boiling point was 0 .52 o C when 6 gm
[CBSE PMT 1989] of a compound X was dissolved in 100 gm of
(a) 0 .513 o C (b) 1 .026 o C water. Molecular weight of X is (K b for water is
(c) 10 .26 o C (d) 1 .832 o C 0.52 per 1000 gm of water)
 178 Solution and Colligative properties

[CPMT 1989] 17. An aqueous solution containing 1g of urea boils at

(a) 120 (b) 60 100 .25 o C . The aqueous solution containing 3 g of
glucose in the same volume will boil at (Molecular
(c) 180 (d) 600
weight of urea and glucose are 60 and 180
9. If the solution boils at a temperature T1 and the respectively)
solvent at a temperature T2 the elevation of [CBSE PMT 2000]
boiling point is given by (a) 100 .75 o C (b) 100 .5 o C
[MP PET 1996]
(c) 100 .25 o C (d) 100 o C
(a) T1  T2 (b) T1  T2 18. When common salt is dissolved in water
(c) T2  T1 (d) T1  T2 [CBSE PMT 1988; MP PET 1995; DCE 2000]
(a) Melting point of the solution increases
10. If for a sucrose solution elevation in boiling point
is 0.1°C then what will be the boiling point of (b) Boiling point of the solution increases
NaCl solution for same molal concentration[BHU 1998, 2005](c) Boiling point of the solution decreases
(a) 0.1°C (b) 0.2°C (d) Both melting point and boiling point decreases

(c) 0.08°C (d) 0.01°C 19. During the evaporation of liquid [DCE 2003]
(a) The temperature of the liquid will rise
11. The molal elevation constant is the ratio of the
elevation in B.P. to [CPMT 1982] (b) The temperature of the liquid will fall
(c) May rise or fall depending on the nature
(a) Molarity (b) Molality
(d) The temperature remains unaffected
(c) Mole fraction of solute (d)Mole fraction of solvent
20. At higher altitudes the boiling point of water
12. The molal boiling point constant for water is lowers because
0 .513 o C kg mol 1 . When 0.1 mole of sugar is [NCERT 1972; CPMT 1994; J & K 2005]
dissolved in 200 ml of water, the solution boils (a) Atmospheric pressure is low
under a pressure of one atmosphere at [AIIMS 1991]
(b) Temperature is low
o o
(a) 100 .513 C (b) 100 .0513 C (c) Atmospheric pressure is high
(c) 100 .256 Co
(d) 101 .025 Co (d) None of these
13. Value of gas constant R is [AIEEE 2002] 21. The elevation in boiling point for one molal
solution of a solute in a solvent is called[MH CET 2001]
(a) 0.082 litre atm (b) 0.987 cal mol 1 K 1 (a) Boiling point constant (b)Molal elevation constant
(c) 8.3 J mol 1 K 1 (d) 83 erg mol 1 K 1 (c) Cryoscopic constant (d) None of these
14. The temperature, at which the vapour pressure of 22. A solution of 1 molal concentration of a solute will
a liquid becomes equal to the atmospheric have maximum boiling point elevation when the
pressure is known as solvent is
[Pb. PMT 2000] [MP PMT 2000]
(a) Freezing point (b) Boiling point (a) Ethyl alcohol (b) Acetone
(c) Absolute temperature (d) None of these (c) Benzene (d) Chloroform
15. The elevation in boiling point of a solution of 13.44g 23. Mark the correct relationship between the boiling
of CuCl2 in 1kg of water using the following points of very dilute solutions of BaCl2 (t1 ) and
information will be KCl (t 2 ) , having the same molarity [CPMT 1984, 93]
(Molecular weight of CuCl2 = 134.4 and Kb = 0.52 K
(a) t1  t 2
molal1)
[IIT 2005] (b) t1  t 2
(a) 0.16 (b) 0.05 (c) t2  t1
(c) 0.1 (d) 0.2 (d) t 2 is approximately equal to t 1
16. When 10g of a non-volatile solute is dissolved in
100 g of benzene, it raises boiling point by 1 o C Depression of freezing point of the solvent
then molecular mass of the solute is (Kb for
benzene =2.53k-m–1) [BHU 2002] 1. Molal depression constant for water is 1 .86 o C .
(a) 223 g (b) 233 g The freezing point of a 0.05 molal solution of a
(c) 243 g (d) 253 g non-electrolyte in water is
[MNR 1990; MP PET 1997]
(a)  1 .86 C o
(b)  0 .93 o C
 Solution and Colligative properties 179
(c)  0 .093 o C (d) 0 .93 o C 10. A solution of urea (mol. mass 56g mol–1) boils at
100.18°C at the atmospheric pressure. If K f and
2. The amount of urea to be dissolved in 500 ml of
water (K =18.6 K mole 1 in 100g solvent) to K b for water are 1.86 and 0.512K kg mol–1
produce a depression of 0 .186 o C in freezing respectively the above solution will freeze at[CBSE PMT 20
point is [MH CET 2000] (a) – 6.54°C (b) 6.54°C
(a) 9 g (b) 6 g (c) 0.654°C (d) –0.654°C
11. The molar freezing point constant for water is
(c) 3 g (d) 0.3 g
1 . 86 o C mole 1 . If 342 gm of canesugar (C12 H 22O11)
3. The maximum freezing point falls in[MP PMT 1986]
are dissolved in 1000 gm of water, the solution
(a) Camphor (b) Naphthalene
will freeze at
(c) Benzene (d) Water [NCERT 1977; CPMT 1989; Roorkee 2000; DCE 2004]
4. Which one of the following statements is FALSE (a)  1 .86 o C (b) 1 .86 o C
[AIEEE 2004]
(c)  3 .92 o C (d) 2 . 42 o C
(a) The correct order of osmotic pressure for 0.01 12. An aqueous solution of a non-electrolyte boils at
M aqueous solution of each compound is 100 . 52 o C . The freezing point of the solution will
BaCl2  KCl  CH3COOH  sucrose. be
(b) The osmotic pressure ( ) of a solution is given (a) 0 o C (b)  1 .86 o C
by the equation   MRT where M is the (c) 1 .86 o C (d) None of the above
molarity of the solution. 13. The freezing point of one molal NaCl solution
(c) Raoult's law states that the vapour pressure assuming NaCl to be 100% dissociated in water
of a component over a solution is proportional is (molal depression constant = 1.86)
to its mole fraction. [CPMT 1985; BHU 1981; MP PMT 1997; UPSEAT 2001]
(d) Two sucrose solutions of same molality (a)  1 .86 o C (b)  3.72 o C
prepared in different solvents will have the
(c)  1 . 86 o C (d)  3.72 o C
same freezing point depression.
14. Heavy water freezes at [CPMT 1993]
5. Solute when dissolved in water [MADT Bihar 1981]
(a) 0 o C (b) 3 .8 o C
(a) Increases the vapour pressure of water
(c) 38 o C (d)  0 .38 o C
(b) Decreases the boiling point of water
15. After adding a solute freezing point of solution
(c) Decreases the freezing point of water
decreases to – 0.186. Calculate Tb if K f  1.86
(d) All of the above
and Kb  0.521 .
6. The freezing point of a solution prepared from
[Orissa JEE 2002, 04; MP PET/PMT 1998; AIEEE 2000]
1.25 gm of a non-electrolyte and 20 gm of water is
(a) 0.521 (b) 0.0521
271 .9 K . If molar depression constant is
(c) 1.86 (d) 0.0186
1 . 86 K mole 1 , then molar mass of the solute will be[AFMC
16.1998; CPMT
Given T f is the depression in freezing point
1999]
that
(a) 105.7 (b) 106.7 of the solvent in a solution of a non-volatile solute
(c) 115.3 (d) 93.9  T f 
of molality m , the quantity lim   is equal to

m 0
7. What is the freezing point of a solution containing  m 
8.1 g HBr in 100 g water assuming the acid to be [IIT 1994; UPSEAT 2001]
1
90% ionised (K f for water  1 . 86 K mole ) (a) Zero (b) One
(c) Three (d) None of the above
[BHU 1981; Pb CET 2004]
17. The freezing point of 1 percent solution of lead
(a) 0 .85 C o
(b)  3 .53 o C nitrate in water will be
(c) 0 o C (d)  0 .35 o C [NCERT 1971, 72; CPMT 1972; JIPMER 1991]
8. If K f value of H 2 O is 1.86. The value of T f for (a) Below 0 o C (b) 0 o C
0 . 1m solution of non-volatile solute is (c) 1o C (d) 2 o C
(a) 18.6 (b) 0.186 18. What is the effect of the addition of sugar on the
(c) 1.86 (d) 0.0186 boiling and freezing points of water [Kerala CET (Med.) 200
9. 1% solution of Ca(NO3 )2 has freezing point (a) Both boiling point and freezing point
increases
[DPMT 1982, 83; CPMT 1977]
(b) Both boiling point and freezing point
(a) 0 o C (b) Less than 0 o C decreases
(c) Greater than 0 o C (d) None of the above
 180 Solution and Colligative properties

(c) Boiling point increases and freezing point (c) Only solute molecules solidify at the freezing
decreases point
(d) Boiling point decreases and freezing point (d) Only solvent molecules solidify at the freezing
increases point
19. During depression of freezing point in a solution 27. Calculate the molal depression constant of a
the following are in equilibrium[IIT Screening 2003] solvent which has freezing point 16 .6 o C and
(a) Liquid solvent, solid solvent latent heat of fusion 180 . 75 Jg 1 . [Orissa JEE 2005]
(b) Liquid solvent, solid solute (a) 2.68 (b) 3.86
(c) Liquid solute, solid solute (c) 4.68 (d) 2.86t6
(d) Liquid solute solid solvent
20. 1.00 gm of a non-electrolyte solute dissolved in 50 Colligative properties of electrolyte
gm of benzene lowered the freezing point of
benzene by 0.40 K. K f for benzene is 5.12 kg 1. If O.P. of 1 M of the following in water can be
mol–1. Molecular mass of the solute will be [DPMT 2004] measured, which one will show the maximum O.P.
[NCERT 1975; CPMT 1977; JIPMER 2001]
(a) 256 g mol 1 (b) 2 .56 g mol 1
(a) AgNO3 (b) MgCl2
(c) 512  10 3 g mol 1 (d) 2 .56  10 4 g mol 1
(c) (NH4 )3 PO4 (d) Na2 SO 4
21. 0.440 g of a substance dissolved in 22.2 g of
benzene lowered the freezing point of benzene by 2. Which of the following solution in water
possesses the lowest vapour pressure [BHU 1996]
0.567 o C . The molecular mass of the substance
(a) 0.1(M) NaCl (b) 0.1(N ) BaCl2
(K f  5.12 o C mol 1 )
(c) 0.1(M) KCl (d) None of these
[BHU 2001; CPMT 2001]
(a) 178.9 (b) 177.8 3. Which of the following solutions in water will
have the lowest vapour pressure [Roorkee 2000]
(c) 176.7 (d) 175.6
(a) 0.1 M, NaCl (b) 0.1 M, Sucrose
22. Which of the following aqueous molal solution
have highest freezing point[UPSEAT 2000, 01, 02; MNR 1988] (c) 0.1 M, BaCl2 (d) 0.1 M Na3 PO4
(a) Urea (b) Barium chloride 4. The vapour pressure will be lowest for [CPMT 2004]
(c) Potassium bromide (d) Aluminium sulphate (a) 0.1 M sugar solution (b) 0.1 M KCl solution
23. Which will show maximum depression in freezing (c) 0.1 M Cu(NO3 )2 solution (d)0.1 M AgNO3 solution
point when concentration is 0.1M
5. Osmotic pressure of 0.1 M solution of NaCl and
[IIT 1989; MNR 1990; UPSEAT 2000; 03; BCECE 2005]
Na2 SO 4 will be [AFMC 1978]
(a) NaCl (b) Urea
(a) Same
(c) Glucose (d) K 2 SO 4
(b) Osmotic pressure of NaCl solution will be
24. The freezing point of a 0.01M aqueous glucose more than Na2 SO 4 solution
solution at 1 atmosphere is  0 .18 o C . To it, an
(c) Osmotic pressure of Na2 SO 4 solution will be
addition of equal volume of 0.002 M glucose
solution will; produce a solution with freezing more than NaCl
point of nearly [AMU 1999] (d) Osmotic pressure of NaSO 4 will be less than
(a)  0 .036 o C (b)  0 .108 o C that of NaCl solution
(c)  0 .216 o C (d)  0 .422 o C 6. Which of the following solutions has highest
osmotic pressure [CPMT 1977]
25. What should be the freezing point of aqueous
solution containing 17 gm of C2 H 5 OH in 1000 gm (a) 1 M NaCl (b) 1 M urea

of water (water K f = 1.86 deg  kg mol 1 [MP PMT 1986] (c) 1 M sucrose (d) 1 M glucose
7. Which one has the highest osmotic pressure
(a)  0 .69 o C (b)  0 .34 o C
[CBSE PMT 1991; DPMT 1991; MP PET 1994]
(c) 0 .0 o C (d) 0 .34 o C (a) M / 10 HCl (b) M / 10 urea
26. In the depression of freezing point experiment, it
(c) M / 10 BaCl2 (d) M / 10 glucose
is found that the [IIT 1999]
(a) Vapour pressure of the solution is less than 8. In equimolar solution of glucose, NaCl and BaCl2 ,
that of pure solvent the order of osmotic pressure is as follow
(b) Vapour pressure of the solution is more than [CPMT 1988, 93; MP PMT/PET 1988; MP PET 1997, 2003]
that of pure solvent (a) Glucose  NaCl  BaCl2
 Solution and Colligative properties 181
(b) NaCl  BaCl2  Glucose 18. Which of the following solutions boils at the
highest temperature [AMU 2001]
(c) BaCl2  NaCl  Glucose
(a) 0.1 M glucose (b) 0.1 M NaCl
(d) Glucose  BaCl2  NaCl (c) 0.1 M BaCl2 (d) 0.1 M Urea
9. The osmotic pressure of which solution is 19. 0 . 01 M solution each of urea, common salt and
maximum (consider that deci-molar solution of Na2 SO 4 are taken, the ratio of depression of
each 90% dissociated)
freezing point is
[MP PMT 2003]
[Roorkee 1990]
(a) Aluminium sulphate
(a) 1 : 1 : 1 (b) 1 : 2 : 1
(b) Barium chloride
(c) 1 : 2 : 3 (d) 2 : 2 : 3
(c) Sodium sulphate
20. Which has the minimum freezing point[CPMT 1991]
(d) A mixture of equal volumes of (b) and (c)
(a) One molal NaCl solution
10. At 25 o C , the highest osmotic pressure is (b) One molal KCl solution
exhibited by 0 . 1 M solution of[CBSE PMT 1994; AIIMS 2000] (c) One molal
CaCl2 solution
(a) CaCl2 (b) KCl
(d) One molal urea solution
(c) Glucose (d) Urea
21. Which of the following has lowest freezing point
11. Which of the following will have the highest
[NCERT 1981]
boiling point at 1 atm pressure [MP PET/PMT 1998]
(a) 0.1 M aqueous solution of glucose
(a) 0.1 M NaCl (b) 0 . 1 M sucrose
(b) 0.1 M aqueous solution of NaCl
(c) 0.1M BaCl2 (d) 0 . 1 M glucose
12. Which one of the following would produce (c) 0.1M aqueous solution of ZnSO 4
maximum elevation in boiling point (d) 0.1 M aqueous solution of urea
[MP PMT 1985; CPMT 1990; NCERT 1982]
22. The freezing points of equimolar solutions of
(a) 0.1 M glucose
glucose, KNO3 and AlCl3 are in the order of [AMU 2000]
(b) 0.2 M sucrose
(c) 0.1 M barium chloride (a) AlCl3  KNO3  Glucose
(d) 0.1 M magnesium sulphate (b) Glucose  KNO3  AlCl3
13. Which of the following solutions will have the (c) Glucose  AlCl3  KNO3
highest boiling point [DPMT 1991; CPMT 1991]
(a) 1% glucose (b) 1% sucrose (d) AlCl3  Glucose  KNO3
(c) 1% NaCl (d) 1% CaCl2 23. Which of the following will have the highest F.P.
14. Which one of the following aqueous solutions will at one atmosphere
exhibit highest boiling point [AIEEE 2004] [BHU 1982; MP PMT 1987, MP PET/PMT 1988]
(a) 0.015 M urea (b) 0.01 M KNO3 (a) 0.1M NaCl solution (b) 0 . 1 M sugar solution
(c) 0.01 M Na2 SO 4 (d) 0.015 M glucose (c) 0.1M BaCl2 solution (d) 0.1M FeCl3 solution
15. Which of the following aqueous solutions 24. Which of the following will produce the maximum
containing 10 gm of solute in each case has depression in freezing point of its aqueous
highest B.P. solution
(a) NaCl solution (b) KCl solution [MP PMT 1996]
(c) Sugar solution (d) Glucose solution (a) 0 . 1 M glucose
16. 0.01 molar solutions of glucose, phenol and (b) 0 . 1 M sodium chloride
potassium chloride were prepared in water. The (c) 0 . 1 M barium chloride
boiling points of
(d) 0 . 1 M magnesium sulphate
(a) Glucose solution = Phenol solution =
Potassium chloride solution 25. Which of the following has the lowest freezing
point
(b) Potassium chloride solution > Glucose
solution > Phenol solution [UPSEAT 2004]

(c) Phenol solution > Potassium chloride solution (a) 0.1 m sucrose (b) 0.1 m urea
> Glucose solution (c) 0.1 m ethanol (d) 0.1 m glucose
(d) Potassium chloride solution > Phenol solution 26. Which of the following has minimum freezing
> Glucose solution point
17. Which one has the highest boiling point[CBSE PMT 1990] [Pb. PMT 1999]
(a) 0.1 N Na2 SO 4 (b) 0.1 N MgSO4 (a) 0 .1 M K2 Cr2 O7 (b) 0.1 M NH 4 Cl
(c) 0.1M Al2 (SO 4 )3 (d) 0.1M BaSO4
 182 Solution and Colligative properties

(c) 0.1 M BaSO4 (d) 0.1 M Al 2 (SO 4 )3 (c) 714.3 (d) 80

27. Which of the following 0.10 m aqueous solution 7. The Van’t Hoff factor calculated from association
data is always...than calculated from dissociation
will have the lowest freezing point[CBSE PMT 1997]
data
(a) Al 2 (SO 4 )3 (b) C5 H10 O5
[JIPMER 2000]
(c) KI (d) C12 H 22O11 (a) Less (b) More
28. For 0.1 M solution, the colligative property will (c) Same (d) More or less
follow the order [AMU 2000]
8. If  is the degree of dissociation of Na2 SO 4 , the
(a) NaCl  Na2 SO 4  Na3 PO4
Vant Hoff's factor (i) used for calculating the
(b) NaCl  Na2 SO 4  Na3 PO4 molecular mass is
[AIEEE 2005]
(c) NaCl  Na2 SO 4  Na3 PO4
(a) 1   (b)
(d) NaCl  Na2 SO 4  Na3 PO4
(c) 1  2 (d) 1  2
29. Which of the following will have the lowest
9. Van't Hoff factor i
vapour pressure
Normal molecular mass
(a) 0.1M KCl solution (a) 
Observed molecular mass
(b) 0 . 1 M urea solution
Observed molecular mass
(c) 0.1M Na2 SO 4 solution (b) 
Normal molecular mass
(d) 0.1M K 4 Fe(CN )6 solution
(c) Less than one in case of dissociation
Abnormal molecular mass (d) More than one in case of association
10. Which of the following compounds corresponds
1. The Van't Hoff factor will be highest for Van't Hoff factor ' i' to be equal to 2 for dilute
solution [NCERT 1978]
(a) Sodium chloride (b) Magnesium chloride
(a) K2 SO 4 (b) NaHSO4
(c) Sodium phosphate (d) Urea
(c) Sugar (d) MgSO4
2. Which of the following salt has the same value of
Van't Hoff factor i as that of K 3 [Fe(CN )6 ] 11. The Van't Hoff factor i for a 0.2 molal aqueous
solution of urea is
[CBSE PMT 1994; AIIMS 1998]
(a) 0.2 (b) 0.1
(a) Al 2 (SO 4 )3 (b) NaCl
(c) 1.2 (d) 1.0
(c) Na2 SO 4 (d) Al(NO3 )3
12. One mole of a solute A is dissolved in a given
3. When benzoic acid dissolve in benzene, the volume of a solvent. The association of the solute
observed molecular mass is take place according to nA ⇄ ( A)n . The Van't Hoff
(a) 244 (b) 61 factor i is expressed as
(c) 366 (d) 122 [MP PMT 1997]
4. The ratio of the value of any colligative property x
(a) i  1  x (b) i  1 
for KCl solution to that for sugar solution is n
nearly [MP PMT 1985]
x
(a) 1 (b) 0.5 1 x 
(c) i  n (d) i  1
(c) 2.0 (d) 3 1
5. Van't Hoff factor of Ca(NO3 )2 is [CPMT 1997] 13. Acetic acid dissolved in benzene shows a
molecular weight of [
(a) 1 (b) 2
(a) 60 (b) 120
(c) 3 (d) 4
(c) 180 (d) 240
6. Dry air was passed successively through a
solution of 5 gm of a solute in 80 gm of water and 14. The observed osmotic pressure of a solution of
benzoic acid in benzene is less than its expected
then through pure water. The loss in weight of
value because
solution was 2.50 gm and that of pure solvent
[CET Pune 1998]
0.04 gm . What is the molecular weight of the
(a) Benzene is a non-polar solvent
solute
(b) Benzoic acid molecules are associated in
[MP PMT 1986]
benzene
(a) 70.31 (b) 7.143
 Solution and Colligative properties 183
(c) Benzoic acid molecules are dissociated in 3. Vapour pressure of a solution of 5 g of non-
benzene electrolyte in 100 g of water at a particular
(d) Benzoic acid is an organic compound temperature is 2985 N / m 2 . The vapour pressure of
15. The experimental molecular weight of an pure water is 3000 N / m 2 . The molecular weight of
electrolyte will always be less than its calculated
the solute is [IIT Screening 1993]
value because the value of Van't Hoff factor “i” is[MP PMT 1993]
(a) 60 (b) 120
(a) Less than 1 (b) Greater than 1
(c) 180 (d) 380
(c) Equivalent to one (d) Zero
4. Azeotropic mixture of HCl and water has
16. The molecular mass of acetic acid dissolved in
[AFMC 1997; JIPMER 2002]
water is 60 and when dissolved in benzene it is
120.This difference in behaviour of CH 3 COOH is (a) 84% HCl (b) 22.2% HCl
because [AMU 2000] (c) 63% HCl (d) 20.2% HCl
(a) Water prevents association of acetic acid 5. The osmotic pressure at 17 o C of an aqueous
(b) Acetic acid does not fully dissolve in water solution containing 1.75 g of sucrose per 150 ml
(c) Acetic acid fully dissolves in benzene solution is

(d) Acetic acid does not ionize in benzene [BHU 2001]

17. The correct relationship between the boiling (a) 0.8 atm (b) 0.08 atm
points of very dilute solutions of AlCl3 (t1 ) and (c) 8.1 atm (d) 9.1 atm
CaCl2 (t 2 ) , having the same molar concentration is[CPMT
6. 1983]
A 1.2 of solution of NaCl is isotonic with 7.2 of
solution of glucose. Calculate the van’t Hoff’s
(a) t1  t 2 (b) t1  t 2
factor of NaCl solution
(c) t 2  t1 (d) t 2  t1 [UPSEAT 2001]
18. The Van't Hoff factor for sodium phosphate would (a) 2.36 (b) 1.50
be (c) 1.95 (d) 1.00
(a) 1 (b) 2 7. 0.6 g of a solute is dissolved in 0.1 litre of a solvent
(c) 3 (d) 4 which develops an osmotic pressure of 1.23 atm
19. The molecular weight of benzoic acid in benzene at 27 o C . The molecular mass of the substance is[BHU 1990
as determined by depression in freezing point 1 1
method corresponds to [IIT 1996]
(a) 149 . 5 g mole (b) 120 g mole

(a) Ionization of benzoic acid (c) 430 g mole 1 (d) None of these
(b) Dimerization of benzoic acid
8. The boiling point of a solution of 0.1050 gm of a
(c) Trimerization of benzoic acid substance in 15.84 gram of ether was found to be
(d) Solvation of benzoic acid 100 o C higher than that of pure ether. What is the
molecular weight of the substance [Molecular
elevation constant of ether per 100 g = 21.6]
(a) 144.50 (b) 143.18
(c) 140.28 (d) 146.66
9. Boiling point of chloroform was raised by 0.323 K,
when 0.5143 g of anthracene was dissolved in 35
1. On adding solute to a solvent having vapour
g of chloroform. Molecular mass of anthracene is
pressure 0.80 atm, vapour pressure reduces to
( K b for CHCl 3 = 3.9 kg mol–1) [Pb PMT 2000]
0.60 atm. Mole fraction of solute is [UPSEAT 2003]
(a) 0.25 (b) 0.75 (a) 79.42 g/mol (b) 132.32 g/mol
(c) 177.42 g/mol (d) 242.32 g/mol
(c) 0.50 (d) 0.33
10. The boiling point of water ( 100 o C ) becomes
2. A solution containing 30 gms of non-volatile
100 . 52 o C , if 3 grams of a nonvolatile solute is
solute in exactly 90 gm water has a vapour
dissolved in 200 ml of water. The molecular
pressure of 21.85 mm Hg at 25 o C . Further 18 gms
weight of solute is
of water is then added to the solution. The
( K b for water is 0.6 K  m ) [
resulting solution has a vapour pressure of 22.15
1
mm Hg at 25 o C . Calculate the molecular weight (a) 12 . 2 g mol (b) 15 .4 g mol
of the solute [UPSEAT 2001] (c) 17 . 3 g mol 1
(d) 20 .4 g mol
(a) 74.2 (b) 75.6
(c) 67.83 (d) 78.7
 184 Solution and Colligative properties

11. Normal boiling point of water is 373 K (at Read the assertion and reason carefully to mark the
760mm). Vapour pressure of water at 298 K is 23 correct option out of the options given below :
mm. If the enthalpy of evaporation is 40.656 (a) If both assertion and reason are true and the
kJ/mole, the boiling point of water at 23 mm reason is the correct explanation of the assertion.
pressure will be [CBSE PMT 1995]
(b) If both assertion and reason are true but reason is
(a) 250 K (b) 294 K not the correct explanation of the assertion.
(c) 51.6 K (d) 12.5 K (c) If assertion is true but reason is false.
12. A 0.2 molal aqueous solution of a weak acid (HX) (d) If the assertion and reason both are false.
is 20% ionised. The freezing point of this solution (e) If assertion is false but reason is true.
is (Given K f  1.86 o C / m for water) [IIT 1995]
1. Assertion : One molal aqueous solution of urea
(a)  0 . 31 o C (b)  0 .45 o C contains 60 g of urea in 1kg (1000 g)
(c)  0 .53 o C (d)  0 .90 o C water.
13. A 0.001 molal solution of [Pt(NH 3 )4 Cl4 ] in water Reason : Solution containing one mole of
had a freezing point depression of 0 .0054 o C . If solute in 1000 g solvent is called as
K f for water is 1.80, the correct formulation for one molal solution.
the above molecule is 2. Assertion : If 100 cc of 0.1 N HCl is mixed with
[Kerala CET (Med.) 2003] 100 cc of 0.2 N HCl , the normality of
(a) [Pt(NH 3 )4 Cl3 ]Cl (b) [Pt(NH3 )4 Cl] Cl2 the final solution will be 0.30.
(c) [Pt(NH 3 )4 Cl2 ]Cl3 (d) [Pt(NH 3 )4 Cl4 ] Reason : Normalities of similar solutions like
14. An aqueous solution of a weak monobasic acid HCl can be added.
containing 0.1 g in 21.7g of water freezes at 3. Assertion : If a liquid solute more volatile than
272.813 K. If the value of K f for water is 1.86 the solvent is added to the solvent,
the vapour pressure of the solution
K/m, what is the molecular mass of the
monobasic acid [AMU 2002] may increase i.e., p s  p o .
(a) 50 g/mole (b) 46 g/mole Reason : In the presence of a more volatile
(c) 55 g/mole (d) 60 g/mole liquid solute, only the solute will
15. K f of 1,4-dioxane is 4.9 mol 1 for 1000 g. The form the vapours and solvent will
not.
depression in freezing point for a 0.001 m
4. Assertion : Azeotropic mixtures are formed
solution in dioxane is
only by non-ideal solutions and they
[DPMT 2001]
may have boiling points either
(a) 0.0049 (b) 4.9 + 0.001
greater than both the components
(c) 4.9 (d) 0.49
or less than both the components.
16. How many litres of CO2 at STP will be formed
Reason : The composition of the vapour
when 100 ml of 0.1 M H 2 SO 4 reacts with excess of
phase is same as that of the liquid
Na2 SO 3 phase of an azeotropic mixutre.
[EAMCET 1998] 5. Assertion : Molecular mass of polymers cannot
(a) 22.4 (b) 2.24 be calculated using boiling point or
(c) 0.224 (d) 5.6 freezing point method.
17. A solution is obtained by dissolving 12 g of urea Reason : Polymers solutions do not possess a
(mol.wt.60) in a litre of water. Another solution is constant boiling point or freezing
obtained by dissolving 68.4 g of cane sugar point.
(mol.wt. 342) in a litre of water at are the same
6. Assertion : The molecular weight of acetic acid
temperature. The lowering of vapour pressure in
determined by depression in
the first solution is [CPMT 2001]
freezing point method in benzene
nd
(a) Same as that of 2 solution and water was found to be
(b) Nearly one-fifth of the 2nd solution different.
(c) Double that of 2nd solution Reason : Water is polar and benzene is non-
(d) Nearly five times that of 2nd solution polar.
7. Assertion : Ca   and K  ions are responsible
for maintaining proper osmotic
pressure balance in the cells of
organism.
 Solution and Colligative properties 185
Reason : Solutions having the same osmotic Reason : At higher pressue cooking occurs
pressure are called isotonic faster.
solutions. [AIIMS 2000]
8. Assertion : Reverse osmosis is used in the 19. Assertion : CCl4 and H 2 O are immiscible.
desalination of sea water.
Reason : CCl4 is a polar solvent. [AIIMS 2002]
Reason : When pressure more than osmotic
pressure is applied, pure water is 20. Assertion : Isotonic solution do not show the
squeezed out of the sea water phenomenon of osmosis.
through the membrane. Reason : Isotonic solutions have equal osmotic
9. Assertion : Camphor is used as solvent in the pressure.
determination of molecular masses [AIIMS 2002]
of naphthalene, anthracene etc. 21. Assertion : Increasing pressure on pure water
Reason : Camphor has high molal elevation decreases its freezing point.
constant. Reason : Density of water is maximum at 273
K.
10. Assertion : Elevation in boiling point and
[AIIMS 2003]
depression in freezing point are
colligative properties.
Reason : All colligative properties are used
for the calculaltion of molecular
masses.
11. Assertion : An increase in surface area
increases the rate of evaporation.
Reason : Stronger the inter-molecular Solubility
attractive forces, fast is the rate of
evaporation at a given temperature. 1 d 2 d 3 c 4 b 5 d
[AIIMS 2002]
6 c
12. Assertion : The boiling and melting points of
amides are higher than
corresponding acids. Method of expressing concentration of solution
Reason : It is due to strong intermolecular
1 c 2 d 3 d 4 e 5 b
hydrogen bonding in their
molecules. [AIIMS 2002] 6 b 7 a 8 d 9 d 10 b
13. Assertion : The freezing point is the 11 a 12 b 13 a 14 a 15 b
temperature at which solid 16 c 17 b 18 e 19 b 20 b
crystallizers from solution.
21 c 22 c 23 c 24 b 25 c
Reason : The freezing point depression is the
difference between that temperature 26 d 27 d 28 c 29 a 30 c
and freezing point of pure solvent.[AIIMS 2000]
31 a 32 c 33 d 34 a 35 d
14. Assertion : On adding NaCl to water its vapour 36 b 37 b 38 b 39 b 40 c
pressure increases.
41 c 42 b 43 c 44 c 45 a
Reason : Addition of non-volatile solute
increases the vapour pressure. [AIIMS 1996]46 ac 47 c 48 b 49 a 50 c
15. Assertion : Molar heat of vaporisation of water 51 c 52 b 53 d 54 b 55 b
is greater than benzene. 56 d 57 b 58 b 59 c 60 a
Reason : Molar heat of vaporisation is the
61 d 62 a 63 a 64 b 65 a
amount of heat required to vaporise
one mole of liquid at constant 66 a 67 c 68 c 69 a 70 d
temperature. [AIIMS 1996] 71 d 72 c 73 c 74 b 75 b
16. Assertion : Ice melts faster at high altitude. 76 c 77 a 78 b 79 c 80 b
Reason : At high altitude atmospheric
81 d 82 b 83 b 84 b 85 d
pressure is high. [AIIMS 1997]
86 d 87 d 88 e 89 b 90 b
17. Assertion : Molecular mass of benzoic acid
when determined by colligative 91 a 92 d 93 a 94 c 95 a
properties is found high. 96 a 97 c 98 d 99 b 100 d
Reason : Dimerisation of benzoic acid. [AIIMS 1998]
101 c 102 d 103 d 104 c 105 d
18. Assertion : Use of pressure cooker reduces
106 b 107 a 108 b 109 d 110 a
cooking time.
 186 Solution and Colligative properties
111 d 112 b 113 c 114 c 115 b 36 c 37 c 38 c 39 b 40 d
116 a 117 b 118 c 119 c 120 d 41 c 42 b 43 c 44 a 45 c
121 b 122 c 123 b 124 a 125 c 46 c 47 b 48 a 49 a 50 b
126 c 127 c 128 c 129 a 130 b 51 d 52 d 53 a 54 b 55 d
131 a 132 c 133 c 134 c 135 c 56 b 57 d 58 a 59 b 60 bcd
136 c 137 c 138 b 139 a 140 b 61 ac
141 d 142 c 143 b 144 a
Elevation of boiling point of the solvent
Colligative properties
1 a 2 b 3 c 4 d 5 b
1 a 2 c 3 a 4 c 5 c 6 b 7 b 8 b 9 b 10 b
6 a 7 b 8 a 9 c 10 a 11 b 12 c 13 c 14 b 15 a
11 ac 16 d 17 c 18 b 19 b 20 a
21 b 22 c 23 b
Lowering of vapour pressure
Depression of freezing point of the solvent
1 a 2 b 3 b 4 d 5 b
6 a 7 a 8 a 9 c 10 b 1 c 2 c 3 a 4 d 5 c
11 a 12 b 13 b 14 c 15 d
6 a 7 b 8 b 9 b 10 d
16 a 17 b 18 d 19 b 20 b
11 a 12 b 13 b 14 b 15 b
21 a 22 a 23 b 24 b 25 b
26 d 27 a 28 c 29 b 30 d 16 d 17 a 18 c 19 a 20 a

31 c 32 a 33 c 34 a 35 c 21 a 22 a 23 d 24 c 25 a

36 b 37 c 38 a 39 b 40 b 26 ad 27 b
41 a 42 b 43 d 44 c

Colligative properties of electrolyte

Ideal and Non-ideal solution
1 c 2 b 3 d 4 c 5 c
1 b 2 d 3 b 4 b 5 d
6 a 7 d 8 d 9 c 10 b 6 a 7 c 8 c 9 a 10 a

11 a 12 c 13 a 14 a 15 d 11 c 12 c 13 d 14 c 15 a
16 b 17 d 18 b 19 a 20 d 16 d 17 c 18 b 19 c 20 c
21 c 22 a 23 d 24 d 25 a
21 b 22 a 23 b 24 c 25 c
26 b 27 a 28 c 29 a 30 a
26 d 27 a 28 b 29 d

Azeotropic mixture
Abnormal molecular mass
1 d 2 c 3 d 4 a 5 b

1 c 2 a 3 a 4 c 5 c
Osmosis and Osmotic pressure of the solution
6 a 7 a 8 c 9 a 10 d

1 c 2 b 3 c 4 a 5 b 11 d 12 c 13 b 14 b 15 b
6 b 7 c 8 b 9 b 10 a 16 b 17 b 18 d 19 b
11 c 12 d 13 b 14 b 15 a
16 b 17 c 18 a 19 d 20 b
Critical Thinking Questions
21 a 22 a 23 d 24 d 25 a
26 b 27 c 28 b 29 b 30 b 1 a 2 c 3 c 4 d 5 a
31 a 32 c 33 b 34 d 35 b
6 c 7 b 8 b 9 c 10 c
 Solution and Colligative properties 187
11 b 12 b 13 b 14 d 15 a 12. (b) 1500 cm 3 of 0.1 N HCl have number of gm
equivalence
16 c 17 a
N  V1 1500  0 .1
 1   0 .15
1000 1000
Assertion & Reason  0.15 gm. equivalent of NaOH
 0.15  40  6 gm.
1 a 2 e 3 c 4 b 5 c w 5.85
13. (a) M    0.2 M
6 a 7 d 8 a 9 c 10 b m. wt.  volume in litre 58 .5  0.5
11 c 12 a 13 b 14 d 15 b 14. (a) Molecular weight of
16 d 17 a 18 a 19 c 20 b
C2 H 5 OH  24  5  16  1  46

21 c Molecular mass of H 2 O  18
414
414g of C2 H 5 OH has  9 mole
46
18
18g of H 2O has   1 mole
18
Mole fraction of water
n1 1 1
    0.1
n1  n 2 1  9 10

Method of expressing concentration of solution

1. (c) M1 V1  M 2 V2  MV
w w
2. (d) M  ; 0 .25  ; w  6 . 625 gm
m  V (l) 106  0 .25
3. (d) N 1 V1  N 2 V2
2 1  N 2  6
N 2  0.33
5 .85
4. (e) 5.85 g NaCl = mole  0 .1 mol
58 .5
90
90 g H 2 O  moles  5 moles
18
0 .1
mole fraction of NaCl =  0 .0196 .
5  0.1
n 0 . 006
5. (b) M    0 . 06
V (l) 0 .1
W  1000 9.8  1000
6. (b) M    0.05 M
mol . mass  Volume in ml . 98  2000
W 1000 5  1000
7. (a) M     0 .5 M
m.wt. Volume in ml. 40  250
8. (d) Basicity of H 3 PO3 is 2.
Hence 0.3 M H 3 PO3  0.6 N .
9. (d) 2 gm. Hydrogen has maximum number of
molecules than others.
11. (a) M1V1  M 2 V2
0.01  19 .85  M2  20
M2  0.009925 ; M  0 .0099 .
 Solution and Colligative properties 185
15. (b) 17 gm NH 3 = 1 mole. 4 .9  1000
N   0.3 N .
32 .6  500
6.02  10 23  4.25
Molecules of NH 3   1.5  10 23 20
17 39. (b) Mole fraction of solute   0.25 .
80
17. (b) (2.5  1  3  0.5)  M 3  5.5
w  1000 4  1000
4 40. (c) N    1 .0 N .
or 2.5  1.5  M 3  5.5 or M 3   0 .73 M. m.wt.  Volume in ml 40  100
5 .5
41. (c) M1 V1  M 2 V2  M 3 V3 ;
20. (b) Normality of 2.3 M H 2 SO 4  M  Valency
1 .5  480  1 .2  520  M  1000
 2 .3  2  4 .6 N
720  624
21. (c) N 1 V1  N 2 V2 , 36  50  N 2  100 M  1.344 M .
1000
36  50
N2   18 ; 18 N H 2 SO 4  9 M H 2 SO 4 . 18  1000
100 44. (c) m   0 .2 m
180  500
22. (c) Molarity
%  10  d 22  10  1 .253
w 171 45. (a) Molarity    0 .805 M .
   0.5 M . GMM 342
m.wt.  volume in litre 342  1
%  10  d 22  10  1 .253
23. (c) N1 V1  N 2 V2  NV Normality    4 .83 N
GEM 342 / 6
4 x  10 (1  x )  6  1 ; 6 x  4 ; x  0 .66
22  1000
Molality   0 . 825 m
24. (b) [H 3 O  ]  2  0 . 02  0 . 04 M 342 (100  22 )
 2 litre solution contains 0.08 mole of H 3 O  . 100  0 .3
46. (a) 100 ml. of 0.30M   0 .03 mole of
25. (c)  10 litre of urea solution contains 240 gm of 1000
urea NaCl
240 100  0 .4
 Active mass   0.4 . 100 ml of 0.40M   0 .04 mole of
60  10 1000
26. (d) NV  N1 V1  N 2 V2  N 3 V3 NaCl
Moles of NaCl to be added
1 1 1
or, 1000 N  1  5   20   30 or N  .  0.04  0.03  0.01 mole
2 3 40
= 0.585 gm
N  eq .wt.  V (ml ) 0 .05  49 .04  100
27. (d) W    0 .2452 . 6  1000
1000 1000 47. (c) N   1.5 N
40  100
29. (a) For HCl M  N  0 .1
It is show highest normality than others.
N 1 V1  N 2 V2 ; 25  N 1  0.1  35
n 0 .1
0 .1  35 0 .1  35 48. (b) M   0 .8   V  125 ml .
N1  ; M   0 .07 . V (l) V (l)
25 25  2
50. (c) Strength of H 2 SO 4  98  19 .8 g / litre
30. (c) We know that
Number of moles of solute S 98  19 .8
Molarity  S  eq. wt.  N ; N    39 .6
Volume of solution in litre eq. wt. 49
0 .5 51. (c) W  1000 gm (H 2 O) ; n  1 mole
 2.0 
Volume of solution in litre W 1000
N   55 .55
 Volume of solution in litre M 18
0 .5 n 1
  0 .250 litre 250 ml . x Solute =  = 0.018.
2.0 n  N 1  55 .55
31. (a) M 
w
; 0 .52 
w
; w  2.84 gm 53. (d) Normality of acid = molarity  basicity
m  V (l) 36 .5  0 .15 i.e., 0.2=molarity  2
32. (c) M 
n
; 0 .5 
n
; n 1  Molarity = 0.2/2 = 0.1
V (l) 2 80
W 828 w 36 68
18
33. (d) N    18 , n   2 55. (b) Mole fraction of H 2 O = = .
M 46 m 18 80 20 77

n 2 2 18 24
x H 2O     0.1 1.5  100
nN 2  18 20 59. (d) Volume strength   8.82 .
w  1000 98 17
34. (a) N  , E  32 .6
E  volume in ml . 3
 186 Solution and Colligative properties
w 82. (b) N 1 V1  N 2 V2
60. (a) n  ; w  n  m  0 .25  98  24 .5 gm
m 10  10  0.1 (10  V)
Mole 20 2
61. (d) Molar concentration [H 2 ]   2. 10  10
V in litre 5 V  10  1000  10  990 ml .
0.1
62. (a) Amount of AgNO3 added in 60 ml of solution
83. (b) Sum of mole fraction is always 1.
 60  0.03  1.8 g
84. (b) An increases in temperature increase the
w w volume of the solution and thus decreases its
63. (a) N   0 .1   w  1 gm
E  V (l) 100  0 . 1 molarity.
w w 85. (d) 10 3 parts of CaCO3 has number of parts = 10
64. (b) N   0.1   w  1 gm
E  V (l) 40  0 .25 10 6 parts of CaCO3 has number of parts
0.2
65. (a) 20  0 .4  40  N or N  0 .2 or M   0. 1 M . 
10
 10 6  10 ,000 ppm .
2
10 3
w  1000 10 .6  1000
69. (a) M    0 .2 M . 86. (d) X 
n
m. wt.  Volume in ml . 106  500 nN
72. (c) M.eq. of HCl = M.eq. of CaCO3 w 3 .65 W 16 .2
n   0 .1, N    0 .9
1 1  1000 m 36 .5 M 18
N  50   1000 ; N   0.4 N
50 50  50 X
0.1
 0.1.
18 0 .1  0 .9
73. (c) molality   0 .1 molal .
180 10
87. (d) 10% glucose solution means 10 g  mole in
74. (b) Molarity of H 2 SO 4  0.5 180
100 cc. i.e., 0.1 litre
Normality of H 2 SO4 (N1 )  0.5  2  1
0 .1  180
Hence 1 mole will be present in =1.8
N1V1  N 2 V2 10
1 litre.
1  1  N 2  10 or N 2   0 .1 N .
88. (e) For methyl alcohol N = M.
10
76. (c) The density of solution  1.8 gm / ml n
89. (b) Mole fraction of glucose =
nN
Weight of one litre of solution  1800 gm
0 .01
 Weight of H2 SO4 in the =  0 .00199
0 .01  5
1800  90
solution  =162gm 6 .02  10 20
100 90. (b) Mole of urea   10  3 moles
6.02  10 23
 Weight of solvent  1800  1620  180 gm
1620 100 Conc. of solution (in molarity)
 Molality    9 .18
98 180 91. (a) Gram molecule of SO 2 Cl2 = 135
77. (a) Suppose the total volume of water = x
w 13 .5
 100 cm 3  0.5 N  x  0.1 N n   0 .1 .
m 135
100  0 .5
x   500 cm 3 92. (d) 1000 ml of 1 N oxalic solution = 63 g
0 .1 500 ml of 0.2 N oxalic acid solution
Therefore the volume of water added 63
=  500  0 .2  6 .3 g .
 Total volume – 100cm 3
 500  100  400 cm 3 . 1000
0 .25  25 7 .8
78. (b) M1 V1  M 2 V2 , M 2   0.0125 . 1
500 93. (a) Mole fraction at C 6 H 6  78  .
7 .8 46 6
wt. of the solute (g) 
79. (c) % by wt.   100 78 92
wt. of the solution g
nH 2 O
10 94. (c) X H 2 O 
  100  10 n H 2 O  nC 2 H 5 OH  nCH 3 COOH
90  10
95. (a) M1V1  M2 V2
w 18  1000
80. (b) Molality   1000   0.4 m i.e. 5  1  M2  10  M2  0.5
m W 180  250
w  1000 0 .5
81. (d) Molality (m )   14 .05 . Normality of the solution   0 .25 .
mW 2
 Solution and Colligative properties 187
w  1000 1  1000 118. (c) 98% H 2 SO 4 means 98g H 2 SO 4 in 100g solution.
96. (a) M    0.1 M .
m  Volume in ml . 40  250 100
cc  54 .3 cc ; 98 g H 2 SO 4  1 mol
w  1000 1 .84
98. (d) N   0.33 N .
eq. wt.  volume in ml . 1
Hence molarity   1000  18 .4 M
54 .3
1.2046  10 24
99. (b) Mole of HCl   2 mole 120. (d) 3 CaCl2  2 Na3 PO4  Ca3 (PO4 )2  6 NaCl
6.023  10 23
Normality = molarity  basidity or acicity  Mole of Na3 PO4  3 mole of CaCl2  1 mole
 2 1  2N Ca3 (PO4 )2
1
100. (d) 10 N  Deca - normal , N = Deci-normal.  0.2 mole of Na3 PO4  0.3 mole of CaCl2 =
10
0.1 mole of Ca3 (PO4 )2 .
w  1000
101. (c) Molarity  X
ml wt.  Volume ml . 121. (b)  0 .2
7 .1  1000 1000
=  0 .5 M . X
142  100 78
4  10 6
102. (d) M  1M . 122. (c) C   0 .1 molar.
40 60
6 123. (b) Molar solution of sulphuric acid is equal to 2N
n 60 0 .1 because it is show dibasic nature.
103. (d) Mole fraction X    .
nN 6 180 10 .1 w  1000 106
 124. (a) N  eq . wt.   53
60 18 eq. wt.  volume in ml . 2
w  1000 10  1000 0 .5  53  500
104. (c) N    1 . 66 N . w  13 .25 .
Eq .wt .  Volume 60  100 1000
106. (b) N  M  bosicity ; N  2  2  4 . 5 .85  1000
125. (c) Molar concentration =  0 .5 Molar .
5  10 6 58 .5  200
108. (b) Concentration  = 5 ppm.
10 6 w  1000 75 .5  1000
126. (c) M   2 .50 M
110. (a) H 3 PO3 is a dibasic acid m.wt.  V in ml 56  540
N 1 V1 (acid)  N 2 V2 (base) 129. (a) N 1 V1  N 2 V2
0.1  2  20  0.1  1  V2 10  10  0 . 1 × Volume of new solution
0 .1  2  20 Volume of water = 1000 – 10 = 990 ml.
 V2   40 ml
M  m. w t.  V 0 .1  98  400
0 .1  1 130. (b) W   3 .92 g .
111. (d) H 3 PO4 ⇌ H   H 2 PO 4 1000 1000
1000
H 2 PO 4 ⇌ H   HPO 42  131. (a) Molarity of pure water   55 .6 M .
18
HPO 42  ⇌ H   PO 43  N 0 .2
132. (c) M   0.1 M
Phosphoric acid does not give 1N strength. 2 2
112. (b) C6 H 5 COOH  NaOH C6 H 5 COONa  H 2 O 180
133. (c) Moles of water   10 mole .
w 12 .2 18
  4 gms . 44
40 122
n CO 2 44 2
113. (c) (H 2 SO 4 ) N 1 V1 = N 2 V2 (dilute acid) 134. (c) Mole fraction of CO2    .
n CO 2  n N 2 44 14 3
N 2  (10  36 ) / 1000  0.36 N . 
44 28
114. (c) H 2 O 2  H 2 O 
1 w w4
O2 136. (c) M  0.1   w  1 gm
2 m  V (l) 40  1
1 M H 2 O2 solution  2 N  34 gm / litre  11 .2 w  1 litre 4 1
137. (c) M   1M .
2  10 m. wt.  Volume litre 40  0.1
So Normality   1 .75
11 .2 w1 w 2 90 300
115. (b) Weight = molarity × m.wt.× v = 138. (b) Number of moles =     10
m 1 m 2 18 60
1  132  2  264 gm.
139. (a) The number of moles of solute dissolved in
w 1 1000 gm of the solvent is called molal
n m 2 solution.
116. (a) Mole fraction     0 .667 .
nN w W 1 8 0 .1  100  392
  140. (b) w   3 .92 g
m M 2 32 1000
 188 Solution and Colligative properties
18 1 88
141. (d)   0 .1 molal. = 88  96 = 184 ; Pp0 x p  y p PT ;  yp
180  1 10 184
n n y p  0 .478
142. (c) M   3   n  3 moles.
V (l) 1 78
143. (b) The unit of molality is mole per kilogram. 16. (a) PB = PBo X B ;  PB  78
 75 ; PB = 50 torr
78 46
144. (a) 0.2 water + 0.8 ethanol; X A  mole fraction 
78 92
of water,
17. (b) Given molecular mass of sucrose = 342
X B  mole fraction of ethanol 100
Moles of sucrose   0 .292 mole
N1 N2 342
XA  , XB 
N1  N 2 N 2  N1 1000
Moles of water N   55 .5 moles and
 Mole fraction of water = 0.2 and ethanol = 18
0.8. Vapour pressure of pure water P 0  23 .8 mm
Hg
Colligative properties According to Raoult’s law
P n P 0 .292
  
3. (a) Osmotic pressure is colligative property. P0 n  N 23 .8 0 .292  55 .5
5. (c) Vapour pressure is not colligative property. 23 .8  0 .292
P   0 .125 mm Hg.
55 .792
Lowering of vapour pressure 18. (d) According to Raoult's law, the relative
lowering in vapour pressure of a dilute
P 0  Ps wM 0 .5  154 solution is equal to mole fraction of the solute
1. (a)   143   143
P0 m W 65  158 present in the solution.
 143  1.03  141 .97 mm . 21. (a) When vapour pressure of solvent decreases,
w then the boiling point of solvent increases.
P 0  Ps 71 .5 m 25. (b) According to Raoult’s Law
4. (d)  m or 0 .00713 
P 0 w W 71 .5 1000 P 0  Ps
   x B (Mole fraction of solute)
m M m 18 P0
m  180 0 .8  0 .6
5. (b) HgI 2 although insoluble in water but shows xB   0.25 .
0 .8
complex formation with KI and freezing point
P 0  Ps
is decreases. 26. (d)  molality  (1 -   x   y  ) the value of
6. (a) For solutions containing non-volatile solutes, P0
the Raoult’s law may be stated as at a given P 0  Ps is maximum for BaCl2 .
temperature, the vapour pressure of a P 0  Ps 18  18
solution containing non-volatile solute is 27. (a)   0.02 .
P0 180  90
directly proportional to the mole fraction of
3 2
the solvent. 30. (d) PT  PP0 X P  PQ0 X Q ; PT  80   60 
1 5 5
7. (a) Vapour pressure 
Boiling po int PT  48  24  72 torr .
When vapour pressure decreases then b.pt. w
increases. P 0  Ps m W w 640  600
31. (c)    
9. (c) Methanol has low boiling point than H 2 O P 0 w W M m 640

Lower is boiling point of solvent more is m M
vapour pressure. w M 40 2.175  78 2 .175  78 640
    ;m  
11. (a) Sucrose will give minimum value of P . m W 640 m  39 .08 39 .08 40
P  P 0  Ps m  69 .45 .
Ps  P 0  P is maximum. 33. (c) The lower is boiling point more is vapour
pressure; boiling point order,
12. (b) The relative lowering of the vapour pressure
HCl  HBr  HI  HF
of dilute solution is equal to the mole fraction
of the solute molecule present in the solution. P 0  Ps n P 0  Ps 1
35. (c) 0
  0
  9.9 P 0  9.9 Ps  P 0
13. (b) Acetone solution has vapour pressure less P N P 9 .9
than pure water. 8 .9 0
1 4 8 .9 P 0  9 .9 Ps  Ps  P  0 .90 P 0
15. (d) PT  Pp0 x p  Ph0 x h = 440   120  9 .9
5 5 38. (a) 1000 ml of CH 3 OH requires methanol = 32 g.
 Solution and Colligative properties 189
150 ml of 2 M CH 3 OH requires methanol  total volume of solution = less than (30 +
32 50 ml)
  150  2  9 .6 g . or  80 ml
1000
39. (b)  P  Ps  P  mole fraction solute
0 0 4. (b) H 2 O and C4 H 9 OH do not form ideal solution

10  P  0 .2 ; 20  P  n  n  0 .4  N  0 . 6 .
0 0 because there is hydrogen bonding between
H 2 O and C4 H 9 OH .
40. (b) According to the Raoult’s law for the non-volatile
solute the relative lowering of vapour pressure of 6. (a) Aromatic compound generally separated by
a solution containing a non-volatile is equal to fractional distillation. e.g. Benzene + Toluene.
the mole fraction of the solute. 7. (d) C 2 H 5 I and C2 H 5 OH do not form ideal
43. (d) Relationship between mole fraction of a solution.
component in the vapour phase and total
vapour pressure of an ideal solution. 19. (a) For the ideal solution H mix and Vmix  0 .

PA x A . PA0 25. (a) For the ideal solution S mix is not equal to
yA  
Ptotal x A . PA0  x B . PB0 zero.
1 1 1 1
    0.2 Azeotropic mixture
1 1  2  2 1  4 5
44. (c) Lowering in weight of solution  solution 1. (d) Azeotropic mixture is constant boiling
pressure mixture, it is not possible to separate the
Lowering in weight of solvent  P 0  Ps components of azeotropic mixture by boiling.
(  p 0  vapour pressure of pure solvent) 3. (d) Azeotropic mixture is a mixture of two liquids
which boils at on particular temperature like
p0  ps Lowering in weight of solvent
 a pure liquid and distils over in the same
ps Lowering in weight of solution composition.
p0  ps w  M

ps m W Osmosis and Osmotic pressure of the solution
0 .05 10  18 2  2 .5 2  250
  m   100 3  1000
2 .5 90  m 0 .05 5 1. (c)   CRT   0 .0821  288  6.56 atm .
180  60
Ideal and Non-ideal solution w1 w2
2. (b) Isotonic solution = 
m 1 V1 m 2 V2
1. (b) In solution showing positive type of deviation
the partial pressure of each component of w1 6 342  6
    34 . 2 .
solution is greater than the vapour pressure 342  1 60  1 60
as expected according to Raoult’s law.
 0 .0821
In solution of methanol & benzene methanol 3. (c)   CRT , C    0 .33  10  2 .
RT 0 .821  300
molecules are held together due to hydrogen
w 0.1
bonding as shown below. 4. (a)    RT   0 .0821  273
m 1
CH 3 CH 3 CH 3
| | | n  m  RT
   O — H    O — H    O — H     5. (b)   RT  M P   
V V 
On adding benzene, the benzene molecules get
5 1 50
in between the molecule of methanol thus 6. (b) C    1000  mol/l
breaking the hydrogen bonds. As the resulting 342 100 342
solution has weak intermolecular attraction, 50
  0 .082  423  5 .07 atm
the escaping tendency of alcohol & benzene 342
molecule from the solution increases. w 1
Consequently the vapour pressure of the 7. (c) P  R.T since wvT are constant thus P 
mv m
solution is greater than the vapour pressure
as expected from Raoult’s law. P2  P1  P3 .
3. (b) Chloroform & acetone form a non-ideal 8. (b) In the osmosis solvent molecule move from
solution, in which A..... B type interaction are lower concentration to higher concentration.
more than A...... A & B...... B type interaction 10. (a) Osmosis occur from dilute solution to
due to H -bonding. Hence, the solution shows, concentrate solution. Therefore solution A is
negative deviation from Raoult’s Law i.e., less concentrated than B.
Vmix  ve ; H mix  ve 11. (c) Molar concentration of cane sugar 
5

1000

50
342 100 342
 190 Solution and Colligative properties

1 1000 10 48. (a) There is no net movement of the solvent

Molar concentration of X =  
m 100 m through the semipermeable membrane
10 50 between two solution of equal concentration.
 or m  68 .4 . w
m 342 50. (b) V  RT
m
12. (d) Osmotic pressure method is especially
suitable for the determination of molecular 4
 6  10  4  1   0.0821  300 ; m  1 .64  10 5 .
masses of macromolecules such as protein & m
polymer because for these substances the 52. (d) According to the dialysis process molecular
value of other colligative properties such as weight increases but sensitivity decreases.
elevation in boiling point or depression in 55. (d)   T ; if T is doubled  is also doubled.
freezing point are too small to be measured on
56. (b) Osmosis reaction are takes place in increases
the other hand osmotic pressure of such
the volume.
substances are measurable.
58. (a) For two non-electrolytic solution if isotonic,
 7.8
13. (b)   C R T ; C    0  31 mol / litre C1  C 2
R T  082  310
8 .6 5  1000
14. (b)   CRT    m  348 .9
60  1 m. wt.  100
w  R  T 68 .4  0 .0821  273
  = 4.92 atm 59. (b) Both urea and glucose are non-electrolytes but
mV 342
NaCl being electrolyte ionises.
n m / MRT
16. (b)   RT 
V V
Elevation of boiling point of the solvent
600 20  0 .0821  288  1000
 ; M  1200
760 500  M M 1 RT 02 18  1 . 987  (373 )2
1 .66  2 .46 1. (a) K b    0 .513 o C
17. (c)    2 .06 atm 1000 H V 1000  9700
2
2. (b) Tb  imk b  0.52  1  2  1.04 .
19. (d) Copper ferrocyanide ppt. acts as a
semipermeable membrane.  Tb  100  1 .04  101 . 04 o C .
20. (b) Osmotic pressure = CRT where C = 1 m Tb 0 . 1  100
3. (c) K b   1K /m .
  CRT  1  0 .0821  300  24 .6 atm m 1 .8
 1000
180
P
23. (d) P  CRT or  RT K b  w  1000 2.16  0.15  1000
C 4. (d) m   = 100 .
Tb  W 0.216  15
 P 0  Ps  dRT
24. (d)   CRT or    0

 M
5. (b) Due to higher pressure inside the boiling point
 P  elevated.
31. (a) Isotonic solutions are those which have same 6. (b) Dissolution of a non-volatile solute raises the
concentration. boiling pt. of a liquid.
32. (c)   CRT  0 .2  0 .0821  293  4 .81 atm. 7. (b) As we know that
35. (b) Equal osmotic pressure only applicable of 1
Boiling point 
non-electrolytes solution at low vapour pre ssure of liquid
concentration. Hence, on decreasing vapour pressure, boiling
38. (c) As soon as the solute molecules increases the point will increase.
osmotic pressure of solution increase. 100  K b  w 100  5 . 2  6
8. (b) Tb   0 . 52 
41. (c) Living cells shrinks in hypertonic solution m W m  100
(plasmolysis) while bursts in hypotonic 100  5 . 2  6
solution (endosmosis). There is no. effect m  60 .
0 . 52  100
when living cells are kept in isotonic solution.
10. (b) Elevation in a boiling point is a colligative
43. (c) V  nRT property as it depends upon the number of
w RT 10 0 .821  (273  69 ) particles.
   = 8.21 atm.
m V 342 0 .1 ∆Tb  n
45. (c) KNO3 dissociates completely while CH 3 COOH For sucrose, n = 1, ∆Tb = 0.1°C
dissociates to a small extent. Hence, P1  P2 . For NaCl, n = 2, ∆Tb = 0.2°C
11. (b) Tb  Kb  m or Kb  Tb / m
47. (b) V  n RT
 0.1 
500 V1 nR  283 V1 1 12. (c) Tb  Kb  m  0.513    1000 
 ;  so V2  5V1  200 
105 .3 V2 nR  298 V2 5
 Solution and Colligative properties 191
 0 .2565 o C , Tb  100 . 256 o C 9. (b) Freezing point is lowered on addition of solute
in it..
15. (a) Tb = i.Kb.m
10. (d) Tb  0.18 ; Tb  mK b
CuCl2  Cu2+ + 2Cl
0 .18 mK b 0 .18  1 .86
1 0 0  ;  T f ; T f  0.653
T f m Kf 0 .512
(1)  2
i = 1 + 2 T 0  Ts  0 . 653 ; T 0  Ts  0 . 653 ; Ts  0  0 .653 o C .
Assuming 100% ionization
 342 
(a) T f  1.86     1.86 ;  T f  1.86 C .
o o
So, i = 3 11.
 342 
Tb = 3  0.52  0.1 = 0.156  0.16
12. (b) Tb  Kb  m i.e. 0 .52  0 .52  m
K  w  1000
16. (d) Tb  b
m W Tf  K f  m  1.86  1  1.86 ; T f  1.86 o C .
K b  w  1000 2 .53  10  1000 13. (b) For NaCl i  2
m   253 g .
Tb  W 1  100 T f  2 K f m  2  1.86  1  3.72
18. (b) Common salt is non-volatile and rises the b.pt. Ts  T  T f  0  3.72  3.72 C
19. (b) In the process of evaporation, high energy
molecules leave the surface of liquid, hence 15. (b) T f  K f  m  0 .186  1 .86  m
average kinetic energy and consequently the So m  0 . 1 , Put the value of m in Tb  Kb  m
temperature of liquid falls.
Tb  0.521  (0.1)  0.0521
20. (a) The boiling occurs at lowers temperature if
atmospheric pressure is lower than 76cm Hg. 17. (a) Dissolution of a non-volatile solute lowers the
23. (b) BaCl2 furnishes more ions than KCl and thus freezing pt. of the solution H 2 O.

shows higher boiling point T1  T2 . K f  1000  w 5 .12  1000  1

20. (a) By using, m  
T f  WSolvent (gm ) 0 .40  50
Depression of freezing point of the solvent  256 gm / mol
Hence, molecular mass of the solute
1. (c) Tf  K f  molality  1.86  0.05  0.093 °C
 256 gm mol 1
Thus freezing point = 0 – 0.093 =  0 .093 o C . K f  w  1000 5 .12  0 .440  1000
21. (a) m    178 .9
100  K  w 100  18 . 6  w T f  W 0 .567  22 .2
2. (c) T f  0 . 186 
m W 60  500 22. (a) KBr  K   Br   2 ions
w  3g BaCl 2  Ba 2   2Cl   3 inos
3. (a) Camphor has the maximum value of Al 2 (SO 4 )3  2 Al 3   3 SO 42   5 ions
K f ( 39 .7) .
 urea is not ionise hence it is shows highest
4. (d) The extent of depression in freezing point freezing point.
varies with the number of solute particles for 23. (d) NaCl  Na  Cl   2 ions
a fixed solvent only and it is a characteristics
K 2 SO 4  2 K   SO 42   3 ions
feature of the nature of solvent also. So for
two different solvents the extent of K2 SO 4 give maximum ion in solution so it
depression may vary even if number of solute shows maximum depression in freezing point.
particles be dissolved. K f  1000  w
24. (c) T f   0.216 o C
K f  1000  w 1 . 86  1000  1 . 25 m W
6. (a) Molar mass  
T f  W 20  1 . 1 1000  1 .86  17
25. (a) T f   0 .69 o C
 105 .68  105 .7 . 46  1000

7. (b) HBr ⇌ H   Br  T f  0  0.69  0.69 o C

(1  )   26. (ad) The depression of freezing point is less
Total = 1 +   i  1    1  0. 9  1. 9 than that of pure solvent and only solvent
8 .1 1000 molecules solidify at the freezing point.
T f  i K f  m  1 .9  1 .86    3 .53 o C
81 100 RT f2
27. (b) K f  , R  8.314 JK 1mol 1
Tf  3.53 o C . 1000  L f
8. (b) T f  K f  m  1.86  0.1  0.186 . Tf  273  16 .6  289 .6 K ; L f  180 .75 Jg 1
 192 Solution and Colligative properties

8 .314  289 .6  289 .6 18. (b) NaCl is a more ionic compare to BaCl2 ,
Kf 
1000  180 .75 glucose and urea solution.
19. (c) Urea = 1 ; Common salt = 1 ; Na2 SO 4  3
Colligative properties of electrolyte
Ratio = 1 : 2 : 3
1. (c) (NH 4 )3 PO4 gives maximum ion. Hence, its 20. (c) CaCl2 gives maximum ion hence it has
osmotic pressure is maximum. minimum freezing point.
2. (b) BaCl2 gives maximum ion hence it is shows 21. (b) NaCl gives maximum ion hence it shows
lowest freezing point
lowest vapour pressure.
23. (b) Lesser the number of particles in solution.
3. (d) Na3 PO4 consist of maximum ions hence it show
Lesser the depression in freezing point, i.e.
lowest vapour pressure. higher the freezing point.
Na 3 PO 4  3 Na   PO 43   4 ion. 24. (c) BaCl2 gives maximum ion hence it shows
4. (c) Vapour pressure of a solvent is lowered by the maximum depression in freezing point.
presence of solute in it. Lowering in vapour 26. (d) We know that lowering of freezing point is a
pressure is a colligative property i.e., it colligative property which is directly
depends on the no. of particles present in the proportional to the number of particles
solution. Cu(NO3 )2 give the maximum no. of formed by one mole of compound therefore
ions. (i.e., 3) so it causes the greatest 0.1M Al2 (SO 4 )3 solution will have minimum
lowering in vapour pressure of water. freezing point.
5. (c) Na2 SO 4 have more osmotic pressure than 27. (a) Al2 (SO 4 )3 gives maximum ion hence its gives
NaCl solution because Na2 SO 4 gives 3 ions. lowest freezing point.
6. (a) NaCl gives maximum ion hence it will show 28. (b) Colligative property in decreasing order
highest osmotic pressure. Na3 PO4  Na2 SO 4  NaCl
8. (c) BaCl2  Ba 2   2Cl   3 ion Na 3 PO 4  3 Na   PO 43   4
NaCl  Na   Cl   2 ion Na 2 SO 4  2 Na   SO 42   3
Glucose  No ionisation
NaCl  Na  Cl   2
 BaCl2  NaCl  Glucose
29. (d) K4 [Fe(CN )6 ] gives maximum ion. Hence it have
9. (a) Al2 (SO 4 )3 gives maximum osmotic pressure
lowest vapour pressure.
because it is gives 5 ion.
10. (a) Highest osmotic pressure is given by solution Abnormal Molecular Mass
which produce maximum number of ions i.e.
CaCl2 . 1. (c) Na3 PO4 gives maximum four ion it is show
11. (c) BaCl2 gives maximum ion. Hence, its shows highest Vant’s haff factor.
highest boiling point. 2. (a) K4 [Fe(CN )6 ] dissociates as 4 K   [Fe (CN )6 ]4  ,
12. (c) BaCl2 gives maximum ion. Hence, its boiling thus 1 molecule dissociates into five particles
point is maximum. in the similar way Al2 (SO 4 )3 also gives five
13. (d) CaCl2 gives maximum ion hence it shows particles per molecule.
highest boiling point. 3. (a) Benzoic acid in benzene undergoes association
14. (c) Elevation in boiling point is a colligative through intermolecular hydrogen bonding.
property which depends upon the number of experiment al C.P.
solute particles. Greater the number of solute 4. (c) vont’s Hoff factor (i ) 
Calculated C.P.
particle in a solution higher the extent of
 1    x   y  , for KCl it is = 2 and for sugar
elevation in boiling point.
it is equal to 1.
Na 2 SO 4  2 Na   SO 42 
5. (c) Ca ( NO 3 )2  Ca 2   2 NO 3 it gives three ions
15. (a) NaCl contain highest boiling point than
other’s compound. hence the Van’t Hoff factor = 3.
5  18  2 .5
16. (d) KCl  C 6 H 5 OH  C 6 H 12 O 6 6. (a) m   70 .31
Boiling po int decreasing order  0 .04  80
Potassium chloride is ionic compound and 8. (c) Na2 SO 4 ⇌ 2 Na   SO 42 
phenol is formed phenoxide ion hence it is Mol. before diss. 1 0 0
shows greater boiling point then glucose. Mol. after diss 1   2 1
17. (c) Al2 (SO 4 )3 gives maximum ion hence it will Exp.C.P.
i  1    2    1  2
show highest boiling point. Normal C.P.
 Solution and Colligative properties 193
10. (d) MgSO4 dissociates to give 2 ions. Kb  w  1000 3.9  0.5143  1000
m 
11. (d) Urea does not give ion in the solution. W  Tb 0.323  35
13. (b) Molecular weight of CH 3 COOH  60  177 .42 g / mol
Hence the molecular weight of acetic acid in 10. (c) First boiling point of water = 100 o C
benzene  2  60  120 . Final boiling point of water = 100 . 52 o
17. (b) AlCl3 furnishes more ions than CaCl2 and w  3 g , W  200 g , K b  0 . 6 kg 1
thus shows higher boiling point i.e. t1  t 2 . Tb  100 .52  100  0 .52 o C
18. (d) Na 3 PO 4  3 Na   PO 33  . K b  w  1000
m
19. (b) Benzoic acid dimerises due to strong hydrogen Tb  W
bonding. 0 . 6  3  1000 1800
   17 . 3 gmol 1 .
0 . 52  200 104
Critical Thinking Questions 11. (b) Applying clausius clapeytron equation
P H V  T2  T1 
P o  Ps n log 2   
1. (a)  ; P o  0 . 80 , Ps  0 . 60 P1 2 .303 R  T1  T2 
Po nN
760 40656  373  T1 
log 
2 . 303  8 .314  373 T 
n 0 .2
   0 . 25 . 23
n  N 0 .8
This gives T1  294 .4 K .
2. (c) We have,
12. (b) Tf  molality  K f  (1   )
p 0  21 .85 30  18
 , for I case .....(i)   0.2 , Molality = 0.2, K f  1.86
21 .85 90  m
wt. of solvent  90  18  108 gm Tf  0.2  1.2  1.86  0.4464 o

p 0  22 .15 30  18 Freezing point =  0 .45 o C .

 , for II case .....(ii)
22 .15 108  m 13. (b) T f  imk f ; 0 . 0054  i  1 . 8  0 . 001
By eq. (1) p m0  21 . 85 m  21 .85  6  131 .1 i  3 so it is [Pt(NH 3 )4 Cl]Cl 2 .
K f  w  1000
By eq. (2) p m0  22 .15 m  22 .15  5  110 .75 14. (d) m   60 g / mole .
T f  W
0.30m = 20.35
20 .35 15. (a) T  K f  Molality  4 .9  0 .001  0 .0049 K
m  67 .83
0 .30 16. (c) Na 2 CO 3  H 2 SO 4  Na 2 SO 4  CO 2 HO
98 gm ( 2 mole ) 1 mole 1 mole
W2 5
0 .02  22 .4
P o
 P M 3000  2985 M 0 .02   0.224 .
3. (c) s
 2 =  2
or M 2  180 2
Po W1 3000 100
M1 18 17. (a) We know that in the first solution number of
Massof urea 1 12 1
4. (d) It is known that azeotropic mixture of HCl the moles of urea      0 .2 and
m.wt. of urea V 60 1
and water 20.2% HCl .
In second solution the number of moles of
1 .75 Mass of cane sugar 68 .4 1
n cane sugar     0 .2 .
5. (a)   CRT  RT  342  0 .0821  290 m.wt. of cane sugar 342 1
V 150
1000 Assertion & Reason
 0.8095  0.81 atm .
6. (c) Vant hoff factor of NaCl about 1.95 because it 1. (a) Molecular weight of urea (NH 2CONH 2 )
will be ionise into two ions.
 14  2  12  16  14  2  60
NaCl ⇌ Na   Cl  Weight 60
Number of moles   1
wRT 0 .6  0 .082  300 molecular weight 60
7. (b) m    120
PV 1 .23  0 .1 2. (e) If 100 cc of 0.1 N HCl is mixed with 100 cc of
Kb  w  1000 0.2 N HCl , the normality of the final solution
8. (b) m   143 .18
Tb  W will be 0.15.
9. (c) Here: Tb  0.323 K N1V1  N 2V2  N 3 V3 i.e., 0 . 1  100  0 .2  100
w  0 .5143 g weight of Anthracene. 0 .3  100
 N3  200 or N 3   0 .15
200
W  35 g weight of chloroform
Kb  Molal elevation constant (3.9 K  Kg / mol )
 194 Solution and Colligative properties

3. (c) Both the solute and solvent will form the correct that malecular mass of benzoic acid
vapour but vapour phase will become richer in when determined by colligative properties is
the more volatile component. found abnormally high. This is because
4. (b) Non-ideal solutions with positive deviation dimerisation of benzoic takes place in solution
i.e., having more vapour pressure than resulting high molecular mass. Therefore,
expected, boil at lower temperature while assertion and reason are true and reason is
those with negative deviation boil at higher correct explanation.
temperature than those of the components. 18. (a) It is fact that use of pressure cooker reduces
cooking time because at higher pressure over
5. (c) The polymer solutions possess very little
the liquid due to cooker lid, the liquid boils at
elevation in boiling point or depression in
higher temperature and cooking occurs faster.
freezing point.
19. (c) The assertion that CCl 4 & H 2 O are immiscible
6. (a) Depression in freezing point is a colligative
property which depends upon the number of is true because CCl4 is non-polar liquid while
particles. The number of particles are water is polar hence assertion is true and
different in case of benzene and water that is reason is false.
why molecular weight of acetic acid
20. (b) It is true that isotonic solution doesn’t show
determined by depression in freezing point
the phenomenon of osmosis. Isotonic solution
method is also different.
are those solution which have same osmotic
7. (d) Sodium ion, Na  and potassium ion, K  are pressure. Here both assertion and reason are
responsible for maintaining proper osmotic true but reason is not correct explanation.
pressure balance inside and outside of the
cells of organisms.
8. (a) If a pressure larger than the osmotic pressure
is applied to the solution side, the pure
solvent flows out of the solution through
semi-permeable membrane and this
phenomenon is called as reverse osmosis.
9. (c) Camphor has high molal depression constant.
10. (b) Elevation in boiling point and depression in
freezing point are colligative properties
because both depend only on the number of
particles (ions or molecules) of the solute in a
definite amount of the solvent but not on the
nature of the solute.
12. (a) The boiling point and melting point are higher
due to presence of the intermolecular
hydrogen bonding.
14. (d) If a non-volatile solute is added to water its
vapour pressure always decreases. Therefore,
both assertion and reason are false.
15. (b) We know that heat of vaporisation of water at
100 o C is 40 .6 kJ and that of benzene is 31 kJ
at 80 o C . The amount of heat required to
vaporise one mole of liquid at constant
temperautre is known as heat of
vapourisation therefore, both assertion and
reason are true but reason is nat the correct
explanation of assertion.
16. (d) See melts slowly at high altitude because
melting is favoured at a high pressure at high
altitude the atmospheric pressure is low and
so ice melts slowly.
17. (a) Colligative properties are the properties of
solutions containing non volatile solute. It is
 194 Solution and Colligative properties

1. The 2 N aqueous solution of H 2 SO 4 contains (a) 50 (b) 70

(a) 49 gm of H 2 SO 4 per litre of solution (c) 85 (d) 80

(b) 4.9 gm of H 2 SO 4 per litre of solution 8. Which one of the following non-ideal solutions
shows the negative deviation
(c) 98 gm of H 2 SO 4 per litre of solution
(a) CH 3 COCH 3  CS 2 (b) C6 H 6  CH 3 COCH 3
(d) 9.8 gm of H 2 SO 4 per litre of solution
(c) CCl4  CHCl 3 (d) CH 3 COCH 3  CHCl 3
2. The amount of KMnO4 required to prepare 100 ml
9. The O.P. of equimolar solution of Urea, BaCl2 and
of 0 . 1 N solution in alkaline medium is[CPMT 1986]
AlCl3 , will be in the order [DCE 2000]
(a) 1.58 gm (b) 3.16 gm
(c) 0.52 gm (d) 0.31 gm (a) AlCl3  BaCl2  Urea

3. What weight of hydrated oxalic acid should be (b) BaCl2  AlCl3  Urea
added for complete neutralisation of 100 ml of
(c) Urea  BaCl2  AlCl3
0.2 N  NaOH solution ? [MP PMT 1997]

(a) 0.45 g (b) 0.90 g (d) BaCl2  Urea  AlCl3

(c) 1.08 g (d) 1.26 g 10. The osmotic pressure of a 5% solution of cane
sugar at 150 o C is (mol. wt. of cane sugar = 342)
4. A 500 g tooth paste sample has 0 .2 g fluoride
[CPMT 1986; Manipal MEE 1995]
concentration. What is the concentration of F in
terms of ppm level [AIIMS 1992] (a) 4 atm (b) 3.4 atm
(a) 250 (b) 200 (c) 5.07 atm (d) 2.45 atm
(c) 400 (d) 1000 11. Which one of the following pairs of solutions can
5. To 5 .85 gm of NaCl one kg of water is added to we expect to be isotonic at the same temperature[NCERT 1
prepare of solution. What is the strength of NaCl (a) 0 . 1 M urea and 0.1M NaCl
in this solution (mol. wt. of NaCl  58 .5 )[CPMT 1990; DPMT 1987]
(b) 0 . 1 M urea and 0.2M MgCl2
(a) 0.1 Normal (b) 0.1 Molal
(c) 0.1 Molar (d) 0.1 Formal (c) 0.1M NaCl and 0.1M Na2SO4

6. The degree of dissociation of Ca(NO3 )2 in a dilute
aqueous solution containing 14g of the salt per
200g of water 100 o C is 70 percent. If the vapour
pressure of water at 100 o C is 760 cm. Calculate
the vapour pressure of the solution
[UPSEAT 2000]
(a) 746.3 mm of Hg (b) 757.5 mm of Hg
(c) 740.9 mm of Hg (d) 750 mm of Hg
7. The vapour pressure of pure benzene at a certain
temperature is 200 mm Hg. At the same
temperature the vapour pressure of a solution
containing 2g of non-volatile non-electrolyte solid
in 78g of benzene is 195 mm Hg. What is the
molecular weight of solid [UPSEAT 2001]
(d) 0.1M Ca(NO3 )2 and 0.1M Na2SO4
12. Which of the following would have the highest
osmotic pressure (assume that all salts are 90%
dissociated)
[NCERT 1982]
(a) Decimolar aluminium sulphate
(b) Decimolar barium chloride
(c) Decimolar sodium sulphate
(d) A solution obtained by mixing equal of (b) and
(c) and filtering
13. Which solution will have the highest boiling point
[NCERT 1981]
 Solution and Colligative properties 195
(a) 1% solution of glucose in water (c) 18 (d) 18.6
(b) 1% solution of sodium chloride in water 17. The freezing point of a solution containing 4.8 g
(c) 1% solution of zinc sulphate in water of a compound in 60 g of benzene is 4.48. What is
the molar mass of the compound (K f  5.1 km 1 ) ,
(d) 1% solution of urea in water
(freezing point of benzene = 5.5o C )
14. The boiling point of a solution of 0.11 gm of a
substance in 15 gm of ether was found to be 0 . 1 o C (a) 100 (b) 200
higher than that of the pure ether. The molecular (c) 300 (d) 400
weight of the substance will be (Kb  2.16 ) [MP PET 2002]
18. When 0.01 mole of sugar is dissolved in 100 g of a
(a) 148 (b) 158 solvent, the depression in freezing point is 0 .40 o .
(c) 168 (d) 178 When 0.03 mole of glucose is dissolved in 50 g of
the same solvent, the depression in freezing point
15. The boiling point of benzene is 353.23 K. When
will be
1.80 gm of a nonvolatile solute was dissolved in
90 gm of benzene, the boiling point is raised to (a) 0 .60 o (b) 0 .80 o
354.11 K. the molar mass of the solute is (c) 1 .60 o (d) 2.40 o
[Kb for benzene = 2.53 K mol–1] [DPMT 2004] 19. The freezing point of equimolal aqueous solution
will be highest for [IIT 1990; DCE 2001]
(a) 5 .8 g mol 1
(a) C 6 H 5 NH 3 Cl  (aniline hydrochloride)
1
(b) 0 .58 g mol
(b) Ca(NO3 )2
1
(c) 58 g mol (c) La(NO3 )3

(d) 0 .88 g mol 1 (d) C6 H 12 O6 (glucose)

16. The boiling point of 0.1 molal aqueous solution of 20. The Van't Hoff factor of the compound K 3 Fe(CN )6

urea is 100 . 18 o C at 1 atm. The molal elevation is

constant of water is (a) 1 (b) 2

(a) 1.8 (b) 0.18 (c) 3 (d) 4

 196 Solution and Colligative properties

(SET -4)

1. (c) Wt. of H 2 SO 4 per litre  N  eq. mass  2  49 = 98g. CaNO3 ⇌ Ca 2   2 NO 3

2. (a) In alkaline medium KMnO4 act as oxidant as
Na2 (SO 4 ) ⇌ 2 Na   SO 42 
follows.
12. (a) Al2 (SO 4 )3 Deci-molar gives maximum ion. ***
2KMnO4  2 KOH  2 K2 MnO4  H 2 O  (O)
Hence, its osmotic pressure is maximum.
Hence its eq . wt . = m. wt.  158
13. (b) NaCl and ZnSO 4 gives 2 ions but NaCl is
Mass 1 more ionic than ZnSO 4 .
Now, Normality  
Eq. mass V( L)
Kb  w  1000
14. (b) m 
mass  0 . 1  158 
100
g  1 . 58 g. Tb  W
1000
Kb  2.16 , w  0.11, W  15 g, Tb  0.1
3. (d) For complete neutralization equivalent of
oxalic acid = equivalent of NaOH = 2 . 16  0 . 11  1000
m  158 . 40 ~ 158 .
0 . 1  15
w NV w 0 . 2  100
    w  1 . 26 gm .
eq. wt 1000 63 1000 15. (c) The elevation (Tb ) in the boiling point

0 .2  354 . 11 K  353 .23 K  0 .88 K

4. (c) F  ions in PPm =  10 6  400
500 Substituting these values in expression
5. (b) 5.85 g NaCl = 0.1 mol as it present in 1 kg of K b  1000  w
M Solute 
wt. 5 .85 Tb  W
water ; molality   =0.1molal
m wt.  l 58 .5  1
Where, w  weight of solute, W  weight of solvent
6. (a) 2 .53  1 .8  1000
M solute   58 gm mol 1
P o  Ps n P o  Ps w  M 0 .88  90
7. (d)  ;   80
P o
nN Po m W Hence, molar mass of the solute  58 gm mol 1
8. (d) CH 3 COCH 3  CHCl 3 is non ideal solution 0 . 18
16. (a) K b   1 .8
which shown negative deviation. 0 .1

9. (a) The particle come of AlCl3 solution will be K f  1000  w 5 .1  1000  4 .8

17. (d) m    400 .
W  T f 60  1 .02
maximum due to ionisation less in BaCl2 and
minimum in urea 18. (d) T f  mk f

AlCl 3  Al 3   3 Cl   4 0 . 01  1000
0 . 40  kf  kf  4
100
BaCl 2  Ba 2   2Cl   3 again T f  mk f

More the number of particles in solution more 0 . 03  1000

 4
is the osmotic pressure a colligative 50
properties.  2 .4
19. (d) La(NO3 )3 will furnish four ions and thus will
5  0 . 0821  1000  423
10. (c)    5 . 07 atm . develop more lowering in freezing point
342  100
whereas glucose gives only one particle and
11. (d) Osmotic pressure is a coligative properties thus minimum lowering in freezing point.
equimolar solution of Ca(NO3 )2 and Na2 SO 4
20. (d) K 3 [Fe (CN )6 ]  3 K   [Fe (CN )6 ]3  .
will produce same number of solute particles.
 Solid State 197

Chapter

5
Solid State

show different property in property in all directions

The solids are the substances which have definite different direction
volume and definite shape. In terms of kinetic
There is a sudden change in There is no sudden change in
molecular model, solids have regular order of their volume when it melts. volume on melting.
constituent particles (atoms, molecules or ions). These
These possess symmetry Not possess any symmetry.
particles are held together by fairly strong forces,
These possess interfacial Not possess interfacial
therefore, they are present at fixed positions. The angles. angles.
properties of the solids not only depend upon the
(2) Crystalline and amorphous silica (SiO2 )
nature of the constituents but also on their
arrangements. Silica occurs in crystalline as well as amorphous
Types and Classification of solids states. Quartz is a typical example of crystalline silica.
Quartz and the amorphous silica differ considerably in
(1) Types of solids
their properties.
Solids can be broadly classified into following Quartz Amorphous silica
two types,
It is crystalline in nature It is light (fluffy) white
(i) Crystalline solids/True solids, powder

(ii) Amorphous solids/Pseudo solids All four corners of SiO 44  The SiO 44  tetrahedra are
tetrahedron are shared by randomly joined, giving rise
others to give a network to polymeric chains, sheets
Crystalline solids Amorphous solids
solid or three-dimensional units
They have long range order. They have short range order.
It has high and sharp It does not have sharp
They have definite melting Not have definite melting melting point (1710°C) melting point
point point
They have a definite heat Not have definite heat of (3) Diamond and graphite
of fusion fusion Diamond and graphite are tow allotropes of
They are rigid and Not be compressed to any carbon. Diamond and graphite both are covalent
incompressible appreciable extent
crystals. But, they differ considerably in their
They are given cleavage i.e. They are given irregular properties.
they break into two pieces cleavage i.e. they break into
with plane surfaces two pieces with irregular Diamond Graphite
surface
It occurs naturally in free It occurs naturally, as well
They are anisotropic They are isotropic because of state as manufactured artificially
because of these substances these substances show same
 A Unique Book For Competition 198
It is the hardest natural It is soft and greasy to touch and electricity. of heat and electricity
substance known. It burns in air at 900°C to It burns in air at 700°C to
It has high relative density Its relative density is 2.3 give CO2 give CO2
(about 3.5) It occurs as octahedral It occurs as hexagonal
It is transparent and has It has black in colour and crystals crystals
high refractive index (2.45) opaque

It is non-conductor of heat Graphite is a good conductor

(4) Classification of crystalline solids
Table : 5.1 Some characteristics of different types of crystalline solids
Types Constituents Bonding Examples Physica M.P. B.P. Electrical
of Solid l Conductivit
Nature y
Ionic Positive and Coulombic NaCl, KCl, CaO, Hard but High (≃1000K) High (≃2000K) Conductor
negative ions MgO, LiF, ZnS, brittle (in molten
network BaSO4 and state and in
systematically K2SO4 etc. aqueous
arranged solution)
Covalent Atoms Electron SiO2 (Quartz), Hard Very high Very high Insulator
connected in sharing SiC, C Hard (≃4000K) (≃5000K) except
covalent bonds (diamond), Hard graphite
C(graphite) etc.
Molecula Polar or non- (i) I2,S8, P4, CO2, Soft Low Low Insulator
r polar Molecular CH4, CCl4 etc. (≃300K to (≃ 450 to 800 K)
molecules interaction 600K)
s Insulator
Starch, sucrose, Soft Low
(intermole
water, dry ice Low
cu-lar (≃373K to 500K)
or drycold (≃400K)
forces)
(solid CO2) etc.
(ii)
Hydrogen
bonding

Metallic Cations in a Metallic Sodium , Au, Ductile High High Conductor

sea of Cu, magnesium, malleabl (≃800K to 1000 (≃1500K to
electrons metals and e K) 2000K)
alloys
Atomic Atoms London Noble gases Soft Very low Very low Poor thermal
dispersion and electrical
force conductors

Crystallography (ii) Axis of symmetry : An axis of symmetry or

“The branch of science that deals with the study of
structure, geometry and properties of crystals is called
crystallography”.
(1) Symmetry in Crystal : A crystal possess
following three types of symmetry,
(i) Plane of symmetry : It is an imaginary plane
which passes through the centre of a crystal can divides
it into two equal portions which are exactly the mirror
images of each other.
axis of rotation is an imaginary line, passing through
the crystal such that when the crystal is rotated about
this line, it presents the same appearance more than
once in one complete revolution i.e., in a rotation
through 360°. Suppose, the same appearance of crystal
is repeated, on rotating it through an angle of 360°/n,
around an imaginary axis, is called an n-fold axis
where, n is known as the order of axis. By order is
meant the value of n in 2 / n so that rotation through
2 / n, gives an equivalent configuration.
Fig. 5.2

Plane of symmetry Rectangular plane Diagonal plane

of symmetry of symmetry
Fig. 5.1 Axis of two fold Axis of three f old symmetry
symmetry
 Solid state 199
(ii) Law of rational indices : This law states that
the ratio of intercepts of different faces of a crystal
with the three axes are constant and can be expressed
by rational numbers that the intercepts of any face of a
crystal along the crystallographic axes are either equal
to unit intercepts (i.e., intercepts made by unit cell) a,
b, c or some simple whole number multiples of them
e.g., na, n' b, n''c, where n, n' and n'' are simple whole
numbers. The whole numbers n, n' and n'' are called
Axis of six fold Weiss indices. This law was given by Hauy.
Axis of four fold symmetry
symmetry (iii) Law of constancy of symmetry : According
to this law, all crystals of a substance have the same
(iii) Centre of symmetry : It is an imaginary
elements of symmetry is plane of symmetry, axis of
point in the crystal that any line drawn through it
symmetry and centre of symmetry.
intersects the surface of the crystal at equal distance on
either side. Miller indices : Planes in crystals are described
Y by a set of integers (h, k and l) known as Miller indices.
Miller indices of a plane are the reciprocals of the
fractional intercepts of that plane on the various
Centre of
crystallographic axes. For calculating Miller indices, a
symmetry of
a cubic reference plane, known as parametral plane, is selected
crystal having intercepts a, b and c along x, y and z-axes,
X respectively. Then, the intercepts of the unknown plane
are given with respect to a, b and c of the parametral
Z Fig. 5.3
plane.
Only simple cubic system have one centre of Thus, the Miller indices are :
symmetry. Other system do not have centre of a
symmetry. h
intercept of the plane along x - axis
The total number of planes, axes and centre of b
symmetries possessed by a crystal is termed as k
intercept of the plane along y - axis
elements of symmetry.
c
l
A cubic crystal possesses total 23 elements of intercept of the plane along z - axis
symmetry.
The distance between the parallel planes in
Plane of symmetry ( 3 + 6)
crystals are designated as d hkl . For different cubic
=9
lattices these interplanar spacing are given by the
Axes of symmetry ( 3 + 4 + 6) = 13
general formula,
Centre of symmetry (1) =1
a
Total symmetry = 23 d(hkl ) 
h2  k 2  l2
(2) Laws of crystallography : Crystallography is
based on three fundamental laws. Where a is the length of cube side while h, k and l
(i) Law of constancy of interfacial angles : This are the Miller indices of the plane.
law states that angle between adjacent corresponding When a plane is parallel to an axis, its intercept
faces is inter facial angles of the crystal of a particular with that axis is taken as infinite and the Miller will be
substance is always constant inspite of different shapes zero.
and sizes and mode of growth of crystal. The size and
Negative signs in the Miller indices is indicated by
shape of crystal depend upon the conditions of
placing a bar on the intercept. All parallel planes have
crystallisation. This law is also known as Steno's Law.
same Miller indices.
Space lattice and Unit cell
Crystal is a homogeneous portion of a crystalline
substance, composed of a regular pattern of structural
Fig. 5.4. Constancy of interfacial units (ions, atoms or molecules) by plane surfaces
angles
 200 Solid State
making definite angles with each other giving a regular (2) Body centred cubic (bcc) : Atoms are
geometric form. arranged at the corners and at the centre of the unit
A regular array of points (showing atoms/ions) in cell.
three dimensions is commonly called as a space lattice, (3) Face centred cubic (fcc) : Atoms are arranged
or lattice. at the corners and at the centre of each faces of the unit
Each point in a space lattice represents an atom cell.
or a group of atoms. (4) Side centered : Atoms are arranged at the
Each point in a space lattice has identical centre of only one set of faces in addition to the atoms
surroundings throughout. at the corner of the unit cell.
A three dimensional group of lattice points which Formation of crystal and Crystal systems
when repeated in space generates the crystal called
The crystals of the substance are obtained by
unit cell.
cooling the liquid (or the melt) of the solution of that
The unit cell is described by the lengths of its substance. The size of the crystal depends upon the rate
edges, a, b, c (which are related to the spacing between of cooling. If cooling is carried out slowly, crystals of
layers) and the angles between the edges, ,  ,Space
. large size are obtained because the particles (ions,
Lattic atoms or molecules) get sufficient time to arrange
e
c themselves in proper positions.
 Atoms of molecules    cluster 
Dissolved

dissolved

 dissolved embryo  nucleus  crystal
b Unit (unstable)

a Cell
(If loosing units dissolves as embryo and if
Unit cell Space lattice & unit
Fig. 5.5 gaining unit grow as a crystals).
cell
Bravais (1848) showed from geometrical
Types of units cells
considerations that there can be only 14 different ways
A units cell is obtained by joining the lattice
in which similar points can be arranged. Thus, there
points. The choice of lattice points to draw a unit cell is
can be only 14 different space lattices. These 14 types
made on the basis of the external geometry of the
of lattices are known as Bravais Lattices. But on the
crystal, and symmetry of the lattice. There are four
other hand Bravais showed that there are only seven
different types of unit cells. These are,
types of crystal systems.
(1) Primitive or simple cubic (sc) : Atoms are
arranged only at the corners of the unit cell.
Table : 5.2 Bravais lattices corresponding to different crystal systems
Crystal system Space lattice Examples
Cubic Simple : Lattice points at Body centered : Points at Face centered : Pb, Hg, Ag,
the eight corners of the unit the eight corners and at Points at the eight Au, Cu , ZnS ,
ab c,
cells. the body centred. corners and at the six
diamond, KCl ,
      90 o face centres.
c CsCl, NaCl,
  Cu 2O, CaF2 and
 alums. etc.
b
a

Tetragonal Simple : Points at the eight Body centered : Points at the eight corners and at SnO 2 , TiO 2 ,
corners of the unit cell. the body centre
ab c , ZnO 2 , NiSO 4
      90 o ZrSiO 4 . PbWO 4 ,
c
white Sn etc.
 

b
a

Orthorhombic Simple: Points End centered : Also Body centered Face centered: KNO 3 , K 2 SO 4 ,
(Rhombic) at the eight called side centered or : Points at the Points at the eight PbCO 3 , BaSO 4 ,
ab c,
corners of the base centered. Points eight corners corners and at the
unit cell. at the eight corners and at the body six face centres. rhombic sulphur,
      90 o and at two face centre MgSO 4 . 7 H 2 O etc.
centres opposite to
each other.
c
 

b
a
 Solid state 201

Rhombohedral Simple : Points at the eight corners of the unit cell NaNO 3 , CaSO 4 ,
or Trigonal calcite, quartz,
As, Sb , Bi etc.
ab c,
      90

Hexagonal Simple : Points at the twelve corners or Points at the twelve corners of the ZnO, PbS , CdS ,
of the unit cell out lined by thick line. hexagonal prism and at the centres of HgS , graphite,
ab c ,
the two hexagonal faces.
ice, Mg, Zn, Cd
    90 o
etc.
  120 o

Monoclinic Simple : Points at the eight corners of End centered : Point at the eight Na 2 SO 4 .10 H 2 O,
ab c, the unit cell corners and at two face centres Na 2 B4 O7 .10 H 2O,
opposite to the each other.
    90 o ,   90 o CaSO 4 .2 H 2 O,
monoclinic
sulphur etc.

Triclinic Simple : Points at the eight corners of the unit cell. CaSO 4 .5 H 2 O,
ab c, K2 Cr2 O7 , H 3 BO3

      90 o
etc.

Analysis of cubic system (2) Co-ordination number (C.N.) : It is defined

as the number of nearest neighbours or touching
(1) Number of atoms in per unit cell
particles with other particle present in a crystal is
The total number of atoms contained in the unit called its co-ordination number. It depends upon
cell for a simple cubic called the unit cell content. structure of the crystal.
The simplest relation can determine for it is, For simple cubic system C.N. = 6.
nc n n
  i
f
For body centred cubic system C.N. = 8
8 2 1
For face centred cubic system C.N. = 12.
Where nc  Number of atoms at the corners of the
(3) Density of the unit cell (  ) : It is defined as
cube=8
the ratio of mass per unit cell to the total volume of
n f  Number of atoms at six faces of the cube = 6 unit cell.
n i  Number of atoms inside the cube = 1 ZM

Cubic unit cell nc nf ni Total atom a 3
N 0
in per unit
Where Z = Number of particles per unit cell
cell
Simple cubic (sc) 8 0 0 1
M = Atomic mass or molecular mass

body centered cubic (bcc) 8 0 1 2 N 0  Avogadro number (6.023  10 23 mol 1 )

Face centered cubic (fcc) 8 6 0 4
a  Edge length of the unit cell= a pm  a  10 10 cm
 202 Solid State
a 3  volume of the unit cell equal to 1. Thus Bragg’s equation may alternatively be
written as
ZM
i.e.   g / cm 3   2d sin = 2 dhkl sin
a  N 0  10 30
3

Where dhkl denotes the perpendicular distance

The density of the substance is same as the
between adjacent planes with the indices hkl.
density of the unit cell.
Close packing in crystalline solids
(4) Packing fraction (P.F.) : It is defined as ratio
of the volume of the unit cell that is occupied by In the formation of crystals, the constituent
spheres of the unit cell to the total volume of the unit particles (atoms, ions or molecules) get closely packed
cell. together. The closely packed arrangement is that in
Let radius of the atom in the packing = r which maximum available space is occupied. This
corresponds to a state of maximum density. The closer
Edge length of the cube = a
the packing, the greater is the stability of the packed
Volume of the cube V = a 3 system.
4 3 (1) Close packing in two dimensions : The two
Volume of the atom (spherical)   r
3 possible arrangement of close packing in two
dimensions.
4 3
r Z
Z (i) Square close packing : In which the spheres in
Packing density   3 3
V a the adjacent row lie just one over the other and show a
horizontal as well as vertical alignment and form
Structur r Volume of Packing % of
square. In this arrangement each sphere is in contact
e related the atom density void
with four spheres.
to a ()
Simple a 4 a
3  100–52 11
r    0 . 52
cubic 2 6 = 48%
3 2
4 2
Face- a 3
2 100 –
r 4  a 
  0 .74
centred  74 =
3  2 2 
2 2 6 3
cubic  26%
Body- 3
3 100 –
4  3 a 
3a
r  0 .68
centred 4  8 68 =
cubic 3  4  32% Fig. 5.6. Square close packing
(ii) Hexagonal close packing : In which the
X-ray study of crystal structure spheres in every second row are seated in the
depression between the spheres of first row. The
Study of internal structure of crystal can be done
with the help of X-rays. The distance of the constituent spheres in the third row are vertically aligned with
particles can be determined from diffraction value by spheres in first row. The similar pattern is noticed
Bragg’s equation. throughout the crystal structure. In this arrangement
n  2d sin each sphere is in contact with11six other
2 spheres.

where,  = Wave length of X-rays, n = order of 6 3

reflection,   Angle of reflection, d = Distance
5 4
between two parallel surfaces
The above equation is known as Bragg’s equation
or Bragg’s law. The reflection corresponding to n = 1
Fig. 5.7. Hexagonal close packing
(for a given family of planes) is called first order
reflection; the reflection corresponding to n = 2 is the
second order reflection and so on. Thus by measuring n
(the order of reflection of the X-rays) and the incidence (2) Close packing in three dimensions : In order
angle , we can know d/. to develop three dimensional close packing, let us
d n retain the hexagonal close packing in the first layer.

 2 sin For close packing, each spheres in the second layer
From this, d can be calculated if  is known and rests in the hollow at the centre of three touching
vice versa. In X-ray reflections, n is generally set as spheres in the layer as shown in figure. The spheres in
the first layer are shown by solid lines while those in
 Solid state 203
second layer are shown by broken lines. It may be
noted that only half of the triangular voids in the first
layer are occupied by spheres in the second layer (i.e.,
either b or c). The unoccupied hollows or voids in the
first layer are indicated by (c) in figure. (iii) Body centred cubic : This arrangement of
spheres (or atoms) is not exactly close packed. This
a a aa a a
structure can be obtained if spheres in the first layer
b b b (A) of close packing are slightly opened up. As a result
a a a a
c
none of these spheres are in contact with each other.
c c
The second layer of spheres (B) can be placed on top of
a a a a a the first layer so that each sphere of the second layer is
in contact with four spheres of the layer below it.
Fig. 5.8. Close packing in three dimensions
Successive building of the third will be exactly like the
first layer. If this pattern of building layers is repeated
There are two alternative ways in which species infinitely we get an arrangement as shown in figure.
in third layer can be arranged over the second layer, This arrangement is found in Li, Na, K, Rb, Ba, Cs, V,
(i) Hexagonal close packing : The third layer lies Nb, Cr, Mo, Fe.
vertically above the first and the spheres in third layer
rest in one set of hollows on the top of the second A A A A A A
A A
layer. This arrangement is called ABAB …. type and
B B B
74% of the available space is occupied by spheres. B
A A A A
This arrangement is found in Be, Mg, Zn, Cd, Sc, A
Y, Ti, Zr, Tc, Ru. B B B
A A A
A A A A A A
A
B Fig. 5.11. Body centred cubic (bcc) close packing in three
B
dimensions
A B
Table : 5.3 Comparison of hcp, ccp and bcc
B
A A Property hcp ccp bcc
A
Arrangeme Close Close Not close
nt of packed packed packed
packing
Fig. 5.9. Hexagonal close packing (hcp) in three
dimensions Type of AB AB A... ABC ABC AB AB
packing A... A...
(ii) Cubic close packing : The third layer is Available 74% 74% 68%
different from the first and the spheres in the third space
layer lie on the other set of hollows marked ‘C’ in the occupied
first layer. This arrangement is called ABCABC….. type Coordinati 12 12 8
and in this also 74% of the available space is occupied on number
by spheres. The cubic close packing has face centred Malleabilit Less Malleable
y and malleable, and ductile
cubic (fcc) unit cell. This arrangement is found in Cu,
ductility hard, brittle
Ag, Au, Ni, Pt, Pd, Co, Rh, Ca, Sr.
Interstitial sites in close packing
B B Even in the close packing of spheres, there is left
some empty space between the spheres. This empty
A
space in the crystal lattice is called site or void or hole.
C Voids are of following types,
A (1) Trigonal void : This site is formed when three
B
spheres lie at the vertices of an equilateral triangle. Size
A of the trigonal site is given by the following relation,
Triogona
r  0 .155 R l
C C void

Fig. 5.10. Cubic close packing (ccp or fcc) in three Fig. 5.12
dimensions
 204 Solid State
r = Radius of the spherical and anions say NaCl structure.
trigonal void Then, rc  ra  a / 2
R = Radius of closely packed spheres where rc and ra are radius of cation and anion.
(2) Tetrahedral void : A tetrahedral void is
(a / 2)2  (a / 2)2 a
developed when triangular voids (made by three spheres Radius of Cl   
in one layer touching each other) have contact with one 2 4
sphere either in the upper layer or in the lower layer.
3a
For bcc lattice say CsCl . rc  ra 
2
(2) Radius ratio : Ionic compounds occur in
crystalline forms. Ionic compounds are made of cations
Fig. 5.13. Tetrahedral void and anions. These ions are arranged in three
The number of tetrahedral voids is double the dimensional array to form an aggregate of the type
number of spheres in the crystal structure. (A+B–)n . Since, the Coulombic forces are non-
directional, hence the structures of such crystals are
r
 0 . 225 mainly governed by the ratio of the radius of cation (r )
R
to that of anion (r ). The ratio r to r (r / r ) is called
where, r is the radius of the tetrahedral void
as radius ratio.
or atom occupying tetrahedral void.
R is the radius of spheres forming r
Radius ratio 
r
tetrahedral void.

(3) Octahedral void : This type of void is

surrounded by six closely
packed spheres, i.e. it is
formed by six spheres. r+/r– = r+/r– < 0.414
r+/r– > 0.732 0.414
The number of Coordination Coordination number
number increases decreases from 6 to
octahedral voids is equal to
from 6 to 8 4
the number of spheres. Fig. 5.17. Effect of radius ratio on co-ordination
Fig. 5.14. Octahedral void number
r
 0 .414
R Table : 5.4 Limiting Radius ratios and Structure

(4) Cubic void : This type Limiting radius ratio C.N. Shape
of void is formed between 8 (r+)/(r–)
closely packed spheres which < 0.155 2 Linear
occupy all the eight corner of
0.155 – 0.225 3 Planar triangle
cube.
r Fig. 5.15. Cubic void
0.225 – 0.414 4 Tetrahedral
 0 . 732
R 0.414 – 0.732 6 Octahedral

0.732 – 0.999 or 1 8 Body-centered

The decreasing order of the size of the various cubic
voids is,
Cubic > Octahedral > Tetrahedral > Trigonal Effect of temperature and Pressure on C.N.
Ionic radii and Radius ratio On applying high pressure NaCl structure having
(1) Ionic radii : X-ray diffraction or electron 6 : 6 co-ordination changes to CsCl structure having
diffraction techniques provides the necessary 8 :8 co-ordination. Thus, increase in pressure
information regarding unit cell. From the dimensions of increases the co-ordination number.
the unit cell, it is possible to calculate ionic radii. Similarly, CsCl structure on heating to about 760
Let, cube of edge K, changes to NaCl structure. In other words, increase
length 'a' having cations Cl– of temperature decreases the co-ordination number.
Pressur
e
Temp
a/2
90°
Na+ Cl–

a/2
Fig. 5.16. Radii of chloride
 Solid state 205
NaCl CsCl
(6 : 6 ) (8 : 8)

Structure of ionic crystals

Table : 5.5 Types of ionic crystal with description

Crystal Brief description Examples Co- Number of

structure ordination formula units
type number per unit cell
Type AB It has fcc arrangement in which Halides of Li, Na, K, Na   6 4
 Rb, AgF, AgBr, NH4Cl,
Rock salt Cl ions occupy the corners and
Cl   6
(NaCl) type face centres of a cube while Na  NH4Br, NH4I etc.
ions are present at the body and
edge of centres.
Zinc blende It has ccp arrangement in which CuCl , CuBr , CuI , AgI , BeS Zn 2   4 4
(ZnS) type 2 2
S ions form fcc and each Zn
S 2  4
ion is surrounded tetrahedrally by
four S 2  ions and vice versa.
Type AB2 It has arrangement in which Ca 2  BaF2 , BaCl2 , SrF2 Ca 2   8 4
2
Fluorite ions form fcc with each Ca ions SrCl2 , CdF2 , PbF2 F  4
(CaF2) type 
surrounded by 8 F ions and each

F ions by 4Ca2+ ions.
Antifluorite Here negative ions form the ccp Na2O Na   4 4
type arrangement so that each positive
O 2  8
ion is surrounded by 4 negative
ions and each negative ion by 8
positive ions
Caesium It has the bcc arrangement with CsCl, CsBr, CsI, CsCN, Cs   8 1
chloride   TlCl , TlBr , TlI and TlCN
Cs at the body centre and Cl
Cl   8
(CsCl) type ions at the corners of a cube or
vice versa.

Defects or Imperfections in solids electron deficient bond formed by the release of an

electron is called a hole. In the presence of electric
Any deviation from the perfectly ordered
field the positive holes move in a direction opposite to
arrangement constitutes a defect or imperfection.
that of the electrons and conduct electricity. The
These defects sometimes called thermodynamic defects
electrons and holes in solids gives rise to electronic
because the number of these defects depend on the
imperfections.
temperature.
(2) Atomic imperfections/point defects : When
(1) Electronic imperfections : Generally,
deviations exist from the regular or periodic
electrons are present in fully occupied lowest energy
arrangement around an atom or a group of atoms in a
states. But at high temperatures, some of the electrons
crystalline substance, the defects are called point
may occupy higher energy state depending upon the
defects. Point defect in a crystal may be classified into
temperature. For example, in the crystals of pure Si or
following three types.
Ge some electrons are released thermally from the
(i) Stoichiometric defects : The compounds in
covalent bonds at temperature above 0 K. these
which the number of positive and negative ions are
electrons are free to move in the crystal and are
exactly in the ratios indicated by their chemical
responsible for electrical conductivity. This type of
formulae are called stoichiometric compounds. The
conduction is known as intrinsic conduction. The defects do not disturb the stoichiometry (the ratio of
 206 Solid State
numbers of positive and negative ions) are called either due to the presence of excess metal ions or
stoichiometric defects. These are of following types, deficiency of metal ions.
(a) Interstitial defect : This type of defect is
(a) Metal excess defects due to anion vacancies : A
caused due to the presence of ions in the normally
compound may have excess metal anion if a negative
vacant interstitial sites in the crystals.
ion is absent from its lattice site, leaving a ‘hole’,
(b) Schottky defect : This type of defect when
which is occupied by electron to maintain electrical
equal number of cations and anions are missing from
their lattice sites so that the electrical neutrality is neutrality. This type of defects are found in crystals
maintained. This type of defect occurs in highly ionic which are likely to possess Schottky defects. Anion
compounds which have high co-ordination number and vacancies in alkali metal halides are reduced by heating
cations and anions of similar sizes. e.g., NaCl, KCl, CsCl the alkali metal halides crystals in an atmosphere of
and KBr etc. alkali metal vapours. The ‘holes’ occupy by electrons
(c) Frenkel defect : This type of defect arises are called F-centres (or colour centres).
when an ion is missing from its lattice site and
(b) Metal excess defects due to interstitial cations :
occupies an interstitial position. The crystal as a whole
Another way in which metal excess defects may occur
remains electrically neutral because the number of
anions and cations remain same. Since cations are is, if an extra positive ion is present in an interstitial
usually smaller than anions, they occupy interstitial site. Electrical neutrality is maintained by the presence
sites. This type of defect occurs in the compounds of an electron in the interstitial site. This type of
which have low co-ordination number and cations and defects are exhibit by the crystals which are likely to
anions of different sizes. e.g., ZnS, AgCl and AgI etc. exhibit Frenkel defects e.g., when ZnO is heated, it
Frenkel defect are not found in pure alkali metal loses oxygen reversibly. The excess is accommodated in
halides because the cations due to larger size cannot interstitial sites, with electrons trapped in the
get into the interstitial sites. In AgBr both Schottky neighborhood. The yellow colour and the electrical
and Frenkel defects occur simultaneously. A+ B– ZnOAis
+ –
A+ B–
conductivity +
of Athe B–
non-stoichiometric due Bto
A+ B– A+ B– A+ B– A+ B– these trapped
A+ electrons.
A+ B– A+ B– A+ B– A+ B– A+
B+ A– A+ B– A+ B– A+

A+ B– A+ B– A+ e– A+ B–
B– A+ B– B– A+ B– Fig. 5.20. Metal excess defect Fig. 5.21. Metal excess defect
due to extra cation due to anion vacancy
Fig. 5.18. Schottky defect Fig. 5.19. Frenkel defect

Consequences of Schottky and Frenkel defects

Presence of large number of Schottky defect
lowers the density of the crystal. When Frenkel defect
alone is present, there is no decrease in density. The
closeness of the charge brought about by Frenkel defect
tends to increase the dielectric constant of the crystal.
Compounds having such defect conduct electricity to a
small extent. When electric field is applied, an ion
moves from its lattice site to occupy a hole, it creates a
new hole. In this way, a hole moves from one end to the
other. Thus, it conducts electricity across the crystal.
Due to the presence of holes, stability (or the lattice
energy) of the crystal decreases.
(ii) Non-stoichiometric defects : The defects
which disturb the stoichiometry of the compounds are
called non-stoichiometry defects. These defects are
Consequences of Metal excess defects
The crystals with metal excess defects are
generally coloured due to the presence of free electrons
in them.
The crystals with metal excess defects conduct
electricity due to the presence of free electrons and are
semiconductors. As the electric transport is mainly by
“excess” electrons, these are called n-type (n for
negative) semiconductor.
The crystals with metal excess defects are
generally paramagnetic due to the presence of unpaired
electrons at lattice sites.
When the crystal is irradiated with white light,
the trapped electron absorbs some component of white
light for excitation from ground state to the excited
state. This gives rise to colour. Such points are called F-
centres. (German word Farbe which means colour)
such excess ions are accompanied by positive ion

vacancies. These vacancies serve to trap holes in the
same way as the anion vacancies trapped electrons. The
colour centres thus produced are called V-centres.
(c) Metal deficiency defect by cation vacancy : In
this a cation is missing from its lattice site. To
maintain electrical neutrality, one of the nearest metal
ion acquires two positive charge. This type of defect
occurs in compounds where metal can exhibit variable
valency. e.g., Transition metal compounds like NiO,
FeO, FeS etc.
(d) By having extra anion occupying interstitial site :
In this, an extra anion is present in the interstitial
position. The extra negative charge is balanced by one
extra positive charge on the adjacent metal ion. Since
anions are usually larger it could not occupy an
interstitial site. Thus, this structure has only a
theoretical possibility. No example is known so far.
A+ B– A+ B–
Cation vacancy
– – +
B B A semiconductor. This is because P has five valence
Metal having
+ – +2 – higher charge
A B A B
B –
A+
B –
A+
Fig. 5.22
Consequences of metal deficiency defects
Due to the movement of electron, an ion A+
changes to A+2 ions. Thus, the movement of an electron
from A+ ion is an apparent of positive hole and the
substances are called p-type semiconductor
(iii) Impurity defect : These defects arise when
foreign atoms are present at the lattice site (in place of
host atoms) or at the vacant interstitial sites. In the
former case, we get substitutional solid solutions while
in the latter case, we get interstitial solid solution. The
formation of the former depends upon the electronic
structure of the impurity while that of the later on the
size of the impurity.
Properties of solids
Some of the properties of solids which are useful
in electronic and magnetic devices such as, transistor,
computers, and telephones etc., are summarised below,
(1) Electrical properties : Solids are classified
into following classes depending on the extent of
conducting nature.
(i) Conductors : The solids which allow the
electric current to pass through them are called
Solid state 207
conductors. These are further of two types; Metallic
conductors and electrolytic conductors. The electrical
conductivity of these solids is high in the range
10 4  10 6 ohm 1 cm 1 . Their conductance decrease with
increase in temperature.
(ii) Insulators : The solids which do not allow the
current to pass through them are called insulators. e.g.,
rubber, wood and plastic etc. the electrical conductivity
of these solids is very low i.e., 10 12  10 22 ohm 1 cm 1 .
(iii) Semiconductors : The solids whose electrical
conductivity lies between those of conductors and
insulators are called semiconductors. The conductivity
of these solid is due to the presence of impurities. e.g.
Silicon and Germanium. Their conductance increase
with increase in temperature. The electrical
conductivity of these solids is increased by adding
impurity. This is called Doping. When silicon is doped
with P (or As, group 5th elements), we get n-type
electrons. It forms 4 covalent bonds with silicon and
the fifth electron remains free and is loosely bound.
This give rise to n-type semiconductor because current
is carried by electrons when silicon is doped with Ga
(or in In/Al, group 3rd elements) we get p-type
semiconductors.
Superconductivity : When any material loses its
resistance for electric current, then it is called
superconductor, Kammerlingh Onnes (1913) observed
this phenomenon at 4K in mercury. The materials
offering no resistance to the flow of current at very low
temperature (2-5K) are called superconducting
materials and phenomenon is called superconductivity.
Examples, Nb 3 Ge alloy (Before 1986)
La1.25 Ba0.15 CuO4 (1986)
YBa 2 Cu 3 O7 (1987)
Following are the important applications of
superconductivity,
(a) Electronics, (b) Building
supermagnets,
(c) Aviation transportation, (d) Power
transmission
“The temperature at which a material enters the
superconducting state is called the superconducting
transition temperature, (Tc ) ”. Superconductivity was
also observed in lead (Pb) at 7.2 K and in tin (Sn) at
 208 Solid State
3.7K. The phenomenon of superconductivity in other (TMTSF)2PF6, where TMTSF is tetra methyl tetra
materials such as polymers and organic crystals. selena fulvalene.
Examples are
(2) Magnetic properties : Based on the behavior
(SN)x, polythiazyl, the subscript x indicates a of substances when placed in the magnetic field, there
large number of variable size. are classified into five classes.
Table : 5.6 Magnetic properties of solids
Alignment of Magnetic
Properties Description Examples Applications
Dipoles
Diamagnetic Feebly repelled by the magnetic fields. All paired electrons TiO2, V2O5, NaCl, Insulator
Non-metallic elements (excepts O2, S) C6H6 (benzene)
inert gases and species with paired
electrons are diamagnetic
Paramagnetic Attracted by the magnetic field due to O 2 , Cu 2  , Fe 3  , TiO , Electronic
the presence of permanent magnetic appliances
dipoles (unpaired electrons). In Ti2O3 , VO, VO2 , CuO
magnetic field, these tend to orient
At least one unpaired
themselves parallel to the direction of
electron
the field and thus, produce magnetism
in the substances.
Ferromagnetic Permanent magnetism even in the Dipoles are aligned in Fe, Ni, Co, CrO2 CrO2 is used in
absence of magnetic field, Above a the same direction audio and
temperature called Curie temperature, video tapes
there is no ferromagnetism.
Antiferromagne This arises when the dipole alignment MnO, MnO2, Mn2O, –
tic is zero due to equal and opposite FeO, Fe2O3; NiO,
alignment. Cr2O3, CoO, Co3O4,
Ferrimagnetic This arises when there is net dipole Fe3O4, ferrites –
moment

(3) Dielectric properties : A dielectric substance
is that which does not allow the electricity to pass
through them but on applying the electric field, induced
charges are produced on its faces. In an insulator, the
electrons are strongly held by the individual atoms.
When an electric field is applied polarization takes
place because nuclei are attracted to one side and the
electron cloud to the other side. As a result, dipoles are
created. Such type of crystals shows the following
properties,
(i) Piezoelectricity : In some of the crystals, the
dipoles may align themselves is an ordered way so as to
give some net dipole moment. When mechanical stress
is applied in such crystals so as to deform them,
electricity is produced due to the displacement of ions.
The electricity thus produced is called piezoelectricity
and the crystals are called piezoelectric crystals.
Examples, Quartz, Rochelle’s salt ( sod. pot. tartarate).
Piezoelectric crystals act as mechanical-electric
transducer. These crystals are used as pick-ups in
record players where they produce electric signals by
application of pressure.
(ii) Pyroelectricity : On heating, some polar
crystals produce a small electric current. The electricity
thus produced is called pyroelectircity.
(iii) Ferroelectricity : In some of the piezoelectric
crystals, a permanent alignment of the dipoles is
always there even in the absence of the electric field,
however, on applying field the direction of polarization
changes. This phenomenon is called ferroelectricity and
the crystals as ferroelectric crystal. Example,
Potassium hydrogen phosphate (KH2 PO4 ) , Barium
titanate (BaTiO3 ) .
(iv) Antiferroelectricity : In some crystals,
the dipoles in alternate polyhedra point up and
down so that the crystals does not possess any net
dipole moment. Such crystals are said to be
antiferroelectric. Example, Lead zirconate
(PbZrO3 ) . Ferroelectrics are used in the
preparation of small sized capacitors of high
capacitance. Pyroelectric infrared detectors are
based on such substances. These can be used in
transistors, telephone, computer etc.
 Solid state 209
(a) Molecular crystal (b) Ionic crystal
(c) Covalent crystal (d) Metallic crystal
5. Value of heat of fusion of NaCl is
(a) Very low
 The reverse of crystallization is the melting of the (b) Very high
solid. (c) Not very low and not very high
 The slower the rate of formation of crystal, the (d) None of the above
bigger is the crystal. 6. Piezoelectric crystals are used in
 The hardness of metals increases with the (a) TV (b) Radio
number of electrons available for metallic (c) Record player (d) Freeze
bonding. Thus Mg is harder than sodium.
7. Which of the following is true for diamond
 Isomorphism is applied to those substances [AFMC 1997]
which are not only similar in their crystalline
(a) Diamond is a good conductor of electricity
form, but also possess an equal number of atoms
united in the similar manner. The existence of a (b) Diamond is soft
substance in more than one crystalline form is (c) Diamond is a bad conductor of heat
known as polymorphism. (d) Diamond is made up of C, H and O

8. NaCl is an example of
(a) Covalent solid (b) Ionic solid
(c) Molecular solid (d) Metallic solid

Properties and Types of solid

1. The three states of matter are solid, liquid and

gas. Which of the following statement is/are true
about them
[AIIMS 1991]
(a) Gases and liquids have viscosity as a common
property
(b) The molecules in all the three states possess
random translational motion
(c) Gases cannot be converted into solids without
passing through the liquid phase
(d) Solids and liquids have vapour pressure as a
common property
2. A pure crystalline substance, on being heated
gradually, first forms a turbid looking liquid and
then the turbidity completely disappears. This
behaviour is the characteristic of substances
forming [BHU 2000]
(a) Isomeric crystals (b) Liquid crystals
(c) Isomorphous crystals (d) Allotropic crystals
3. Which of the following is ferroelectric compound
[AFMC 1997]
(a) BaTiO3 (b) K 4 [Fe(CN )6 ]
(c) Pb 2 O 3 (d) PbZrO3
4. Solid CO2 is an example of
 208 Solid state
9. Amorphous substances show 18. Dulong and Petit’s law is valid only for[KCET 2004]
(A) Short and long range order (a) Metals (b) Non-metals
(B) Short range order (c) Gaseous elements (d) Solid elements
(C) Long range order 19. Which of the following is an example of metallic
(D) Have no sharp M.P. crystal solid
(a) C (b) Si
(a) A and C are correct (b) B and C are correct
(c) W (d) AgCl
(c) C and D are correct (d) B and D are correct
10. The characteristic features of solids are[AMU 1994] 20. Under which category iodine crystals are placed
among the following
(a) Definite shape
(a) Ionic crystal (b) Metallic crystal
(b) Definite size
(c) Molecular crystal (d) Covalent crystal
(c) Definite shape and size
21. Among solids the highest melting point is
(d) Definite shape, size and rigidity
established by
11. Which one of the following is a good conductor of
[Kerala CET (Med.) 2002]
electricity
(a) Covalent solids (b) Ionic solids
[MP PMT 1994; AFMC 2002]
(c) Pseudo solids (d) Molecular solids
(a) Diamond (b) Graphite
22. To get a n- type semiconductor, the impurity to be
(c) Silicon (d) Amorphous carbon
added to silicon should have which of the
12. A crystalline solid [Kerala CET (Med.) 2003]
following number of valence electrons [KCET (Engg.) 2001
(a) Changes abruptly from solid to liquid when (a) 1 (b) 2
heated
(c) 3 (d) 5
(b) Has no definite melting point
23. Which of the following is non-crystalline solid
(c) Undergoes deformation of its geometry easily
(a) CsCl (b) NaCl
(d) Has an irregular 3-dimensional arrangements
(c) CaF2 (d) Glass
(e) Softens slowly
13. Diamond is an example of 24. The lustre of a metal is due to [AFMC 1998]

[MP PET/PMT 1998; CET Pune 1998] (a) Its high density (b) Its high polishing
(a) Solid with hydrogen bonding (c) Its chemical inertness (d)Presence of free electrons
(b) Electrovalent solid 25. A crystalline solid have [DCE 2001]

(c) Covalent solid (a) Long range order (b) Short range order
(d) Glass (c) Disordered arrangement (d) None of these
14. The solid NaCl is a bad conductor of electricity 26. Crystalline solids are [Pb. PMT 1999]
since (a) Glass (b) Rubber
[AIIMS 1980] (c) Plastic (d) Sugar
(a) In solid NaCl there are no ions 27. Davy and Faraday proved that[Kerala CET (Med.) 2002]
(b) Solid NaCl is covalent
(a) Diamond is a form of carbon
(c) In solid NaCl there is no velocity of ions
(b) The bond lengths of carbon containing
(d) In solid NaCl there are no electrons compounds are always equal
15. The existence of a substance in more than one
(c) The strength of graphite is minimum
solid modifications is known as or Any compound
compared to platinum
having more than two crystal structures is called
[MP PMT 1993; MP PET 1999]
(d) Graphite is very hard
(a) Polymorphism (b) Isomorphism 28. Which one of the following metal oxides is
(c) Allotropy (d) Enantiomorphism antiferromagnetic in nature [MP PET 2002]

16. Which is not a property of solids [MP PET 1995] (a) MnO 2 (b) TiO2
(a) Solids are always crystalline in nature (c) VO2 (d) CrO 2
(b) Solids have high density and low 29. In graphite, carbon atoms are joined together due
compressibility to
(c) The diffusion of solids is very slow [AFMC 2002]
(d) Solids have definite volume
(a) Ionic bonding (b) Vander Waal’s forces
17. Which solid will have the weakest intermolecular
(c) Metallic bonding (d) Covalent bonding
forces
(a) Ice (b) Phosphorus 30. Which of the following is not correct for ionic
crystals
(c) Naphthalene (d) Sodium fluoride
[Orissa JEE 2002]
 Solid state 209
(a) They possess high melting point and boiling (c) In ionic compounds having Frenkel defect the
point 
ratio is high
(b) All are electrolyte 
(c) Exhibit the property of isomorphism (d) The coordination number of Na  ion in NaCl
(d) Exhibit directional properties of the bond is 4
31. Which of the following is a molecular crystal 2. Which of the following is correct [DPMT 1997]
(a) SiC (b) NaCl Crystal Axial Axial Examples
system distance angles
(c) Graphite (d) Ice
32. Quartz is a crystalline variety of [Pb. PMT 2000]
(a) Cubic a b=c  =    Cu, KCl
= 90o
(a) Silica (b) Sodium silicate
(b) Monoclini a b=c = = PbCrO2,
(c) Silicon carbide (d) Silicon c = 90o PbCrO4
33. Which type of solid crystals will conduct heat and (c) Rhomboh a=b=c = = CaCO3,
electricity edral  90o HgS
[RPET 2000]
(d) Triclinic a=b=c    =  K2Cr2O7,
(a) Ionic (b) Covalent
 90o CuSO4.
(c) Metallic (d) Molecular 5H2O
34. Which of the following is an example of covalent 3. Tetragonal crystal system has the following unit
crystal solid cell dimensions [MP PMT 1993]
(a) Si (b) NaF
(a) a  b  c and       90 o
(c) Al (d) Ar
35. Which of the following is an example of ionic (b) a  b  c and       90 o
crystal solid (c) a  b  c and       90 o
(a) Diamond (b) LiF
(d) a  b  c and     90 o ,   120 o
(c) Li (d) Silicon
4. Rhombic sulphur has the following structure
36. Which one is an example of amorphous solid
(a) Open chain
(a) Glass (b) Salt
(b) Tetrahedral
(c) Cesium chloride (d) Calcium fluoride
(c) Puckered 6-membered ring
37. Silicon is [MHCET 2004]
(d) Puckered 8-membered ring
(a) Semiconductor (b) Insulator
5. Space lattice of CaF2 is [MP PMT 1993]
(c) Conductor (d) None of these
38. Which of the following statements about (a) Face centred cubic
amorphous solids is incorrect [KCET 2004] (b) Body centred cubic
(a) They melt over a range of temperature (c) Simple cubic
(b) They are anisotropic (d) Hexagonal closed packing
(c) There is no orderly arrangement of particles 6. For cubic coordination the value of radius ratio is
(d) They are rigid and incompressible (a) 0.732  1.000 (b) 0 .225  0 .414
39. The ability of a given substance to assume two or (c) 0 .000  0 . 225 (d) 0.414  0.732
more crystalline structure is called [DCE 2004] 7. How many space lattices are obtainable from the
(a) Amorphism (b) Isomorphism different crystal systems [MP PMT 1996; MP PET/PMT 1998]
(c) Polymorphism (d) Isomerism (a) 7 (b) 14
40. Glass is (c) 32 (d) 230
8. Example of unit cell with crystallographic
(a) Supercooled liquid (b) Crystalline solid
dimensions a  b  c,     90 o ,   90 o is[AFMC 1998]
(c) Amorphous solid (d) Liquid crystal
(a) Calcite (b) Graphite
Crystallography and Lattice (c) Rhombic sulphur (d) Monoclinic sulphur
9. In a face-centered cubic lattice, a unit cell is
1. The correct statement in the following is [MP PET 1997] shared equally by how many unit cells [CBSE PMT 2005]
(a) The ionic crystal of AgBr has Schottky defect (a) 8 (b) 4
(c) 2 (d) 6
(b) The unit cell having crystal parameters,
a  b  c, 10. The maximum radius of sphere that can be fitted
in the octahedral hole of cubical closed packing of
    90 o ,   120 o is hexagonal sphere of radius r is
(a) 0.732 r (b) 0.414 r
 210 Solid state
(c) 0.225 r (d) 0.155 r (a) 0 .155  0 . 225 (b) 0 .225  0 .414
11. The unit cell of a NaCl lattice (c) 0.414  0.732 (d) 0.732  1.000
(a) Is body centred cube (b) Has 3 Na  ions 23. Structure similar to zinc blende is found in
(c) Has 4 NaCl units (d) Is electrically (a) AgCl (b) NaCl
charged
(c) CuCl (d) TlCl
12. For tetrahedral coordination number, the radius 24. The structure of Na 2 O crystal is
r
ratio c is [KCET 2000] (a) CsCl type (b) NaCl type
ra 
(c) ZnS type (d) Antifluorite
(a) 0.732  1.000 (b) 0.414  0.732 25. Structure of ZnS is
(c) 0 .225  0 .414 (d) 0 .155  0 .225 (a) Body centred cubic (b) Face centred cubic
13. What type of lattice is found in potassium (c) Simple cube (d) Fluorite structure
chloride crystal 26. The crystal system of a compound with unit cell
[MP PMT 1996] dimensions a  0.387 , b  0.387 and c  0 .504 nm
(a) Face centred cubic (b) Body centred cubic and     90 o and   120 o is [AIIMS 2004]
(c) Simple cubic (d) Simple tetragonal (a) Cubic (b) Hexagonal
14. The three dimensional graph of lattice points (c) Orthorhombic (d) Rhombohedral
which sets the pattern for the whole lattice is 27. The number of tetrahedral voids in the unit cell of
called a face centered cubic lattice of similar atoms is [Kerala PM
(a) Space lattice (b) Simple lattice (a) 4 (b) 6
(c) Unit cell (d) Crystal lattice (c) 8 (d) 10
15. Crystals can be classified into ...... basic crystal 28. An fcc unit cell of aluminium contains the
habits equivalent of how many atoms [DCE 2003]
[MP PMT 1994]
(a) 1 (b) 2
(a) 3 (b) 7
(c) 3 (d) 4
(c) 14 (d) 4
16. How many molecules are there in the unit cell of Crystal packing
sodium chloride [MP PMT 1996; MP PET 1997]
(a) 2 (b) 4
1. If ‘Z’ is the number of atoms in the unit cell that
(c) 6 (d) 8 represents the closest packing sequence
17. In a crystal, the atoms are located at the position    A B C A B C   , the number of tetrahedral
of
voids in the unit cell is equal to
[AMU 1985]
[AIIMS 2005]
(a) Maximum P.E. (b) Minimum P.E.
(c) Zero P.E. (d) Infinite P.E. (a) Z (b) 2 Z
18. The total number of lattice arrangements in (c) Z/2 (d) Z/4
different crystal systems is [KCET (Engg.) 2001] 2. The close packing represents ABC ABC...... order
(a) 3 (b) 7 of
(c) 8 (d) 14 (a) Body centred cubic packing
19. Monoclinic crystal has dimension [DCE 2000] (b) Face centred cubic packing
(a) a  b  c,     90 ,   90  (c) Simple cubic packing
(b) a  b  c,       90  (d) Hexagonal cubic closed packing
(c) a  b  c,       90  3. The arrangement ABC ABC ABC ….. is referred as
(d) a  b  c,       90  [MP PET 2001]
20. The low solubility of BaSO4 in water can be (a) Octahedral close packing (b) H
attributed to (c) Tetragonal close packing (d) C
[CBSE PMT 1991] 4. The number of close neighbour in a body-centred
(a) High lattice energy (b) Dissociation energy cubic lattice of identical sphere is [MP PET 2001]
(c) Low lattice energy (d) Ionic bond (a) 8 (b) 6
21. Bravais lattices are of [MP PMT 1997] (c) 4 (d) 2
(a) 8 types (b) 12 types 5. The number of equidistant oppositely charged
(c) 14 types (d) 9 types ions in a sodium chloride crystal is [MP PET 2001]
22. The structure of TlCl is similar to CsCl . What (a) 8 (b) 6
would be the radius ratio in TlCl (c) 4 (d) 2
 Solid state 211
6. Na and Mg crystallize in BCC and FCC type 17. In the fluorite structure, the coordination number
crystals respectively, then the number of atoms of of Ca 2  ion is
Na and Mg present in the unit cell of their (a) 4 (b) 6
respective crystal is (c) 8 (d) 3
[AIEEE 2002] 18. The ratio of close-packed atoms to tetrahedral
(a) 4 and 2 (b) 9 and 14 holes in cubic close packing is [Pb. PMT 1998]
(c) 14 and 9 (d) 2 and 4 (a) 1 : 1 (b) 1 : 2
7. An AB 2 type structure is found in [AIIMS 2002] (c) 1 : 3 (d) 2 : 1
(a) NaCl (b) Al 2 O3 19. A solid is made of two elements X and Z . The
atoms Z are in CCP arrangement while the atom
(c) CaF2 (d) N 2 O X occupy all the tetrahedral sites. What is the
8. Potassium crystallizes with a [MP PET/PMT 1998] formula of the compound
[UPSEAT 2004]
(a) Face-centred cubic lattice
(a) XZ (b) XZ 2
(b) Body-centred cubic lattice
(c) X 2 Z (d) X 2 Z3
(c) Simple cubic lattice
(d) Orthorhombic lattice 20. An ionic compound has a unit cell consisting of A
ions at the corners of a cube and B ions on the
9. If the number of atoms per unit in a crystal is 2,
centres of the faces of the cube. The empirical
the structure of crystal is
formula for this compound would be [CBSE PMT 2004; AIEE
(a) Octahedral
(a) AB (b) A2 B
(b) Body centred cubic bcc
(c) AB 3 (d) A3 B
(c) Face centred cubic fcc
21. The vacant space in the bcc unit cell is
(d) simple cubic
(a) 32% (b) 23%
10. The intermetallic compound LiAg crystallizes in
(c) 26% (d) None of these
cubic lattice in which both lithium and silver have
22. The number of octahedral voids in a unit cell of a
coordination number of eight. The crystal class is
cubical closest packed structure is
[CBSE PMT 1997]
(a) 1 (b) 2
(a) Simple cube (b) Body-centred cube (c) 4 (d) 8
(c) Face-centred cube (d) None of these 23. In the closest packed structure of a metallic
11. The number of octahedral sites per sphere in a fcc lattice, the number of nearest neighbours of a
structure is [MP PMT 2000, 01] metallic atom is
(a) 8 (b) 4 [JIPMER 2002]
(c) 2 (d) 1 (a) Twelve (b) Four
12. Hexagonal close packed arrangement of ions is (c) Eight (d) Six
described as 24. In the rock salt structure, the number of formula
[MP PMT 1994] units per unit cell is equal to
(a) ABC ABA (b) ABC ABC (a) 1 (b) 2
(c) ABABA (d) ABBAB (c) 3 (d) 4
13. An example of a body cube is [AIIMS 1996] 25. Hexagonal close packing is found in crystal lattice
(a) Sodium (b) Magnesium of
(c) Zinc (d) Copper [MH CET 2002]
14. An example of fluorite structure is (a) Na (b) Mg
(a) NaF (b) SrF2 (c) Al (d) None of these
(c) AlCl3 (d) SiF4 26. Which ion has the largest radius from the
following ions
15. In which of the following crystals alternate
tetrahedral voids are occupied? [IIT 2005] (a) Na  (b) Mg 2 
(a) NaCl (b) ZnS (c) Al 3  (d) Si 4 
(c) CaF2 (d) Na2O
16. Which of the following contains rock salt
Mathematical analysis of cubic system and
structure
Bragg’s equation
(a) SrF2 (b) MgO
(c) Al 2 O3 (d) All
 212 Solid state
1. The formula for determination of density of unit  d
(c) 2n  d sin (d) n  sin
cell is 2 2
a3  N o NM
(a) g cm  3 (b) 3 g cm  3 10. The number of atoms in 100 g of an fcc crystal
NM a  No
with density d  10 g / cm 3 and cell edge equal to
a3  M M  No
(c) g cm  3 (d) g cm  3 100 pm, is equal to [CBSE PMT 1994; KCET 2002]
N  No a3  N
(a) 4  10 25 (b) 3  10 25
2. Potassium fluoride has NaCl type structure. What
is the distance between K  and F  ions if cell (c) 2  10 25 (d) 1  10 25
edge is a cm 11. In the crystals of which of the following ionic
(a) 2a cm (b) a / 2 cm compounds would you expect maximum distance
(c) 4 a cm (d) a / 4 cm between centres of cations and anions[CBSE PMT 1998]

3. An element occurring in the bcc structure has (a) LiF (b) CsF
12 .08  10 23 unit cells. The total number of atoms (c) CsI (d) LiI
of the element in these cells will be [MP PET 1994] 12. The number of unit cells in 58 .5 g of NaCl is
(a) 24 .16  10 23 (b) 36 .18  10 23 nearly
(c) 6.04  10 23 (d) 12 .08  10 23 [MP PMT 2000, 01]
4. If an atom is present in the centre of the cube, the
(a) 6  10 20
(b) 3  10 22
participation of that atom per unit cell is
1 (c) 1.5  10 23 (d) 0.5  10 24
(a) (b) 1
4 13. How many unit cells are present in a cube-shaped
1 1 ideal crystal of NaCl of mass 1.00 g [Atomic
(c) (d)
2 8 masses: Na  23, Cl  35 .5] [AIEEE 2003]
5. For an ionic crystal of the general formula AX
and coordination number 6, the value of radius (a) 2.57  10 21 unit cells (b) 5.14  10 21
unit cells
ratio will be (c) 1 .28  10 21 unit cells (d) 1.71  10 21 unit cells
[MP PMT 1993]
14. In the Bragg’s equation for diffraction of X-
(a) Greater than 0.73 rays, n represents for [MP PMT 2000]
(b) In between 0.73 and 0.41
(a) Quantum number (b) An integer
(c) In between 0.41 and 0.22
(c) Avogadro’s numbers (d) Moles
(d) Less than 0.22
15. In a face centred cubic cell, an atom at the face
6. The number of spheres contained (i) in one body
contributes to the unit cell
centred cubic unit cell and (ii) in one face centred
cubic unit cell, is [Karnataka (Engg./Med.) 2000; AFMC 2001]
(a) In (i) 2 and in (ii) 4 (b) In (i) 3 and in (ii) 2 (a) 1/4 part (b) 1/8 part
(c) In (i) 4 and in (ii) 2 (d) In (i) 2 and in (ii) 3 (c) 1 part (d) 1/2 part
7. CsBr crystal has bcc structure. It has an edge 16. The interionic distance for cesium chloride crystal
length of 4 . 3 Å. The shortest interionic distance will be
[MP PET 2002]
between Cs  and Br  ions is [IIT 1995]
a
(a) 1 .86 Å (b) 3 .72 Å (a) a (b)
2
(c) 4 .3 Å (d) 7 .44 Å
3a 2a
(c) (d)
8. In octahedral holes (voids) 2 3
(a) A simple triangular void surrounded by four 17. Sodium metal crystallizes as a body centred cubic
spheres lattice with the cell edge 4.29 Å. What is the
(b) A bi-triangular void surrounded by four radius of sodium atom
spheres [AIIMS 1999]
(c) A bi-triangular void surrounded by six spheres 8 7
(a) 1.857  10 cm (b) 2.371  10 cm
(d) A bi-triangular void surrounded by eight
spheres (c) 3.817  10 8
cm (d) 9 .312  10 7 cm
9. 18.
Bragg's law is given by the equation[MP PMT 1995, 2002] For an ionic crystal of the type AB , the value of
(a) n  2 sin (b) n  2d sin (limiting) radius ratio is 0.40. The value suggests
that the crystal structure should be
(a) Octahedral (b) Tetrahedral
 Solid state 213
(c) Square planar (d) Plane triangle 3
19. Potassium has a bcc structure with nearest (c) 2r (d) r
2
neighbour distance 4 . 52 Å. Its atomic weight is
39. Its density (in kg m 3 ) will be [AIIMS 1991]
Crystal structure and Coordination number
(a) 454 (b) 804
1. A solid has a structure in which 'W ' atoms are
(c) 852 (d) 908 located at the corners of a cubic lattice ' O ' atoms
r  at the centre of edges and ' Na ' atoms at the
20. If the value of ionic radius ratio  c  is 0.52 in an centre of the cube. The formula for the compound
 ra 
is [KCET 1996]
ionic compound, the geometrical arrangement of
(a) NaWO 2 (b) NaWO 3
ions in crystal is
(a) Tetrahedral (b) Planar (c) Na 2 WO 3 (d) NaWO 4
(c) Octahedral (d) Pyramidal 2. Potassium crystallizes in a bcc lattice, hence the
21. The number of atoms/molecules contained in one coordination number of potassium in potassium
face centred cubic unit cell of a monoatomic metal is
substance is [KCEE 1993]
[CPMT 1989, 94; CBSE PMT 1989, 96; NCERT 1990; (a) 0 (b) 4
MP PET 1993; KCET 1999] (c) 6 (d) 8
(a) 1 (b) 2 3. Body centered cubic lattice has a coordination
(c) 4 (d) 6 number of
22. The number of atoms/molecules contained in one [AIIMS 1996; MP PMT 2002]
body centered cubic unit cell is (a) 4 (b) 8
(a) 1 (b) 2 (c) 12 (d) 6
(c) 4 (d) 6 4. A compound is formed by elements A and B . This
23. It the distance between Na and Cl 
ions in  crystallizes in the cubic structure when atoms
sodium chloride crystal is X pm, the length of the A are the corners of the cube and atoms B are at
edge of the unit cell is [KCET 2004] the centre of the body. The simplest formula of
the compounds is
(a) 4X pm (b) X/4 pm
[KCET 1993; CBSE PMT 2000; Kerala PMT 2002]
(c) X/2 pm (d) 2X pm
(a) AB (b) AB 2
24. The edge of unit cell of FCC Xe crystal is 620 pm .
(c) A2 B (d) AB 4
The radius of Xe atom is [MP PET 2004]
(a) 219.25 Pm (b) 235.16 Pm 5. Coordination number for Cu is [AMU 1982]
(c) 189.37 Pm (d) 209.87 Pm (a) 1 (b) 6
25. In orthorhombic, the value of a, b and c are (c) 8 (d) 12
respectively 4 .2 Å, 8 .6 Å and 8 .3 Å . given the 6. In the crystal of CsCl , the nearest neighbours of
each Cs ion are [MP PET 1993]
molecular mass of the solute is 155 gm mol 1 and
(a) Six chloride ions (b) Eight chloride ions
that of density is 3.3 gm / cc , the number of
(c) Six Cs ions (d) Eight Cs ions
formula units per unit cell is 7. In a cubic structure of compound which is made
[Orrisa JEE 2005] from X and Y, where X atoms are at the corners of
(a) 2 (b) 3 the cube and Y at the face centres of the cube. The
(c) 4 (d) 6 molecular formula of the compound is [AIIMS 2000]
26. A metal has bcc structure and the edge length of (a) X 2Y (b) X3Y
its unit cell is 3 .04 Å . The volume of the unit cell (c) XY 2 (d) XY 3
in cm 3 will be
8. Ferrous oxide has a cubic structure and each edge
[Orrisa JEE 2005]
of the unit cell is 5.0 Å. Assuming density of the
(a) 1 .6  10 21 cm 3 (b) 2 .81  10 23 cm 3 oxide as 4.0 g  cm 3 , then the number of Fe 2  and
(c) 6 .02  10 23 cm 3 (d) 6 .6  10 24 cm 3 O 2  ions present in each unit cell will be [MP PET 2000]
27. In face centred cubic unit cell edge length is [DPMT 2005] (a) Four Fe 2  and four O 2 
(a)
4
r (b)
4
r (b) Two Fe 2  and four O 2 
3 2 (c) Four Fe 2  and two O 2 
(d) Three Fe 2  and three O 2 
 214 Solid state
9. Which of the following statements is not true (c) Spherically symmetrical
about NaCl structure [DCE 2001] (d) Arranged in planes
(a) Cl  ions are in fcc arrangement 19. An example of a non-stoichiometric compound is
[NCERT 1983]
(b) Na  ions has coordination number 4
(a) Al 2 O3 (b) Fe 3 O 4
(c) Cl  ions has coordination number 6
(c) NiO2 (d) PbO
(d) Each unit cell contains 4 NaCl molecules
20. If the radius ratio is in the range of 0 .731  1, then
10. In CsCl structure, the coordination number of
the coordination number will be
Cs  is
(a) 2 (b) 4
[MP PMT 2001]
(c) 6 (d) 8
(a) Equal to that of Cl  , that is 6
21. If the radius ratio is in the range of 0 .414  0 .732 ,
(b) Equal to that of Cl  , that is 8 then the coordination number will be
(c) Not equal to that of Cl  , that is 6 (a) 2 (b) 4
(d) Not equal to that of Cl  , that is 8 (c) 6 (d) 8
11. In a solid ‘AB’ having the NaCl structure, ‘A’ 22. What is the coordination number of sodium in
atoms occupy the corners of the cubic unit cell. If Na 2 O
all the face-centered atoms along one of the axes
[AIIMS 2003]
are removed, then the resultant stoichiometry of
the solid is [IIT Screening 2001] (a) 6 (b) 4
(a) AB 2 (b) A2 B (c) 8 (d) 2

(c) A4 B3 (d) A3 B4 23. The ratio of cationic radius to anionic radius in an

ionic crystal is greater than 0.732. Its coordination
12. In solid CsCl each Cl is closely packed with how number is
many Cs [MP PET 2003] [KCET 2003]
(a) 8 (b) 6 (a) 6 (b) 8
(c) 10 (d) 2
(c) 1 (d) 4
13. In A  B  ionic compound, radii of A  and B  ions
24. In CsCl lattice the coordination number of Cs 
are 180 pm and 187 pm respectively. The crystal
ion is
structure of this compound will be
(a) 2 (b) 4
(a) NaCl type (b) CsCl type
(c) 8 (d) 12
(c) ZnS type (d) Similar to diamond
25. Crystal structure of NaCl is [NCERT 1982; BHU 1995]
14. In which of the following substances the carbon
atom is arranged in a regular tetrahedral (a) fcc (b) bcc
structure [NCERT 1978] (c) Both (a) and (b) (d) None
(a) Diamond (b) Benzene 26. In NaCl lattice the coordination number of Cl 
(c) Graphite (d) Carbon black ion is
15. The coordination number of a metal crystallizing (a) 2 (b) 4
in a hexagonal close packed structure is
(c) 6 (d) 8
[NCERT 1978; IIT 1999]
27. In zinc blende structure the coordination number
(a) 4 (b) 12
of Zn 2  ion is
(c) 8 (d) 6
(a) 2 (b) 4
16. The structure of MgO is similar to NaCl . What
would be the coordination number of magnesium (c) 6 (d) 8
(a) 2 (b) 4 28. Coordination number of Na  ion in rock salt is
(c) 6 (d) 8 [BVP 2004]
17. How many chloride ions are there around sodium (a) 12 (b) 4
ion in sodium chloride crystal[NCERT 1979, 80; CPMT 1988; (c) 8 (d) 6
BHU 1982, 87; MP PET 1995, 99]
29. The number of Cl  ions around one Na  in NaCl
(a) 3 (b) 8 crystal lattice is [MP PET 1996; BVP 2004]
(c) 4 (d) 6 (a) 12 (b) 4
18. Most crystals show good cleavage because their (c) 8 (d) 6
atoms, ions or molecules are [CBSE PMT 1991]
30. The number of atoms present in unit cell of a
(a) Weakly bonded together monoatomic substance of simple cubic lattice is [Pb. PMT
(b) Strongly bonded together
 Solid state 215
(a) 6 (b) 3 (c) 3  10 3 mol % (d) 4  10 3 mol %
(c) 2 (d) 1 6. In the laboratory, sodium chloride is made by
31. The coordination number of a metal crystallizing burning the sodium in the atmosphere of chlorine
in a hexagonal close packed chep structure is [MP PMT 2004]which is yellow in colour. The cause of yellow
(a) 12 (b) 8 colour is
(c) 4 (d) 6 (a) Presence of Na  ions in the crystal lattice
32. Which of the following statement(s) is(are)
(b) Presence of Cl  ions in the crystal lattice
correct
[IIT 1998] (c) Presence of electron in the crystal lattice
(a) The coordination number of each type of ion (d) Presence of face centered cubic crystal lattice
in CsCl crystal is 8 7. Frenkel defect is caused due to [MP PET 1994]
(b) A metal that crystallizes in bcc structure has (a) An ion missing from the normal lattice site
a coordination number of 12 creating a vacancy
(c) A unit cell of an ionic crystal shares some of (b) An extra positive ion occupying an interstitial
its ions with other unit cells position in the lattice
(d) The length of the unit cell in NaCl is 552 pm
(c) An extra negative ion occupying an interstitial
(rNa   95 pm ; rCl   181 pm ) position in the lattice
33. The co-ordination number of Na  in NaCl is (d) The shift of a positive ion from its normal
[Orrisa JEE 2005]
lattice site to an interstitial site
(a) 6 (b) 8 8. Which one of the following has Frenkel defect
[MP PMT 2000]
(c) 4 (d) 1
34. In the calcium fluoride structure the co- (a) Sodium chloride (b) Graphite
ordination number of the cation and anions are (c) Silver bromide (d) Diamond
respectively [J & K 2005] 9. Schottky defect generally appears in [DCE 2004]
(a) 6, 6 (b) 8, 4 (a) NaCl (b) KCl
(c) 4, 4 (d) 4, 8 (c) CsCl (d) All of these
10. Schottky defect in crystals is observed when
Defects in crystal [CBSE PMT 1998; KCET 2002]
(a) Density of crystal is increased
1. Certain crystals produce electric signals on (b) Unequal number of cations and anions are
application of pressure. This phenomenon is missing from the lattice
called [BHU 2005]
(c) An ion leaves its normal site and occupies an
(a) Pyroelectricity (b) Ferroelectricity interstitial site
(c) Peizoelectricity (d) Ferrielectricity (d) Equal number of cations and anions are
2. Which defect causes decrease in the density of missing from the lattice
crystal 11. Ionic solids, with Schottky defects, contain in
[KCET 2000, 05] their structure
(a) Frenkel (b) Schottky [CBSE PMT 1994]
(c) Interstitial (d) F  centre (a) Equal number of cation and anion vacancies
3. The correct statement regarding F  centre is (b) Anion vacancies and interstitial anions
(a) Electron are held in the voids of crystals (c) Cation vacancies only
(b) F  centre produces colour to the crystals (d) Cation vacancies and interstitial cations
(c) Conductivity of the crystal increases due to 12. The following is not a function of an impurity
F  centre present in a crystal [MP PET 1995]

(d) All (a) Establishing thermal equilibrium

4. Doping of silicon (Si) with boron (B) leads to (b) Having tendency to diffuse
[UPSEAT 2004] (c) Contributing to scattering
(a) n -type semiconductor (b) p -type semiconductor (d) Introducing new electronic energy levels
13. Due to Frenkel defect, the density of ionic solids
(c) Metal (d) Insulator
[MP PET 1996; MP PMT 2002]
5. If NaCl is doped with 10 3 mol % SrCl 2 , then the (a) Increases (b) Decreases
concentration of cation vacancies will be (c) Does not change (d) Changes
(a) 1  10 3 mol % (b) 2  10 3 mol % 14. Point defects are present in [MP PMT 1997]
 216 Solid state
(a) Ionic solids (b) Molecular solids (c) Supercooled liquid
(c) Amorphous solids (d) Liquids (d) Substance with definite melting point
15. If a non-metal is added to the interstitial sites of a 2. Silicon is found in nature in the form of [MH CET 2002]
metal then the metal becomes [DCE 2001] (a) Body centered cubic structure
(a) Softer (b) Less tensile (b) Hexagonal close-packed structure
(c) Less malleable (d) More ductile (c) Network solid
16. In AgBr crystal, the ion size lies in the order (d) Face centered cubic structure
3. A match box exhibits [MP PET 1993, 95]
Ag   Br  . The AgBr crystal should have the
(a) Cubic geometry (b) Monoclinic geometry
following characteristics
(c) Orthorhombic geometry (d)Tetragonal geometry
(a) Defectless (perfect) crystal
4. Which has no rotation of symmetry[Orrisa JEE 2004]
(b) Schottky defect only
(a) Hexagonal (b) Orthorhombic
(c) Frenkel defect only
(c) Cubic (d) Triclinic
(d) Both Schottky and Frenkel defects
5. Which of the following molecules has three-fold
17. Frenkel and Schottky defects are [BHU 2003]
axis of symmetry [UPSEAT 2004]
(a) Nucleus defects (b) Non-crystal defects
(a) NH 3 (b) C2 H 4
(c) Crystal defects (d) None of these
(c) CO2 (d) SO 2
18. Which one of the following is the most correct
statement 6. Which one possess a antifluorite structure
(a) Brass is an interstitial alloy, while steel is a (a) Na 2 O (b) MgO
substitutional alloy (c) Fe 2 O 3 (d) Al 2 O3
(b) Brass is a substitutional alloy, while steel is 7. Which one of the following is the biggest ion[MP PET 1993]
an interstitial alloy
(a) Al 3 (b) Ba 2
(c) Brass and steel are both substitutional alloys
(d) Brass and steel are both interstitial alloys (c) Mg 2 (d) Na 
19. The flame colours of metal ions are due to [KCET 2003]8. The edge length of face centred unit cubic cell is
508 pm. If the radius of the cation is 110 pm, the
(a) Frenkel defect (b) Schottky defect
radius of the anion is
(c) Metal deficiency defect (d)Metal excess defect
[CBSE PMT 1998]
20. Which one of the following crystals does not
(a) 285 pm (b) 398 pm
exhibit Frenkel defect [MP PET 2002]
(a) AgBr (b) AgCl (c) 144 pm (d) 618 pm
(c) KBr (d) ZnS 9. An element (atomic mass 100 g / mol ) having bcc
21. In a solid lattice the cation has left a lattice site structure has unit cell edge 400 pm. Then density
and is located at an interstitial position, the of the element is
lattice defect is [CBSE PMT 1996; AIIMS 2002]
[AIIMS 1982, 1991; DCE 2002; J & K 2005] 3
(a) 10 . 376 g / cm (b) 5 .188 g / cm 3
(a) Interstitial defect (b) Valency defect
(c) Frenkel defect (d) Schottky defect (c) 7 .289 g / cm 3 (d) 2 .144 g / cm 3
22. When electrons are trapped into the crystal in 10. If the pressure on a NaCl structure is increased,
anion vacancy, the defect is known as [BHU 2005] then its coordination number will [AFMC 2000]
(a) Schotky defect (b) Frenkel defect (a) Increase (b) Decrease
(c) Stoichiometric defect (d) F-centres (c) Remain the same (d) Either (b) or (c)
23. Schottky defect defines imperfection in the lattice 11. The pyknometric density of sodium chloride
structure of a [AIIMS 2002]
crystal is 2 . 165  10 3 kg m 3 while its X-rays density
(a) Solid (b) Liquid
(c) Gas (d) Plasma is 2 . 178  10 3 kg m 3 . The fraction of unoccupied
sites in sodium chloride crystal is [CBSE PMT 2003]
(a) 5.96  10 3 (b) 5 .96
2
(c) 5.96  10 (d) 5.96  10 1
12. Which of the following statements is correct for
CsBr3
[IIT 1996]
(a) It is a covalent compound
1. Amorphous solids are
(a) Solid substance in real sense (b) It contains Cs 3  and Br  ions
(b) Liquid in real sense (c) It contains Cs  and Br 3 ions
 Solid state 217
(d) It contains Cs  , Br  and lattice Br2 molecule 2. Assertion : In crystal lattice, the size of the
cation is larger in a tetrahedral hole
13. In which compound 8 : 8 coordination is found
than in an octahedral hole.
[EAMCET 1984]
(a) CsCl (b) MgO Reason : The cations occupy more space than
anions in crystal packing.[AIIMS 1996]
(c) Al 2 O3 (d) All of these
3. Assertion : Crystalline solids have short range
14. If the coordination of Ca 2  in CaF2 is 8, then the order.
coordination number of F  ion would be Reason : Amorphous solids have long range
(a) 3 (b) 4 order.
(c) 6 (d) 8 [AIIMS 1999]
15. For some crystals, the radius ratio for cation and 4. Assertion : In any ionic solid (MX) with
anion is 0.525, its coordination number will be Schottky defects, the number of
(a) 2 (b) 4 positive and negative ions are same.
(c) 6 (d) 8 Reason : Equal number of cation and anion
16. The basic building unit of all silicates is[UPSEAT 2002] vacancies are present.
(a) SiO4 square planar (b) [SiO 4 ] 4  tetrahedron [IIT Screening 2001]
(c) SiO4 octahedron (d) SiO4 linear 5. Assertion : Space or crystal lattice differ in
17. What type of crystal defect is indicated in the symmetry of the arrangement of
diagram below points.
[AIEEE 2004] Reason : n  2d sin  , is known as Bragg’s
      equation.
Na Cl Na Cl Na Cl
    6. Assertion : In close packing of spheres, a
Cl  Cl Na  Na
tetrahedral void is surrounded by
Na  Cl   Cl  Na  Cl  four spheres whereas an octahedral
  
Cl Na Cl Na  Na  
void is surrounded by six spheres.
(a) Interstitial defect Reason : A tetrahedral void has a tetrahedral
(b) Schottky defect shape whereas an octahedral void
(c) Frenkel defect has an octahedral shape.
(d) Frenkel and Schottky defects 7. Assertion : Cyclic silicates and chain silicates
18. Which of the following is a three dimensional have the same general molecular
silicate formula.
[MHCET 2003] Reason : In cyclic silicates, three corners of
(a) Mica (b) Spodumene each SiO4 tetrahedron are shared
(c) Zeolite (d) None of these while in chain silicates only two are
(e) 12 shared with other tetrahedra.
8. Assertion : The presence of a large number of
Schottky defects in NaCl lowers its
density.
Reason : In NaCl , there are approximately
10 6 Schottky pairs per cm 3 at room
temperature.
Read the assertion and reason carefully to mark the 9. Assertion : Anion vacancies in alkali halides
correct option out of the options given below : are produced by heating the alkali
(a) If both assertion and reason are true and the halide crystals with alkali metal
reason is the correct explanation of the assertion. vapour.
(b) If both assertion and reason are true but reason is Reason : Electrons trapped in anion
not the correct explanation of the assertion. vacancies are referred to as F -
(c) If assertion is true but reason is false. centres.
(d) If the assertion and reason both are false. 10. Assertion : Electrical conductivity of
(e) If assertion is false but reason is true. semiconductors increases with
increasing temperature.
1. Assertion : Diamond is a precious stone. Reason : With increase in temperature, large
number of electrons from the
Reason : Carbon atoms are tetrahedrally
valence band can jump to the
arranged in diamond. [AIIMS 1994 ]
conduction band.
 218 Solid state
11. Assertion : On heating ferromagnetic or 6 a 7 b 8 c 9 b 10 a
ferrimagnetic substances, they
11 c 12 c 13 a 14 b 15 d
become paramagnetic.
Reason : The electrons change their spin on 16 c 17 a 18 b 19 d 20 c
heating. 21 c 22 b 23 d 24 a 25 c
12. Assertion : Lead zirconate is a piezoelectric
26 b 27 b
crystal.
Reason : Lead zirconate crystals have no
dipole moment. Crystal structure and Coordination number

1 b 2 d 3 b 4 a 5 d

6 b 7 d 8 a 9 b 10 b

11 d 12 a 13 b 14 a 15 b

16 c 17 d 18 d 19 b 20 d
Type of solid and Their properties
21 c 22 b 23 b 24 c 25 a

1 a 2 b 3 a 4 a 5 b 26 c 27 b 28 d 29 d 30 d

6 c 7 c 8 b 9 d 10 d 31 a 32 acd 33 a 34 b
11 b 12 a 13 c 14 c 15 a
16 a 17 a 18 d 19 c 20 c Defects in crystal
21 b 22 d 23 d 24 d 25 a
26 d 27 a 28 a 29 d 30 d 1 c 2 b 3 d 4 d 5 a

31 d 32 a 33 c 34 a 35 b 6 c 7 d 8 c 9 d 10 d

36 a 37 a 38 b 39 c 40 ac 11 a 12 a 13 c 14 a 15 b

16 c 17 c 18 c 19 d 20 c
Crystallography and Lattice
21 c 22 d 23 a

1 b 2 c 3 b 4 d 5 a
6 a 7 b 8 d 9 d 10 b Critical Thinking Questions
11 c 12 c 13 a 14 c 15 b
1 c 2 c 3 c 4 d 5 a
16 b 17 b 18 b 19 a 20 a
21 c 22 d 23 c 24 d 25 b 6 a 7 b 8 c 9 b 10 a

26 b 27 c 28 d 11 a 12 c 13 a 14 b 15 c

16 b 17 b 18 c
Crystal packing
Assertion & Reason
1 b 2 b 3 d 4 a 5 b
6 d 7 c 8 b 9 b 10 b 1 b 2 d 3 d 4 a 5 b
11 d 12 c 13 a 14 b 15 b
6 c 7 c 8 b 9 b 10 a
16 b 17 c 18 b 19 c 20 c
11 a 12 c
21 a 22 c 23 a 24 d 25 b
26 a

Mathematical analysis of cubic system and

Bragg’s equation

1 b 2 b 3 a 4 b 5 b
 218 Solid state
Properties and Types of solids
1. (a) Both gases and liquids possess fluidity and
hence viscosity molecules in the solid state do
not have translational motion.
2. (b) It is a characteristic of liquid crystal.
3. (a) BaTiO3 is a ferroelectric compound.
5. (b) The value of heat of fusion of NaCl is very
high due to fcc arrangement of its ions.
6. (c) Piezoelectric crystals are used in record
player.
8. (b) NaCl is a ionic solid in which constituent
particles are positive ( Na  ) and negative
 which constituent particles are positive (Li  )
(Cl ) ions.
9. (d) Amorphous solids have short range order but
no sharp in melting point.
10. (d) Solids have definite shape, size and rigidity.
12. (a) In crystalline solid there is perfect arrangement
of the constituent particles only at 0K. As the
temperature increases the chance that a lattice
site may be unoccupied by an ion increases. As
the number of defects increases with
temperature solid change in liquid.
13. (c) Diamond is a covalent solid in which
constituent particles are atoms.
14. (c) Solid NaCl is a bad conductor of electricity
because ions are not free to move.
15. (a) The existence of a substance in more than one
crystalline form is known as polymorphism.
16. (a) Solids are also non-crystalline in nature.
17. (a) Ice has the lowest melting point out of the
given solids, hence it has the weakest
intermolecular forces.
19. (c) All metals and some alloys are metallic
crystal.
20. (c) Iodine crystals are molecular crystals, in
which constituent particles are molecules
having interparticle forces are Vander Waal’s
forces.
21. (b) Ionic solids have highest melting point due to
strong electrostatic forces of attraction.
22. (d) For n-type, impurity added to silicon should
have more than 4 valence electrons.
23. (d) Glass is an amorphous solid.
25. (a) Crystalline solids have regular arrangement of
constituent particles, sharp melting points
and are anisotropic.
26. (d) Sugar is a crystalline solid while glass, rubber
and plastic are amorphous solids.
28. (a) MnO2 is antiferromagnetic.
29. (d) Graphite is sp 2 hybridised and a covalent
crystal.
30. (d) Ionic crystals exhibit non-directional
properties of the bond.
31. (d) Ice is a molecular crystal in which the
constituent units are molecules and the
interparticle forces are hydrogen bonds.
32. (a) Quartz is a covalent crystal having a
framework of silicates or silica, i.e. a three
dimensional network when all the four oxygen
atoms of each of SiO4 tetrahedron are shared.
33. (c) Metallic crystals are good conductor of heat
and current due to free electrons in them.
34. (a) Silicon is a covalent crystal in which
constituent particles are atoms.
35. (b) LiF is an example of ionic crystal solid, in
and negative (F  ) ions.
36. (a) Amorphous solids neither have ordered
arrangement (i.e. no definite shape) nor have
sharp melting point like crystals, but when
heated, they become pliable until they assume
the properties usually related to liquids. It is
therefore they are regarded as super-cooled
liquids.
37. (a) Silicon is a semiconductor because it is a
thermal active and its conductivity increased
with increasing temperature.
38. (b) Amorphous solids are isotropic, because of
these substances show same properties in all
directions.
39. (c) Polymorphism is a ability of a substances
which show two or more crystalline structure
40. (ac) Amorphous solids
neither have ordered arrangement (i.e. no
definite shape) nor have sharp melting point
like crystals, but when heated, they become
pliable until they assume the properties
usually related to liquids. It is therefore they
are regarded as super-cooled liquids.
Crystallography and Lattice
1. (b) A crystal system is hexagonal if its unit cell
having a  b  c axial ratio and     90 ,
  120  axial angles.
2. (c) Rhombohedral crystal system
a  b  c ,       90 o
ex – NaNO3 , CaSO4 , calcite CaCO3 , HgS
3. (b) Tetragonal system has the unit cell dimension
a  b  c,      90  .
 Solid state 219
5. (a) Space lattice of CaF2 is face centred cubic. 2. (b) The system ABC ABC…… is also referred to as
face-centred cubic or fcc.
6. (a) For body centred cubic arrangement co-
ordination number is 8 and radius ratio (r / r ) 3. (d) It represents ccp arrangement.
4. (a) BCC has a coordination number of 8.
is 0.732  1.000 .
5. (b) In rock salt structure the co-ordination
7. (b) There are 14 Bravais lattices (space lattices).
number of Na  : Cl  is 6 : 6 .
8. (d) Monoclinic sulphur is an example of 6. (d) The bcc cell consists of 8 atoms at the corners
Monoclinic crystal system. and one atom at centre.
10. (b) r  0.414 r .  1
 n  8    1  2 .
11. (c) Each unit cell of NaCl contains 4 NaCl units.  8
12. (c) For tetrahedral arrangement co-ordination The fcc cell consists of 8 atoms at the eight
number is 4 and radius ratio (r / r ) is corners and one atom at each of the six faces.
This atom at the face is shared by two unit
0 .225  0 .414 .
cells.
13. (a) Face-centred cubic lattice found in KCl and
1  1
NaCl .  n  8   6    4 .
8  2
14. (c) Definition of unit cell.
7. (c) AB 2 type of structure is present in CaF2
16. (b) In NaCl (rock salt) : Number of Na  ions  12
 AB 2 ⇌ A 2   2 B  ; CaF2 ⇌ Ca 2  2 F 
1
(at edge centers)   1 (at body 8. (b) Potassium (K) has bcc lattice.
4
 9. (b) Number of atoms per unit cell in bcc system =
centre) 1  4 . Number of Cl ions  8 (at
2.
1 1
corners)   6 (at face centre)   4 . Thus 10. (b) In body centred cubic, each atom/ion has a
8 2
coordination number of 8.
4 formula units per unit cell.
11. (d) Number of octahedral sites = Number of
17. (b) Lowest potential energy level provides stable
sphere in the packing.
arrangement.
 Number of octahedral sites per sphere  1 .
18. (b) The seven basic crystal lattice arrangements 12. (c) ABAB …… is hexagonal close packing.
are :- Cubic, Tetragonal, Orthorhombic, 13. (a) Sodium (Na ) is a body cube.
Monoclinic, Hexagonal, Rhombohedral and
14. (b) SrF2 has fluorite (CaF2 ) type structure.
Triclinic.
19. (a) The conditions for monoclinic crystal system. 15. (b) In ZnS structure, sulphide ions occupy all FCC
20. (a) High lattice energy of BaSO4 causes low lattice points while Zn2+ ions are present in
alternate tetrahedral voids.
solubility of BaSO4 in water. 16. (b) MgO contains rock salt (NaCl ) structure.
21. (c) 14 kinds of Bravais lattices (space lattices) are 17. (c) CaF2 (fluorite) has fcc structure with 8 : 4
possible in a crystal.
coordination number.
22. (d) Radius ratio in TlCl is 0.732 – 1.000 and co- 18. (b) Every constituent has two tetrahedral voids.
ordination number is 8 and arrangement is In ccp lattice atoms
body centred cubic. 1 1
23. (c) Zinc blende (ZnS ) has fcc structure and is an 8 6  4
8 2
ionic crystal having 4 : 4 co-ordination  Tetrahedral void  4  2  8 ,
number. Thus ratio  4 : 8 :: 1 : 2 .
24. (d) Na2 O has antifluorite ( A2 B) type structure. 19. (c) Tetrahedral sites one double comparable to
25. (b) Zinc blende (ZnS ) has fcc structure and is an octahedral sites then ratio of X and Z
ionic crystal having 4 : 4 co-ordination respectively 2 : 1 since formula of the
number. compound X 2 Z .
1 20. (c) A atoms are at eight corners of the cube.
28. (d)  8 (at corners)  1 Therefore, the no. of A atoms in the unit cell =
8
8
1  1 . B atoms are at the face centre of six
 6 (at face centre)  3 8
2
faces. Therefore, its share in the unit cell =
Z  1  3  4 (total no. of atoms)
6
 3 . The formula is AB3.
2
Crystal packing
21. (a) In bcc structure 68% of the available volume
is occupied by spheres. Thus vacant space is
1. (b) Number of tetrahedral voids in the unit cell
32%.
= 2  number of atoms =
2Z.
 220 Solid state
22. (c) Number of atoms in the cubic close packed One unit cell contains 4 Na  Cl  units. Hence
structure = 8.
number of unit cell present
1
Number of octahedral voids   8  4 . 6 .02  10 23
2   1 .5  10 23 .
23. (a) Co-ordination number in HCP and CCP 4
arrangement is 12 while in bcc arrangement is 1
13. (a)  6.023  10 23  1 .029  10 22
8. 58 .5
24. (d) In NaCl (rock salt) : Number of Na  ions  12 A unit cell contains 4 Na  ion and 4 Cl  ions
1
(at edge centers)   1 (at body centre) 1  4 . 1.029  10 22
4 Unit cell   2.57  10 21 unit cell.
1 4
Number of Cl  ions  8 (at corners)   6 (at
8 14. (b) Bragg’s equation is n  2d sin
1 where n is an integer i.e. 1, 2, 3, 4 etc.
face centre)   4 . Thus 4 formula units per
2 15. (d) Face centred cubic structure contribute of 1/8
unit cell. by each atom present on the corner and 1/2 by
25. (b) Co-ordination number in HCP =12 each atom present on the face.
Co-ordination number in Mg is also = 12 16. (c) As CsCl is body-centred, d  3a / 2 .
26. (a) All are the iso-electronic species but Na  has
3a 3  4.29
low positive charge so have largest radius. 17. (a) Radius of Na (if bcc lattice)  
4 4
Mathematical analysis of cubic system and  1.8574 Å  1.8574  10 8 cm
Bragg’s equation 18. (b) The crystals in which radius ratio value is
found between 0 .225  0 .414 shows
1. (b) Density of unit cell tetrahedral crystal structure.
N  mol . wt.( M )
 g cm  3 3
V ( a 3 )  avogadro no. (N o ) 19. (d) For bcc, d  a or
2
1 2d 2  4.52
2. (b) Distance between K  and F    length of a   5.219 Å  522 pm
2 3 1.732
the edge ZM 2  39
3. (a) There are two atoms in a bcc unit cell.
 
a 3  N 0  10 30 (522 )  (6.023  10 23 )  10 30
3

So, number of atoms in 12 .08  10 23

unit cells
 0 . 91 g / cm 3  910 kg m 3
 2  12 .08  10 23  24 .16  10 23 atom .
20. (c) The value of ionic radius ratio is 0.52 which is
4. (b) bcc structure has one atom shared by 1 unit
between 0 .414  0 .732 , then the geometrical
cell.
arrangement of ions in crystal is octahedral.
5. (b) The structural arrangement of co-ordination
number ‘6’ is octahedral and its radius ratio is 21. (c) The number of atoms present in sc, fcc and bcc
0.414  0.732 . The example of octahedral is unit cell are 1, 4, 2 respectively.
KCl and NaCl . 22. (b) The number of atoms present in sc, fcc and bcc
6. (a) The number of spheres in one body centred unit cell are 1, 4, 2 respectively.
cubic and in one face centred cubic unit cell is 2 23. (d) Cl  Na  Cl 
and 4 respectively.
7. (b) Closest approach in bcc lattice
x
1 1 3 a = 2x
 of body diagonal   3 a   4.3  3.72 Å . a
2 2 2
a 620
  a 3  N 0  10 30 24. (a) r  ; r  219 .25 Pm
10. (a) M  2 2 2 2
z
V  N0 d
10  (100 )  (6.02  10 23 )  10 30
3
25. (c) Z 
  15 .05 M
4
4.2  8.6  8.3  10 24  6.023  10 23  3.3
No. of atoms in 100 g   3 . 84  4
155
6.02  1023
  100  4  10 25 . 26. (b) Volume of unit cell  a 3
15.05
 (3.04  10 8 cm)3  2.81  10 23 cm 3
11. (c) Cs  and I  have largest sizes.
27. (b) In FCC
12. (c) 58 .5 g NaCl  1 mole  6.02  10 23 Na  Cl units .
 Solid state 221
4 r  2a  8
1 1
 4 3
4r 8 2
a (corners ) (face  centred )
2 Number of B atoms per unit cell
1
Crystal structure and Coordination number  12  + 14
4
(edge centred ) ( body centred )
1 Hence the resultant stoichiometry is A3 B4
1. (b) In a unit cell, W atoms at the corner   8  1
8
12. (a) In Cs  Cl  crystal co-ordination number of each
1
O atoms at the centre of edges   12  3 ion is 8.
4 180
Na atoms at the centre of the cube = 1 13. (b) r / r   0 .962 which lies in the range of
187
W : O : Na  1 : 3 : 1, hence formula  NaWO3 0.732  1.000 , hence co-ordination number = 8
2. (d) For bcc lattice, co-ordination number is 8. i.e. the structure is CsCl type.
3. (b) Body centered cubic lattice has a co-ordination 14. (a) In diamond, C-atoms are arranged in a regular
number 8. tetrahedral structure.
4. (a) A atoms are at eight corners of the cube. 15. (b) In hcp, co-ordination no. is 12.
Therefore, the number of A atoms in the unit 16. (c) Mg has 6 co-ordination number (fcc
8 structure).
cell   1 , atoms B per unit cell = 1. Hence
8 17. (d) In NaCl crystal every Na  ion is surrounded by
the formula is AB.
6 Cl  ion and every chloride ion is surrounded by
5. (d) Co-ordination number for Cu is 12.
6 Na  ion.
6. (b) Each Cs  in CsCl is surrounded by eight Cl 
and each Cl  in CsCl is surrounded by eight 18. (d) Crystals show good cleavage because their
constituent particles are arranged in planes.
Cs  .
19. (b) Fe3 O4 is a non-stoichiometric compound
7. (d) X atoms are at eight corners of the cube.
Therefore, the number of X atoms in the unit because in it the ratio of the cations to the
8 anions becomes different from that indicated
cell   1 . by the chemical formula.
8
20. (d) The radius ratio for co-ordination number 4, 6
Y atoms are at the face centre of six faces.
and 8 lies in between the ranges
6
Therefore, its share in the unit cell   3 . [0 .225  0 .414 ], [0 .414  0 .732 ] and [0 .732  1]
2
respectively.
The formula is XY 3 .
21. (c) The radius ratio for co-ordination number 4, 6
8. (a) Let the units of ferrous oxide in a unit cell  n , and 8 lies in between the ranges
molecular weight of ferrous oxide [0 .225  0 .414 ], [0 .414  0 .732 ] and [0 .732  1]
(FeO )  56  16  72 g mol 1 , respectively.
72  n 22. (b) In Na2 O, each oxide ions (O 2 ) is co-ordinated
weight of n units 
6 .023  10 23
to 8 Na  ions and each Na  ion to 4 oxide ions.
Volume of one unit  (length of corner ) 3
Hence it has 4 : 8 co-ordination.
 (5 Å)3  125  10 24 cm 3 23. (b) When radius ratio between 0.732  1, then co-
wt. of cell ordination number is 8 and structural
Density  , arrangement is body-centred cubic.
volume
72  n 24. (c) Each Cs  is surrounded by eight Cl  ions in
4 .09 
6 .023  10 23  125  10  24 CsCl crystal lattice because its co-ordination
number is 8 : 8.
3079 .2  10 1
n  42 .7  10 1  4.27  4 25. (a) NaCl has fcc arrangement of ions.
72
26. (c) Each Na  is surrounded by six Cl  ions in
9. (b) In NaCl crystal Na  ions has coordination NaCl crystal lattice because its co-ordination
number 6. number is 6 : 6.
10. (b) Cl  ions in CsCl adopt BCC type of packing. 27. (b) Zinc blende (ZnS ) has fcc structure and is an
11. (d) There were 6 A atoms on the face-centres ionic crystal having 4 : 4 co-ordination
removing face-centred atoms along one of the number.
axes means removal of 2 A atoms. 30. (d) In a simple cubic structure
Now, number of A atoms per unit cell 1
z   8 (atoms one at a corners)
8
 222 Solid state
z 1
31. (a) Co-ordination number in hcp structure is 12.
32. (acd) A metal that crystallizes in bcc structure has
a co-ordination number of 8.
33. (a) In sodium chloride, each Na  ion is
surrounded by six Cl ions and each Cl  ion
 missing of anions are occupied by electrons,
is surrounded by six Na  ions. Thus, both the
ions have coordination number six.
34. (b) The Ca 2  ions are arranged in (ccp)
arrangement, i.e. Ca 2  ions are present at all
corners and tat the centre of each face of the
cube. the fluoride ions occupy all the
tetrahedral sites. This is 8 : 4 arrangement
i.e., each Ca 2  ion is surrounded by 8 F  ions
and each F  ion by four Ca 2  ions.
Defects in crystal
1. (c) When polar crystal is subjected to a
mechanical stress, electricity is produced – a
case of piezoelectricity. Reversely, if electric
field is applied, mechanical stress is
developed. Piezoelectric crystal acts as a
mechanical electrical transductor.
2. (b) More is the Schottky defect in crystal more is
the decrease in density.
3. (d) All the given statements are correct about F-
centres.
5. (a) As each Sr 2 ion introduces one cation
vacancy, therefore concentration of cation
vacancies = mol % of SrCl 2 added.
6. (c) Yellow colour on heating NaCl in presence of
Na is due to presence of electrons in anion
vacancies (F-centres).
7. (d) Frenkel’s defect is due to shift of an ion from
the normal lattice site (Creating a vacancy)
and occupy interstitial spaces.
8. (c) AgBr exhibits Frenkel defect due to large
difference in the size of Ag  and Br  ions.
9. (d) Schottky defects occurs in highly ionic
compounds which have high co-ordination
number ex. NaCl, KCl, CsCl .
10. (d) Schottky defect is due to missing of equal
number of cations and anions.
11. (a) Schottky defect is due to missing of equal
number of cations and anions.
12. (a) Impurity present in a crystal does not
establish thermal equilibrium.
18. (c) Brass, Cu  80 %, Zn  20 % substitutional alloy.
Steel is an interstitial alloy because it is an alloy
of Fe with C, C atoms occupy the interstitial
voids of Fe crystal.
19. (d) In metal excess defect when holes created by
there sites are called F-centres and are
responsible for colour in the crystal.
20. (c) KBr exhibits Schottky defect and not Frenkel
defect.
21. (c) When cation shifts from lattice to interstitial
site, the defect is called Frenkel defect.
22. (d) F-centres are the sites where anions are missing
and instead electrons are present. they are
responsible for colour.
Critical Thinking Questions
1. (c) Amorphous solids neither have ordered
arrangement (i.e. no definite shape) nor have
sharp melting point like crystals, but when
heated, they become pliable until they assume
the properties usually related to liquids. It is
therefore they are regarded as super-cooled
liquids.
2. (c) Silicon due to its catenation property form
network solid.
3. (c) Orthorhombic geometry has a  b  c and
      90  . The shape of match box obey
this geometry.
4. (d) In a triclinic crystal has no notation of
symmetry.
5. (a) In NH 3 molecule, the original appearance is
repeated as a result of rotation through 120 o .
Such as axis is said to be an axis of three-fold
symmetry or a triad axis.
6. (a) Na2 O has antifluorite ( A2 B) type structure.
7. (b) Cationic radius increases down the group and
decreases along the period.
8. (c) Distance between centres of cation and anion
d 508
   254 pm
2 2
rc  ra  254 pm or 110  ra  254 or ra  144 pm
nM
9. (b)  
a 3  N 0  10  30
2  100
  5 . 188 g/cm 3
(400 )  (6.02  10 23 )  10 30
3

13. (c) Since no ions are missing from the crystal as a High
10. (a) NaCl structure CsCl structure
whole, there is no effect on density. (6 : 6 co.  ord. )
pressure
760 K (8 : 8 co.  ord. )
15. (b) On adding non-metal in metal the metal
becomes less tensile. 11. (a) Difference  2.178  10  2.165  10 3  0 . 013  10 3
3

16. (c) AgBr exhibits Frenkel defect due to large 0.013  10 3

Fraction unoccupied   5 .96  10 3
difference in the size of Ag  and Br  ions. 2.178  10 3
17. (c) Both are stoichiometric crystalline defects. 12. (c) CsBr3 consist of Cs  and Br3 ions.
 Solid state 223
13. (a) Each Cs  is surrounded by eight Cl  ions in 7. (c) Two corners per tetrahedron one shared in
CsCl crystal lattice because its co-ordination both the cases.
number is 8 : 8. 8. (b) When an atom or an ion is missing from its
14. (b) In each CaF2 each calcium cation is normal lattice site, a lattice vacancy or defect
surrounded by eight fluoride anions in a body is created, which is called schottky defect. Due
centred cubic arrangement. Each fluoride ion to missing density of crystal will be lowered.
is in contact with four calcium ions. Thus
CaF2 has 8 : 4 co-ordination number. 9. (b) On heating, the metal atoms deposit on the
surface and finally they deffuse into the
15. (c) The radius ratio for co-ordination number 4, 6
crystal and after ionisation the alkali metal
and 8 lies in between the ranges
ion occupies cationic vacancy where as
[0 .225  0 .414 ], [0 .414  0 .732 ] and [0 .732  1]
electron occupies anionic vacancy.
respectively.
O O
16. (b) 10. (a) In case of semiconductors, the gap between
valence band and the conduction band is small
and there fore some of the electrons may jump
Si O from valence band to conduction band and
thus on increasing temperature conductivity
O is also increased.
O O O
O 11. (a) All magnetically ordered solids (ferromagnetic
and antiferromagnetic solids) transform to
17. (b) In this diagram, equal number of cations
the paramagnetic state at high temperature
( Na  ) and anions (Cl  ) are missing, so it, due to the randomisation of spins.
shows schottky defect.
12. (c) In piezoelectric crystals, the dipoles may align
18. (c) Zeolite is a three dimensional silicate because them selves in an ordered manner such that
of in the silicates all the four oxygen atoms at there is a net dipole moment in the crystal.
(SiO 4 )4 tetrahedra are shared with other
tetrahedra, vesulting in a three dimensional
network.

Assertion & Reason

1. (b) It is true that in the dimond structure, carbon

atoms are arranged in tetrahedrally
( sp 3 hybridized) but it is not the correct
explanation of assertion.
2. (d) Tetrahedral holes are smaller in size than
octahedral holes. Cations usually occupy
less space than anions.
3. (d) Crystalline solids have regular arrangement of
constituent particles and are anisotropic
whereas amorphous solids have no regular
arrangement and are isotropic.
4. (a) Schottky defect is due to missing of equal
number of cations and anions.
5. (b) Space or crystal lattice is a regular repeating
arrangement of points in space and forms the
basis of classification of all structures.
6. (c) Tetrahedral void is so called because it is
surrounded by four spheres tetrahedrally
while octahedral void is so called because it is
surrounded by six spheres octahedrally.
 Solid State 223

1. Particles of quartz are packed by 7. The second order Bragg's diffraction of X  rays
(a) Electrical attraction forces with   1 Å from a set of parallel planes in a

(b) Vander Waal's forces metal occurs at an angle of 60 o . The distance

between the scattering planes in the crystal is[CBSE PMT 1
(c) Covalent bond forces
(d) Strong electrostatic attraction forces (a) 0 .575 Å (b) 1 .00 Å

2. Crystals of covalent compounds always have[BHU 1984] (c) 2 .00 Å (d) 1 .15 Å
(a) Atoms as their structural units 8. The edge length of the unit cell of NaCl crystal
(b) Molecules as structural units lattice is 552 pm. If ionic radius of sodium ion is
(c) Ions held together by electrostatic forces 95 pm, what is the ionic radius of chloride ion[KCET 1998]
(d) High melting points (a) 190 pm (b) 368 pm
3. Wax is an example of
(c) 181 pm (d) 276 pm
(a) Ionic crystal (b) Covalent crystal
9. The ionic radii of Rb  and I  are 1.46 Å and
(c) Metallic crystal (d) Molecular crystal
2.16Å. the most probable type of structure
4. Among the following which crystal will be soft exhibited by it is
and have low melting point [UPSEAT 2004]
(a) Covalent (b) Ionic (a) CsCl type (b) ZnS type
(c) Metallic (d) Molecular (c) NaCl type (d) CaF2 type
5. In zinc blende structure, zinc atom fill up
10. The coordination number of a cation occupying a
(a) All octahedral holes tetrahedral hole is
(b) All tetrahedral holes (a) 6 (b) 8
(c) Half number of octahedral holes (c) 12 (d) 4
(d) Half number of tetrahedral holes 11. If a electron is present in place of anion in a
6. Which ion has the lowest radius from the crystal lattice, then it is called
following ions (a) Frenkel defect
[Kurukshetra CEE 1998] (b) Schottky defect
 2
(a) Na (b) Mg (c) Interstitial defects

(c) Al 3  (d) Si 4  (d) F  centre

 224 Solid State

(SET -5)

1. (c) Quartz is a covalent solid in which constituent

particles are atoms which are held together by
covalent bond forces.

2. (a) Constituent particles of covalent compounds

are atoms.

3. (d) Iodine crystals are molecular crystals, in

which constituent particles are molecules
8. (c) Distance between centres of Na  and Cl 
having interparticle forces are Vander Waal’s
forces. rNa   rCl   276 pm or 95  rCl   276 pm

4. (d) Molecular crystals are soft and have low or rCl   276  95  181 pm
melting point.

5. (d) In zinc blende (ZnS ) half number of rc  1.46

9. (c)   0.676
tetrahedral holes are filled by zinc atoms. ra  2.16

6. (d) All are the iso-electronic species but Si 4  has It permits co-ordination number 6 and
high positive charge so have lowest radius. octahedral structure of type NaCl .

7. (d) 2d sin  n or 2  d  sin 60   2  1 Å 10. (d) The co-ordination number of a cation

occupying a tetrahedral hole is 4.
or 2  d  0 .8660  2
11. (d) When electrons are trapped in anion
vacancies, these are called F-centres.
or d  1 .15 Å (sin 60   3 / 2 or 0 .8660 ) .
**
*
 Gaseous State 225

Chapter

6
Gaseous state

(i) The volume, V, of the gas.

The state of matter in which the molecular forces
of attraction between the particles of matter are (ii) Its pressure, P
minimum, is known as gaseous state. It is the simplest (iii) Its temperature, T
state and shows great uniformity in behaviour. (iv) The amount of the gas (i.e., mass or number
Characteristics of gases of moles).
(2) Volume : (i) Since gases occupy the entire
(1) Gases or their mixtures are homogeneous in
space available to them, the measurement of volume of
composition.
a gas only requires a measurement of the container
(2) Gases have very low density due to negligible
confining the gas.
intermolecular forces.
(ii) Volume is expressed in litres (L),
(3) Gases have infinite expansibility and high
compressibility. millilitres (mL) or cubic centimetres (cm 3 ) or cubic
(4) Gases exert pressure. metres (m 3 ) .
(5) Gases possess high diffusibility.
(iii) 1L  1000 mL ; 1 mL  10 3 L ; 1 L  1 dm 3  10 3 m 3
(6) Gases do not have definite shape and volume
like liquids. 1 m 3  10 3 dm 3  10 6 cm 3  10 6 mL  10 3 L
(7) Gaseous molecules move very rapidly in all
(3) Mass : (i) The mass of a gas can be
directions in a random manner i.e., gases have highest
determined by weighing the container in which the gas
kinetic energy.
is enclosed and again weighing the container after
(8) Gaseous molecules collide with one another and removing the gas. The difference between the two
also with the walls of container with perfectly elastic weights gives the mass of the gas.
collisions.
(ii) The mass of the gas is related to the
(9) Gases can be liquified, if subjected to low
number of moles of the gas i.e.
temperatures (below critical) or high pressures.
Mass in grams m
(10) Thermal energy of gases >> molecular moles of gas (n)  
attraction. Molar mass M
(11) Gases undergo similar change with the (4) Temperature : (i) Gases expand on increasing
change of temperature and pressure. In other words, the temperature. If temperature is increased twice, the
gases obey certain laws known as gas laws. square of the velocity (v 2 ) also increases two times.
Measurable properties of gases
(ii) Temperature is measured in centigrade
(1) The characteristics of gases are described fully degree ( o C) or celsius degree with the help of
in terms of four parameters or measurable properties :
 226 Gaseous State
thermometers. Temperature is also measured in Absolute pressure = Gauge pressure + Atmosphere
Fahrenheit (Fo). pressure.
(iii) S.I. unit of temperature is kelvin (K) or (xi) When the pressure in a system is less than
absolute degree. atmospheric pressure, the gauge pressure becomes
negative, but is frequently designated and called
K  o C  273
vacuum. For example, 16 cm vacuum will be
o
C F o  32 76  16
(iv) Relation between F and o C is   1 .013  0 .80 bar .
5 9 76
(5) Pressure : (i) Pressure of the gas is the force (xii) If ‘h’ is the height of the fluid in a column or
exerted by the gas per unit area of the walls of the the difference in the heights of the fluid columns in the
container in all directions. Thus, Pressure two limbs of the manometer, d is the density of the
Force( F) Mass(m )  Accelerati on (a) fluid
(P)  
Area( A) Area (a)
(Hg  13 .6  10 3 Kg / m 3  13 .6 g / cm 3 ) and g is the gravity,
(ii) Pressure exerted by a gas is due to kinetic then pressure is given by, Pgas  Patm  h dg
1
energy (KE  mv 2 ) of the molecules. Kinetic energy of (xiii) Two sets of conditions are widely used as
2
'standard' values for reporting data.
the gas molecules increases, as the temperature is
increased. Thus, Pressure of a gas  Temperature (T). Condition T P Vm (Molar
volume)
(iii) Pressure of a pure gas is measured by
manometer while that of a mixture of gases by S.T.P./N.T. 273.15 K 1 atm 22.414 L
barometer. P.

(iv) Commonly two types of manometers are used, S.A.T.P*. 298.15 K 1 bar 24.800 L
* Standard ambient temperature and pressure.
(a) Open end manometer; (b) Closed end
manometer Boyle's law
(v) The S.I. unit of pressure, the pascal (Pa), is (1) In 1662, Robert Boyle discovered the first of
defined as 1 newton per metre square. It is very small several relationships among gas variables (P, T, V).
unit. (2) It states that, “For a fixed amount of a gas at
constant temperature, the gas volume is inversely
1 Pa  1 Nm 2  1 kg m 1 s 2
proportional to the gas pressure.”
(vi) C.G.S. unit of pressure is dynes cm 2 . Thus, P  1 / V at constant temperature and
mass
(vii) M.K.S. unit of pressure is kgf / m 2 . The unit or P  K / V (where K is constant)
kgf / cm 2 sometime called ata (atmosphere technical or PV  K or P1 V1  P2 V2  K (For two or more
absolute). gases)
(viii) Higher unit of pressure is bar, KPa or MPa. (3) Graphical representation of Boyle's law :
1 bar  10 5 Pa  10 5 Nm 2  100 KNm 2  100 KPa Graph between P and V at constant temperature is
called isotherm and is an equilateral (or rectangular)
(ix) Several other units used for pressure are, hyperbola. By plotting P versus 1 / V , this hyperbola
Name Symbol Value can be converted to a straight line. Other types of
isotherms are also shown below,
bar bar 1bar  10 Pa
5

atmosphe atm 1 atm  1 .01325  10 5 Pa T3

re T2
T1< T2< T3
Torr Torr 101325
1 Torr  Pa  133 .322 Pa P P T1
760
millimetr mm Hg 1 mm Hg  133 .322 Pa
T3
e of T2 T1< T2< T3
mercury T1
O O
V or 1/V or
(x) The pressure relative to the atmosphere is 1/d d
called gauge pressure. The pressure relative to the
perfect vacuum is called absolute pressure. T1< T2< T3
PV T3
T2
T1 log P

O O
P log
 Gaseous State 227

1/d or
V

1/d
or 22.4 L mol–1 =
V V0
O t(oC)
(4) At constant mass and temperature density of a – 0o
T(k 273.15oC C
gas is directly proportional to its pressure and
inversely proportional to its volume. (5) At constant
) mass and pressure density of a gas
is inversely proportional to it absolute temperature.
1  mass 
Thus, d  P   V  d 
V   1 1  mass 
Thus, d    V  d 
d1 P V T V  
or  1  2  .......  K
d 2 P2 V1
d1 T2 V2
(5) At altitudes, as P is low d of air is less. That is or    ......  K
d 2 T1 V1
why mountaineers carry oxygen cylinders.
(6) Use of hot air balloons in sports and
Charle's law
meteorological observations is an application of
(1) French chemist, Jacques Charles first studied Charle's law.
variation of volume with temperature, in 1787.
(2) It states that, “The volume of a given mass of a
Gay-Lussac's law (Amonton's law)
gas is directly proportional to the absolute temperature (1) In 1802, French chemist Joseph Gay-Lussac
( o C  273 ) at constant pressure”. studied the variation of pressure with temperature and
Thus, V  T at constant pressure and mass extende the Charle’s law so, this law is also called
or V  KT  K (t( C)  273 .15 ) ,
o
(where k is Charle’s-Gay Lussac’s law.

constant), (2) It states that, “The pressure of a given mass of

V V V a gas is directly proportional to the absolute
K or 1  2  K (For two or more gases)
T T1 T2 temperature ( C  273 ) at constant volume.”
o

(3) If t  0 o C , then V  V0 Thus, P  T at constant volume and mass

hence, V0  K  273 .15 or P  KT  K(t(o C)  273 .15 ) (where K is

V0 constant)
 K
273 .15 P P P
K or 1  2  K (For two or more gases)
V0  t  T T1 T2
V [t  273 .15 ]  V0 1    V0 [1   v t]
273 .15  273 . 15 
(3) If t  0 o C , then P  P0
where  v is the volume coefficient,
Hence, P0  K  273 .15
V  V0 1
v    3.661  10  3 o C 1 P0
tV0 273 .15  K
273 .15
Thus, for every 1 o change in temperature, the P0  t 
P [t  273 .15 ]  P0 1    P0 [1  t]
1  1  273 .15  273 . 15 
volume of a gas changes by   of the
273 . 15  273 
where  P is the pressure coefficient,
volume at 0 o C .
P  P0 1
P    3.661  10  3 o C 1
(4) Graphical representation of Charle's law : tP0 273 .15
Graph between V and T at constant pressure is called
isobar or isoplestics and is always a straight line. A plot Thus, for every 1 o change in temperature, the
1  1 
of V versus t( o C ) at constant pressure is a straight line pressure of a gas changes by   of the
273 . 15  273 
cutting the temperature axis at  273 .15 o C . It is the
pressure at 0 o C .
lowest possible temperature.
 228 Gaseous State
(4) This law fails at low temperatures, because If all the above law's combines, then
the volume of the gas molecules be come significant. nT
V
(5) Graphical representation of Gay-Lussac's P
law : A graph between P and T at constant V is called nRT
or V ( R  Ideal gas constant)
isochore. P
V1< V2< V3< V4 or PV  nRT
V1
V2 This is called ideal gas equation. R is called ideal
V3 gas constant. This equation is obeyed by isothermal
P V4
P and adiabatic processes.
(2) Nature and values of R : From the ideal gas
PV Pressure  Volume
equation, R  
nT mole  Temperatur e
O O T
T(k Force
 Volume
) Force  Length
Avogadro's law  Area 
mole  Temperatur e mole  Temperatur e
(1) According to this law, “Equal volumes of any Work or energy
two gases at the same temperature and pressure contain  .
mole  Temperatur e
the same number of molecules.”
R is expressed in the unit of work or energy
Thus, V  n (at constant T and P) 1 1
mol K .
or V  Kn (where K is constant)
Since different values of R are summarised below
V V :
or 1  2  .......  K
n1 n 2 R  0 . 0821 L atm mol 1
K 1
Example, 2 H 2 (g) O 2 (g)  2 H 2 O(g)  8 .3143 joule mol 1 K 1 (S.I. unit)
2 moles 1 mole 2 moles

 8 . 3143 Nm mol 1 K 1
2 volumes 1 volume 2 volumes
2 litres 1 litre 2 litres
1 litre 1 / 2 litre 1 litre
1n litre 1 / 2 n litre 1n litre  8 .3143 KPa dm 3 mol 1 K 1
(2) One mole of any gas contains the same  8 . 3143 MPa cm 3 mol 1 K 1
number of molecules (Avogadro's number  6 .02  10 ) 23
 5 .189  10 19 eV mol 1 K 1
and by this law must occupy the same volume at a
given temperature and pressure. The volume of one  1 . 99 cal mol 1 K 1
mole of a gas is called molar volume, Vm which is 22.4
(3) Gas constant, R for a single molecule is called
L mol 1 at S.T.P. or N.T.P. Boltzmann constant (k)
(3) This law can also express as, “The molar gas R 8.314  10 7
volume at a given temperature and pressure is a specific k  ergs mole 1 degree 1
N 6.023  10 23
constant independent of the nature of the gas”.
 1 .38  10 16 ergs mol 1 de gree 1
Thus, Vm  specific constant  22 . 4 L mol 1 at
S.T.P. or N.T.P. or 1 .38  10 23 joule mol 1 degree 1

Ideal gas equation (4) Calculation of mass, molecular weight and

density of the gas by gas equation
(1) The simple gas laws relating gas volume to
m
pressure, temperature and amount of gas, respectively, PV  nRT  RT
M
are stated below :
 mass of the gas (m ) 
 n  
Molecular weight of the gas (M ) 
1 1
Boyle's law : P or V  (n and T 
V P
constant) mRT
 M
Charle's law : VT (n and P PV
constant) PM  m
d  d  
Avogadro's law : V  n (T and P RT  V
constant)
 Gaseous State 229
dT M M (4) Applications : This law is used in the
or  ,  Constant
P R R calculation of following relationships,
(  M and R are constant for a particular gas) (i) Mole fraction of a gas ( X 1 ) in a mixture
dT d T d T Partial pr essure of a gas (P1 )
Thus, or 1 1  2 2 = Constant of gas 
P P1 T2 PTotal

(For two or more different temperature and (ii) % of a gas in mixture

pressure) Partial pr essure of a gas (P1 )
  100
(5) Gas densities differ from those of solids and PTotal
liquids as, (iii) Pressure of dry gas collected over water :
(i) Gas densities are generally stated in When a gas is collected over water, it becomes moist
g/L instead of g / cm 3 . due to water vapour which exerts its own partial
pressure at the same temperature of the gas. This
(ii) Gas densities are strongly dependent on
partial perssure of water vapours is called aqueous
pressure and temperature as, d  P  1 / T
tension. Thus, Pdry gas  Pmoist gas or PTotal  Pwater vapo ur
Densities of liquids and solids, do depend
somewhat on temperature, but they are far less or Pdry gas  Pmoist gas  Aqueous tension (Aqueous
dependent on pressure. tension is directly proportional to absolute
(iii) The density of a gas is directly proportional temperature)
to its molar mass. No simple relationship exists (iv) Relative humidity (RH) at a given temperature
between the density and molar mass for liquid and is given by,
solids. Partial pr essure of water in air
RH  .
molar mass Vapour pre ssure of water
(iv) Density of a gas at STP 
22 .4
(5) Limitations : This law is applicable only when
28 the component gases in the mixture do not react with
d(N 2 ) at STP   1.25 g L1 ,
22 .4 each other. For example, N 2 and O 2 , CO and CO2 , N 2
32 and Cl2 , CO and N 2 etc. But this law is not applicable
d(O 2 ) at STP   1.43 g L1
22 .4 to gases which combine chemically. For example, H 2
Dalton's law of partial pressures and Cl2 , CO and Cl2 , NH 3 , HBr and HCl, NO and O 2
(1) According to this law, “When two or more etc.
gases, which do not react chemically are kept in a closed (6) Another law, which is really equivalent to the
vessel, the total pressure exerted by the mixture is equal law of partial pressures and related to the partial
to the sum of the partial pressures of individual gases.” volumes of gases is known as Law of partial volumes
Thus, Ptotal  P1  P2  P3  ......... given by Amagat. According to this law, “When two or
more gases, which do not react chemically are kept in a
Where P1 , P2 , P3 ,...... are partial pressures of gas
closed vessel, the total volume exerted by the mixture is
number 1, 2, 3 ......... equal to the sum of the partial volumes of individual
(2) Partial pressure is the pressure exerted by a gases.”
gas when it is present alone in the same container and Thus, VTotal  V1  V2  V3  ......
at the same temperature.
Where V1 , V2 , V3 ,...... are partial volumes of gas
Partial pressure of a gas
Number of moles of the gas (n1 )  PTotal number 1, 2, 3.....
(P1 )   Mole fraction ( X 1 )  PTotal
Total number of moles (n) in the mixture Graham's law of diffusion and Effusion
(3) If a number of gases having volume
(1) Diffusion is the process of spontaneous
V1 , V2 , V3 ...... at pressure P1 , P2 , P3 ........ are mixed
spreading and intermixing of gases to form
together in container of volume V, then, homogenous mixture irrespective of force of gravity.
P1 V1  P2 V2  P3 V3 ..... While Effusion is the escape of gas molecules through
PTotal 
V a tiny hole such as pinhole in a balloon.
RT  All gases spontaneously diffuse into one another
or  (n1  n 2  n 3 .....) ( PV  nRT )
V when they are brought into contact.
RT  Diffusion into a vacuum will take place much
or  n ( n  n1  n2  n3 .....)
V more rapidly than diffusion into another place.
 230 Gaseous State
 Both the rate of diffusion of a gas and its rate of (iv) The volume of gas effused through a given
effusion depend on its molar mass. Lighter gases surface per unit time is also called rate of effusion.
diffuses faster than heavier gases. The gas with highest (5) Applications : Graham's law has been used as
rate of diffusion is hydrogen. follows,
(2) According to this law, “At constant pressure (i) To determine vapour densities and
and temperature, the rate of diffusion or effusion of a molecular weights of gases.
gas is inversely proportional to the square root of its (ii) To prepare Ausell’s marsh gas
vapour density.” indicator, used in mines.
1
Thus, rate of diffusion (r)  (T and P (iii) Atmolysis : The process of separation of two
d gases on the basis of their different rates of diffusion
constant) due to difference in their densities is called atmolysis.
For two or more gases at constant pressure and It has been applied with success for the separation of
temperature, isotopes and other gaseous mixtures.
r1

d2 Kinetic theory of gases
r2 d1
(1) Kinetic theory was developed by Bernoulli,
(3) Graham's law can be modified in a number of Joule, Clausius, Maxwell and Boltzmann etc. and
ways as, represents dynamic particle or microscopic model
(i) Since, 2  vapour density (V.D.) = for different gases since it throws light on the
Molecular weight behaviour of the particles (atoms and molecules) which
r1 d2 d2  2 M2 constitute the gases and cannot be seen. Properties of
then,    gases which we studied earlier are part of macroscopic
r2 d1 d1  2 M1
model.
where, M1 and M 2 are the molecular weights
(2) Postulates
of the two gases.
(i) Every gas consists of a large number of
(ii) Since, rate of diffusion
small particles called molecules moving with very high
Volume of a gas diffused
(r)  then, velocities in all possible directions.
Time taken for diffusion
(ii) The volume of the individual molecule
r1 V /t w /t d2
 1 1  1 1  is negligible as compared to the total volume of the gas.
r2 V2 / t 2 w 2 / t 2 d1
(iii) Gaseous molecules are perfectly elastic so that
(a) When equal volume of the two gases
there is no net loss of kinetic energy due to their
diffuse, i.e. V1  V2
collisions.
r1 t 2 d2 (iv) The effect of gravity on the motion of the
then,  
r2 t1 d1 molecules is negligible.
(b) When volumes of the two gases diffuse in the (v) Gaseous molecules are considered as point
same time, i.e. t1  t 2 masses because they do not posses potential energy. So
the attractive and repulsive forces between the gas
r1 V d2
then,  1  molecules are negligible.
r2 V2 d1
(vi) The pressure of a gas is due to the continuous
(iii) Since, r  p (when p is not constant)
bombardment on the walls of the containing vessel.
r1 P M2  P  (vii) At constant temperature the average K.E. of
then,  1  r  
 M 
r2 P2 M1  all gases is same.
(4) Rate of diffusion and effusion can be (viii) The average K.E. of the gas molecules is
determined as, directly proportional to the absolute temperature.
(i) Rate of diffusion is equal to distance (3) Kinetic gas equation : On the basis of above
travelled by gas per unit time through a tube of postulates, the following gas equation was derived,
uniform cross-section.
1
(ii) Number of moles effusing per unit time PV  2
mnu rms
3
is also called rate of diffusion.
where, P = pressure exerted by the gas
(iii) Decrease in pressure of a cylinder per unit
time is called rate of effusion of gas. V = volume of the gas
m = average mass of each molecule
 Gaseous State 231
n = number of molecules (ii) The total number of bimolecular
u = root mean square (RMS) velocity of the gas. 1
collision per unit time are given by, Z AA   2 u av . n 2
(4) Calculation of kinetic energy 2
(iii) If the collisions involve two unlike molecules,
We know that,
the number of bimolecular collision are given by,
1
K.E. of one molecule  mu 2 2  (M A  M B ) 
1/ 2
2 Z AB   AB 8RT 
 MAMB 
1 3
K.E. of n molecules  mnu 2  PV  A  B
2 2 where,  AB 
2
1
( PV  mnu 2 ) M A , M B are molecular weights (M  mN 0 )
3
3 (iv) (a) At particular temperature; Z  p 2
n = 1, Then K.E. of 1 mole gas  RT
2 (b) At particular pressure; Z  T 3 / 2
( PV  RT ) (c) At particular volume; Z  T 1 / 2
3 (3) During molecular collisions a molecule covers
  8 .314  T  12 .47 T Joules . a small distance before it gets deflected. The average
2
distance travelled by the gas molecules between two
Average K.E. per mole 3 RT 3
   KT successive collision is called mean free path ().
N (Avogadro number ) 2 N 2
Average distance travelled per unit time( u av )
 .
 R  No. of collisions made by single molecule per unit time (Z A )
K   Boltzmann constant
 N  u av 1
 
This equation shows that K.E. of translation of a 2 2 u avr. n 2n  2

gas depends only on the absolute temperature. This is (4) Based on kinetic theory of gases mean free
known as Maxwell generalisation. Thus average K.E.  T
path,   . Thus,
T. P
(i) Larger the size of the molecules,
If T  0 K (i.e.,  273 .15 o C) then, average K.E. = 0.
1
Thus, absolute zero (0K) is the temperature at which smaller the mean free path, i.e.,  
(radius)2
molecular motion ceases.
(ii) Greater the number of molecules per
Molecular collisions
unit volume, smaller the mean free path.
(1) The closest distance between the centres of (iii) Larger the temperature, larger the mean free
two molecules taking part in a collision is called path.
molecular or collision diameter (). The molecular (iv) Larger the pressure, smaller the mean free
diameter of all the gases is nearly same lying in the path.
order of 10 8 cm . (5) Relation between collision frequency (Z) and
u
mean free path () is given by, Z  rms
 
Molecular
diameter
Molecular speeds or velocities
(1) At any particular time, in the given sample of
(2) The number of collisions taking place in unit gas all the molecules do not possess same speed, due to
time per unit volume, called collision frequency (z). the frequent molecular collisions with the walls of the
(i) The number of collision made by a container and also with one another, the molecules
single molecule with other molecules per unit time are move with ever changing speeds and also with ever
given by, Z A  2 2 u av. n changing direction of motion.
(2) According to Maxwell, at a particular
where n is the number of molecules per unit
temperature the distribution of speeds remains
molar volume,
constant and this distribution is referred to as the
Avogadro number( N 0 ) 6 . 02  10 23  3
n  m Maxwell-Boltzmann distribution and given by the
Vm 0 . 0224 following expression,
3/2
dn0  M  2
 4   .e  Mu / 2 RT
.u 2 dc
n  2RT 
 232 Gaseous State
where, dn0  Number of molecules out of total (ii) Average velocity (v av ) : It is the average
number of molecules n, having velocities between c and of the various velocities possessed by the molecules.
c  dc , dn0 / n  Fraction of the total number of v1  v 2  v 3  ...... v n 8 RT 8 kT
v av  ; v av  
molecules, M = molecular weight, T = absolute n M m
(iii) Most probable velocity ( mp ) : It is the
2
temperature. The exponential factor e  Mu / 2 RT is called
Boltzmann factor. velocity possessed by maximum number of molecules of
(3) Maxwell gave distribution curves of molecular a gas at a given temperature.
speeds for CO2 at different temperatures. Special 2 RT 2 PV 2P
 mp   
features of the curve are : M M d
(i) Fraction of molecules with two high or two low (5) Relation between molecular speeds or
speeds is very small. velocities,
(ii) No molecules has zero velocity. (i) Relation between u rms and v av :
(iii) Initially the fraction of molecules increases
v av  0.9213  urms
in velocity till the peak of the curve which pertains to
most probable velocity and thereafter it falls with or urms  1.085  vav
increase in velocity. (ii) Relation between  mp and urms :
Ump  mp  0.816  urms
300 K (T1) or u rms  1.224   mp
T1<T2<T3
Ump
Uav
(iii) Relation between  mp and v av :
Urms
Ump
v av  1.128   mp
Fraction of
molecules

1500 K (T2) 1800 K (T3) (iv) Relation between  mp , v av and urms

 mp : v av : urms
Molecular speed
2 RT 8 RT 3 RT
: :
(4) Types of molecular speeds or Velocities M M M
(i) Root mean square velocity (urms) : It is 8
the square root of the mean of the squares of the 2 : : 3

velocity of a large number of molecules of the same
1.414 : 1.595 : 1.732
gas.
1 : 1.128 : 1.224 i.e.,
u12  u 22  u 32  ..... u n2  mp  v av  u rms
u rms 
n
Real and Ideal gases
(1) Gases which obey gas laws or ideal gas
3 PV 3 RT 3 RT 3 kT 3P equation (PV  nRT ) at all temperatures and pressures
u rms     
(mN 0 )  M (mN 0 )  M M m d
are called ideal or perfect gases. Almost all gases
R deviate from the ideal behaviour i.e., no gas is perfect
where k = Boltzmann constant 
N0 and the concept of perfect gas is only theoretical.

(a) For the same gas at two different (2) Gases tend to show ideal behaviour more and
temperatures, the ratio of RMS velocities will be, more as the temperature rises above the boiling point
of their liquefied forms and the pressure is lowered.
u1 T1
 Such gases are known as real or non ideal gases. Thus, a
u2 T2
“real gas is that which obeys the gas laws under low
(b) For two different gases at the same pressure or high temperature”.
temperature, the ratio of RMS velocities will be,
(3) The deviations can be displayed, by plotting
u1 M2 the P-V isotherms of real gas and ideal gas.

u2 M1
H2
(c) RMS velocity at any temperature t o C
3 P(273  t) He
may be related to its value at S.T.P. as, u t  .
273 d
PV
Z 
nRT
O2
N2
CH4
CO2
P
 Gaseous State 233
(2) Vander Waal's equation is obeyed by the real
gases over wide range of temperatures and pressures,
hence it is called equation of state for the real gases.
(3) The Vander Waal's equation for n moles of the
(4) It is difficult to determine quantitatively the
gas is,
deviation of a real gas from ideal gas behaviour from
the P-V isotherm curve as shown above.  2 
P  n a  [V  nb]  nRT
Compressibility factor Z defined by the equation,  V 2 
 Volume correction for
PV  ZnRT or Z  PV / nRT  PVm / RT Pressure correction
for molecular attraction
finite size of molecules

is more suitable for a quantitative description of a and b are Vander Waal's constants whose values
the deviation from ideal gas behaviour. depend on the nature of the gas. Normally for a gas
(5) Greater is the departure of Z from unity, more a  b .
is the deviation from ideal behaviour. Thus, when (i) Constant a : It is a indirect measure of
(i) Z  1 , the gas is ideal at all magnitude of attractive forces between the molecules.
temperatures and pressures. In case of N 2 , the value of Greater is the value of a, more easily the gas can be
liquefied. Thus the easily liquefiable gases (like
Z is close to 1 at 50 o C . This temperature at which a
SO 2  NH 3  H 2 S  CO 2 ) have high values than the
real gas exhibits ideal behaviour, for considerable
range of pressure, is known as Boyle's temperature or permanent gases (like N 2  O2  H 2  He ) .
Boyle's point (TB ) . Units of 'a' are : atm. L2 mol 2 or atm. m 6 mol 2 or
(ii) Z  1 , the gas is less compressible than N m 4 mol 2 (S.I. unit).
expected from ideal behaviour and shows positive
(ii) Constant b : Also called co-volume or
deviation, usual at high P i.e. PV  RT .
excluded volume,
(iii) Z  1 , the gas is more compressible than 4 
expected from ideal behaviour and shows negative b  4 N 0 v  4 N 0  r 3 
3 
deviation, usually at low P i.e. PV  RT .
It's value gives an idea about the effective size
(iv) Z  1 for H 2 and He at all pressure i.e.,
of gas molecules. Greater is the value of b, larger is the
always shows positive deviation. size and smaller is the compressible volume. As b is the
(v) The most easily liquefiable and highly effective volume of the gas molecules, the constant
soluble gases (NH 3 , SO 2 ) show larger deviations from value of b for any gas over a wide range of temperature
ideal behaviour i.e. Z  1 . and pressure indicates that the gas molecules are
(vi) Some gases like CO2 show both negative and incompressible.
Units of 'b' are : L mol 1 or m 3 mol 1 (S.I. unit)
positive deviation.
(6) Causes of deviations of real gases from (iii) The two Vander Waal's constants and Boyle's
temperature (TB ) are related as,
ideal behaviour : The ideal gas laws can be derived
from the kinetic theory of gases which is based on the a
TB 
following two important assumptions, bR
(i) The volume occupied by the molecules is (4) Vander Waal's equation at different
negligible in comparison to the total volume of gas. temperature and pressures
(ii) The molecules exert no forces of attraction (i) When pressure is extremely low : For
upon one another. It is because neither of these one mole of gas,
assumptions can be regarded as applicable to real gases  a  a ab
 P  2  (V  b)  RT or PV  RT   Pb  2
that the latter show departure from the ideal  V  V V
behaviour. (ii) When pressure is extremely high : For
Vander Waal's equation one mole of gas,
PV Pb Pb
(1) To rectify the errors caused by ignoring the PV  RT  Pb ; 1 or Z  1 
RT RT RT
intermolecular forces of attraction and the volume where Z is compressibility factor.
occupied by molecules, Vander Waal (in 1873) modified (iii) When temperature is extremely high : For
the ideal gas equation by introducing two corrections,
one mole of gas,
(i) Volume correction (ii) Pressure PV  RT .
correction (iv) When pressure is low : For one mole of gas,
 234 Gaseous State
 a  a ab
(iii) Wohl equation : P 
RT

a

c
 P  2  (V  b)  RT or PV  RT  Pb   2
 V  V V (V  b ) V (V  b ) V 2
PV a a RT
or 1 or Z  1  (iv) Dieterici equation : P  .e a / RTV .
RT VRT VRT V b
(v) For hydrogen : Molecular mass of The expression is derived on the basis of the
hydrogen is small hence value of 'a' will be small owing concept that molecules near the wall will have higher
a potential energy than those in the bulk.
to smaller intermolecular force. Thus the terms and
V (v) Kammerlingh Onnes equation : It is
ab the most general or satisfactory expression as equation
may be ignored. Then Vander Waal's equation
V2 expresses PV as a power series of P at a given
becomes, temperature.

PV  RT  Pb or
PV
1
Pb PV  A  BP  CP 2  DP 3  ......
RT RT Here coefficients A, B, C etc. are known as first,
Pb second and third etc. virial coefficients.
or Z  1 
RT (a) Virial coefficients are different for different
In case of hydrogen, compressibility factor is gases.
always greater than one. (b) At very low pressure, first virial coefficient, A
(5) Merits of Vander Waal's equation = RT.
(i) The Vander Waal's equation holds good for (c) At high pressure, other virial coefficients also
real gases upto moderately high pressures. become important and must be considered.
(ii) The equation represents the trend of the The critical state
isotherms representing the variation of PV with P for (1) A state for every substance at which the
various gases. vapour and liquid states are indistinguishable is known
(iii) From the Vander Waal's equation it is as critical state. It is defined by critical temperature
possible to obtain expressions of Boyle's temperature, and critical pressure.
critical constants and inversion temperature in terms
(2) Critical temperature (Tc) of a gas is that
of the Vander Waal's constants 'a' and 'b'.
temperature above which the gas cannot be liquified
(iv) Vander Waal's equation is useful in obtaining however large pressure is applied. It is given by,
a 'reduced equation of state' which being a general 8a
equation of state has the advantage that a single curve Tc 
27 Rb
can be obtained for all gases when the equation if
(3) Critical pressure (Pc) is the minimum
graphically represented by plotting the variables.
pressure which must be applied to a gas to liquify it at
(6) Limitations of Vander Waal's equation
a
(i) This equation shows appreciable its critical temperature. It is given by, Pc 
27 b 2
deviations at too low temperatures or too high
(4) Critical volume (Vc) is the volume occupied
pressures.
by one mole of the substance at its critical temperature
(ii) The values of Vander Waal's constants a and critical pressure. It is given by, Vc  3b
and b do not remain constant over the entire ranges of
(5) Critical compressibility factor (Zc) is given
T and P, hence this equation is valid only over specific
PV 3
range of T and P. by, Z c  c c   0.375
RTc 8
(7) Other equations of state : In addition to
Vander Waal's equation, there are also equations of A gas behaves as a Vander Waal’s gas if its critical
state which have been used to explain real behaviour of compressibility factor (Z c ) is equal to 0.375. A
gases are, substance is the gaseous state below Tc is called vapour
(i) Clausius equation : and above Tc is called gas.
 a 
P  2 
(V  b)  RT . Here 'c' is another constant Degrees of freedom of a gaseous molecule
 T (V  c) 
(1) The motion of atoms and molecules is
besides a, b and R.
generally described in terms of the degree of freedom
 a  which they possess.
(ii) Berthelot equation :  P   (V  b)  RT .
 
2
TV (2) The degrees of freedom of a molecule are
defined as the independent number of parameters
 Gaseous State 235
required to describe the state of the molecule (v) For monoatomic gas,
completely. 5
Cp R
(3) When a gaseous molecule is heated, the ( )   2  1 .66 .
Cv 3
energy supplied to it may bring about three kinds of R
motion in it, these are, 2
7
(i) The translational motion (ii) The Cp R
rotational motion (iii) The vibrational (vi) For diatomic gas ( )   2  1 .40
Cv 5
motion. R
2
This is expressed by saying that the molecule Cp 8R
(vii) For triatomic gas ( )    1 .33
possesses translational, rotational and vibrational degrees of Cv 6R
freedom.
Liquefaction of gases
(4) For a molecule made up of N atoms, total
degrees of freedom = 3N. Further split up of these is as (1) A gas may be liquefied by cooling or by the
follows, application of high pressure or by the combined effect
of both. The first successful attempt for liquefying
Translational Rotational
gases was made by Faraday.
Vibrational
(2) Gases for which the intermolecular forces of
For linear molecule : 3 2 3N – 5
attraction are small such as H 2 , N 2 , Ar and O 2 , have
For non-linear molecule : 3 3 3N – 6
low values of Tc and cannot be liquefied by the
Specific and Molar heat capacity of gases
application of pressure are known as “permanent
(1) Specific heat (or specific heat capacity) of a gases” while the gases for which the intermolecular
substance is the quantity of heat (in calories, joules, forces of attraction are large, such as polar molecules
kcal, or kilo joules) required to raise the temperature of NH 3 , SO 2 and H 2 O have high values of Tc and can be
1g of that substance through 1 o C . It can be measured liquefied easily.
at constant pressure (c p ) and at constant volume (cv ) . (3) Methods of liquefaction of gases : The modern
(2) Molar heat capacity of a substance is the methods of cooling the gas to or below their Tc and hence
quantity of heat required to raise the temperature of 1 of liquefaction of gases are done by Linde's method and
mole of the substance by 1 o C . Claude's method.
 Molar heat capacity = Specific heat capacity  (i) Linde's method : This process is based
Molecular weight, i.e., upon Joule-Thomson effect which states that “When a
Cv  cv  M and C p  c p  M . gas is allowed to expand adiabatically from a region of
(3) Since gases upon heating show considerable high pressure to a region of extremely low pressure, it
tendency towards expansion if heated under constant is accompained by cooling.”
pressure conditions, an additional energy has to be (ii) Claude's method : This process is
based upon the principle that when a gas expands
supplied for raising its temperature by 1 o C relative to
adiabatically against an external pressure (as a piston
that required under constant volume conditions, i.e.,
in an engine), it does some external work. Since work
C p  Cv or C p  Cv  Work done on expansion, PV ( R)
is done by the molecules at the cost of their kinetic
where, C p  molar heat capacity at constant energy, the temperature of the gas falls causing
pressure; Cv  molar heat capacity at constant volume. cooling.
(4) Some useful relations of Cp and Cv (iii) By adiabatic demagnetisation.
(i) C p  Cv  R  2 calories 8.314 J (4) Uses of liquefied gases : Liquefied and gases
compressed under a high pressure are of great importance
3
(ii) Cv  R (for monoatomic gas) and in industries.
2
(i) Liquid ammonia and liquid sulphur
3
Cv   x (for di and polyatomic gas), where x varies dioxide are used as refrigerants.
2
(ii) Liquid carbon dioxide finds use in soda
from gas to gas.
Cp fountains.
(iii)   (Ratio of molar capacities) (iii) Liquid chlorine is used for bleaching and
Cv
disinfectant purposes.
(iv) For monoatomic gas Cv  3 calories whereas,
(iv) Liquid air is an important source of oxygen in
C p  Cv  R  5 calories rockets and jet-propelled planes and bombs.
 236 Gaseous State
(v) Compressed oxygen is used for welding  1 Cal = 4.2 Joule, 1 Kcal = 4200 Joule
purposes.
(vi) Compressed helium is used in airships.
 The gas which has least mean free path has
maximum value of a, is easily liquefied and has
(5) Joule-Thomson effect : When a real gas is
allowed to expand adiabatically through a porous plug maximum value of Tb.
or a fine hole into a region of low pressure, it is  Tc < Tb < Ti
accompanied by cooling (except for hydrogen and
 For critical constants, compression factor Z is < 1.
helium which get warmed up).
Cooling takes place because some work is done to  Boyle’s law and Avogadro’s law are applicable
overcome the intermolecular forces of attraction. As a under limiting condition. This limiting condition
result, the internal energy decreases and so does the is P  0.
temperature.  Tc = 0.296 Tb ; Ti = 6.75 Tc
Ideal gases do not show any cooling or heating
 Mean free path increases if H2 is replaced by He.
because there are no intermolecular forces of attraction
i.e., they do not show Joule-Thomson effect.
During Joule-Thomson effect, enthalpy of the
system remains constant.
Joule-Thomson coefficient.   (T / P)H .

For cooling,   ve (because dT and dP will be

ve )
For heating   ve (because dT  ve, dP  ve ) .

For no heating or cooling   0 (because dT  0 ) .

(6) Inversion temperature : It is the temperature

at which gas shows neither cooling effect nor heating
effect i.e., Joule-Thomson coefficient   0 . Below this
temperature, it shows cooling effect and above this
temperature, it shows heating effect.
Any gas like H 2 , He etc, whose inversion
temperature is low would show heating effect at room
temperature. However, if these gases are just cooled
below inversion temperature and then subjected to
Joule-Thomson effect, they will also undergo cooling.

 If the number of molecules present in 1 c.c. of

the gas or vapour at S.T.P., then that is called
loschmidt number. Its value is 2.687  1019 per
c.c.
 CO2 > SO2 > SO3 > PCl3 is order of rate of
diffusion.
 Vapour density is independent of temperature
and has no unit while absolute density is
dependent of temperature and has unit of gm–1
 The isotherms of CO2 were first studied by
Andrews.
 Gaseous State 235
9. Which of the following relations for expressing
volume of a sample is not correct
(a) 1 L  10 3 ml (b) 1 dm 3  1 L

(c) 1 L  10 3 m 3 (d) 1L  10 3 cm3

10. One atmosphere is numerically equal to
Characteristics and Measurable properties of gases approximately
(a) 10 6 dynes cm 2 (b) 10 2 dynes cm 2
1. Which one of the following statements is not
correct about the three states of matter i.e. solid, (c) 10 4 dynes cm 2 (d) 10 8 dynes cm 2
liquid and gaseous
11. 2gm of O 2 at 27 o C and 760mm of Hg pressure
(a) Molecules of a solid possess least energy
has volume [BCECE 2005]
whereas those of a gas possess highest
energy (a) 1.5 lit. (b) 2.8 lit.
(b) The density of solid is highest whereas that of (c) 11.2 lit. (d) 22.4 lit.
gases is lowest 12. Pressure of a gas in a vessel can be measured by
(c) Gases like liquids possess definite volumes (a) Barometer (b) Manometer
(d) Molecules of a solid possess vibratory motion (c) Stalgometer (d) All the baove
2. The temperature and pressure at which ice, liquid 13. Volume occupied by a gas at one atmospheric
water and water vapour can exist together are pressure and 0 o C is V mL. Its volume at 273 K
will be
(a) 0 o C, 1 atm (b) 2o C, 4.7 atm
[Bihar MADT 1982]
(c) 0 o C, 4.7 mm (d)  2o C, 4.7 mm (a) V ml (b) V/2 ml
3. Which of the following is true about gaseous state (c) 2 V (d) None of these
(a) Thermal energy = Molecular attraction 14. Which one of the following statements is wrong
for gases
(b) Thermal energy >> Molecular attraction
[CBSE PMT 1999]
(c) Thermal energy << Molecular attraction
(a) Gases do not have a definite shape and
(d) Molecular forces >> Those in liquids volume
4. Kinetic energy of molecules is highest in (b) Volume of the gas is equal to the volume of
(a) Gases (b) Solids the container confining the gas
(c) Liquids (d) Solutions (c) Confined gas exerts uniform pressure on the
5. Which of the following statement is correct walls of its container in all directions
(a) In all the three states the molecules possess (d) Mass of the gas cannot be determined by
random translational motion weighing a container in which it is enclosed
15. Which of the following exhibits the weakest
(b) Gases cannot be converted into solids without
intermolecular forces [AIIMS 2000]
passing through liquid state
(a) NH 3 (b) HCl
(c) One of the common property of liquids and
gases is viscosity (c) He (d) H 2O
(d) According to Boyle's law V/P is constant at 16. N2 is found in a litre flask under 100 kPa
constant T
pressure and O 2 is found in another 3 litre flask
6. A volume of 1 m 3 is equal to under 320 kPa pressure. If the two flasks are
3 3
(a) 1000 cm (b) 100 cm connected, the resultant pressures is
[Kerala PMT 2004]
(c) 10 dm 3 (d) 10 6 cm 3
(a) 310 kPa (b) 210 kPa
7. Which one of the following is not a unit of (c) 420 kPa (d) 365 kPa
pressure (e) 265 kPa
(a) Newton (b) Torr
(c) Pascal (d) Bar Ideal gas equation and Related gas laws
8. 1o C rise in temperature is equal to a rise of
1. If P, V, T represent pressure, volume and
(a) 1o F (b) 9 / 5 o F temperature of the gas, the correct representation
of Boyle's law is
(c) 5 / 9 o F (d) 33 o F
[BIT Ranchi 1988]
 236 Gaseous state
1 (c) Degree Fahrenheit (d) None
(a) V  (at constant P) (b) PV  RT
T 9. Which of the following expression at constant
(c) V  1 / P (at constant T) (d) PV  nRT pressure represents Charle's law [AFMC 1990]

2. At constant temperature, in a given mass of an 1 1

(a) V  (b) V 
ideal gas T T2
[CBSE PMT 1991]
(c) V  T (d) V  d
(a) The ratio of pressure and volume always
10. Use of hot air balloons in sports and
remains constant
meteorological obsevations is an application of [Kerala ME
(b) Volume always remains constant
(a) Boyle's law (b) Newtonic law
(c) Pressure always remains constant
(c) Kelvin's law (d) Charle's law
(d) The product of pressure and volume always
remains constant 11. A 10 g of a gas at atmospheric pressure is cooled
3. Air at sea level is dense. This is a practical from 273 o C to 0 o C keeping the volume constant,
application of its pressure would become
[Kerala CEE 2000] (a) 1/2 atm (b) 1/273 atm
(a) Boyle's law (b) Charle's law (c) 2 atm (d) 273 atm
(c) Avogadro's law (d) Dalton's law 12. Pressure remaining the same, the volume of a
3 3 given mass of an ideal gas increases for every
4. If 20 cm gas at 1 atm. is expanded to 50 cm at degree centigrade rise in temperature by definite
constant T, then what is the final pressure[CPMT 1988]
fraction of its volume at
1 1 [CBSE PMT 1989]
(a) 20  (b) 50 
50 20 (a) 0 C o
(b) Its critical
1 temperature
(c) 1   50 (d) None of these
20 (c) Absolute zero (d) Its Boyle
temperature
5. Which of the following statement is false[BHU 1994]
13. A certain sample of gas has a volume of 0.2 litre
(a) The product of pressure and volume of fixed
amount of a gas is independent of measured at 1 atm. pressure and 0 o C . At the same
temperature pressure but at 273 o C , its volume will be[EAMCET 1992, 93
(b) Molecules of different gases have the same (a) 0.4 litres (b) 0.8 litres
K.E. at a given temperature (c) 27.8 litres (d) 55.6 litres
(c) The gas equation is not valid at high pressure 14. 400 cm 3 of oxygen at 27 o C were cooled to  3 o C
and low temperature without change in pressure. The contraction in
(d) The gas constant per molecule is known as volume will be
Boltzmann constant (a) 40 cm 3 (b) 30 cm 3
6. Which of the following graphs represent Boyle's (c) 44.4 cm 3 (d) 360 cm 3
law 15. The pressure p of a gas is plotted against its
absolute temperature T for two different constant
P PV volumes, V1 and V2 . When V1  V2 , the
(a) (b) (a) Curves have the same slope and do not
V P intersect
(b) Curves must intersect at some point other
PV PV than T  0
(c) Curve for V2 has a greater slope than that
(c) V
(d)
P for V1
7. Densities of two gases are in the ratio 1 : 2 and (d) Curve for V1 has a greater slope than that
their temperatures are in the ratio 2 : 1, then the for V2
ratio of their respective pressures is [BHU 2000]
16. Two closed vessels of equal volume containing air
(a) 1 : 1 (b) 1 : 2 at pressure P1 and temperature T1 are connected
(c) 2 : 1 (d) 4 : 1 to each other through a narrow tube. If the
8. At constant pressure, the volume of fixed mass of temperature in one of the vessels is now
an ideal gas is directly proportional to[EAMCET 1985] maintained at T1 and that in the other at T2 , what
(a) Absolute temperature (b) Degree centigrade will be the pressure in the vessels
 Gaseous State 237
2 P1T1 T1 (a) 1.987 cal K–1 mol–1 (b) 8.3 cal K–1 mol–1
(a) (b)
T1  T2 2 P1T2 –1
(c) 0.0821 lit K mol –1 (d) 1.987 Joules K–1 mol–1
2 P1T2 2 P1 25. The constant R is [Orissa 1990]
(c) (d) (a) Work done per molecule
T1  T2 T1  T2
(b) Work done per degree absolute
17. “One gram molecule of a gas at N.T.P. occupies
22.4 litres.” This fact was derived from[CPMT 1981, 1995] (c) Work done per degree per mole
(a) Dalton's theory (d) Work done per mole
(b) Avogadro's hypothesis 26. Select one correct statement. In the gas equation,
PV  nRT [CBSE PMT 1992]
(c) Berzelius hypothesis
(a) n is the number of molecules of a gas
(d) Law of gaseous volume
(b) V denotes volume of one mole of the gas
18. In a closed flask of 5 litres, 1.0 g of H 2 is heated
(c) n moles of the gas have a volume V
from 300 to 600 K. which statement is not correct[CBSE PMT(d)1991]
P is the pressure of the gas when only one
(a) Pressure of the gas increases mole of gas is present
(b) The rate of collision increases 27. The correct value of the gas constant R is close to
(c) The number of moles of gas increases [CBSE PMT 1992]
(d) The energy of gaseous molecules increases (a) 0.082 litre-atmopshere K
19. Which one of the following statements is false (b) 0.082 litre-atmosphere K 1 mol 1
[Manipal PMT 1991]
(c) 0.082 litre- atmosphere 1 K mole 1
(a) Avogadro number  6.02  10 21

(b) The relationship between average velocity (v ) (d) 0.082 litre1 atmosphere 1 K mol
and root mean square velocity (u) is 28. S.I. unit of gas constant R is [CPMT 1994]
v  0.9213 u
(a) 0.0821 litre atm K–1 mole–1
(c) The mean kinetic energy of an ideal gas is (b) 2 calories K–1 mole–1
independent of the pressure of the gas
(c) 8.31 joule K–1 mole–1
(d) The root mean square velocity of the gas can
(d) None
be calculated by the formula (3 RT / M )1 / 2
29. Gas equation PV  nRT is obeyed by [BHU 2000]
20. The compressibility of a gas is less than unity at
STP. Therefore [IIT 2000] (a) Only isothermal process (b)Only adiabatic process
(a) Vm  22 .4 litres (b) Vm  22 .4 litres (c) Both (a) and (b) (d) None of these
(c) Vm  22 .4 litres (d) Vm  44 .8 litres 30. For an ideal gas number of moles per litre in
terms of its pressure P, gas constant R and
21. In the equation of sate of an ideal gas PV  nRT , temperature T is
the value of the universal gas constant would [AIEEE 2002]
depend only on (a) PT/R (b) PRT
[KCET 2005]
(c) P/RT (d) RT/P
(a) The nature of the gas 31. If two moles of an ideal gas at 546 K occupy a
(b) The pressure of the gas volume of 44.8 litres, the pressure must be
(c) The units of the measurement [NCERT 1981; JIPMER 1991]
(d) None of these (a) 2 atm (b) 3 atm
22. In the ideal gas equation, the gas constant R has (c) 4 atm (d) 1 atm
the dimensions of [NCERT 1982] 32. How many moles of He gas occupy 22.4 litres at
(a) mole-atm K–1 (b) litre mole 30 o C and one atmospheric pressure [KCET 1992]
(c) litre-atm K–1 mole–1 (d) erg K–1 (a) 0.90 (b) 1.11
23. In the equation PV  nRT , which one cannot be (c) 0.11 (d) 1.0
the numerical value of R [BIT 1987] 33. Volume of 0.5 mole of a gas at 1 atm. pressure and
(a) 8.31  10 7 erg K 1mol 1 273 K is
[EAMCET 1992]
(b) 8.31  10 7 dyne cm K 1mol 1 (a) 22.4 litres (b) 11.2 litres
(c) 44.8 litres (d) 5.6 litres
(c) 8.31 JK 1mol 1
34. At 0 o C and one atm pressure, a gas occupies 100
(d) 8.31 atm. K 1mol 1 cc. If the pressure is increased to one and a half-
24. Which one of the following indicates the value of time and temperature is increased by one-third of
the gas constant R [EAMCET 1989] absolute temperature, then final volume of the
gas will be
 238 Gaseous state
[DCE 2000] ml at 740 mm pressure, the temperature of the
(a) 80 cc (b) 88.9 cc gas will be
(c) 66.7 cc (d) 100 cc [Vellore CMC 1991]
35. Correct gas equation is[CBSE PMT 1989; CPMT 1991] o
(a) 21 .6 C o
(b) 240 C
VT VT PV T
(a) 1 2  2 1 (b) 1 1  1 (c)  33 C o
(d) 89 .5 o C
P1 P2 P2 V2 T2
44. The total pressure exerted by a number of non-
P1T2 P2 V2 V1V2 reacting gases is equal to the sum of the partial
(c)  (d)  P1 P2
V1 T2 T1T2 pressures of the gases under the same conditions
36. Two separate bulbs contain ideal gases A and B. is known as [CPMT 1986]
The density of gas A is twice that of gas B. The (a) Boyle's law (b) Charle's law
molecular mass of A is half that of gas B. The two (c) Avogadro's law (d) Dalton's law
gases are at the same temperature. The ratio of 45. “Equal volumes of all gases at the same
the pressure of A to that of gas B is temperature and pressure contain equal number
[BHU 1994] of particles.” This statement is a direct
(a) 2 (b) 1/2 consequence of [Kerala MEE 2002]
(c) 4 (d) 1/4 (a) Avogadro’s law (b) Charle's law
37. 16 g of oxygen and 3 g of hydrogen are mixed and (c) Ideal gas equation (d) Law of partial
kept at 760 mm pressure and 0 o C . The total pressure
46. 1991]
volume occupied by the mixture will be nearly[Vellore CMC If three unreactive gases having partial pressures
(a) 22.4 litres (b) 33.6 litres PA , PB and PC and their moles are 1, 2 and 3
(c) 448 litres (d) 44800 ml respectively then their total pressure will be[CPMT 1994]
38. Pure hydrogen sulphide is stored in a tank of 100 P  PB  PC
(a) P  PA  PB  PC (b) P  A
litre capacity at 20 o C and 2 atm pressure. The 6
mass of the gas will be [CPMT 1989] PA  PB  PC
(a) 34 g (b) 340 g (c) P  (d) None
3
(c) 282.4 g (d) 28.24 g
39. At N.T.P. the volume of a gas is found to be 273 47. Dalton's law of partial pressure will not apply to
ml. What will be the volume of this gas at 600 mm which of the following mixture of gases[Bihar MADT 1981]
(a) H 2 and SO 2 (b) H 2 and Cl2
Hg and 273 o C
[CPMT 1992] (c) H 2 and CO2 (d) CO2 and Cl2
(a) 391.8 mL (b) 380 ml 48. Which of the following mixtures of gases does not
(c) 691.6 ml (d) 750 ml obey Dalton's law of partial pressure
40. One litre of a gas weighs 2 g at 300 K and 1 atm [CBSE PMT 1996: Kerala PMT 2000]
pressure. If the pressure is made 0.75 atm, at (a) O 2 and CO2 (b) N 2 and O 2
which of the following temperatures will one litre
(c) Cl2 and O 2 (d) NH 3 and HCl
of the same gas weigh one gram
[CBSE PMT 1992] 49. To which of the following gaseous mixtures is
(a) 450 K (b) 600 K Dalton's law not applicable
(c) 800 K (d) 900 K (a) Ne  He  SO2 (b) NH3  HCl  HBr
41. A wheather balloon filled with hydrogen at 1 atm (c) O2  N 2  CO2 (d) N 2  H2  O2
and 27 o C has volume equal to 12000 litres. On 50. Equal amounts of two gases of molecular weight 4
ascending it reaches a place where the and 40 are mixed. The pressure of the mixture is
temperature is  23 o C and pressure is 0.5 atm. 1.1 atm. The partial pressure of the light gas in
The volume of the balloon is this mixture is
[CBSE PMT 1991] [CBSE PMT 1991]
(a) 24000 litres (b) 20000 litres (a) 0.55 atm (b) 0.11 atm
(c) 10000 litres (d) 12000 litres (c) 1 atm (d) 0.12 atm
42. The density of a gas at 27 o C and 1 atm is d. 51. Rate of diffusion of a gas is [IIT 1985; CPMT 1987]
Pressure remaining constant at which of the (a) Directly proportional to its density
following temperatures will its density become (b) Directly proportional to its molecular mass
0.75 d [CBSE PMT 1992] (c) Directly proportional to the square root of its
(a) 20 o C (b) 30 o C molecular mass
(c) 400 K (d) 300 K (d) Inversely proportional to the square root of its
o molecular mass
43. A sample of gas occupies 100 ml at 27 C and 740
mm pressure. When its volume is changed to 80 52. Which of the following gas will have highest rate
of diffusion
 Gaseous State 239
[Pb. CET Sample paper 1993; CPMT 1990] 62. At constant volume and temperature conditions,
(a) NH 3 (b) N 2 the rate of diffusion DA and DB of gases A and B
(c) CO2 (d) O 2 having densities  A and  B are related by the
expression [IIT 1993]
53. Which of the following relationship is correct,
1/2 1/2
where r is the rate of diffusion of a gas and d is      
(a) D A   DB  A  (b) D A   DB  B 
its density [CPMT 1994]
 B    A
(a) r  1 / d (b) r  d 1/2 1/2
   
(c) r  d (d) r  d (c) DA  DB  A 
 (d) DA  DB  B 

 B   A 
54. According to Grahman's law at a given
temperature, the ratio of the rates of diffusion 63. Atmolysis is a process of
rA / rB of gases A and B is given by [IIT 1998] (a) Atomising gas molecules
(b) The breaking of atoms to sub-atomic particles
(a) (PA / PB )(M A / M B )1 / 2 (c) Separation of gases from their gaseous
(b) (M A / M B )(PA / PB )1 / 2 mixture
(d) Changing of liquids to their vapour state
(c) (PA / PB )(M B / M A )1 / 2 64. A bottle of ammonia and a bottle of dry hydrogen
1/ 2 chloride connected through a long tube are
(d) (M A / M B )(PB / PA )
opened simultaneously at both ends, the white
(where P and M are the pressures and molecular ammonium chloride ring first formed will be[IIT 1988]
weights of gases A and B respectively) (a) At the centre of the tube
55. The ratio of the rate of diffusion of a given (b) Near the hydrogen chloride bottle
element to that of helium is 1.4. The molecular (c) Near the ammonia bottle
weight of the element is
(d) Throughout the length of the tube
[Kerala PMT 1990]
65. Which of the following pairs will diffuse at the
(a) 2 (b) 4 same rate through a porous plug [EAMCET 1990]
(c) 8 (d) 16 (a) CO, NO2 (b) NO2 , CO2
56. A gas diffuse 1/5 times as fast as hydrogen. Its (c) NH3 , PH3 (d) NO C2 H6
molecular weight is [CPMT 1992; Bihar CEE 1982]
66.
If 4 g of oxygen diffuse through a very narrow
(a) 50 (b) 25
hole, how much hydrogen would have diffused
(c) 25 2 (d) 50 2 under identical conditions [CPMT 1971]
57. The molecular weight of a gas which diffuses (a) 16 g (b) 1 g
through a porous plug at 1/6th of the speed of (c) 1/4 g (d) 64 g
hydrogen under identical conditions is[EAMCET 1990] 67. A gas diffuse at a rate which is twice that of
(a) 27 (b) 72 another gas B. The ratio of molecular weights of A
(c) 36 (d) 48 to B is [EAMCET 1986]
(a) 1.0 (b) 0.75
58. Molecular weight of a gas that diffuses twice as
rapidly as the gas with molecular weight 64 is[EAMCET 1994](c) 0.50 (d) 0.25
68. Two grams of hydrogen diffuse from a container
(a) 16 (b) 8
in 10 minutes. How many grams of oxygen would
(c) 64 (d) 6.4 diffuse through the same container in the same
59. The densities of hydrogen and oxygen are 0.09 time under similar conditions [MNR 1980]
and 1.44 g L1 . If the rate of diffusion of hydrogen (a) 0.5 g (b) 4 g
is 1 then that of oxygen in the same units will be[RPMT 1994](c) 6 g (d) 8 g
(a) 4 (b) 1/4 69. The rate of diffusion of methane at a given
(c) 16 (d) 1/16 temperature is twice that of X. The molecular
60. If rate of diffusion of A is 5 times that of B, what weight of X is
will be the density ratio of A and B [AFMC 1994] [MNR 1995; Kerala CEE 2001]
(a) 1/25 (b) 1/5 (a) 64.0 (b) 32.0
(c) 25 (d) 4 (c) 40.0 (d) 80.0
61. The densities of two gases are in the ratio of 1 : 70. X ml of H 2 gas effuses through a hole in a
16. The ratio of their rates of diffusion is[CPMT 1995] container in 5 seconds. The time taken for the
(a) 16 : 1 (b) 4 : 1 effusion of the same volume of the gas specified
(c) 1 : 4 (d) 1 : 16 below under identical condition is
[IIT 1996]
 240 Gaseous state
(a) 10 seconds : He (b) 20 seconds : O 2 1
(b) that of SO 2
(c) 25 seconds : CO (d) 55 seconds : CO2 2
71. At what temperature, the rate of effusion of N 2 (c) Twice that of SO 2

would be 1.625 times that of SO 2 at 50 o C [CBSE PMT 1996] (d) One fourth that of SO 2
(a) 110 K (b) 173 K 81. Five grams each of the following gases at 87 o C
(c) 373 K (d) 273 K and 750 mm pressure are taken. Which of them
72. Given the reaction C(s)  H2O(l)  CO(g)  H2 (g) will have the least volume [MNR 1991]

calculate the volume of the gases produced at STP (a) HF (b) HCl
from 48.0 g of carbon (c) HBr (d) HI
(a) 179.2 L (b) 89.6 L 82. Who among the following scientists has not done
(c) 44.8 L (d) 22.4 L any important work on gases [Bihar MADT 1980]
73. 4.4 g of a gas at STP occupies a volume of 2.24 L, (a) Boyle (b) Charles
the gas can be [Haryana CEET 2000] (c) Avogadro (d) Faraday
(a) O 2 (b) CO 83. A closed vessel contains equal number of nitrogen
(c) NO2 (d) CO2 and oxygen molecules at a pressure of P mm. If
nitrogen is removed from the system then the
74. Under what conditions will a pure sample of an pressure will be
ideal gas not only exhibit a pressure of 1 atm but
[MP PMT 1985]
also a concentration of 1 mole litre  1
(a) P (b) 2P
(R  0.082 litreatm mol 1 deg 1 ) [CBSE PMT 1993]
(c) P / 2 (d) P 2
(a) At STP
84. If the four tubes of a car are filled to the same
(b) When V  22 .4 litres pressure with N 2 , O2 , H2 and Ne separately, then
(c) When T  12 K which one will be filled first [Manipal PMT 2001]
(d) Impossible under any conditions (a) N 2 (b) O 2
75. There are 6.02  10 22 molecules each of N 2 , O2 and (c) H 2 (d) Ne
H 2 which are mixed together at 760 mm and 273 85. Which of the following gas mixture is not
K. The mass of the mixture in grams is [Pb. PMT 1997] applicable for Dalton’s law of partial pressure[Pb. CET 200
(a) 6.2 (b) 4.12 (a) SO 2 and Cl2 (b) CO2 and N 2
(c) 3.09 (d) 7 (c) CO and CO2 (d) CO and N 2
76. Volume of 4.4 g of CO2 at NTP is [Pb. CET 1997]
86. At what pressure a quantity of gas will occupy a
(a) 22.4 L (b) 44.8 L volume of 60 ml , if it occupies a volume of 100 ml
(c) 2.24 L (d) 4.48 L at a pressure of 720 mm ? (while temperature is
77. The energy of an ideal gas depends only on its constant) : [Pb. CET 2000]
(a) Pressure (b) Volume (a) 700 mm (b) 800 mm
(c) Number of moles (d) Temperature
(c) 100 mm (d) 1200 mm
78. A bottle of cold drink contains 200 ml liquid in
which CO2 is 0.1 molar. Suppose CO2 behaves 87. At constant temperature and pressure which gas
will diffuse first H 2 or O 2 ? [Pb. CET 2000]
like an ideal gas, the volume of the dissolved CO2
at STP is [CBSE PMT 1991] (a) Hydrogen
(a) 0.224 litre (b) 0.448 litre (b) Oxygen
(c) 22.4 litre (d) 2.24 litre (c) Both will diffuse in same time
79. The vapour density of a gas is 11.2. The volume (d) None of the above
occupied by 11.2 g of this gas at N.T.P. is 88. When a jar containing gaseous mixture of equal
[MNR 1982; CBSE PMT 1991] volumes of CO2 and H 2 is placed in a solution of
(a) 1 L (b) 11.2 L sodium hydroxide, the solution level will[Pb. CET 2001]
(c) 22.4 L (d) 20 L (a) Rise (b) Fall
80. A pre-weighed vessel was filled with oxygen at (c) Remain constant (d) Become zero
N.T.P. and weighted. It was then evacuated, filled 89. At S.T.P. 1g CaCO3 on decomposition gives CO2
with SO 2 at the same temperature and pressure, [Pb. CET 2000]
and again weighted. The weight of oxygen will be[NCERT 1989]
(a) 22.4 litre (b) 2.24 litre
(a) The same as that of SO 2 (c) 0.224 litre (d) 11.2 litre
 Gaseous State 241
90. At NTP, the density of a gas, whose molecular 101. A certain mass of gas occupies a volume of 300
weight is 45 is c.c. at 27C and 620 mm pressure. The volume of
[Pb. CET 2001, 03] this gas at 47 o C and 640 mm pressure will be [MH CET 20
(a) 44.8 gm/litre (b) 11.4 gm/litre (a) 400 c.c. (b) 510 c.c.
(c) 2 gm/ litre (d) 3 gm/litre (c) 310 c.c. (d) 350 c.c.
91. What is the ratio of diffusion rate of oxygen and 102. What will be the volume of the mixture after the
hydrogen reaction?
NH 3  HCl  NH 4 Cl [BVP 2004]
[Pb. CET 2003] 4 litre 1.5 litre (solid)
(a) 1 : 4 (b) 4 : 1 (a) 0.5 litre (b) 1 litre
(c) 1 : 8 (d) 8 : 1 (c) 2.5 litre (d) 0.1 litre
92. The maximum number of molecules is present in 103. The pressure and temperature of 4dm 3 of carbon
[CBSE PMT 2004] dioxide gas are doubled. Then the volume of
(a) 0.5 g of H 2 gas (b) 10 g of O 2 gas carbon dioxide gas would be [KCET 2004]
(c) 15 L of H 2 gas at STP (d) 5 L of N 2 gas at STP (a) 2 dm 3 (b) 3dm 3
93. One litre oxygen gas at STP will weigh[Pb. CET 2004] (c) 4 dm 3 (d) 8 dm 3
(a) 1.43 g (b) 2.24 g 104. If the absolute temperature of an ideal gas
(c) 11.2 g (d) 22.4 g become double and pressure become half, the
94. How will you separate mixture of two gases[AFMC 2004] volume of gas would be
(a) Fractional distillation technique [Kerala CET 2005]
(b) Grahams law of diffusion technique (a) Remain unchange (b) Will be double
(c) Osmosis (c) Will be four time (d) will be half
(d) Chromatography (e) Will be one fourth
95. The rate of diffusion of hydrogen gas is 105. At what temperature, the sample of neon gas
[MH CET 2003; Pb. CET 2000] would be heated to double of its pressure, if the
(a) 1.4 times to He gas (b) Same as He gas initial volume of gas is/are reduced to 15% at
(c) 5 times to He gas (d) 2 times to He gas 75 o C [Kerala CET 2005]
96. Hydrogen diffuses six times faster than gas A .
(a) 319 o C (b) 592 o C
The molar mass of gas A is [KCET 2004]
(a) 72 (b) 6 (c) 128 o C (d) 60 o C
o
(c) 24 (d) 36 (e) 90 C
97. At what pressure will a quantity of gas, which 106. Equation of Boyle's law is [DPMT 2005]
occupies 100 ml at a pressue of 720 mm , occupy a dP dV dP dV
(a)  (b) 
volume of 84 ml [DPMT 2004] p V P V
(a) 736.18 mm (b) 820.20 mm d2P dV d2P d 2V
(c)  (d) 
(c) 784.15 mm (d) 857.14 mm P dT P dT
98. Containers A and B have same gases. Pressure,
volume and temperature of A are all twice that of
Kinetic molecular theory of gases and
B, then the ratio of number of molecules of A
and B are [AFMC 2004] Molecular collisions
(a) 1 : 2 (b) 2
(c) 1 : 4 (d) 4 1. Postulate of kinetic theory is [EAMCET 1980]
99. A mixture of NO2 and N 2O4 has a vapour density (a) Atom is indivisible
of 38.3 at 300 K . What is the number of moles of (b) Gases combine in a simple ratio
NO2 in 100 g of the mixture [Kerala PMT 2004] (c) There is no influence of gravity on the
(a) 0.043 (b) 4.4 molecules of a gas
(c) 3.4 (d) 3.86 (d) None of the above
(e) 0.437 2. According to kinetic theory of gases,[EAMCET 1980]
100. A cylinder of 5 litres capacity, filled with air at (a) There are intermolecular attractions
NTP is connected with another evacuated cylinder (b) Molecules have considerable volume
of 30 litres of capacity. The resultant air pressure
(c) No intermolecular attractions
in both the cylinders will be [BHU 2004]
(a) 10.8 cm of Hg (b) 14.9cm of Hg (d) The velocity of molecules decreases after each
(c) 21.8 cm of Hg (d) 38.8 cm of Hg collision
 242 Gaseous state
3. In deriving the kinetic gas equation, use is made 12. According to kinetic theory of gases, for a
of the root mean square velocity of the molecules diatomic molecule
because it is [MNR 1991]
[Bihar MADT 1980] (a) The pressure exerted by the gas is
(a) The average velocity of the molecules proportional to the mean velocity of the
(b) The most probable velocity of the molecules molecules
(b) The pressure exerted by the gas is
(c) The square root of the average square velocity
proportional to the root mean square velocity
of the molecules
of the molecules
(d) The most accurate form in which velocity can
(c) The root mean square velocity is inversely
be used in these calculations
proportional to the temperature
4. Kinetic energy of a gas depends upon its[Bihar (d) The mean translational kinetic energy of the
MADT 1982]
molecules is proportional to the absolute
(a) Molecular mass (b) Atomic mass temperature
(c) Equivalent mass (d) None of these 13. At STP, 0.50 mol H 2 gas and 1.0 mol He gas
5. The kinetic theory of gases perdicts that total [CBSE PMT 1993, 2000]
kinetic energy of a gaseous assembly depends on[NCERT 1984]
(a) Have equal average kinetic energies
(a) Pressure of the gas (b) Have equal molecular speeds
(b) Temperature of the gas (c) Occupy equal volumes
(c) Volume of the gas (d) Have equal effusion rates
(d) Pressure, volume and temperature of the gas 14. Which of the following expressions correctly
6. According to kinetic theory of gases, the energy represents the relationship between the average
per mole of a gas is equal to [EAMCET 1985] molar kinetic energy, K.E. , of CO and N 2
(a) 1.5 RT (b) RT molecules at the same temperature
(c) 0.5 RT (d) 2.5 RT [CBSE PMT 2000]
7. Internal energy and pressure of a gas per unit
(a) KECO  KE N 2
volume are related as [CBSE PMT 1993]
2 3 (b) KECO  KE N 2
(a) P  E (b) P  E
3 2
(c) KECO  KE N 2
1
(c) P  E (d) P  2 E (d) Cannot be predicted unless the volumes of the
2
gases are given
8. The translational kinetic energy of an ideal gas
depends only on its 15. Indicate the correct statement for a 1-L sample of
(a) Pressure (b) Force N 2 (g) and CO2 (g) at 298 K and 1 atm pressure
(c) Temperature (d) Molar mass (a) The average translational KE per molecule is
9. Helium atom is two times heavier than a the same in N 2 and CO2
hydrogen molecule at 298 K, the average kinetic (b) The rms speed remains constant for both N 2
energy of helium is [IIT 1982]
and CO2
(a) Two times that of a hydrogen molecule
(b) Same as that of a hydrogen molecule (c) The density of N 2 is less than that of CO2
(c) Four times that of a hydrogen molecule (d) The total translational KE of both N 2 and
(d) Half that of a hydrogen molecule CO2 is the same
10. Which of the following is valid at absolute zero
[Pb. CET 1985] 16. With increase of pressure, the mean free path
(a) Kinetic energy of the gas becomes zero but the [Pb. CET 1985]
molecular motion does not become zero (a) Decreases (b) Increases
(b) Kinetic energy of the gas becomes zero and (c) Does not change (d) Becomes zero
molecular motion also becomes zero 17. Which one of the following statements is NOT
(c) Kinetic energy of the gas decreases but does true about the effect of an increase in
not become zero temperature on the distribution of molecular
(d) None of the above speeds in a gas [AIEEE 2005]
11. The average K.E. of an ideal gas in calories per (a) The most probable speed increases
mole is approximately equal to [EAMCET 1989] (b) The fraction of the molecules with the most
(a) Three times the absolute temperature probable speed increases
(b) Absolute temperature (c) The distribution becomes broader
(c) Two times the absolute temperature (d) The area under the distribution curve remains
(d) 1.5 times the absolute temperature the same as under the lower temperature
 Gaseous State 243
18. If P, V, M, T and R are pressure, volume, molar (2) A negative value of  JT (Joule Thomson
mass, temperature and gas constant respectively, coefficient corresponds to warming of a gas
then for an ideal gas, the density is given by[CBSE PMT 1989, 91] on expansion.
RT P (3) The temperature at which neither cooling nor
(a) (b)
PM RT heating effect is observed is known as
M PM inversion temperature.
(c) (d)
V RT Which of the above statements are correct
19. An ideal gas will have maximum density when[CPMT 2000] (a) 1 and 2 (b) 1 and 3
(a) P  0.5 atm, T  600 K (c) 2 and 3 (d) 1, 2 and 3
28. Vibrational energy is [Pb. CET 1985]
(b) P  2 atm, T  150 K
(a) Partially potential and partially kinetic
(c) P  1 atm, T  300 K
(b) Only potential
(d) P  1.0 atm, T  500 K (c) Only kinetic
20. If the inversion temperature of a gas is  80 C , o (d) None of the above
then it will produce cooling under Joule-Thomson 29. At the same temperature and pressure, which of
effect at the following gases will have the highest kinetic
(a) 298 K (b) 273 K energy per mole
(c) 193 K (d) 173 K [MNR 1991]
21. Ratio of C p and Cv of a gas 'X' is 1.4. The number (a) Hydrogen (b) Oxygen
of atoms of the gas 'X' present in 11.2 litres of it at (c) Methane (d) All the same
N.T.P. is 30. Dimensions of pressure are the same as that of
[CBSE PMT 1989] [CBSE PMT 1995]

(a) 6.02  10 23
(b) 1.2  10 24 (a) Energy (b) Force
(c) Energy per unit volume (d)Force per unit volume
(c) 3.01  10 23
(d) 2.01  10 23
31. The density of a gas An is three times that of a gas
22. The density of air is 0.00130 g/ml. The vapour B. if the molecular mass of A is M, the molecular
density of air will be [DCE 2000]
mass of B is
(a) 0.00065 (b) 0.65 [CPMT 1987]
(c) 14.4816 (d) 14.56
(a) 3 M (b) 3M
23. At 100 o C and 1 atm, if the density of liquid water
(c) M / 3 (d) M / 3
is 1.0 g cm3 and that of water vapour is 0.0006 g
m 3 , then the volume occupied by water Molecular speeds
molecules in 1 litre of steam at that temperature
is [IIT 2000] 1. The ratio of root mean square velocity to average
(a) 6 cm 3
(b) 60 cm 3 velocity of gas molecules at a particular
temperature is [IIT 1981]
3
(c) 0.6 cm (d) 0.06 cm 3
(a) 1.086 : 1 (b) 1 : 1.086
24. The ratio  for inert gases is [AFMC 1990]
(c) 2 : 1.086 (d) 1.086 : 2
(a) 1.33 (b) 1.66
2. Which is not true in case of an ideal gas[CBSE PMT 1991]
(c) 2.13 (d) 1.99
(a) It cannot be converted into a liquid
25. The density of neon will be highest at[CBSE PMT 1990]
(b) There is no interaction between the molecules
(a) S.T.P. (b) 0 o C, 2 atm
(c) All molecules of the gas move with same
(c) 273 o C, 1 atm (d) 273 o C, 2 atm speed
(d) At a given temperature, PV is proportional to
26. Absolute zero is defined as the temperature
the amount of the gas
[CBSE PMT 1990]
3. The ratio among most probable velocity, mean
(a) At which all molecular motion ceases
velocity and root mean square velocity is given by[CBSE PM
(b) At which liquid helium boils
(a) 1 : 2 : 3 (b) 1 : 2 : 3
(c) At which ether boils
(d) All of the above (c) 2 : 3 : 8 / (d) 2 : 8 / : 3
27. Consider the following statements : 4. Which of the following has maximum root mean
(1) Joule-Thomson experiment is isoenthalpic as square velocity at the same temperature[Manipal PMT 200
well as adiabatic. (a) SO 2 (b) CO2
(c) O 2 (d) H 2
 244 Gaseous state
5. The temperature at which RMS velocity of SO 2 14. Molecular velocities of the two gases at the same
molecules is half that of He molecules at 300 K is[NTSE 1991]temperature are u1 and u 2 . Their masses are m1
(a) 150 K (b) 600 K and m 2 respectively. Which of the following
(c) 900 K (d) 1200 K expressions is correct
[BHU 1994]
6. At 27 o C , the ratio of rms velocities of ozone to m1 m2
oxygen is (a)  (b) m1u1  m2u2
u12 u 22
[EAMCET 1992]
m1 m 2
(a) 3/5 (b) 4/3 (c)  (d) m1u12  m 2u22
u1 u2
(c) 2/3 (d) 0.25 15. The temperature of the gas is raised from 27 o C
7. The average kinetic energy of an ideal gas per to 927 o C , the root mean square velocity is[CBSE PMT 1994
o
molecule in SI units at 25 C will be[CBSE PMT 1996] (a) 927 / 27 times the earlier value
(a) 6.17  10 21 kJ (b) 6.17  10 21 J (b) Same as before
(c) Halved
(c) 6.17  10 20 J (d) 7.16  10 20 J
(d) Doubled
8. At what temperature the RMS velocity of SO 2 be 16. The ratio between the root mean square velocity
same as that of O 2 at 303 K [KCET 2001] of H2 at 50 K and that of O 2 at 800 K is [IIT 1996]
(a) 4 (b) 2
(a) 273 K (b) 606 K
(c) 1 (d) 1/4
(c) 303 K (d) 403 K 17. The root mean square velocity of an ideal gas at
9. Among the following gases which one has the constant pressure varies density (d) as [IIT 2000]
lowest root mean square velocity at 25 o C [EAMCET 1983] (a) d 2 (b) d
(a) SO 2 (b) N 2 (c) d (d) 1 / d
(c) O 2 (d) Cl2 18. Consider a mixture of SO 2 and O 2 kept at room
10. The root mean square velocity of an ideal gas in a temperature. Compared to the oxygen molecule,
closed container of fixed volume is increased from the SO 2 molecule will hit the wall with
5  10 4 cm s 1 to 10  10 4 cm s 1 . Which of the (a) Smaller average speed (b)Greater average speed
(c) Greater kinetic energy (d) Greater mass
following statement correctly explains how the
19. The rms speed of N 2 molecules in a gas is u. If the
change is accomplished
[Pb. CET 1986] temperature is doubled and the nitrogen
molecules dissociate into nitrogen atoms, the rms
(a) By heating the gas, the temperature is doubled
speed becomes
(b) By heating the gas, the pressure is quadrupled (a) u / 2 (b) 2u
(i.e. made four times) (c) 4u (d) 14u
(c) By heating the gas, the temperature is 20. Choose the correct arrangement, where the
quadrupled symbols have their usual meanings
(d) By heating the gas, the pressure is doubled (a) u  u p  urms (b) urms  u  u p
11. The rms velocity at NTP of the species can be (c) u p  u  urms (d) u p  urms  u
calculated from the expression [EAMCET 1990]
21. The ratio of most probable velocity to that of
3P 3 PV average velocity is [JEE Orissa 2004]
(a) (b)
d M (a)  / 2 (b) 2 / 
3 RT (c)  / 2 (d) 2 / 
(c) (d) All the above 22. The r.m.s. velocity of a certain gas is v at 300 K .
M
The temperature, at which the r.m.s. velocity
12. Root mean square velocity of a gas molecule is
becomes double
proportional to [CBSE PMT 1990]
[Pb. CET 2002]
(a) m1 / 2 (b) m 0 (a) 1200 K (b) 900 K
(c) m 1 / 2 (d) m (c) 600 K (d) 150 K
13. At constant volume, for a fixed number of moles 23. The r.m.s. velocity of a gas depends upon[DCE 2002]
of a gas, the pressure of the gas increases with (a) Temperature only
increase in temperature due to [IIT 1992] (b) Molecular mass only
(a) Increase in the average molecular speed (c) Temperature and molecular mass of gas
(b) Increased rate of collision amongst molecules (d) None of these
(c) Increase in molecular attraction
(d) Decrease in mean free path
 Gaseous State 245
24. What is the pressure of 2 mole of NH 3 at 27 o C  a 
(b)  P  2  (V  b)  nRT
when its volume is 5 litre in vander Waal’s  V 
equation (a = 4.17, b = 0.03711) [JEE Orissa 2004]  na 
(a) 10.33 atm (b) 9.33 atm (c)  P  2  (nV  b)  nRT
 V 
(c) 9.74 atm (d) 9.2 atm
25. The root mean square velocity of one mole of a  n 2a 
(d)  P  2  (V  nb)  nRT
monoatomic having molar mass M is Urms . The  V 

relation between the average kinetic energy (E) of
6. Any gas shows maximum deviation from ideal gas
the Urms is
at
[IIT-JEE Screening 2004] [CPMT 1991]
3E 2E o
(a) U rms  (b) U rms  (a) 0 C and 1 atmospheric pressure
2M 3M
(b) 100 o C and 2 atmospheric pressure
2E E
(c) U rms  (d) U rms  (c)  100 o C and 5 atmospheric pressure
M 3M
26. Ratio of average to most probable velocity is (d) 500 o C and 1 atmospheric pressure
[Orissa JEE 2005] 7. The temperature at which the second virial
(a) 1.128 (b) 1.224 coefficient of real gas is zero is called [AFMC 1993]
(c) 1.0 (d) 1.112 (a) Critical temperature
27. If the vrms is 30 R1 / 2 at 27 o C then calculate the (b) Eutetic point
molar mass of gas in kilogram. [DPMT 2005] (c) Boiling point
(a) 1 (b) 2 (d) Boyle's temperature
(c) 4 (d) 0.001
8. When is deviation more in the behaviour of a gas
from the ideal gas equation PV  nRT
Real gases and Vander waal’s equation [DPMT 1981; NCERT 1982; CBSE PMT 1993]
(a) At high temperature and low pressure
1. The Vander Waal's equation explains the
behaviour of (b) At low temperature and high pressure
[DPMT 1981] (c) At high temperature and high pressure
(a) Ideal gases (b) Real gases (d) At low temperature and low high pressure
(c) Vapour (d) Non-real gases 9. Vander Waal's constants 'a' and 'b' are related
2. Gases deviate from the ideal gas behaviour with..... respectively [RPMT 1994]
because their molecules [NCERT 1981] (a) Attractive force and bond energy of molecules
(a) Possess negligible volume
(b) Volume and repulsive force of molecules
(b) Have forces of attraction between them
(c) Are polyatomic (c) Shape and repulsive forces of molecules
(d) Are not attracted to one another (d) Attractive force and volume of the molecules
3. The compressibility factor of a gas is defined as 10. Gas deviates from ideal gas nature because
Z  PV / RT . The compressibility factor of ideal molecules
gas is [CPMT 1996]
[Pb. CET 1986] (a) Are colourless
(a) 0 (b) Infinity (b) Attract each other
(c) 1 (d) –1
(c) Contain covalent bond
4. In Vander Waal's equation of state for a non-ideal
gas, the term that accounts for intermolecular (d) Show Brownian movement
forces is 11. The Vander Waal's equation reduces itself to the
[CBSE PMT 1990; IIT 1988] ideal gas equation at[Kerala MEE 2001; CBSE PMT 2002]
(a) (V  b) (b) (RT )1 (a) High pressure and low temperature
 a  (b) Low pressure and low temperature
(c)  P  2  (d) RT (c) Low pressure and high temperature
 V 
5. Vander Waal's equation of state is obeyed by real (d) High pressure and high temperature
gases. For n moles of a real gas, the expression 12. The compressibility factor for an ideal gas is[IIT 1997]
will be (a) 1.5 (b) 1.0
[IIT 1992; Pb. CET 1986; DPMT 1986] (c) 2.0 (d) 
 P na   V  13. When an ideal gas undergoes unrestrained
(a)   2     RT
 n V  n b  expansion, no cooling occurs because the
molecules [IIT 1984, 89]
(a) Are above the inversion temperature
 246 Gaseous state
(b) Exert no attractive force on each other 20. In van der Waal’s equation of state of the gas law,
(c) Do work equal to loss in kinetic energy the constant ‘ b ’ is a measure of [AIEEE 2004]
(d) Collide without loss of energy (a) Volume occupied by the molecules
14. A gas is said to behave like an ideal gas when the (b) Intermolecular attraction
relation PV / T  constant . When do you expect a
(c) Intermolecular repulsions
real gas to behave like an ideal gas
(d) Intermolecular collisions per unit volume
[IIT 1999; CBSE PMT 1990; CPMT 1991]
(a) When the temperature is low 21. In which molecule the vander Waal’s force is
likely to be the most important in determining the
(b) When both the temperature and pressure are
m.pt. and b.pt.
low
[DPMT 2000]
(c) When both the temperature and pressure are
high (a) H 2 S (b) Br2
(d) When the temperature is high and pressure is (c) HCl (d) CO
low
22. Pressure exerted by 1 mole of methane in a 0.25
15. A real gas most closely approaches the behaviour litre container at 300K using vander Waal's
of an ideal gas at [KCET 1992] equation (given
(a) 15 atm and 200 K (b) 1 atm and 273 K 1  2 . 253 atm l 2 mol 2 , b  0 . 0428 lit mol 1 ) is
(c) 0.5 atm and 500 K (d) 15 atm and 500 K [Orissa JEE 2005]
16. The temperature at which real gases obey the (a) 82.82 atm (b) 152.51 atm
ideal gas laws over a wide range of pressure is
(c) 190.52 atm (d) 70.52 atm
called
[AFMC 1993; IIT 1981, 94] Critical state and Liquefaction of gases
(a) Critical temperature
(b) Boyle temperature 1. Which set of conditions represents easiest way to
liquefy a gas [NCERT 1983]
(c) Inversion temperature
(a) Low temperature and high pressure
(d) Reduced temperature
(b) High temperature and low pressure
17. At low pressure, the Vander Waal's equation is (c) Low temperature and low pressure
reduced to
(d) High temperature and high pressure
pVm ap pVm b
(a) Z  1 (b) Z  1 p 2. Adiabatic demagnetisation is a technique used for
RT RT RT RT [BHU 1984]
pVm a (a) Adiabatic expansion of a gas
(c) pVm  RT (d) Z  1
RT RT (b) Production of low temperature
18. At high temperature and low pressure, the Vander (c) Production of high temperature
Waal's equation is reduced to (d) None
 a  3. An ideal gas can't be liquefied because[CBSE PMT 1992]
(a)  p  2  (Vm )  RT
 Vm  (a) Its critical temperature is always above 0 o C

(b) Its molecules are relatively smaller in size
(b) pVm  RT
(c) It solidifies before becoming a liquid
(c) p(Vm  b)  RT (d) Forces operative between its molecules are
 negligible
a 
(d)  p  2  (Vm  b)  RT 4. However great the pressure, a gas cannot be
 Vm 
 liquefied above its
19. When helium is allowed to expand into vacuum, (a) Boyle temperature
heating effect is observed. Its reason is that[CPMT 1987] (b) Inversion temperature
(a) Helium is an ideal gas (c) Critical temperature
(b) Helium is an inert gas (d) Room temperature
(c) The inversion temperature of helium is very 5. An ideal gas obeying kinetic theory of gases can
low be liquefied if [CBSE PMT 1995]
(a) Its temperature is more than critical
(d) The boiling point of helium is the lowest
temperature Tc
among the elements
(b) Its pressure is more than critical pressure Pc
 Gaseous State 247
(c) Its pressure is more than Pc at a temperature 1. As the temperature is raised from 20 o C to 40 o C
less than Tc the average kinetic energy of neon atoms changes
by a factor of which of the following [AIEEE 2004]
(d) It cannot be liquefied at any value of P and T
6. The Vander Waal's parameters for gases W, X, Y (a) 313/293 (b) (313 / 293 )
and Z are (c) 1/2 (d) 2
Gas a (atm L2 mol–2) b (L mol–1) 2. A gas is found to have a formula [CO]x . If its
W 4.0 0.027 vapour density is 70, the value of x is [DCE 2004]
X 8.0 0.030 (a) 2.5 (b) 3.0
Y 6.0 0.032
(c) 5.0 (d) 6.0
Z 12.0 0.027
3. Which of the given sets of temperature and
Which one of these gases has the highest critical
pressure will cause a gas to exhibit the greatest
temperature
deviation from ideal gas behavior [DCE 2003]
(a) W (b) X
(c) Y (d) Z (a) 100 o C and 4 atm (b) 100 o C and 2 atm
7. The Vander Waal's constant 'a' for the gases (c)  100 o C and 4 atm (d) 0 o C and 2 atm
O2 , N 2 , NH 3 and CH 4 are 1.3, 1.390, 4.170 and
4. The molecular weight of O 2 and SO 2 are 32 and
2.253 L2 atm mol 2 respectively. The gas which can
64 respectively. If one litre of O 2 at 15 o C and
be most easily liquefied is
[IIT 1989] 750 mm pressure contains 'N' molecules, the
(a) O 2 (b) N 2 number of molecules in two litres of SO 2 under
(c) NH 3 (d) CH 4 the same conditions of temperature and pressure
will be [CBSE 1990; MNR 1991]
8. A gas can be liquefied [AFMC 2005]
(a) Above its critical temperature (a) N / 2 (b) N
(b) At its critical temperature (c) 2N (d) 4N
(c) Below its critical temperature 5. What is the relationship between the average
(d) At any temperature velocity (v), root mean square velocity (u) and
9. Which of the following is correct for critical most probable velocity (a)
temperature [AFMC 1994]
(a) It is the highest temperature at which liquid
and vapour can coexist (a)  : v : u :: 1 : 1.128 : 1.224
(b) Beyond the critical temperature, there is no (b)  : v : u :: 1.128 : 1 : 1.224
distinction between the two phases and a gas (c)  : v : u :: 1.128 : 1.224 : 1
cannot be liquefied by compression
(c) At critical temperature (Tc ) the surface (d)  : v : u :: 1.124 : 1.228 : 1
tension of the system is zero 6. Consider the following statements : For diatomic
(d) At critical temperature the gas and the liquid gases, the ratio C p / Cv is equal to
phases have different critical densities (1) 1.40 (lower temperature)
10. A gas has a density of 2.68 g / L at stp. Identify
(2) 1.66 (moderate temperature)
the gas
(3) 1.29 (higher temperature)
(a) NO2 (b) Kr
which of the above statements are correct
(c) COS (d) SO 2
(a) 1, 2 and 3 (b) 1 and 2
11. Weight of 112 ml of oxygen at NTP on liquefaction
would be [DPMT 1984] (c) 2 and 3 (d) 1 and 3
(a) 0.32 g (b) 0.64 g 7. The compressibility factor for an ideal gas is[MP PET 2004
(c) 0.16 g (d) 0.96 g (a) 1.5 (b) 1.0
(c) 2.0 (d) 
8. The compressibility factor of a gas is less than 1
at STP. Its molar volume Vm will be [MP PET 2004]
(a) Vm  22.42 (b) Vm  22.42
(c) Vm  22.42 (d) None
9. If some moles of O 2 diffuse in 18 sec and same
moles of other gas diffuse in 45 sec then what is
the molecular weight of the unknown gas[CPMT 1988]
 248 Gaseous state
45 2 18 2 16. The volume of 1 g each of methane (CH 4 ) , ethane
(a)  32 (b)  32
18 2
45 2 (C2 H6 ) , propane (C3 H8 ) and butane (C4 H10 ) was
measured at 350 K and 1 atm. What is the
18 2 45 2 volume of butane [NCERT 1981]
(c) (d)
45 2  32 18 2  32
(a) 495 cm 3 (b) 600 cm 3
10. The ratio of rates of diffusion of SO 2 , O2 and CH 4
is (c) 900 cm 3 (d) 1700 cm 3
[BHU 1992] 17. The ratio of the rate of diffusion of helium and
methane under identical condition of pressure
(a) 1 : 2 : 2 (b) 1 : 2 : 4 and temperature will be [IIT 2005]
(c) 2 : 2 : 1 (d) 1 : 2 : 2 (a) 4 (b) 2
11. If C1, C2 , C3 ...... represent the speeds of n1, n2 , n3 ..... (c) 1 (d) 0.5
molecules, then the root mean square speed is[IIT 1993]
18. At what temperature in the celsius scale, V
 n1C12
1/2
 (volume) of a certain mass of gas at 27 o C will be
  n2 C 22  n3 C32
 ..... 
(a) doubled keeping the pressure constant[Orissa 1993]
 n1  n2  n3  ..... 
 
(a) 54 o C (b) 327 o C
(n C 2  n2C22  n3 C32  .....) 1 / 2
(b) 1 1 (c) 427 o C (d) 527 o C
n1  n2  n3  .....
19. Pressure of a mixture of 4 g of O 2 and 2 g of H 2
(n C 2 )1 / 2 (n2C22 )1 / 2 (n3 C32 )1 / 2
(c) 1 1    ...... confined in a bulb of 1 litre at 0 o C is [AIIMS 2000]
n1 n2 n3
(a) 25.215 atm (b) 31.205 atm
1/2
 (n C  n2 C 2  n3 C3  ....) 2  (c) 45.215 atm (d) 15.210 atm
(d)  1 1 
 (n1  n2  n3  ....)  20. If pressure becomes double at the same absolute
temperature on 2 L CO2 , then the volume of CO2
12. 50 ml of hydrogen diffuses out through a small
hole from a vessel in 20 minutes. The time needed becomes
for 40 ml of oxygen to diffuse out is[CBSE PMT 1994] [AIIMS 1992]
(a) 12 min (b) 64 min (a) 2 L (b) 4 L
(c) 8 min (d) 32 min (c) 25 L (d) 1 L
13. At what temperature will the average speed of 21. Volume of the air that will be expelled from a
CH 4 molecules have the same value as O 2 has at
vessel of 300 cm 3 when it is heated from 27 o C to
300 K
37 o C at the same pressure will be
[CBSE PMT 1989]
(a) 1200 K (b) 150 K (a) 310 cm 3 (b) 290 cm 3
(c) 600 K (d) 300 K (c) 10 cm 3 (d) 37 cm 3
14. A sample of O 2 gas is collected over water at
22. 300 ml of a gas at 27 o C is cooled to  3 o C at
23 o C at a barometric pressure of 751 mm Hg constant pressure, the final volume is
(vapour pressure of water at 23 o C is 21 mm Hg). [NCERT 1981, MP PMT 1992]
The partial pressure of O 2 gas in the sample
(a) 540 ml (b) 135 ml
collected is [CBSE PMT 1993]
(c) 270 ml (d) 350 ml
(a) 21 mm Hg (b) 751 mm Hg
(c) 0.96 atm (d) 1.02 atm
15. In an experiment during the analysis of a carbon
compound, 145 l of H 2 was collected at 760 mm
Hg pressure and 27 o C temperature. The mass of
H 2 is nearly
Read the assertion and reason carefully to mark the
[MNR 1987]
correct option out of the options given below :
(a) 10 g (b) 12 g
(a) If both assertion and reason are true and the
(c) 24 g (d) 6 g reason is the correct explanation of the assertion.
(b) If both assertion and reason are true but reason is
not the correct explanation of the assertion.
 Gaseous State 249
(c) If assertion is true but reason is false. 11. Assertion : Pressure exerted by gas in a
(d) If the assertion and reason both are false. container with increasing
(e) If assertion is false but reason is true. temperature of the gas.
Reason : With the rise in temperature, the
1. Assertion : Plot of P Vs. 1 / V (volume) is a average speed of gas molecules
straight line. increases.
Reason : Pressure is directly proportional to
[AIIMS 1995]
volume.
2. Assertion : Jet aeroplane flying at high altitude 12. Assertion : Gases do not settle to the bottom of
need pressurization of the cabin. container.
Reason : Oxygen is not present at higher Reason : Gases have high kinetic energy.
altitude. [AIIMS 1997]
3. Assertion : 1 mol of H 2 and O 2 each occupy
13. Assertion : A mixture of He and O 2 is used for
22.4 L of volume at 0 o C and 1 bar respiration for deep sea divers.
pressure.
Reason : Molar volume for all gases at the Reason : He is soluble in blood. [AIIMS 1998]
same temperautre and pressure has 14. Assertion : Wet air is heavier than dry air.
the same volume.
Reason : The density of dry air is more than
4. Assertion : Pressure exerted by a mixture of density of water. [AIIMS 1999]
reacting gases is equal to the sum
of their partial pressures. 15. Assertion : All molecules in a gas have some
speed.
Reason : Reacting gases react to form a new
gas having pressure equal to the Reason : Gas contains molecules of different
sum of both. size and shape. [AIIMS 2001]
5. Assertion : Greater the value of Vander Waal’s 16. Assertion : Effusion rate of oxygen is smaller
constant ' a' greater is the than nitrogen.
liquefaction of gas.
Reason : Molecular size of nitrogen is
Reason : ' a' indirectly measures the
smaller than oxygen. [AIIMS 2004]
magnitude of attractive forces
between the molecules.
6. Assertion : Carbondioxide has greater value of
root mean square velocity  rms than
carbon monoxide.
Reason :  rms is directly proportional to
molar mass.
7. Assertion : 4.58 mm and 0 .0098 o C is known to Characteristics and Measurable properties of gases
be triple point of water.
Reason : At this pressure and temperature all
the three states i.e., water, ice and 1 c 2 c 3 b 4 a 5 c
vapour exist simultaneously. 6 d 7 a 8 b 9 c 10 a
8. Assertion : 1/4th of the gas is expelled if air 11 a 12 b 13 a 14 d 15 c
present in an open vessel is heated
16 e
from 27 o C to 127 o C .
Reason : Rate of diffusion of a gas is
inversely proportional to the square Ideal gas equation and Related gas laws
root of its molecular mass.
9. Assertion : Compressibility factor for hydrogen 1 c 2 d 3 a 4 a 5 a
varies with pressure with positive
6 bc 7 a 8 a 9 c 10 d
slope at all pressures.
Reason : Even at low pressures, repulsive 11 a 12 a 13 a 14 a 15 c
forces dominate hydrogen gas.[AIIMS 2005]
16 c 17 b 18 c 19 a 20 b
10. Assertion : vander Waal’s equation is 21 c 22 c 23 d 24 a 25 c
applicable only to non-ideal gases.
26 c 27 b 28 c 29 c 30 c
Reason : Ideal gases obey the equation
PV  nRT . 31 a 32 a 33 b 34 b 35 b
 250 Gaseous state
36 c 37 d 38 c 39 c 40 a 21 b 22 a

41 b 42 c 43 c 44 d 45 a
46 a 47 b 48 d 49 b 50 c

51 d 52 a 53 a 54 c 55 a
56 a 57 b 58 a 59 b 60 a
61 b 62 d 63 c 64 b 65 d

66 b 67 d 68 a 69 a 70 b

71 c 72 a 73 d 74 c 75 a

76 c 77 d 78 b 79 b 80 b

81 d 82 d 83 c 84 c 85 a

86 d 87 a 88 a 89 c 90 c

91 a 92 c 93 a 94 b 95 a

96 a 97 d 98 b 99 e 100 a

101 c 102 c 103 c 104 c 105 a

106 a

Kinetic molecular theory of gases and

Molecular collisions

1 d 2 c 3 d 4 d 5 b

6 a 7 a 8 c 9 b 10 b

11 a 12 d 13 a 14 a 15 acd

16 a 17 b 18 d 19 b 20 d

21 a 22 d 23 c 24 b 25 b

26 a 27 d 28 a 29 d 30 c
31 c

Molecular speeds

1 a 2 c 3 d 4 d 5 d

6 c 7 b 8 b 9 d 10 b

11 d 12 c 13 a 14 d 15 d

16 c 17 d 18 d 19 b 20 b

21 c 22 a 23 c 24 b 25 c

26 a 27 d

Real gases and Vander waal’s equation

1 b 2 b 3 c 4 c 5 d
6 c 7 d 8 b 9 d 10 b
11 c 12 b 13 b 14 d 15 c
16 b 17 a 18 b 19 c 20 a
 Gaseous State 249
14. (d) The mass of gas can be determined by
Critical state and Liquefaction of gases weighing the container, filled with gas and
again weighing this container after removing
1 a 2 b 3 d 4 c 5 d the gas. The difference between the two
weights gives the mass of the gas.
6 d 7 c 8 c 9 abc 10 c
15. (c) Nobel gases has no intermolecular forces due to
11 c inertness.
16. (e) Total volume of two flasks = 1+ 3 = 4
Critical Thinking Questions If P1 the pressure of gas N 2 in the mixture of
N 2 and O 2 then
1 a 2 c 3 c 4 c 5 a P = 100 kPa , P1  ? , V = 1 litre ,
6 d 7 b 8 b 9 a 10 a V1  4 litre
11 a 12 b 13 b 14 c 15 b applying Boyle's law PV  P1V1
100  1 = P1  4 ; P1  25
16 a 17 b 18 b 19 a 20 d
If P2 is the pressure of O 2 gas in the mixture
21 c 22 c
of O 2 and N 2 then, 320  3 = P2  4 ; P2  240
Assertion & Reason Hence, Total pressure P  P1  P2  25  240
 265 kPa
1 c 2 c 3 a 4 d 5 a
6 d 7 a 8 b 9 a 10 b
Ideal gas equation and Related gas laws
11 a 12 a 13 c 14 e 15 d 1
1. (c) Boyle's law is V  at constant T
16 c P
1
2. (d) According to Boyle's law V 
P
Constant
V ; VP = Constant.
P
3. (a) At sea level, because of compression by air
above the proximal layer of air, pressure
increases hence volume decreases i.e. density
Characteristics and Measurable properties of gases increases. It is Boyle’s law.
4. (a) At constant T, P1V1  P2V2
1. (c) Gases do not have definite shape and volume. 20
Their volume is equal to the volume of the 1  20  P2  50 ; P2 
1
50
container.
5. (a) P.V = constant at constant temperature. As
2. (c) All the three phases of water can coexist at
temperature changes, the value of constant
0 o C & 4.7 mm pressure. also changes.
3. (b) It is characteristic of gases i.e. Thermal 6. (b,c)According to Boyle's Law PV = constant, at
energy >> molecular attraction constant temperature either P increases or V
4. (a) In gases, molecular attraction is very less and increases both (b) & (c) may be correct.
intermolecular spaces are large hence kinetic d 1 T 2 P V T T .d
energy of gases is highest. 7. (a) 1  , 1   1  2  1  1 1
d 2 2 T2 1 P2 V1 T2 T2 .d 2
5. (c) Gases and liquids, both can flow and posses
P1 2 1 1
viscosity.  . 
7. (a) Newton is unit of force. P2 1 2 1
C o F o  32 8. (a) Absolute temperature is temperature
8. (b)  o
5 9 measured in Kelvin , expressed by T
9. (c) 1 L  10 3 m 3  10 3 cm 3  1dm 3  10 3 ml . 11. (a) T1  273 o C  273  273 o K  546 o K
10. (a) 1 atm = 10 6 dynes cm-2 T2  0 o C  273  0 o C  273 o K
12. (b) Barometer is used to measure atmospheric P1  1 ; P2  ?
pressure of mixture of gases. Staglometer is
According to Gay-Lussac’s law
used to measure surface tension. Only
P1 P2 PT 1  273 o K 1
manometer is used to measure pressure of   P2  1 2  o
atm; atm.
pure gas in a vessel. T1 T2 T1 546 K 2
13. (a) 0 o C is equivalent to 273 o K i.e. conditions are 12. (a) Vt  Vo (1   v t)
same so volume will be V ml.  (V2  V1 )  V  Vo(t 2  t1 )
 250 Gaseous State
if t 2  t1  1o then V  Vo nRT 2  0.0821  546
31. (a) P    2 atm.
o
For every 1 C increase in temperature, the V 44 .8 l
volume of a given mass of an ideal gas P1 V1 P2 V2 PVT
32. (a)   n2  2 2 1 n1
1 n1 T1 n2 T2 P1 V1 T2
increases by a definite fraction of Vo .
273 .15 at STP n1  one mole. at T  273 o  30 o  303 o K
Here Vo is volume at 0 o C temperature. P1 = 1 atm. P2  1 atm
V T T 546 o K V1 = 22.4 lt V2  22 .4
13. (a) 1  1  V2  2 V1   0.2 L  0.4 L.
V2 T2 T1 273 o K T1 = 273oK
270 o K 1 22 .4 273
14. (a) V2 
T2
.V1  . 400 cm 3  360 cm 3 n2     1  0 .9 moles
T1 300 o K 1 22 .4 303
nRT 0.5  0.082  273 o K
contraction  V1  V2  400  360  40 cm 3 33. (b) V    11 .2lit
P 1
15. (c) At constant volumes P  T
P1 V1T2
P = constant T; PV = nRT  P 
nR
T 34. (b) V2   P1  P ; T1  273 o K
V P2 T1
nR 3 T 4
slope = m   V2  V1 P2 P ; T2  T1  1   273 o K
V 2 3 3
m1 V2 2 P 4 273 800
  m1  m 2 is curve for V2 has a greater V2     100 cc  cc  88 .888 cc
m 2 V1 3 P 3 273 9
slope than for V1 = 88.9 cc
PV PV PV T
16.
P P
(c) 1  1 
P

P 35. (b) 1 1  2 2  1 1  1
T1 T1 T1 T2 T1 T P2 V2 T2
36. (c) da  2db ; 2 Ma  Mb
2 P1  T  T2  2 P1 (T1 T2 ) 2 P1 T2
 P  1  ; P 
  m m RT dRT
T1  T1T2  T1 (T1  T2 ) T1  T2 PV  nRT  RT ; P  . 
M V M M
18. (c) At constant V of a definite mass
Pa d a M b 2d b 2 M a
P1 P2 P1 300 1    4
    i.e. pressure increases Pb d b M a db Ma
T1 T2 P2 600 2
16 1
and on increasing temperature energy of 37. (d) n of O2  
32 2
molecules increases so the rate of collisions
3
also increases and number of moles remains n of H 2 
constant because there is neither addition nor 2
removal of gas in the occurring. 3 1
Total no. of moles =  2
19. (a) Avogadro number = 6.0224  1023 2 2
PV nRT 2  .082  273
20. (b) Compressibility =  1 at STP (as given) V   44 .8 lit = 44800 ml
nRT P 1
nRT  PV R = 0.821 PV m
38. (c) n  
N  0.0821  273  1Vm T = 273oK RT M
22 .41 litres Vm P=1 MPV 34  2  100
m   282 .4 gm
n=1 RT 0 .082  293
21. (c) The value of universal gas constant can be PV T 760 546
39. (c) V2  1 1 1    273  691 .6 ml .
expressed in different units and its value T1 P2 600 273
would depend only on the units of the
P1V1 P2 V2 P V m
measurement. 40. (a)   T2  2 2 T1 1
n1T1 n2 T2 P1 V1 m2
22. (c) PV = nRT
PV 0 .75 1 2
R  litre . atm. K–1 mole–1     300 o K  450 o K
nT 1 1 1
23. (d) (atm. K-1 mol–1) is not a unit of R P1 T2 1 250
41. (b) V2  .V1    12000 lit.  20000 lit.
24. (a) 8.31 J.K-1 mol–1 P2 T1 0.5 300
1 cal = 4.2 J. 42. (c) At constant pressure
8 .31
 cal.K 1mol 1 = 1.987 cal K–1 mol–1 V  nT 
m
T
4 .2 M
n P 300 o K 0 . 75 d
30. (c) PV = nRT   V1 m1 T1 T V m d
V RT   1  1  2  2  
V2 m 2 T2 T2 m1 V2 d1 T2 d
 Gaseous State 251
300 2
d a  rb 
2
T2   400 o K 1 1
0 .75 60. (a) ra  5rb ;     
d b  ra  5 25
PV PV PV 740 80
43. (c) 1 1  2 2  T2  2 2  T1    300
T1 T2 P1 V1 740 100 d1 1 r d2 4
61. (b)  ; 1   16 
 240 K  33 C
o o d 2 16 r2 d1 1
47. (b) Because H 2 & Cl2 gases may react with each 1 1
D B  B  2  B  2
other to produce HCl gas hence Dalton's law 62. (d) A    ;  D A  DB  

is not applicable. DB A  A   A 
48. (d) Because HCl & NH 3 gases may react to 63. (c) Gases may be separated by this process because
produce NH4 Cl gas. Dalton's Law is of different rates of diffusion due to difference
applicable for non reacting gas mixtures. in their densities.
49. (b) NH 3 and HCl & HBr is a reacting gas mixture 64. (b) NH4 Cl ring will first formed near the HCl
to produce NH4 Cl & NH4 Br so Dalton's law is bottle because rate of diffusion of NH 3 is more
not applicable. than that of HCl because
m M NH 3 : M HCl  17 : 36 .5) . SO NH 3 will reach first
50. (c) No. of moles of lighter gas 
4 to the HCl bottle & will react there with HCl to
m form NH4 Cl ring
No. of moles of heavier gas 
40 65. (d) Because both NO and C2 H6 have same
m m 11 m
Total no. of moles    
molecular weights M NO  M C 2 H 6  30 and rate 
4 40 40 of diffusion  molecular weight.
m 2
10 M A  rB r 1 1 1
Mole fraction of lighter gas  4  67. (d)    rA  2rB  B     .25
11 m 11 M B  rA

 rA 2 (2)2 4
40 2gm xgm
10 68. (a) rH  if rO 
Partial pressure due to lighter gas  Po  10 min 10 min
11
M H2 2 2
10
 1 .1 
 1atm. rO  rH 
11 M O2 10 32
52. (a) m. wt. of NH 3  17 ; m.wt. of N 2  28 x 2 1
  gm.  .5 gm
m.wt. of CO2  44 ; m.wt. of O2  32 10 10  4 2
beacuse NH 3 is lightest gas out of these gases 69. (a) rCH 4  2rg
2
   rCH 
r 
1
 M g  M CH 4  4   16  2 2  64
 rg 
 Molecular Weight   
1 Volume effused V
rg M He r 2 He 4 4 70. (b) r  r 
55. (a)   M g  M He . 2   2 M time taken t
rHe Mg r g (1 .4 )2 1 .96

Note : 1.4  2 
V 1
 for same volumes (V constant)
t M
1
56. (a) rg  .rH t1 M1
5 2 t M 
t2 M2
2
Mg  rH 
 2   (5)  25 ; M g  2  25  50
2
M He 4
M H2  rg  t He  t H 2 5  5 2 s.
M H2 2
2
1  rH 
57. (b) rg  rH 2 ; M g  M H 2 . 2   2  6  2  36  72
2 32
tO 2  t  5  20 s
6  rg  2
58. (a) M1  64 ; r2  2r1 28 44
2
tCO  5  5 14 s ; tCO 2  5  5 22 s
r  1 2 2
M 2  M 1  1   64   16
 
r2 4 rN 2 Vrms N 2 TN 2 M So 2 TN 2 64
71. (c)   .  
dH 0 09 1 1
rSO 2 Vrms SO 2 TSO 2 M N2 323 28
59. (b) rO  rH 1  
dO 1 . 44 16 4 TN 2 16
1 .625  .
323 7
 252 Gaseous State
(1.625 )2  323  7 84. (c) H 2 will be filled first because of lower
TN 2   373 o K
16 molecular weight
72. (a) C  H 2O  COg   H 2 g  85. (a) Mixture of SO 2 and Cl2 are reacted chemically
12 gm  1mol  1mol and forms SO 2Cl2 . That is why mixture of
12 gm C produces 2mole of gases (1mole CO & 1 these gases is not applicable for Dalton's law.
mole of H2) 86. (d) According to Boyle's law
48 P1V1  P2 V2  P1  60  720  100
48 gm C may produce  2  4  2  8 mole
12 720  100
P1   1200 mm
 22 . 4  8 L gases  179 .2 L gas. 60
mRT 4.4  .082  273 1
73. (d) Molecular weight =  87. (a) Rate of diffusion 
PV 1  2.24 Molecular Mass
= 44 that is why H 2 gas diffuse first
So the gas should be CO2
88. (a) Solution level will rise, due to absorption of
74. (c) PV  nRT CO2 by sodium hydroxide.
n n
P  RT   C  P  CRT 2 NaOH  CO2  Na2 CO3  H 2 O
V V
89. (c) CaCo3 ˆ CaO  CO2 

P 1
T   12 o K (40 12 16 3 ) 100 gm 22 .4 litre
CR 1  .821
 At S.T.P. 100 g CaCO3 produce= 22 .4 litre of
75. (a) 6 .02  10 22 molecules of each N 2 , O2 and H 2
CO2
6.02  10 22 
 moles of each At S.T.P. 1g CaCO3 produce =
6 .02  10 23
22 .4
Weight of mixture = weight of 0.1 mole N 2   .224 litre of CO2
100
weight of 0.1 mole H 2 + weight of 0.1 mole of
Molecularwt. Of Metal
O2 90. (c) The density of gas 
Volume
 (28  0.1)  (2  0.1)  (32  0 .1)  6.2 gm 45

76. (c) M.wt of CO2 = 12+16+16 = 44 22 .4
Volume of 44 gm of CO2 at NTP = 22.4 litre = 2 gmlitre1
22 . 4
1 gm of CO2 at NTP = 91. (a) M1  32 g for O 2 , M 2  2 g for H 2
44
4.4 gm of CO2 at N.T.P r1 M2 r1 2 1 1
 ;   
22 .4 r2 M1 r2 32 16 4
  4 .4 litre  2 . 24 litre
44 92. (c) In 22 . 4 l of H 2 maximum number of molecules
78. (b) No. of moles of CO2 present in 200 ml solution
 6 .023  10 23
200 In 1l of H 2 maximum number of molecules
= molarity  Volume (in lt.)  0 .1   .02
1000
6.023  10 23
Volume of 0.02 mole of 
22 .4
CO2  22 .4  .02 lt.  0 . 448 lit.
In 15 l of H 2 maximum number of molecules
79. (b) Molecular weight = V.d.  2 = 11.2  2 = 22.4
Volume of 22.4 gm Substance of NTP = 22.4 6 .023  10 23
  15  4 .03  10 23 molecules.
litre 22 .4
22 .4 93. (a) 22 .4 l O2 at S.T.P.  32 gm of O 2
1 gm substance at NTP = litre
22 .4 32
1l O 2 at S.T.P.   1 .43 gm of O 2
11.2 gm substance of NTP = 11.2 litre 22 .4
M . wt. of O2 M 32 1 95 (a) We know that molecular mass of hydrogen
80. (b)  1  
M . wt. of SO 2 M2 64 2 M1  2 and that of helium M 2  4 , we also
1 know that Graham's law of diffusion
The weight of oxygen will be that of SO 2
2 r1 M2 4
   2  1 . 4 ; r1  1.4 m
81. (b) For HI has the least volume because of r2 M1 2
1
greater molecular weight V  rA MH r 2
M 96. (a)   
83. (c) Since no. of molecules is halved so pressure rH MA 6r MA
should also be halved.
 Gaseous State 253
M A  6  6  2  72 g P
P2 , V2  ?, T2  T
97. (d) Given that: 2
V1  100 ml , P1  720 mm , V2  84 ml , P2  ? According to gas equation
P1 V1 P2 V2 PV PV2
By using P1V1  P2 V2 [According to the Boyle's  or 
T1 T2 T 2T
law]
 V2  4 V
P1V1 720  100
P2    857 .142 105. (a) P1  P, V1  V, T1  273  75  348 K
V2 84
85
Hence, P2  857 .14 mm P2  2 P, V2  , T2  ?
100
98. (b) According to gas law
P  V 2 P  85 V 348  2  85
PV   T2 
PV  nRT , n  398 T2  100 100
RT
 T2  591 .6 K  318 .6 o C
P1 V1
nA RT1 n PV T 106. (a) Boyle's law  PV = constant
 ; A  1 1 2 On differentiating the equation,
nB P V
2 2 nB T1 P2 V2
d (PV )  d (C)  PdV  VdP  0
RT2
dP dV
n A 2 P  2V T n 2  VdP   PdV   .
  ; A  P V
nB 2T PV nB 1
99. (e) No. of molecules  2  V.d Kinetic molecular theory of gases
2  38 .3  76 .3 and Molecular collisions
wt. of NO2  x
So that wt. of N 2O4  100  x 3
4. (d) Kinetic energy  RT
2
x 100  x 100 2 x  100  x 100
Hence,     3
46 92 76 .6 92 76 .6 5. (b) K.E = RT it means that K.E depends upon T
2
20 .10
x = 20.10, no. of mole. of NO 2   0 .437 (absolute temperature) only.
46
3 3
100. (a) Given that 7. (a) KE  RT  PV
P1  76 cm of Hg (Initial pressure at N.T.P.) 2 2
2 E 2
P2  ? , V1  5litre , V2  30  5  35 litres P  for unit volume (V = 1)  P  E
3 V 3
According to Boyle's law
P1V1  P2 V2 ; 76  5  P2  35 3 RT
8. (c) Tr. K. E.  it means that the Translational
2
76  5
P2   P2  10 .8 cm of Hg Kinetic energy of Ideal gas depends upon
35
temperature only.
101. (c) Given initial volume V1   300 cc , initial
E He THe
temperature T1   27 o
C  300 K , initial 9. (b)  so energies will be same for
EH2 TH 2
pressure P1   620 mm , final temperature
He & H 2 at same temperature.
T2  47 C  320 K and
o
final pressure
P2   640 mm .We know from the general gas 11. (a) K. E. 
3 3
.RT  .2 .T  R  2 calK 1 mol 1
2 2
equation
P1 V1 P2 V2 620  300 640  V2 K . E.  3 T
    V2  310 cc
T1 T2 300 320 12. (d) All molecules of an ideal gas show random
motion. They collide with each other and walls
102. (c) NH3  HCl  NH4 Cl
of container during which they lose or gain
4 litre 1.5litre energy so they may not have same kinetic
HCl is a limiting compound. That's why energy always.
1 . 5 litre of HCl reacts with 1 . 5 litre of NH 3 and 13. (a) For same temperature kinetic energies of
forms NH4 Cl . Thus (4 - 1.5) 2 .5 litre NH 3 H 2 & He molecules will be same because
remains after the reaction. kinetic energy depends only on temperature.
PV PV P  4 2 P1  V2 14. (a) For same temp. kinetic energies would be
103. (c) 1 1  2 2 ; 1 
T1 T2 T1 2T1 equal for all molecules, what ever their
8  2  V2 so V2  4 dm 3 molecular weights will be, it doesn't matter.
104. (c) P1  P, V1  V, T1  T
 254 Gaseous State
15. (a,c,d)Kinetic energies per molecule will be same  Actual volume of H 2O molecules in 6 gm
because it is proportional to absolute steam
temperature only. = mass of steam/density of water
dN2 M N2 28 = 0.6 gm /1 gm/cm3  0 .6 cm 3
  i.e. dN 2  dCO2
d CO 2 M CO 2 44 CP 5
24. (b) r    1 .66 (For Monoatomic as
Total translational kinetic energy will also be CV 3
same because at same temperature & pressure He , Ne , Ar )
number of molecules present in same volume
25. (b) The density of neon will be highest at 0 o C 2
would be same (according to Avogadro's Law)
P
16. (a) On increasing pressure, the volume decreases atm according to d 
T
and density increases. So molecules get closer
3
to each other hence mean free path also 29. (d) K.E. per mole  RT
decreases. 2
so all will have same K.E. at same
17. (b) Most probable velocity increase and fraction
temperature.
of molecule possessing most probable velocity
30. (c)  W  P.dV  E
decrease.
 Energy per unit volume = P
m
18. (d) PV  nRT  RT 31.
d
(c) d  M  1  1 ;
M 3d

M
; M2 
M
.
M d2 M 2 d M2 3
m PM
   density
V RT Molecular speeds
P P
19. (b) d  the value of is maximum for (b)
T T 3 RT 8 RT V 3
1. (a) Vrms  , Vav  ; rms 
20. (d) If inversion temperature is 80 C  193 K then
o o M M Vav 8
the temperature, at which it will produce
66 1 . 086
cooling under Joule Thomson’s effect, would  
be below inversion temperature except 56 1
173 o K all other values given as 3. (d) most probable velocity : mean velocity : Vrms
CP 2 RT 8 RT 3 RT 8
21. (a) Since  1 .4 , the gas should be diatomic.  : :  2: : 3
CV M M M 
1 3 RT 1
If volume is 11.2 lt then, no. of moles = 4. (d) Vrms   Vrms  at same T
2 M M
1
 no. of molecules =  Avagadro’s No. because H 2 has least molecular weight so its
2
r.m.s. velocity should be maximum.
no. of atoms = 2  no. of molecules
U SO 2 1 M He TSO 2 4 TSO 2
2
1
 Avagadro’s No. 5. (d)    .
2 U He 2 M SO 2 THe 64 300

 6 .0223  10 23 4 TSO 2 1
  ; TSO 2  1200 o K
M 64 300 4
22. (d) Density =
V UO 3 M O2 32 2
v.d  2 6. (c)   
d M  V .d  2  UO 2 M O3 48 3
V
dV 7. (b) Average kinetic energy per molecule
V .d 
2 3 3
 KT   1 .38  10  23  300 J = 6.17  10 21 J
0 .00130  22400 2 2
V .d   14 .56 gm 1
2 U SO 2 M O 2 TSO 2 32  TSO 2
23. (c) Volume of steam = 1lt = 10 3 cm 3 8. (b)   1
UO2 M SO 2 TO 2 64  303
 m  d .V
mass of 10 3 cm 3 steam = density  Volume 32  TSO 2
1  TSO 2  606
0.0006 gm 64 303
=  10 3 cm 3  0.6 gm
cm 3 9. (d) Among these Cl2 has the highest molecular
Actual volume occupied by H 2O molecules is weight so it will posses lowest root mean
equal to volume of water of same mass square velocity.
 Gaseous State 255
2 3  300
U1 T1 T1  5  10 4 
 1  M 1 gm  0 .001 kg .
10. (b)    30  30
U2 T2 T2  10  10 4 
 4
1
12. (c) Vrms 
3 KT
i.e. Vrms 
1 
 (m ) 2 Real gases and Vander waal’s equation
Molecular weight m
13. (a) When average speed of molecule is increased 2. (b) Because molecules of real gases have
due to increase in temperature then the intermolecular forces of attraction so the
change in momentum during collision effective impact on the wall of container is
between wall of container and molecules of diminished. Pressure of real gas is reduced by
gas also increases. a
factor hence behaviour of real gas deviate
v2
U1 m 2 T1
14. (d)  .  T1  T2 from ideal behaviour.
U2 m1 T2
PV
2
3. (c) Z   for ideal gas PV = RT so Z = 1
U1 m RT
 2  m1U1  m 2U2
2 2

U2
2
m1 PV
12. (b) Z  ; for ideal gas PV = RT; so Z = 1
RT
T2 1200 13. (b) Ideal gas has no attractive force between the
15. (d) U 2  U1  U1  U1  2
T1 300 particles
r.m.s. velocity will be doubled. 14. (d) PV = nRT is a ideal gas equation it is allowed
when the temperature is high and pressure is
UH 2 TH 2 M O2 50 32 low.
16. (c)  .  . 1
UO 2 MH2 TH 2 2 800 16. (b) At Boyle temperature real gas is changed into
ideal gas
3 RT 3 PV 3P 1 17. (a) When pressure is low
17. (d) U    U 
M M d d  a 
 P  2  V  b   RT
U1 n1T1 nT 1 1  V 
19. (b)    
U2 n2 T2 2n  2 T 4 2 a ab
or PV  RT  Pb   2 or
PV
1
a
V V RT VRT
U2  2U1  2U
a  PV 
2 RT Z   Z
VRT  RT 
Vmp
 M   18. (b) At high temperature and low pressure, Vander
21. (c)
Vav 8 RT 2 Waal’s equation is reduced to ideal gas
M equation.
3 RT PV = nRT
22. (a) Vrms   Vrms  T PV = RT (For 1 mole of gas)
M
20. (a) Vander waal's constant for volume correction
Given V1  V , T1  300 K , V2  2V , T2  ? b is the measure of the effective volume
2
V1 T1  V  300 occupied by the gas molecule.
 ;     T2  300  4  1200 K
V2 T2  2V  T2  n 2a 
22. (a)  P  2  (V  nb )  nRT
 n 2a   V 
24. (b)  P  2 V  nb   nRT
 2 .253 
 V  P   (0 .25  0 .0428 )  0 .0821  300
 0 .25  0 .25 
 
 P  (2)  4 . 17
2
5  2  . 03711   2  .0821  300 or (P  36 .048 )(0 .2072 )  24 .63
 (5 )2 
   P  36 .048  118 .87  P  82 .82 atm.
2  .0821  300 4.7  2 2
P   10  0.66  9 .33 atm
5  2  .03711 52 Critical state and Liquefaction of gases
26. (a) Average speed : most probable speed
2. (b) A diabatic demagnetisation is a technique of
8 RT 2 RT 8
:  : 2  1.128 : 1. liquefaction of gases in which temperature is
M M 
reduced.
3 RT 3. (d) An ideal gas can’t be liquefied because
27. (d) v rms 
M molecules of ideal gas have not force of
attraction between them.
3 RT 3 R  300
30 2 R   30  30 R  4. (c) At above critical temperature, substances are
M M existing in gaseous state, since gas cannot be
liquefied above it.
 256 Gaseous State
5. (d) Absence of inter molecular attraction ideal gas PV
Z  1 (For ideal gas)
cannot be liquefied at any volume of P and T. nRT
6. (d) For Z gas of given gases, critical temperature 8. (b) If Z  1 then molar volume is less than 22.4 L
is highest x x
8a 8  12 9. (a) rO 2  mole / sec  rg  mol / sec
Tc   Tc   1603 .98 K 18 45
27 Rb 27  .0821  .027 2
 rO  2
  32  x  45   32  45
2
7. (c) Value of constant a is greater than other for M g  MO 2  2
NH 3 that’s why NH 3 can be most easily  rg   18 x  18 2
 
liquefied. 1 1 1
10. (a) rSO 2 : rO2 : rCH 4  : :
8. (c) The temperature below which the gas can be M SO 2 O2 CH 4
liquefied by the application of pressure alone
is called critical temperature. 1 1
 
M 64 : 32 : 16 4 : 2 :1
10. (c) d   M  d V
V 1 1 1 2 2 2
M  2 .68  22 .4 at N.T.P.  V  22 .41 
: : ; : : ; 1: 2 :2
2 2 1 2 2 1
M  60 .03 gm 11. (a) Root mean square
m. wt of COS  12  16  32  60  n1c12
1/2
 n2 c 22  .... 
 n3 c32
11. (c) 22400 ml is the volume of O 2 at N.T.P =32gm speed    .
 n1  n2  n3  ...... 
of O 2
12. (b) If 40 ml O 2 will diffuse in t min. then.
32
1ml is the volume of O 2 at NTP = 40
22400 rO2 
112 ml is the volume of O 2 at NTP = t

32 50 M H2 50 2 50 1
 112 rH   rO  rH 2   .
22400 20 M O2 20 32 20 4
 0.16 gm of O 2 40 50 40  80
 t   60 min.
t 80 50
Critical Thinking Questions
Vav CH 4 TCH 4 M O2
1. (a) Average kinetic energy  (T Kelvin) 13. (b)  . 1
Vab O2 TO 2 M CH 4
K. E2 T2 40  273 313
(Factor)    TCH 432
K. E1 T1 20  273 293 .  1 ; TCH 4  150 o K
300 16
2. (c) M. wt. = V.d.  2
m .wt . 40 14. (c) Pressure of O 2 (dry) = 751-21 = 730 mm Hg
= 70  2 = 140  x   5
wt .of [CO ] 12  16  730
  0 .96 atm
3. (c) Gas deviate from ideal gas behaviour to real 760
gas (according to Vander Waal's at low PV 1  145
15. (b) PV  nRT , n    5 .8  6 mole .
temperature and high pressure) RT 0 .082  3
4. (c) At same temperature and pressure, equal nRT m RT 1 0 . 82  350
16. (a) V   .    0 . 495 lit.
volumes have equal number of molecules. If P M P 58 1
1lit. of oxygen consists N molecules then at = 495 cm3
same temperature and pressure 1 lit of SO 2 M CH 4
rHe 16
will consists N molecules. So 2 lit. of SO 2 will 17. (b)  = 2
rCH 4 M He 4
contain 2 N molecules.
V1 T1 TV 2V
5. (a) Vav : Vrms : Vmost probable = 18. (b)   T2  1 2  300 o K,  600 o K
V2 T2 V1 V
V : U :
T2  600 o K  (600  273 )o C  327 o C
8 RT 3 RT 2 RT
: : 4
M M M 19. (a) no. of moles of O2   0 .125
32
8
 :V :U  2 : : 3  1 : 1 . 128 : 1 . 224 2
 no. of moles of H 2  1
2
Cp
6. (d) ratio for diatomic gases is 1.40 at lower total no. of moles = 1  0 . 125  1 .125
Cv
nRT 1 .125  0 .082  273
temperature & 1.29 at higher temperature so P   25 .184 atm.
V 1
the answer is 'd'.
7. (b) PV  nRT (For ideal gas) P1  V P 2
20. (d)  , 1  2 
P2 2 V2 P1 1
 Gaseous State 257
2L 2 11. (a) When the temperature increase, the average
 ; V2  1L
V2 1 speed of gas molecules increases and by this
increase the pressure of gas is also increases.
V2 T2
21. (c)  12. (a) It is correct that gases do not settle to the
V1 T1 bottom of container and the reason for this is
T2 310 o K that due to higher kinetic energy of gaseous
 V2  V1   300 cm 3  310 cm 3 molecules they diffuse.
T1 300 o K
13. (c) The assertion, that a mixture of helium and
T 270 o K oxygen is used for deep sea divers, is correct.
22. (c) V2  2 .V1   300 ml  270 ml
T1 300 o K The He is not soluble in blood. Therefore, this
mixture is used.
Assertion & Reason 14. (e) Dry air is heavier than wet air because the
density of dry air is more than water.
1. (c) Pressure is inversly proportional to volume 15. (d) All molecule of a gas have different speed.
1 Therefore, they move by its own speed.
(Boyle’s law). p  (n, T constant). 16. (c) Assertion is true but reason is false because of
V
1
2. (c) The air pressure decreases with increase in effusion rate  (Molecular weight) but it
altitude. So the partial pressure of Oxygen is M
not sufficient for breathing at higher altitude does not depend on molecular size.
and thus pressurization is needed.
3. (a) At a given temperature and pressure the
volume of a gas is directly proportional to the
amount of gas Vn (P and T constant).
4. (d) According to Dalton’s law of partial pressure,
the pressure exerted by a mixture of non –
interacting gases is equal to the sum of their
partial pressures (pressure exerted by
individual gases in mixture)
PTotal  P1  P2  P3 … (T and V constant). Both
the gases if non-interacting would spread
uniformly to occupy the whole volume of the
vessel.
5. (a) Considering the attractive force pressure in
ideal gas equation (PV = nRT) is correct by
an 2
introducing a factor of where a is a
V2
vander waal’s constant.
3 RT
6. (d) rms  is inversly related to molecular
M
mass. Therefore, rms(CO)  rms(CO2 ).
V1 V2 V1
8. (b)  (Initial fraction 1 when
T1 T2 V2
temperature is 27 o C . At 127 o C the new
V1 300 3
fraction is    air expelled
V2 400 4
3 1
1  
4 4
9. (a) In case of H2, compressibility factor increases
with the pressure. At 273 K, Z > 1 which
shows that it is difficult to compress the gas
as compared to ideal gas. In this case
repulsive forces dominate.
10. (b) In real gases, the intermolecular forces of
attraction and the volume occupied by the gas
molecules cannot be neglected.
 Gaseous State 257

1. Same mass of CH 4 and H 2 is taken in container. (a) 1.21 / 1 (b) 1.46 / 1

The partial pressure caused by H 2 is[IIT 1989; CPMT 1996] (c) 1.14 / 1 (d) 4 / 1
7. Which of the following volume (V) – temperature
(a) 8 / 9 (b) 1 / 9
(T) plots represents the behaviour of one mole of
(c) 1 / 2 (d) 1 an ideal gas at one atmospheric pressure[IIT Screening 200

2. The following graph illustrates [JIPMER 2000]

V(L) V(L)
(36.8 (28.6
(22.4 L (22.4 L
L 373 K) L 373 K)
V 273 K) 273 K)
(a) (b)

T(K) T(K)
Temp.
(oC) V(L) V(L)
(30.6
(a) Dalton's law (b) Charle's law (22.4 L (22.4
L 373 K) L
(c) Boyle's law (d) Gay-Lussac's law 273 K) 273 K) (14.2 L
373 K)
3. If the pressure and absolute temperature of 2 (c) (d)
litres of CO2 are doubled, the volume of CO2 T(K) T(K)
8. If the average velocity of N 2 molecule is 0.3 m / s
would become
at 27 o C , then the velocity will be 0.6 m / s at[Pb. CET 2001]
[CBSE PMT 1991]
(a) 1200 K (b) 600 K
(a) 2 litres (b) 4 litres
(c) 400 K (d) 1800 K
(c) 5 litres (d) 7 litres
9. Equal volumes of two gases which do not react
o together are enclosed in separate vessels. Their
4. What is kinetic energy of 1 g of O 2 at 47 C
pressures at 100 mm and 400 mm respectively. If
[Orissa JEE 2004]
the two vessels are joined together, then what
(a) 1 .24  10 2 J (b) 2 .24  10 2 J will be the pressure of the resulting mixture
(temperature remaining constant) [CBSE PMT 1981]
(c) 1 .24  10 3 J (d) 3 .24  10 2 J
(a) 125 mm (b) 500 mm
5. The root mean square speeds at STP for the gases
(c) 1000 mm (d) 250 mm
H2 , N 2 , O2 and HBr are in the order
10. A gas of volume 100 cc is kept in a vessel at
[Pb. CET 1994; CBSE PMT 1991]
pressure 10 4 Pa maintained at temperature 24 o C .
(a) H 2  N 2  O2  HBr If now the pressure is increased to 10 5 Pa, keeping
(b) HBr  O2  N 2  H 2 the temperature constant, then the volume of the
gas becomes [AFMC 1992]
(c) H2  N 2  O2  HBr
(a) 10 cc (b) 100 cc
(d) HBr  O2  H 2  N 2 (c) 1 cc (d) 1000 cc
11. If a gas is expanded at constant temperature[IIT 1986]
6. By what ratio the average velocity of the molecule
in gas change when the temperature is raised (a) The pressure increases

from 50 to 200 o C (b) The kinetic energy of the molecules remains

the same
[DCE 2003]
 Gaseous State 253
(c) The kinetic energy of the molecules decreases (a) 1 : 2 (b) 1 : 32
(d) The number of molecules of the gas increases (c) 1 : 2 (d) 1 : 4
12. The rate of diffusion of SO 2 and O 2 are in the
ratio
[Assam JET 1991; EAMCET 1980]

(SET -6)

(a) N CH 4 = number of moles of CH 4 

m V1 T1 T 22 .4  373
1. 7. (c)   V2  V1 . 2   30 .6 L
16 V2 T2 T1 273
m
N H 2 = number of moles of H 2  3 RT
2 8. (a) Vrms  ; Vrms  T
fraction partial pressure of H 2 is M

m m Given, V1  V , T1  300 K
nH2 2 8
H2    2  V2  2V , T2  ?
n H 2  n CH 4 m m 9 m 9
 2
2 16 16 V1 T1  V  300
    
2. (b) According to Charle's Law V  T V2 T2  2 V  T2
Vt  Vo  Vot
T2  300  4  1200 K
compare it with Y = C + mx
PV T P 2T 9. (d) When two vessels are joined together, the
3. (a) V 2  1 1 . 2   2lt   2lt
T1 P2 2 P T volume will be doubled hence effective
pressure will be halved
3 3 1
4. (a) K.E.  nRT    8 .314  320 J . P1  P2 100  400
2 2 32 P   250 mm
2 2
 1 .24  10 J
2

1 10. (a) P1V1  P2 V2 at constant T

5. (b) Vrms 
m 10 4 . 100  10 5  V2
1 1 1 1
U H 2 : U N 2 : U O2 : U HBr  : : : is V2  10 cc
2 20 32 81
UHB r  UO 2  U N 2  UH 2 11. (b) Kinetic energy will also remain constant if
Temperature is constant.
6. (c) T1  150  273  423 K ; T2  50  273  323 K
rSO 2 M O2 32 1
(Vav )1 T1 423 1 . 14 12. (a)   
Hence,    rO2 M SO 2 64 2
(Vav )2 T2 323 1

***
 Nuclear Chemistry 259

Chapter

7
Nuclear Chemistry

“The branch of chemistry which deals with the substance, the phenomenon is called induced or
study of composition of atomic nucleus and the nuclear artificial radioactivity.
transformations is known as nuclear chemistry”. Radioactivity can be detected and measured by a
The common examples of nuclear processes are number of devices like ionisation chamber, Geiger
radioactivity, artificial transmutations, nuclear fission Muller counter, proportional counter, flow counter, end
and nuclear fusion. The nuclear is also an important window counter, scintillation counter, Wilson cloud
aspect of chemistry because the energies involved in chamber, electroscope, etc.
some of these are million times greater than those in Nature and characteristics of radioactive
ordinary chemical reactions. emissions
Radioactivity The phenomenon of
“Radioactivity is a process in which nuclei of radioactivity arises because Photographic
certain elements undergo spontaneous disintegration of the decay of unstable plate
nuclei or certain element. 
without excitation by any external means.’’ and the
The nature of the radiations  
elements whose atoms disintegrate and emit radiations
are called radioactive elements. emitted from a radioactive
Henry Becquerel (1891) observed the spontaneous substance was investigated Radioactive
emission of invisible, penetrating rays from potassium by Rutherford (1904) by Lead block substance

uranyl sulphate K 2 UO2 (SO4 )2 , which influenced applying electric and Fig. 7.1
magnetic fields. When these
photographic plate in dark and were able to produce
radiation were subjected to electric or magnetic field,
luminosity in substances like ZnS.
these were split into three types ,  and  –rays.
Later on, M.M. Curie and her husband P. Curie
Characteristics of radioactive rays
named this phenomenon of spontaneous emission of
-Ray -Ray -Ray
penetrating rays as, Radioactivity.
Charge and mass : It It carries -1 It has no
Curies also discovered a new radioactive element carries +2 charge and charge and no charge and
Radium from pitchblende (an ore of U i.e. U3 O8 ) which 4 unit mass. mass. negligible
mass.
is about 3 million times more radioactive than uranium.
Identity : Helium Electron  1e 0 High energy
Now a days about 42 radioactive elements are known.
nuclei or helium raditons.
The radioactivity may be broadly classified into ion 4
or He2+.
2 He
two types,
Action of magnetic Deflected to Not
(1) If a substance emits radiations by itself, it is field : Deflected anode. deflected.
said to possess natural radioactivity. towards the cathode.
(2) If a substance starts emitting radiations on Velocity : 1/10th to Same as that of Same as that
that of light. light. of light.
exposure to rays from some natural radioactive
 260 Nuclear Chemistry
Ionizing power : Very Low nearly 100 Very low. Beta particle emission is due to the result of decay of
high nearly 100 times times to that of -
neutron into proton and electron. 0 n1  1 p 1  1 e 0
to that of -rays. rays.
Effect on ZnS plate : Very little effect. Very little The electron produced escapes as a beta-particle-
They cause effect. leaving proton in the nucleus.
luminescence.
-β
Penetrating power : 100 times that of 10 times that Parent element    Daughter element
Low -particles. of -particles. Atomic mass : W W
Atomic number : Z Z 1
Range : Very small. More than - More
particles. (iii) -ray emission : -rays are emitted due to
Nature of product : Product obtained There is no secondary effects. The excess of energy is released in
Product obtained by by the loss of 1 - change in the the form of -rays. Thus -rays arise from energy re-
the loss of 1 -particle particle has atomic
arrangements in the nucleus. As -rays are short
has atomic number atomic number number as
less by 2 units and more by 1 unit, well as in wavelength electromagnetic radiations with no charge
mass number less by 4 without any mass and no mass, their emission from a radioactive element
units. change in mass number. does not produce new element.
number.
Special case : If in a radioactive transformation 1
Theory of radioactivity disintegration alpha and 2 beta-particles are emitted, the resulting
Rutherford and Soddy, in 1903, postulated that nucleus possesses the same atomic number but atomic
radioactivity is a nuclear phenomenon and all the mass is less by 4 units. A radioactive transformation of
radioactive changes are taking place in the nucleus of this type always produces an isotope of the parent
the atom. They presented an interpretation of the element.
α W 4 β W 4 β W 4
radioactive processes and the origin of radiations in the Z A W 
 Z 2 B 
 Z 1 C 
 ZD
form of a theory known as theory of radioactive
A and D are isotopes.
disintegration. The main points of this theory are,
(1) The atomic nuclei of the radioactive elements
Group displacement law
are unstable and liable to disintegrate any moment. Soddy, Fajans and Russell (1911-1913) observed
that when an -particle is lost, a new element with
(2) The disintegration is spontaneous, i.e.,
atomic number less by 2 and mass number less by 4 is
constantly breaking. The rate of breaking is not
formed. Similarly, when -particle is lost, new element
affected by external factors like temperature, pressure,
with atomic number greater by 1 is obtained. The
chemical combination etc.
element emitting then  or -particle is called parent
(3) During disintegration, atoms of new elements
element and the new element formed is called daughter
called daughter elements having different physical and
element. The above results have been summarized as,
chemical properties than the parent elements come into
(1) When an -particle is emitted, the new
existence.
element formed is displaced two positions to the left in
(4) During disintegration, either alpha or beta the periodic table than that of the parent element
particles are emitted from the nucleus. (because the atomic number decreases by 2).
The disintegration process may proceed in one of (2) When a -particle is emitted, the new element
the following two ways, formed is displaced one position to the right in the
(i) -particle emission : When an -particle periodic table than that of the parent element (because
4
(2 He ) is emitted from the nucleus of an atom of the atomic number increased by 1).
parent element, the nucleus of the new element, called (3) When a positron is emitted, the daughter
daughter element possesses atomic mass or atomic element occupies its position one group to the left of
mass number less by four units and nuclear charge or the parent element in periodic table.
atomic number less by 2 units because -particle has Group displacement law should be applied with
mass of 4 units and nuclear charge of two units. great care especially in the case of elements of

Parent element - α Daughter element


lanthanide series (57 to 71), actinide series (89 to 103),
Atomic mass : W W 4 VIII group (26 to 28; 44 to 46; 76 to 78), IA and IIA
Atomic number : Z Z 2
groups.
(ii) -particle emission : -particle is merely an To determine the number of - and - particles
electron which has negligible mass. Whenever a beta emitted during the nuclear transformation. It can be
particle is emitted from the nucleus of a radioactive done in following manner, a
X  bd Y  x 42 He  y 0
c 1 e
atom, the nucleus of the new element formed possesses
ab
the same atomic mass but nuclear charge or atomic a  b  4 x or x  .....(i)
4
number is increased by 1 unit than the parent element.
 Nuclear Chemistry 261
c  d  2x  y .....(ii) force which is used in rapid exchange of Pi-mesons
where x = no. of -emitted, y = no. of -emitted between nucleons are also called exchange forces.
substituting the value of x from eq. (i) in eq. (ii) The binding forces between unlike nucleons (p
ab a  b  and n) are explained by the oscillation of a charged -
we get c  d   2  y ; y  d   c
 4   2  meson (+ or   )
Radioactive disintegration series (a) p1  n 2 n1     n 2 n1  p 2

The phenomenon of natural radioactivity (b) p1  n 2 n1    p 2 n1  p 2
continues till stable nuclei are formed. All the nuclei
from the initial element to the final stable element Binding forces between like nucleons (p - p or n -
constitute a series known as disintegration series. n) result from the exchange of neutral mesons (0) as
Further we know that mass numbers change only when represented below.
-particles are emitted (and not when -particles are (a) p1 p 2   0 or p1   0 p2
emitted) causing the change in mass of 4 units at each (b) n1 n 2   or n1  
0 0
n2
step. Hence the mass numbers of all elements in a
series will fit into one of the formulae. 4n, 4 n  1 , 4 n  2 Nuclear stability
and 4 n  3 , hence there can be only four disintegration Nuclides can be grouped on the basis of nuclear
series.
stability, i.e. stable and unstable nucleus. The most
4n 4n + 1 4n + 2 4n + 3 acceptable theory about the atomic nuclear stability is
n 58 59 59 58
based upon the fact that the observed atomic mass of
Parent 232
Pu 241 238 235
90 Th 94 92 U 92 U all known isotopes (except hydrogen) is always less
element
Half life 1 .39  10 10 10 4 .5  10 9 7.07  10 8
from the sum of the weights of protons and neutrons
(yrs) present in it. Electron (- particle) from a radioactive
Half life 1 .39  10 10 2 .2  10 6 4 .5  10 9 13.5 nucleus may be regarded as derived from a neutron in
(yrs) the following way,
Name of Thorium Neptuniu Uranium Actinium Neutron  Proton  Electron
series (Natural m (Natural (Natural
) (Artificia ) ) Similarly, photons are produced from internal
l) stresses within the nucleus.
End 208
Bi 209 206 207
82 Pb 83 82 Pb 82 Pb
product The stability of nucleus may be discussed in terms
n 52 52 51 51 of any one of the following,
Number of  6  8  8  7
(1) Nuclear Binding Energy and Mass defect : It
lost  4  5  6  4
particles is observed that atomic mass of all nuclei (except
hydrogen) is different from the sum of masses of
Nuclear structure and Nuclear forces
protons and neutrons. The difference is termed mass
According to an earlier hypothesis, the nucleus is defect.
considered as being composed of two building blocks,
Mass defect = Total mass of nucleons – obs.
proton's and neutron's, which are collectively called
atomic mass
nucleons. The forces, which hold the nucleons together
means stronger proton – proton, neutron – neutron and The mass defect is converted into energy.
even proton – neutron attractive forces, exist in the This energy is called the binding energy. This is
nucleus. These attractive forces are called nuclear forces. the energy required to break the nucleus into is
Nuclear forces operate only within small distance of constituents (p and n).
about 1  10 15 m or 1 fermi (1 fermi = 10 13 cm ) and Binding energy = Mass defect 931 MeV
drops rapidly to zero at a distance of 1  10 13 cm . These
The stability of the nucleus is explained on the
are referred to as short range forces. Nuclear forces are
value of binding energy per nucleon and not on the
nearly 10 21 times stronger than electrostatic forces. basis of total binding energy . Binding energy per
Yukawa in 1935, put forward a postulate that nucleon is maximum (8.7 MeV) in the case of iron (56).
neutrons and protons are held together by very rapid The value of binding energy per nucleon can be
exchange of nuclear particles called Pi-mesons (- increased either by fusion of lighter nuclei or fission of
mesons have mass equal to 275 times of the mass of an heavier nuclei.
electron and a charge equal to +1, 0 or –1. These are Value of binding energy predicts the relative
designated as + 0 and – respectively). The nuclear stability of the different isotopes of an element. If the
 262 Nuclear Chemistry
value of binding energy is negative, the product nucleus series terminate into stable isotope of lead (magic
or nuclei will be less stable than the reactant nucleus. number for proton = 82, magic number for neutron =
Thus the relative stability of the different isotopes of 126). Nuclei with nucleons just above the magic
an element can be predicted by the values of binding numbers are less stable and hence these may emit some
energy for each successive addition of one neutron to particles to attain magic numbers.
the nucleus. (4) Neutron-proton ratio or causes of
3
 0 n  2 He  20 .5 MeV
1 4 radioactivity It has been found that the stability of
2 He
nucleus depends upon the neutron to proton ratio
2 He
4
 0 n1  2 He 5  0 . 8 MeV (n/p). If we plot the number of neutrons against
number of protons for nuclei of various elements, it has
4 3
Therefore, 2 He is more stable than 2 He and been observed that most of the stable (non-radioactive)
5 nuclei lie in a belt shown by shaded region in figure
2 He .
this is called stability belt or stability zone. The nuclei
(2) Packing fraction : The difference of actual whose n/p ratio does notStability
lie in the belt are unstable and
isotopic mass and the mass number in terms of packing belt

number (n)
undergo spontaneous radioactive disintegration.
Neutron

Neutron
fraction is defined as,
rich nuclei n/p=1
Actualisotopicma ss  Mass number Proton
Packing fraction   10 4
Mass number rich nuclei

The value of packing fraction depends upon the 20 40 60 80100 120

manner of packing of the nucleons with in the nucleus. Atomic number
Its value can be negative, positive or even zero. A (p)7.2
Fig.
negative packing fraction generally indicates stability
of the nucleus.
It has been observed that,
In general, lower the packing fraction, greater is (i) n / p ratio for stable nuclei lies quite close to
the binding energy per nucleon and hence greater is the
unity for elements with low atomic numbers (20 or
stability. The relatively low packing fraction of He, C
less) but it is more than one for nuclei having higher
and O implies their exceptional stability, packing
atomic numbers. Nuclei having n / p ratio either very
fraction is least for Fe (negative) and highest for H
(+78). high or low undergo nuclear transformation.
(ii) When n / p ratio is higher than required for
(3) Magic number : Nucleus of atom, like extra-
stability, the nuclei have the tendency to emit   rays
nuclear electrons, also has definite energy levels
(shells). i.e., a neutron is converted into a proton.
(iii) When n / p ratio is lower than required for
Nuclei with 2, 8, 20, 28, 50, 82 or 126 protons or
neutrons have been found to be particularly stable with stability, the nuclei increase the ratio, either by
a large number of isotopes. These numbers, commonly emitting   particle or by emitting a position or by K-
known as Magic numbers are defined as the number of electron capture.
nucleons required for completion of the energy levels Rate of radioactive decay
of the nucleus. Nucleons are arranged in shells as two “According to the law of radioactive decay, the
protons or two neutrons (with paired spins) just like quantity of a radio-element which disappears in unit
electrons arranged in the extra-nuclear part. Thus the
time (rate of disintegration) is directly proportional to
4
following nuclei 2 He , 8 O16 , 20 Ca 40 and 82 Pb 208 the amount present.”
containing protons 2, 8, 20 and 82 respectively (all The law of radioactive decay may also be
magic numbers) and neutrons 2, 8, 20 and 126 expressed mathematically.
respectively (all magic numbers) are the most stable. Suppose N0 be the number of atoms of the
Magic numbers for protons : 2, 8, 20, 28, 50, radioactive element present at the commencement of
82,114 observation, t  0 and after time t, the number of atoms
remaining unchanged is N t . The rate of disintegration
Magic numbers for neutrons : 2, 8, 20, 28, 50, 126,
184, 196  dN t 
   at any time t is directly proportional to N.
When both the number of protons and number of  dt 
neutrons are magic numbers, the nucleus is very stable. dN t
Then,  = N
That is why most of the radioactive disintegration dt
 Nuclear Chemistry 263
where  is a radioactive constant or decay Thus, Average life (T)
constant.  1.44  Half life(T1 / 2 )  2  t1 / 2
Various forms of equation for radioactive decay
are, Thus, the average life period of a radioisotope is
N t  N0e  t
; log N 0  log N t  0.4343 t approximately under-root two times of its half life
period.
N0 t 2.303 N
log  ;  log 0
Nt 2 .303 t Nt (3) Activity of population or specific activity : It
is the measure of radioactivity of a radioactive
This equation is similar to that of first order
reaction, hence we can say that radioactive substance. It is defined as ' the number of radioactive
disintegration are examples of first order reactions. nuclei, which decay per second per gram of radioactive
However, unlike first order rate constant (K), the decay isotope.' Mathematically, if 'm' is the mass of
constant () is independent of temperature. radioactive isotope, then
Rate of decay of nuclide is independent of Rate of decay N Avogadro number
temperature, so its energy of activation is zero. Specific activity    
m m Atomic mass in g
(1) Half-life period (T1/2 or t1/2) : The half-life
where N is the number of radioactive nuclei
period of a radioelement is defined, as the time
which undergoes disintegration.
required by a given amount of the element to decay to
one-half of its initial value. (4) Radioactive equilibrium : Suppose a
radioactive element A disintegrates to form another
0 .693
t1 / 2  radioactive element B which in turn disintegrates to

still another element C.
Now since  is a constant, we can conclude that
half-life period of a particular radioelement is
A  B  C
independent of the amount of the radioelement. In B is said to be in radioactive equilibrium with A if
other words, whatever might be the amount of the its rate of formation from A is equal to its rate of decay
radioactive element present at a time, it will always into C.
decompose to its half at the end of one half-life period. It is important to note that the term equilibrium
Let the initial amount of a radioactive substance is used for reversible reactions but the radioactive
be N 0 reactions are irreversible, hence it is preferred to say
that B is in a steady state rather than in equilibrium
Amount of radioactive substance left after n half- state.
life periods N A  B T A t 1 / 2  A
At a steady state,   
1
n
N B  A T B t 1 / 2 B
N    N0
2 Thus at a steady state (at radioactive equilibrium),
Total time T  n  t1 / 2 where n is a whole number. the amounts (number of atoms) of the different
radioelements present in the reaction series are inversely
(2) Average-life period (T) : Since total decay proportional to their radioactive constants or directly
period of any element is infinity, it is meaningless to proportional to their half-life and also average life
use the term total decay period (total life period) for periods.
radioelements. Thus the term average life is used. (5) Units of radioactivity : The standard unit in
Sum of lives of the nuclei radioactivity is curie (c) which is defined as that
Average life (T)  amount of any radioactive material which gives
Total number of nuclei
3.7  10 10 disintegration’s per second (dps), i.e.,1c =
Average life (T) of an element is the inverse of its
Activity of 1g of Ra 226  3.7  10 10 dps
1
decay constant, i.e., T  , Substituting the value of 
 The millicurie (mc) and microcurie (c) are equal
in the above equation, to 10 3 and 10 6 curies i.e. 3.7  10 7 and 3.7  10 4 dps
respectively.
t1 / 2
T   1 . 44 t1 / 2
0 . 693 1c  10 3 mc  10 6 c ; 1c  3.7  10 10 dps

1mc  3.7  10 7 dps ; 1c  3.7  10 4 dps

 264 Nuclear Chemistry
But now a day, the unit curie is replaced by recent accelerating instrument is called the
rutherford (rd) which is defined as the amount of a synchrotron or bevatron. It is important to note that
radioactive substance which undergoes 10 6 dps . i.e., this instrument cannot accelerate the neutrons, being
neutral.
1 rd  10 6 dps . The millicurie and microcurie
When a target element is bombarded with
correspondingly rutherford units are millirutherford neutrons, product depends upon the speed of neutrons.
(mrd) and microrutherford (rd) respectively. Slow neutrons penetrate the nucleus while a high-
1 c  3 .7  10 10 dps  37  10 3 rd speed neutron passes through the nucleus.
92 U
238
 0n
1
 92 U 239 ; 92 U
238
 0n
1
 92 U 237  2 0 n1
1 mc  3 .7  10 7 dps  37 rd slow speed high speed

1 c  3.7  10 4 dps  37 mrd Thus slow neutrons, also called thermal neutrons
are more effective in producing nuclear reactions than
However, in SI system the unit of radioactivity is
high-speed neutrons.
Becquerel (Bq)
Alchemy : The process of transforming one
1 Bq = 1 disintegration per second = 1 dps = element into other is known as alchemy and the person
1rd, 10 6 Bq  1 rd , 3 .7  10 10 Bq  1 c involved in such experiments is called alchemist.
Although, gold can be prepared from lead by alchemy,
(6) The Geiger-Nuttal relationship : It gives the
the gold obtained is radioactive and costs very high
relationship between decay constant of an -
than natural gold.
radioactive substance and the range of the -particle
(i) Transmutation by -particles
emitted.
(a) , n type
log   A  B log R
4 Be 9 ( , n) 6 C 12 i.e. 4 Be 9  2 He 4  6 C 12  0 n1
Where R is the range or the distance which an -
94 Pu 239 ( , n) 96 Cm 242 i.e.
particle travels from source before it ceases to have
ionizing power. A is a constant which varies from one 94 Pu 239  2 He 4  94 Cm 242  0 n1
series to another and B is a constant for all series. It is (b) , p type
obvious that the greater the value of  the greater the
9F
19
( , p ) 10 Ne 22 ie. 9 F19  2 He 4  10 Ne 22  1 H 1
range of the -particle.
7 N 14
( , p) 8 O 17 i.e., 7 N 14  2 He 4  8 O 17  1 H 1
Artificial transmutation of elements
(c) ,  type
The conversion of one element into another by
26 Fe 59 ( ,  ) 29 Cu 63 i.e., 26 Fe 59  2 He 4  29 Cu 63  1 e 0
artificial means, i.e., by means of bombarding with
some fundamental particles, is known as artificial (ii) Transmutation by protons
transmutation. The phenomenon was first applied on (a) p, n type
nitrogen whose nucleus was bombarded with - 15 P 31 ( p, n) 16 S 31 i.e., 15 P 31  1 H 1  16 S 31  0 n1
particles to produce oxygen. (b) p,  type
7N
14
 2 He
4
 8O
17
 1H 1
6C
12
( p,  ) 7 N 13 i.e., 6C
12
 1 H 1  N 13  
Nitrogen isotope Alpha particle Oxygen isotope Proton
(c) p, d type
The element, which is produced, shows
4 Be 9 ( p, d ) 4 Be 8 i.e., 4 Be 9  1 H 1  4 Be 8  1 H 2
radioactivity, the phenomenon is known as Induced
radioactivity. The fundamental particles which have (d) p,  type
been used in the bombardment of different elements 8O
16
( p,  ) 7 N 31 i.e., 8O
16
 1 H 1  7 N 13  2 He 4
are, (iii) Transmutation by neutrons
-particle : 2 He 4 ; Proton : 1 H 1 (a) n,p type
Deutron : 1 H 2 or 1 D 2 ; Neutron : 0 n1 13 Al 27 (n, p) 12 Mg 27 i.e., 13 Al 27  0 n1  12 Mg 27  1 H 1

Since -particles, protons and deutrons carry (b) n, type

positive charge, they are repelled by the positively 8O
16
(n,  ) 12 Mg 27 i.e., 8O
16
 0 n1  6 C 13  2 He 4
charged nucleus and hence these are not good (c) n,  type
projectiles. On the other hand, neutrons, which carry 238
(n,  ) 92 U 239 i.e., 238
 0 n1  92 U 238  
92 U 92 U
no charge at all, are the best projectiles. Cyclotron is
(d) n, type
the most commonly used instrument for accelerating
these particles. The particles leave the instrument with 8O
18
(n,  ) 9 F19 i.e., 8O
18
 0 n1  9 F19  1e 0
a velocity of about 25,000 miles per second. A more (iv) Transmutation by deutrons

(a) d,p type
3 Li (d , p ) 3 Li i.e., 3 Li  1 H  3 Li  1 H
6 7 6 2 7 1
32 As 75 (d , p) 32 As 76 i.e., 32 As 75  1 H 2  32 As 76  1 H 1
(v) Transmutation by -radiations
(a) , n type
4 Be 9 ( , n) 4 Be 8 i.e., 4 Be 9    4 Be 8  0 n1
Synthetic elements : Elements with atomic
number greater than 92 i.e. the elements beyond
uranium in the periodic table are not found in nature
like other elements. All these elements are prepared by
artificial transmutation technique and are therefore
known as transuranic elements or synthetic elements.
Nuclear fission and Nuclear fusion
(1) Nuclear fission : The splitting of a heavier
atom like that of uranium – 235 into a number of
fragments of much smaller mass, by suitable
bombardment with sub-atomic particles with liberation
of huge amount of energy is called Nuclear fission.
Hahn and Startsman discovered that when uranium-235
is bombarded with neutrons, it splits up into two
relatively lighter elements.
U 235  0 n 1  Ba 140  36 Kr 93  3 0 n 1 +
92 56
energy
Spallation reactions are similar to nuclear fission.
However, they differ by the fact that they are brought
by high energy bombarding particles or photons.
Elements capable of undergoing nuclear fission
and their fission products. Among elements capable of
undergoing nuclear fission, uranium is the most
common. The natural uranium consists of three
isotopes, namely U 234 (0.006 %) ,
U 238 (99 .3%) . Of the three isomers of uranium, nuclear
fission of U 235 and U 238 are more important. Uranium-
238 undergoes fission by fast moving neutrons while
U 235 undergoes fission by slow moving neutrons; of
these two, U 235 fission is of much significance. Other
examples are Pu 239 and U 233 .
Uranium-238, the most abundant (99.3%) isotope
of uranium, although itself does not undergo nuclear
fission, is converted into plutonium-239.
92 U
238
 0 n 1  92 U 239 ; 92 U
239
 92 NP 239  1 e 0
93 Np 238  94 Pu 239  1 e 0
Which when bombarded with neutrons, undergo
fission to emit three neutrons per plutonium nucleus.
Such material like U-238 which themselves are non-
fissible but can be converted into fissible material (Pu-
239) are known as fertile materials.
Nuclear Chemistry 265
Nuclear chain reaction : With a small lump of
U 235 , most of the neutrons emitted during fission escape
but if the amount of U 235 exceeds a few kilograms
(critical mass), neutrons emitted during fission are
absorbed by adjacent nuclei causing further fission and
so producing more neutrons. Now since each fission
releases a considerable amount of energy, vast
quantities of energy will be released during the chain
reaction caused by U 235 fission.
Uranium
E Neutron
3E
9
E
Fig. 7.3
Atomic bomb : An atomic bomb is based upon the
process of that nuclear fission in which no secondary
neutron escapes the lump of a fissile material for which
the size of the fissile material should not be less than a
Huge amount of minimum size called the critical size. There is
accordingly a sudden release of a tremendous amount
of energy, which represents an explosive force much
greater than that of the most powerful TNT bomb. In
the world war II in 1945 two atom bombs were used
against the Japanese cities of Hiroshima and Nagasaki,
the former contained U-235 and the latter contained
Pu-239.
Atomic pile or Nuclear reactor : It is a device to
obtain the nuclear energy in a controlled way to be used
U 235 (0.7%) and for peaceful purposes. The most common reactor
consists of a large assembly of graphite (an allotropic
form of carbon) blocks having rods of uranium metal
(fuel). Many of the neutrons formed by the fission of
nuclei of U 235 escape into the graphite, where they
92
are very much slow down (from a speed of about 6000
or more miles/sec to a mile/sec) and now when these
low speed neutrons come back into the uranium metal
they are more likely to cause additional fissions. Such a
substance like graphite, which slow down the neutrons
without absorbing them is known as a moderator.
Heavy water, D2O is another important moderator
where the nuclear reactor consists of rods of uranium
metal suspended in a big tank of heavy water
(swimming pool type reactor). Cadmium or boron are
used as control rods for absorbing excess neutrons.
Plutonium from a nuclear reactor : For such
purposes the fissile material used in nuclear reactors is
the natural uranium which consists mainly (99.3%) of
U-238. In a nuclear reactor some of the neutrons
produced in U-235 (present in natural uranium) fission
 266 Nuclear Chemistry
converts U-238 to a long-lived plutonium isotope, Pu- hydrogen bomb having power of 1 million tonnes of
239 (another fissionable material). Plutonium is an TNT
important nuclear fuel. Such reactors in which A hydrogen bomb is far more powerful than an atom
neutrons produced from fission are partly used to carry bomb. Thus if it is possible to have sufficiently high
out further fission and partly used to produce some temperatures required for nuclear fusion, the deuterium
other fissionable material are called Breeder reactors. present in sea (as D2O) is sufficient to provide all energy
Nuclear reactors in India : India is equipped with requirements of the world for millions of years. The first
the five nuclear reactors, namely nuclear reactor was assembled by Fermi in 1942.
(i) Apsara (1952) (ii) Cirus (1960) Difference between Nuclear fission and fusion
(iii) Zerlina (1961) (iv) Purnima (1972) and Nuclear fission Nuclear fusion
R-5 The process occurs only in The process occurs only in
Purnima uses plutonium fuel while the others utilize the nuclei of heavy elements. the nuclei of light elements.
uranium as fuel. The process involves the The process involves the
fission of the heavy nucleus fission of the lighter nuclei
(2) Nuclear fusion : “Oposite to nuclear fission,
to the lighter nuclei. to heavy nucleus.
nuclear fusion is defined as a process in which lighter The process can take place at The process takes place at
nuclei fuse together to form a heavier nuclei. However, ordinary temperature. higher temperature
such processes can take place at reasonable rates only ( 10 8 o C) .
at very high temperatures of the order of several The energy liberated during The energy liberated during
million degrees, which exist only in the interior of this process is high the process is
stars. Such processes are, therefore, called (200 MeV per fission) comparatively low
(3 to 24 MeV per fusion)
Thermonuclear reactions (temperature dependent
Percentage efficiency of the Percentage efficiency of the
reactions). Once a fusion reaction initiates, the energy energy conversion is energy conversion is high
released in the process is sufficient to maintain the comparatively less. (four times to that of the
temperature and to keep the process going on. fission process).
The process can be The process cannot be
4 1H 1  2 He
4
 2 1e 0  Energy
Hydrogen Helium Positron
controlled for useful controlled.
purposes.
This is not a simple reaction but involves a set of
the thermonuclear reactions, which take place in stars
Application of radioactivity
including sun. In other words, energy of sun is derived Radioisotopes find numerous applications in a
due to nuclear fission. variety of areas such as medicine, agriculture, biology,
Controlled nuclear fusion : Unlike the fission chemistry, archeology, engineering and industry.
process, the fusion process could not be controlled. (1) Age determination : The age of earth has
Since there are estimated to be some 10 17
pounds of been determined by uranium dating technique as
deuterium ( 1 H 2 ) in the water of the earth, and since follows. Samples of uranium ores are found to contain

each pound is equivalent in energy to 2500 tonnes of - and -decays. Now

Pb 206 as a result of long series of

coal, a controlled fusion reactor would provide a if it is assumed that the ore sample contained no lead
virtually inexhaustible supply of energy. at the moment of its formation, and if none of the lead

Hydrogen bomb : Hydrogen bomb is based on the formed from U 238 decay has been lost then the
fusion of hydrogen nuclei into heavier ones by the measurement of the Pb 206 / U 238 ratio will give the value
thermonuclear reactions with release of enormous of time t of the mineral.
energy. No. of atoms of Pb 206
 e  t 1
As mentioned earlier the above nuclear reactions No. of atoms of U 238 left
can take place only at very high temperatures.
where  is the decay constant of uranium-238
Therefore, it is necessary to have an external source of
energy to provide the required high temperature. For Alternatively,
this purpose, the atom bomb, (i.e., fission bomb) is used 2.303 Initial amount of U 238
t log
as a primer, which by exploding provides the high  Amount of U 238 in the mineral pr esent till date
temperature necessary for successful working of
Similarly, the less abundant isotope of uranium,
hydrogen bomb (i.e., fusion bomb). In the preparation 235
U eventually decays to Pb 207 ; Th 232 decays to Pb 208 and
of a hydrogen bomb, a suitable quantity of deuterium
or tritium or a mixture of both is enclosed in a space thus the ratios of Pb 207 / U 235 and Pb 208 / Th 232 can be used
surrounding an ordinary atomic bomb. The first to determine the age of rocks and minerals.
hydrogen bomb was exploded in November 1952 in
Marshall Islands; in 1953 Russia exploded a powerful

6C
14
(half-life 5760 years) was used by Willard
Libby (Nobel lauret) in determining the age of carbon-
bearing materials (e.g. wood, animal fossils, etc.)
Carbon-14 is produced by the bombardment of nitrogen
atoms present in the upper atmosphere with neutrons
(from cosmic rays).
7 N 14  0 n1  6 C 14  1 H 1
Thus carbon-14 is oxidised to CO 2 and eventually
ingested by plants and animals. The death of plants or
animals puts an end to the intake of C 14
14
atmosphere. After this the amount of C in the dead
tissues starts decreasing due to its disintegration.
6C
14
 7 N 14  1 e
0
It has been observed that on an average, one gram
of radioactive carbon emits about 12 -particles per
minute. Thus by knowing either the amount of C-14 or
the number of -particles emitted per minute per gram
of carbon at the initial and final (present) stages, the
age of carbon material can be determined by using the
following formulae.
2 .303 N 2 .303 N
 log 0 or t  log 0
t Nt  Nt
where t = Age of the fossil,  = Decay constant, N 0 =
Initial radioactivity (in the fresh
Radioactivity in the fossil
The above formula can be modified as,
2.303 Initial ratio of C 14 / C 12 (in fresh wood)
t log
 C 14 / C 12 ratio in the old wood
Similarly, tritium 1 H 3 has been used for
dating purposes.
(2) Radioactive tracers (use of radio–isotopes) :
A radioactive isotope can be easily identified by its
radioactivity. The radioactivity can, therefore act as a
tag or label that allows studying the behaviour of the
element or compounding which contains this isotope.
An isotope added for this purpose is known as isotopic
tracer. The radioactive tracer is also known as an
isotopic tracer. The radioactive tracer is also known as
an indicator because it indicates the reaction.
Radioisotopes of moderate half-life periods are used for
tracer work. The activity of radioisotopes can be
detected by means of electroscope, the electrometer or
the Geiger-Muller counter. Tracers have been used in
the following fields,
(i) To diagnose many diseases : For example,
Arsenic – 74 tracer is used to detect the presence of
tumours, Sodium – 24 tracer is used to detect the
presence of blood clots and Iodine –131 tracer is used to
study the activity of the thyroid gland. It should be
Nuclear Chemistry 267
noted that the radioactive isotopes used in medicine
have very short half-life periods.
(ii) In agriculture : The use of radioactive
phosphorus 32 P in fertilizers has revealed how
phosphorus is absorbed by plants. This study has led
to an improvement in the preparation of fertilizers.
14
C is used to study the kinetics of photo synthesis.
(iii) In industry : Radioisotopes are used in
industry to detect the leakage in underground oil
pipelines, gas pipelines and water pipes. Radioactive
from the carbon has been used as a tracer in studying
mechanisms involved in many reactions of industrial
importance such as alkylation, polymerization,
catalytic synthesis etc.
(iv) In analysis : Several analytical procedures
can be used employing radioisotopes as tracers.
(a) A small amount of radioactive isotope is mixed
with the inactive substance and the activity is studied
before and after adsorption. Fall in activity gives the
amount of substance adsorbed.
(b) The solubility of lead sulphate in water may
be estimated by mixing a known amount of radioactive
lead with ordinary lead.
(c) Ion exchange process of separation is readily
followed by measuring activity of successive fractions
wood), Nt = eluted from the column.
(d) By labelling oxygen of the water, mechanism
of ester hydrolysis has been studied.
(e) The efficiency of analytical procedures may be
measured by adding a known amount of radio-isotopes
to the sample before analysis begins. After the
completion, the activity is again determined. The
comparison of activity tells about the efficiency of
separation.
(3) Use of  rays :  rays are used for
disinfecting food grains and for preserving food stuffs.
Onions, potatoes, fruits and fish etc., when irradiated
with  rays, can be preserved for long periods. High
yielding disease resistant varieties of wheat, rice,
groundnut, jute etc., can be developed by the
application of nuclear radiations. The  rays radiations
are used in the treatment of cancer. The  radiations
emitted by cobalt –60 can burn cancerous cells. The 
radiations are used to sterilize medical instruments
like syringes, blood transfusion sets. etc. These
radiations make the rubber and plastics objects heat
resistant.
Hazards of radiations
The increased pace of synthesis and use of radio
isotopes has led to increased concern about the effect of
radiations on matter, particularly in biological systems.
 268 Nuclear Chemistry
The accident of Chernobyl occurred in 1986 in USSR is one ton of coal.
no older when radioisotopes caused a hazard there. The  Beryllium has been found to be the best moderator
nuclear radiations (alpha, beta, gamma as well as X- as it occupies small space and have low absorption
rays) possess energies far in excess of ordinary bond cross-section.
energies and ionisation energies. Consequently, these  The total life span of a radioactive element is
radiations are able to break up and ionise the molecules infinite.
present in living organisms if they are exposed to such
 The  - radiation of total energy 1.02 MeV,
radiations. This disrupts the normal functions of living
emitted when a positron and an electron interact
organisms. The damage caused by the radiations,
are known as annilation radiation.
however, depends upon the radiations received. The
resultant radiation damage to living system can be
classified as,
(1)Somatic or pathological damage : This affects
the organism during its own life time. It is a permanent
damage to living civilization produced in body. Larger
dose of radiations cause immediate death whereas
smaller doses can cause the development of many
diseases such as paralysis, cancer, leukaemia, burns,
fatigue, nausea, diarrhoea, gastrointestinal problems
etc. some of these diseases are fatal. Many scientists
presently believe that the effect of radiations is
proportional to exposure, even down to low exposures.
This means that any amount of radiation causes some
finite risk to living civilization.
(2) Genetic damage : As the term implies,
radiations may develop genetic effect. This type of
damage is developed when radiations affect genes and
chromosomes, the body's reproductive material. Genetic
effects are more difficult to study than somatic ones
because they may not become apparent for several
generations.

 The particle like mesons, positron, neutrino, etc,

about 20 in number are created by stresses in
nucleus but do not exist as component of nucleus.
 Highest degree of radioactivity is shown by radium.
 The nuclear forces are not governed by inverse
square law.
 About 42 radioactive nuclides (Z > 82) occur in
nature. Each of these gives stable end product of
an isotope of lead.
 The half life is independent of physical or
chemical state of a radioactive element.
 The average life of the natural radioactive element
vary from 10–6s 1010 years or more.
 It has been observed that fusion of 45 mg of
hydrogen produce as much energy as obtained from
 Nuclear Chemistry
267
(c) 7 N 14  0 n 1  6 C 14  1 H 1

(d) 7 N 14  1 H 3  0 n 1  6 C 14  2 He 4

9. Deuterons when bombarded on a nuclide produce

38
18 Ar and neutrons. The target is [CPMT 1982, 87]

(a) Cl 35 (b) K 27
Nucleus (Stability and Reaction) 17 19

(c) 17 Cl 37 (d) 19 K 39
1. Nucleons are [CPMT 1982]
10. Which can be used for carrying out nuclear
(a) Protons and electrons reaction
(b) Protons and neutrons [AFMC 2003]
(c) Electrons and neutrons (a) Uranium – 238 (b) Neptunium – 239
(d) Electrons, protons and neutrons (c) Thorium – 232 (d) Plutonium – 239
2. A deutron contains [NCERT 1982; CPMT 1994] 11. On comparing chemical reactivity of C 12 and C 14 ,
(a) A neutron and a positron it is revealed that
(b) A neutron and a proton (a) C 12 is more reactive (b) C 14 is more reactive
(c) A neutron and two protons (c) Both are inactive (d) Both are equally
active
(d) A proton and two neutrons
234
3. The nucleus of radioactive element possesses 12. The radionucleide 90 Th undergoes two successive

(a) Low binding energy (b) High binding energy

 -decays followed by one  -decay. The atomic
number and the mass number respectively of the
(c) Zero binding energy (d) High potential
resulting radionucleide are [
energy
(a) 92 and 234 (b) 94 and 230
4. On bombarding 7 N 14 with  -particles, the nuclei
(c) 90 and 230 (d) 92 and 230
of the product formed after the release of a
13. Hydrogen and deuterium differ in [CPMT 1980]
proton will be or In nuclear reaction
(a) Reactivity with oxygen (b)Reactivity with chlorine
7 N
14
 2 He 4  Z X A  1 H 1 , the term Z X
A
(c) Melting point (d) Reducing action
represents [NCERT 1979; MP PMT 1989; MNR 1995;
14. A nuclear reaction must be balanced in terms of
MP PET 1996; BHU 1996]
(a) Only energy (b) Only mass
(a) 8 O 17 (b) 9 F 18 (c) Mass and energy (d) None of these
(c) 9 F 17 (d) 8 O 18 15. In the following nuclear reaction, the other
product is 52 Te 130 1 H 2  53 I131  ? [MP PET 1991]
5. Nuclear energy is based on the conversion of
(a) Protons into neutrons (a) Positron (b) Alpha particle
(b) Mass into energy (c) One neutron (d) Proton

(c) Neutrons into protons 16. The reaction 5B

8
4 Be 8 1 e 0 is due to[MP PMT 1991]
(d) Uranium into radium (a) Loss of  -particles (b) Loss of  -particles
6. Positron has nearly the same weight as that of (c) Loss of positron (d) Electron loss
[NCERT 1975; JIPMER 1991; BHU 1995] 17. Positronium is the name given to an atom-like
(a)  -particle (b) Proton combination formed between[NCERT 1980; JIPMER 1991]
(c) Neutron (d) Electron (a) A positron and a proton
(b) A positron and a neutron
7. In the reaction Li  (?)  2 He 4  1 H 3 .
6
The
3
(c) A positron and  -particle
missing particle is [CPMT 1983, 84]
(d) A positron and an electron
(a) Electron (b) Neutron
18. An electrically charged atom or a group of atoms
(c) Proton (d) Deutron is known as [
14
8. The 6C in upper atmosphere is generated by the (a) A meson (b) A proton
nuclear reaction [MP PET 1993] (c) An ion (d) A cyclotron
(a) 7 N 14
 1 H  6 C
1 14
 1 e
0
 1H 1 19. The charge on positron is equal to the charge on
which one of the following [NCERT 1977]
(b) 7 N 14  6 C 14  1 e
0
(a) Proton (b) Electron
 268 Nuclear Chemistry
(c)  -particle (d) Neutron 29. In the carbon cycle, from which hot stars obtain
20. In the nuclear reaction Mg 24
 2 He 4
 0 n  ? The
1 their energy, the 6 C 14 nucleus is
12

product nucleus is [BHU 1987] (a) Completely converted into energy

(b) Regenerated at the end of the cycle
(a) 13 Al 27 (b) 14 Si 27
(c) Combined with oxygen to form carbon
(c) 13 Al 28 (d) 12 Mg 25 monoxide
14 (d) Broken up into its constituents protons and
21. 6C is formed from 7 N 14 in the upper
neutrons
atmosphere by the action of the fundamental
30. The atomic mass of lead is 208 and atomic
particle [Orissa JEE 2002]
number is 82. The atomic mass of bismuth is 209
(a) Positron (b) Neutron
and atomic number is 83. The ratio of n/p in the
(c) Electron (d) Proton
atom is [EAMCET 1982]
22. In the nuclear reaction
(a) Higher of lead (b) Higher of bismuth
 82 Pb 206  x 2 He 4  y 1 
238 0
92 U
(c) Same (d) None of these
the value of x and y are respectively ……..
31. Which of the following is an n, p reaction[BHU 1995]
[Orissa JEE 2002]
(a) 8, 6 (b) 6, 4 (a) 5C
13
 1 H 1  6 C 14
(c) 6, 8 (d) 8, 10
(b) 7 N 14  1 H 1  8 O 15
23. If an isotope of hydrogen has two neutrons in its
atom, its atomic number and atomic mass number (c) 13 Al 27  0 n 1  12 Mg 27  1 H 1
will respectively be
(d) 92 U 235  0 n 1  54 Xe 140  38 Sr
93
 3 0 n1
[CBSE 1992]
(a) 2 and 1 (b) 3 and 1 32. Which one of the following statements is incorrect
(c) 1 and 1 (d) 1 and 3 [MP PET 1997]
24. Which one of the following nuclear (a) Mass defect is related with binding energy
transformation is (n, p ) type [AIIMS 1980, 83] (b) ‘Meson’ was discovered by Yukawa
(a) 3 Li
7
 1 H 1  4 Be 7  0 n1 (c) The size of the nucleus is of the order of
(b) As 75
 2 He  35 Br
4 78
 0n 1 10 12  10 13 cm
33
(d) Magnetic quantum number is a measure of
(c) 83 Bi 209  1 H 2  84 Po 210  0 n 1 ‘orbital angular momentum’ of the electron
(d) 21 Sc 45  0 n 1  20 Ca 45  1 H 1 33. In the sequence of following nuclear reactions
   n 
25. What is X in the following nuclear reaction 92 X
238

 Y 
 Z   L  84 M 218

7 N 14  1 H 1  8 O 15  X [AIIMS 1983; MP PET 1997] The value of n will be [MP PMT 1999]

(a) 0
(b) 1 (a) 3 (b) 4
1 e 0n
(c) 5 (d) 6
(c)  (d) 1 e
0
34. The introduction of a neutron into the nuclear
26. In the reaction 93 Np 239  94 Pu 239 + (?), the composition of an atom would lead to a change in[MNR 19
missing particle is [MNR 1987] (a) The number of the electrons also
(a) Proton (b) Positron (b) The chemical nature of the atom
(c) Electron (d) Neutron (c) Its atomic number
27. According to the nuclear reaction (d) Its atomic weight
4 Be  2 He  6 C 12  0 n 1 , mass
4
number of (Be ) atom
35. The composition of tritium ( 1 H 3 ) is
is
[Manipal MEE 1995; DPMT 1982,96]
[AFMC 2002]
(a) 4 (b) 9 (a) 1 electron, 1 proton, 1 neutron
(c) 7 (d) 6 (b) 1 electron, 2 protons, 1 neutron
28. Which of the following nuclides has the magic (c) 1 electron, 1 proton, 2 neutrons
number of both protons and neutrons[EAMCET 1989] (d) 1 electron, 1 proton, 3 neutrons
115 206
(a) 50 Sn (b) 82 Pb 36. Identify ' X ' in 16 S 32  X  15 P 30  2 He 4
(c) 82 Pb 208 (d) 50 Sn 118 (a) 1 H1 (b) 1 D2

(c) 0n
1
(d) e 
 Nuclear Chemistry
269
37. In terms of energy 1 a. m.u. is equal to 48. The nucleus of an atom is made up of X protons
[MP PET/PMT 1998] and Y neutrons. For the most stable and abundant
(a) 100 J (b) 931.1 MeV nuclei
[NCERT 1980]
(c) 931.1 kcal (d) 10 7 erg
(a) X and Y are both even (b)X and Y are both odd
38. Positron is [AIIMS 1997]
(c) X is even and Y is odd (d)X is odd and Y is even
(a) Electron with +ve charge
49. Atom A possesses higher values of packing
(b) A helium nucleus fraction than atom B. The relative stabilities of A
(c) A nucleus with two protons and B are
(d) A nucleus with one neutron and one proton (a) A is more stable than B
  
39. X 
 Y 
 Z 
 W (b) B is more stable than A
In the above sequence of reaction, the elements (c) A and B both are equally stable
which are isotopes of each other are [JIPMERdoes
(d) Stability 1997]
not depend on packing fraction
(a) X and W (b) Y and Z 50. How many neutrons are present in the nucleus of
(c) X and Z (d) None of these Ra
40. Stable nuclides are those whose n/p ratio is[MP PMT 1993] [CPMT 1980]

(a) n / p  1 (b) n / p  2 (a) 88 (b) 226

(c) n / p  1 (d) n / p  1 (c) 140 (d) 138
51. In a nuclear explosion, the energy is released in
41. Neutrino has [NCERT 1981]
the form of
(a) Charge +1, mass 1 (b) Charge 0, mass 0
[CPMT 1994]
(c) Charge – 1, mass 1 (d) Charge 0 , mass 1
(a) Kinetic energy (b) Electrical energy
42. Which one of the following nuclear reaction is
(c) Potential energy (d) None of these
correct
[CPMT 1997] 52. In equation 11 Na 23
1 H 1 12 Mg 23  x , x
(a) 6C
13
 1 H 1 7 N 13     v  represents
[MP PMT 1990; MP PET 1999]
(b) 11 Na 23  1 H 1  10 Ne 20  2 He 4 (a) Neutron (b) Deutron
(c) 13 Al 23
 0n 1
11 Na 23
e 0 (c)  -particle (d) Positron

(d) None of these 53. Which of the following atomic mass of uranium is
the most radioactive [AFMC 1997]
43. Formation of nucleus from its nucleons is
accompanied by (a) 238 (b) 235
[NCERT 1975; RPET 2000] (c) 226 (d) 248
(a) Decrease in mass (b) Increase in mass 54. Which of the following particle is emitted in the
reaction 13 Al 27  2 He 4 14 P 30  ..... [DCE 1999]
(c) No change of mass (d) None of them
1 0
44. A particle having the same charge and 200 times (a) 0n (b) 1 e
greater mass than that of electron is 1
(c) 1H (d) 1 H 2
(a) Positron (b) Proton
55. Which of the following sub-atomic particles is not
(c) Neutrino (d) Meson
present in an atom [JIPMER 1999]
45. The positron is [AFMC 1997] (a) Neutron (b) Proton
0 0
(a) 1 e (b) 1 e (c) Electron (d) Positron
1 1 56. Electromagnetic radiation with maximum wave
(c) 1 H (d) 0n
length is
46. Which of the following is the most stable atom [DCE 2000; UPSEAT 2000]
[AFMC 1997] (a) Ultraviolet ray (b) Radiowave
(a) Bi (b) Al (c) X-ray (d) Infrared
(c) U (d) Pb 57. Neutrons are obtained by [JIPMER 1999]
47. The positron is discovered by [RPMT 1997] (a) Bombardment of Ra with -particles
(a) Pauling (b) Anderson (b) Bombardment of Be with -particles
(c) Yukawa (d) Segar (c) Radioactive disintegration of uranium
(d) None of these
 270 Nuclear Chemistry
 
58. In the reaction, Po 
 Pb 
 Bi, if Bi, (c) Moseley (d) Einstein
belongs to group 15, to which Po belongs [DCE 2000]
(a) 14 (b) 15 Radioactivity and ,  and - rays
(c) 13 (d) 16
1. Which of the following does not contain material
59. In the nuclear reaction 9
4 Be ( p,  ) X , the X is
particles
[MP PMT 2000] [BHU 2002]
4 6
(a) 2 He (b) 3 Li (a) Alpha rays (b) Beta rays
(c) 7
Li (d) 8
Be (c) Gamma rays (d) Canal rays
3 4
2. Radioactive substances emit -rays, which are
60. Which of the following does not contain number of
40
[Orissa JEE 2002]
neutrons equal to that of 18 Ar [MP PMT 2000]
(a) + ve charged particle (b) – ve charged particle
41 43
(a) 19 K (b) 21 Sc (c) Massive particle (d) Packet of energy
40 42 3. Which statement is incorrect [CPMT 1982]
(c) 21 Sc (d) 20 Ca
(a)  -rays have more penetrating power than  -
61. Nuclear reactivity of Na and Na  is same because rays
both have [Pb. PMT 2000]
(b)  -rays have less penetrating power than  -
(a) Same electron and proton rays
(b) Same proton and same neutron (c)  -rays have less penetrating power than  -
(c) Different electron and proton rays
(d) Different proton and neutron (d)  -rays have more penetrating power than  -
62. Which of the following is the heaviest metal rays
[MH CET 2001] 4. The velocity of  -rays is approximately[CPMT 1982]
(a) Hg (b) Pb (a) Equal to that of the velocity of light
(c) Ra (d) U
(b) 1/10 of the velocity of light
63. In the following reaction, x will be (c) 10 times more than the velocity of light
29 Cu 64
 28 Ni 64  x (d) Uncomparable to the velocity of light
(a) A proton (b) An electron 5. The radiations having high penetrating power and
(c) A neutron (d) A positron not affected by electrical and magnetic field are[Kerala CET 1
64. Which one out of the following statements is not (a) Alpha rays (b) Beta rays
correct for ortho and para hydrogen [Orissa JEE 2002] (c) Gamma rays (d) Neutrons
(a) They have different boiling point 6. Alpha particles are ...... times heavier
(approximately) than neutrons [CPMT 1971]
(b) Ortho form is more stable than para form
(a) 2 (b) 4
(c) They differ in the spin of their protons
1
(d) The ratio of ortho to para hydrogen increases (c) 3 (d) 2
with increase in temperature and finally pure 2
235
ortho form is obtained 7. Uranium 92 U on bombardment with slow
65. For the nuclear reaction, 24
12 Mg  1 D    ? , the
2
neutrons produces [CPMT 1982]
missing nucleide is [Kurukshetra CEE 2002] (a) Deutrons (b) Fusion reaction
(a) 22
Na (b) 23
Na (c) Fission reaction (d) Endothermic
11 11
reaction
23 26
(c) 12 Mg (d) 12 Mg 8. -particles can be detected using [AIIMS 2005]
66. Z X M  2 He 4 15 P 30  0 n 1 . Then [KCET 2002] (a) Thin aluminum sheet (b) Barium sulphate
(a) Z  12, M  27 (b) Z  13, M  27 (c) Zinc sulphide screen (d) Gold foil
9. Alpha rays consist of a stream of [BHU 1979]
(c) Z  12, M  17 (d) Z  13 , M  28
(a) H  (b) He 2
67. An element 96 X
227
emits 4 and 5  particles to (c) Only electrons (d) Only neutrons
form new element Y. Then atomic number and 10. Which is the correct statement [CPMT 1971]
mass number of Y are [MH CET 2002]
(a) Isotopes are always radioactive
(a) 93; 211 (b) 211; 93
(b)  -rays are always negatively charged
(c) 212; 88 (d) 88; 211
particles
68. Meson was discovered [MH CET 2004]
(c)  -rays are always negatively charged
(a) Yukawa (b) Austin particles
 Nuclear Chemistry
271
(d)  -rays can be deflected in magnetic field 21. Of the following radiations, the one most easily
11. The  -particle is identical with stopped by air is [MP PMT 1991]

[CPMT 1972, 82, 86; BHU 1984;

(a)  -rays (b)  -rays
MP PMT 1990, 91, 93; MP PET 1999] (c)  -rays (d) X-rays
(a) Helium nucleus 22. Uranium ultimately decays into a stable isotope of
(b) Hydrogen nucleus [MP PET 1995]
(c) Electron (a) Radium (b) Carbon
(d) Proton (c) Lead (d) Neptunium
12. If by mistake some radioactive substance gets 23. Which leaves no track on Wilson cloud chamber
inside the human body, then from the point of [AFMC 1988]
view of radiation damage, the most harmful will (a) Electrons (b) Protons
be the one which emits (c)  -particles (d) Neutrons
[DPMT 1986] 24. Which has the least penetrating power[CPMT 1994]
(a)  -rays (b) Neutrons (a)  -rays (b)  -rays
(c)  -particles (d)  -particles (c)  -rays (d) X -rays
13. Radioactivity was discovered by 25. There exists on  -rays
[CPMT 1983, 88; DPMT 1982; AMU 1983; [MP PMT 1996; Pb. PMT 2004; EAMCET 2004]
MADT Bihar 1982] (a) Positive charge
(a) Henry Becquerel (b) Rutherford (b) Negative charge
(c) J. J. Thomson (d) Madam Curie (c) No charge
14. Which of the following is radioactive element[CPMT 1988] (d) Sometimes positive charge, sometimes
negative charge
(a) Sulphur (b) Polonium
26. Which is not emitted by radioactive substance
(c) Tellurium (d) Selenium
[AIIMS 1997]
15. Penetrating power of -particle is [MP PMT 2002]
(a)  -rays (b)  -rays
(a) More than -rays (b) More than -rays
(c) Positron (d) Proton
(c) Less than -rays (d) None of these
27. The radiations from a naturally occurring radio
16. -particle is emitted in radioactivity by element, as seen after deflection in a magnetic
[AIEEE 2002; MP PMT 2004] field in one direction, are
(a) Conversion of proton to neutron [IIT 1984; MP PMT 1986;
(b) Form outermost orbit MP PET/PMT 1988 JIPMER 1999]

(c) Conversion of neutron to proton (a) Definitely -rays (b) Definitely -rays
(d) -particle is not emitted (c) Both  and -rays (d) Either  or -rays

17.  -rays have [CPMT 1973, 78; NCERT 1977] 28. The 88 Ra 226 is [AIIMS 2001]

(a) Positive charge (a) n-mesons (b) u-mesons

(b) Negative charge (c) Radioactive (d) Non-radioactive
(c) No charge 29. During -decay [UPSEAT 2001]

(d) Sometimes positive charge and sometimes (a) An atomic electron is ejected
negative charge (b) An electron which is already present with in
18. X-rays are produced due to [JIPMER 2002] the nucleus is ejected
(a) Bombarding of electrons on solids (c) A neutron in the nucleus decays emitting an
(b) Bombarding of -particle on solids electron
(c) Bombarding of -rays on solids (d) A part of binding of the nucleus is converted
(d) Bombarding of neutron on solids into an electron
19. 30.
Choose the element which is not radioactive[CPMT 1988] The element californium belongs to the family of
(a) Cm (b) No [UPSEAT 2002]
(c) Mo (d) Md (a) Actinide series (b) Alkali metal family
20. A magnet will cause the greatest deflection of (c) Alkaline earth family (d) Lantanide series
[MP PMT 1991] 31. Which of the following is not deflected by
(a)  -rays (b)  -rays magnetic field
(c)  -rays (d) Neutrons [MP PMT 2001]
 272 Nuclear Chemistry
(a) Deuteron (b) Positron [MP PMT 1999]
(c) Proton (d) Photon (a) 4 n and 4 n  1 radioactive disintegration series
32. Which of the following can be used to convert (b) 4 n  1 and 4 n  2 radioactive disintegration
14 17 series
7 N into 8 O [MP PMT 2001]
(c) 4 n  1 and 4 n  3 radioactive disintegration
(a) Deuteron (b) Proton series
(c) -particle (d) Neutron (d) 4 n  1 and 4 n radioactive disintegration series
33. The amount of energy, which is required to 2. Group displacement law states that the emission
separate the nucleons from a nucleus. The energy of  or  particles results in the daughter
is called
element occupying a position, in the periodic
[UPSEAT 2001] table, either to the left or right of that of the
(a) Binding energy (b) Lattice energy parent element. Which one of the following
(c) Kinetic energy (d) None of these alternatives gives the correct position of the
daughter element
34. What happens when -particle is emitted
On emission of  particles On emission of  particles
[CBSE PMT 1989; JIPMER 2002]
(a) Mass number decreases by 12 unit, atomic (a) 2 groups to the right 1 group to the right
number decreases by 4 unit (b) 2 groups to the right 1 group to the left
(b) Mass number decreases by 4 unit, atomic (c) 2 groups to the left 1 group to the left
number decreases by 2 unit (d) 2 groups to the left 1 group to the right
(c) Only mass number decreases 3. The nuclides (A nuclide is the general name for
(d) Only atomic number decreases any nuclear species) 6 C 12 , 26 Fe 56 and 92 U 238 have
35. The charge on gamma rays is 12, 56 and 238 nucleons respectively in the nuclei.
[Pb. PMT 2004; EAMCET 2004] The total number of nucleons in a nucleus is equal
to [NCERT 1975]
(a) Zero (b) +1
(a) The total number of neutrons in the nucleus
(c) –1 (d) +2
(b) The total number of neutrons in the atom
36. A nuclear reaction is accompanied by loss of mass
equivalent to 0.01864 amu . Energy liberated is (c) The total number of protons in the nucleus
(d) The total number of protons and neutrons in
[DCE 2002]
the nucleus
(a) 931 MeV (b) 186 .6 MeV 4. Radioactivity is due to [DPMT 1983, 89; AIIMS 1988]
(c) 17 .36 MeV (d) 460 MeV (a) Stable electronic configuration
37. Nuclear theory of the atom was put forward by (b) Unstable electronic configuration
[KCET 2004] (c) Stable nucleus
(a) Rutherford (b) Aston (d) Unstable nucleus

(c) Neils Bohr (d) J.J. Thomson 5. Radioactive disintegration differs from a chemical
change in being [MNR 1991]
38. Decrease in atomic number is observed during [IIT 1998]
(a) An exothermic change
(a) Alpha emission (b) Beta emission
(b) A spontaneous process
(c) Positron emission (d) Electron capture
(c) A nuclear process
39. Calculate mass defect in the following reaction
(d) A unimolecular first order reaction
1 H 1 H 1 He  0 n
2 3 4 1
6. 238
92 U emits 8 -particles and 6 -particles. The
(Given : mass H  2 . 014 , H  3 .016 , He  4 . 004 ,
2 3
neutron/proton ratio in the product nucleus is
n  1.008 amu ) [Kerala CET 2005] [AIIMS 2005]
(a) 60/41 (b) 61/40
(a) 0.018 amu (b) 0.18 amu
(c) 62/41 (d) 61/42
(c) 0.0018 amu (d) 1.8 amu
7. The element with atomic number 84 and mass
(e) 18 amu
number 218 change to other element with atomic
number 84 and mass number 214. The number of
Causes of radioactivity
 and  -particles emitted are respectively[CPMT 1989]
and Group displacement law
(a) 1, 3 (b) 1, 4
(c) 1, 2 (d) 1, 5
1. 95 Am 241 and 90 Th 234 belong respectively to
 Nuclear Chemistry
273
8. A radium 88 Ra 224 isotope, on emission of an  - 16. Nd (Z  60 ) is a member of group -3 in periodic
particle gives rise to a new element whose mass table. An isotope of it is  -active. The daughter
number and atomic number will be nuclei will be a member of
[CPMT 1980; EAMCET 1985; MP PMT 1993] (a) Group -3 (b) Group - 4
(a) 220 and 86 (b) 225 and 87 (c) Group -1 (d) Group - 2
(c) 228 and 88 (d) 224 and 86 17. Number of neutrons in a parent nucleus X , which
9. 89 Ac 231 gives 82 Pb 207 after emission of some gives 7 N 14 nucleus after two successive 
 and  -particles. The number of such  and  - emissions would be
particles are respectively[MP PMT 1993; UPSEAT 2001] [CBSE PMT 1998; MP PMT 2003]

(a) 5, 6 (b) 6, 5 (a) 9 (b) 8

(c) 7, 5 (d) 5, 7 (c) 7 (d) 6
10. The number of  and  - particles emitted in the 18. The disintegration of an isotope of sodium.
11 Na
24
12 Mg 24  1 e 0 shown is due to
nuclear reaction 90 Th 228  83 Bi 212 are respectively
[AMU (Engg.) 2000]
[MNR 1992; MP PMT 1993; AFMC 1998, 2001;
(a) The emission of -radiation
MH CET 1999; UPSEAT 2000, 01; AMU 2001; CPMT 2002]
(b) The formation of a stable nuclide
(a) 4, 1 (b) 3, 7
(c) The fall in the neutron : proton ratio
(c) 8, 1 (d) 4, 7
(d) None of these
11. The number of neutrons in the parent nucleus
19. After losing a number of  and -particles. 92 U
238
is
which gives N 14 on  -emission and the parent
nucleus is changed to 82 Pb
206
. The total number of -particles
[EAMCET 1985; MNR 1992; lost in this process is [UPSEAT 1999, 2000]
Kurukshetra CEE 1998; UPSEAT 2000, 01] (a) 10 (b) 5
(a) 8 , C 14 (b) 6, C 12 (c) 8 (d) 32
20. Which element is the end product of each natural
(c) 4 , C 13 (d) None of these radioactive series[MP PMT 1996; MP PET/PMT 1998]
12. After the emission of  -particle from the atom (a) Sn (b) Bi
238
92 X , the number of neutrons in the atom will (c) Pb (d) C
be 21. 27
13 Al is a stable isotope. 29
13 Al is expected to
[MNR 1993; UPSEAT 1999, 2001, 02] disintegrate by
(a) 138 (b) 140 [IIT 1996; UPSEAT 2001]
(c) 144 (d) 150 (a)  -emission (b)  -emission
13. When a radioactive element emits an electron the (c) Positron emission (d) Proton emission
daughter element formed will have[EAMCET 1988; MP PET 1994] X
22. An isotope Y A undergoes a series of m alpha
(a) Mass number one unit less
and n beta disintegration to form a stable isotope
(b) Atomic number one unit less X  32
Y 10 B . The values of m and n are respectively[MP PET
(c) Mass number one unit more
(a) 6 and 8 (b) 8 and 10
(d) Atomic number one unit more
(c) 5 and 8 (d) 8 and 6
14. If the amount of radioactive substance is
23. During a  -decay the mass of the atomic nucleus
increased three times, the number of atoms
disintegrated per unit time would [MP PMT 1994] [MP PET 1996]
(a) Be double (b) Be triple (a) Decreases by one unit (b)Increases by one unit
(c) Remain one third (d) Not change (c) Decreases by two units (d)Remains unaffected
15.  -particles are emitted from the atom 24. Which one of the following notations shows the
product incorrectly [MP PET/PMT 1998]
(a) Due to disintegration of neutron
(a) 242
96 Cm ( , 2n) 97
243
Bk (b) 10
5 B ( , n) 13
7 N
(b) Due to disintegration of proton
14
(c) Due to removal of electron from K shell (c) 7 N (n, p ) 14
6 C (d) 28
14
29
Si (d , n) 15 P
(d) Due to removal of electron from outermost 25. An atom has mass number 232 and atomic number
orbit 90. How many  -particles should it emit after
emission of two  -particles, so that the new
 274 Nuclear Chemistry
element's atom has mass number 212 and atomic 34. How many alpha particles are emitted in the
number 82 nuclear transformation 84 Po 215  82 Pb 211 [CPMT 1993]
(a) 4 (b) 5 (a) 0 (b) 1
(c) 6 (d) 3 (c) 2 (d) 3
26. After the emission of one  -particle followed by 35. If uranium (mass no. 238 and atomic no. 92)
one   particle from the atom of 92 X 238 , the emits  -particle, the product has mass number
number of neutrons in the atom will be[CBSE PMT 1995] and atomic number
(a) 142 (b) 146 [CPMT 1984, 90, 93, 94; MNR 1991; IIT 1981]

(c) 144 (d) 143 (a) 234, 90 (b) 236, 92

27. A nuclide of an alkaline earth metal undergoes (c) 238, 90 (d) 236, 90
radioactive decay by emission of the   particles 36. Initial mass of a radioactive element is 40 g. How
in succession. The group of the periodic table to many grams of it would be left after 24 years, if
which the resulting daughter element would its half-life period is 8 years [MP PMT 1985]
belong is [CBSE PMT 2005] (a) 2 (b) 5
(a) Gr.14 (b) Gr.16 (c) 10 (d) 20
(c) Gr.4 (d) Gr.6 37. What is the symbol for the nucleus remaining
after 20 Ca 42 undergoes  -emission[MNR 1987; UPSEAT 200
28. Which one of the following is not correct[MP PMT 1997]
42
(a) 21 Ca (b) Sc 42
(a) 3 Li 7  1 H 1  4 Be 7  0 n 1 20

42 41
(c) 21 Sc (d) 21 Sc
(b) 21 Sc 45  0 n 1  20 Ca 45  0 n 1
38. When a radioactive nucleus emits an  -particle,
(c) 33 As 75  2 He 4  35 Br 78  0 n 1
the mass of the atom [NCERT 1973, 82]
(d) 83 Bi 209  1 H 2  84 Po 210  0 n 1 (a) Increases and its at. number decreases
29. The end product of (4 n  2) radioactive (b) Decreases and its at. number decreases
disintegration series is (c) Decreases and its at. number increases
[MP PET 1997; Pb. PMT 1998; BHU 2000] (d) Remains same and its at. number decreases
(a) 208
(b) Pb 206 39. A photon of hard gamma radiation knocks a
82 Pb 82
24
proton out of 12 Mg nucleus to form [AIEEE 2005]
(c) 82 Pb 207 (d) 83 Bi 210
(a) The isotope of parent nucleus
30. The element 90Th232 belongs to thorium series.
(b) The isobar of parent nucleus
Which of the following will act as the end product
23
of the series (c) The nuclide 11 Na
[BHU 2005] (d) The isobar of 23
Na
11
208
(a) 82Pb (b) 82Bi209
206 40. Pb 210
 82 Pb 206
 2 He 4 . From the above
(c) 82Pb (d) 82Pb207 84

equation, deduce the position of polonium in the

31. On bombarding 8 O 16 with deutrons, the nuclei of
periodic table (lead belongs to group IV A)[AIIMS 1980]
the product formed will be [NCERT 1978]
(a) II A (b) IV B
18 17
(a) 9 F (b) 9 F (c) VI B (d) VI A
(c) 8 O 17 (d) 7 N 14 41. Whenever the parent nucleus emits a -particle, the
daughter element is shifted in the periodic table [NCERT 19
32. An element with atomic number 84 and mass
number 218 loses one  -particle and two  - (a) One place to the right
particles in three successive stages, the resulting (b) One place to the left
element will have (c) Two places to the right
[NCERT 1979; CPMT 1990] (d) Two places to the left
(a) At. no. 84 and mass number 214 42. In the nuclear reaction 92 U 238  82 Pb 206 , the
(b) At. no. 82 and mass number 214 number of alpha and beta particles decayed are
(c) At. no. 84 and mass number 218 [DPMT 1983; MNR 1985; Roorkee Qualifying 1998]
(d) At. no. 82 and mass number 218 (a) 4, 3  (b) 8, 6 
33. Group displacement law was given by [DPMT 1984] (c) 6, 4  (d) 7, 5 
(a) Becquerel (b) Rutherford
43. Atomic number after a  -emission from a nucleus
(c) Soddy and Fajan (d) Madam Curie
having atomic number 40, will be [BHU 1981]
 Nuclear Chemistry
275
(a) 36 (b) 39 52. When an radioactive element emits an alpha
(c) 41 (d) 44 particle, the daughter element is placed in the
periodic table
44. A certain nuclide has a half-life period of 30
[MP PET 1991; MADT Bihar 1981]
minutes. If a sample containing 600 atoms is
allowed to decay for 90 minutes, how many atoms (a) Two positions to the left of the parent element
will remain [NCERT 1978] (b) Two positions to the right of the parent
(a) 200 atoms (b) 450 atoms element
(c) One position to the right of the parent element
(c) 75 atoms (d) 500 atoms
(d) In the same position as the parent element
45. The reaction which disintegrates neutron is or
neutron is emitted (which completes first) 53. If the quantity of a radioactive element is
doubled, then its rate of disintegration per unit
[IIT 1988; MP PMT 1991; KCET 2005]
time will be
(a) 96 Am 240
 2 He 4  97 Bk 244  1e 0 [NCERT 1972, 92; MP PET 1989]
(a) Unchanged
(b) 15 P 30  14 Si
30
 1e 0
(b) Reduced to half
(c) 6C
12
 1 H 1  7 N 13
(c) Increased by 2 times
(d) 13 Al 27
 2 He  4
15 P
30
(d) Doubled
54. The number of  and  -particles emitted during the
46. If 92 U
236
nucleus emits one  -particle, the
transformation of 90 Th 232 to 82 P 208 are respectively
remaining nucleus will have
[MNR 1978; NCERT 1984;CPMT 1989;
[MP PMT 1976, 80; BHU 1985; CPMT 1980]
RPET 1999; MP PMT 2001; KCET 2003]
(a) 119 neutrons and 119 protons
(a) 4, 2 (b) 2, 2
(b) 142 neutrons and 90 protons
(c) 8, 6 (d) 6, 4
(c) 144 neutrons and 92 protons
55. The atomic number of a radioactive element
(d) 146 neutrons and 90 protons
increases by one unit in [EAMCET 1997]
47.  -rays have high ionization power because they
(a) Alpha emission (b) Beta emission
possess
[CPMT 1982] (c) Gamma emission (d) Electron capture
(a) Lesser kinetic energy 56. The end (4 n  1)
product of
radioactive
(b) Higher kinetic energy disintegration series is
[MP PMT 1999]
209 210
(c) Lesser penetrating power (a) 83 Bi (b) 84 Po
(d) Higher penetrating power 208
(c) 82 Pb (d) 82 Pb 207
48. When radium atom which is placed in II group,
loses an  - particle, a new element is formed 57. When a  -particle emits from the atom of an
which should be placed in group[CPMT 1979, 80, 94; NCERT 1979,
element,
82] then
(a) Second (b) First [MP PET 1990]
(c) Fourth (d) Zero (a) Atomic number increases by two units
49. Starting from radium, the radioactive (b) Atomic number increases by three units
disintegration process terminates when the
(c) Atomic number decreases by one unit
following is obtained [CPMT 1979]
(d) Atomic number increases by one unit
(a) Lead (b) Radon
(c) Radium A (d) Radium B 58. The number of -particles emitted in radioactive
change 92 U 238  82 Pb 206  2 He 4 is [KCET 2000]
50. The appreciable radioactivity of uranium minerals
is mainly due to [NCERT 1980] (a) 2 (b) 4
(a) An uranium isotope of mass number 235 (c) 6 (d) 10
(b) A thorium isotope of mass number 232 59. If half-life of a certain radioactive nucleus is
(c) Actinium 1000 s, the disintegration constant is [MP PET 2001]
(d) Radium
(a) 6 .93  10 2 s 1 (b) 6.93  10 4 s
51. After losing a number of  and  -particles,
238 (c) 6 .93  10 4 s 1 (d) 6 .93  10 3 s
92 U changed to 82 Pb 206 . The total number of
60. Radioactivity of naptunium stops when it is
particles lost in this process is [MNR 1985]
converted to
(a) 14 (b) 5
[JIPMER 2001]
(c) 8 (d) 32
 276 Nuclear Chemistry
(a) Bi (b) Rn (c) 3.26  10 3 year 1 (d) 4.33  10 12 year 1
(c) Th (d) Pb 70. The number of  and   particles emitted in the
61. The highest binding energy per nucleon will be nuclear reaction 238
90 Th 234 91 Pa 234 are
92 U
for
respectively
[AIIMS 2001]
[Pb.CET 2001]
(a) Fe (b) H 2
(a) 1 and 1 (b) 1 and 2
(c) O 2 (d) U
(c) 2 and 1 (d) 2 and 2
62. In the Thorium series, 90 Th
232
loses total of 6 - 71. In which radiation mass number and atomic
particles and 4 -particles in ten stages. The final number will not change [JEE Orissa 2004]
isotope produced in the series is [MP PET 2001] (a)  (b) 
(c)  (d)  and 2 
209 209
(a) 82 Pb (b) 83 Bi

208 206 72. Disintegration constant for a radioactive substance

(c) 82 Pb (d) 82 Pb

63. All the nuclei from the initial element to the final is 0.58 hr 1 . Its half-life period [BHU 2004]
(a) 8.2 hr
element constitute a series which is called [Kerala (Med.) 2002] (b) 5.2 hr
(a) g-series (b) b-series (c) 1.2 hr (d) 2.4 hr
(c) b-g series (d) Disintegration series 73. A radioactive nucleus will not emit [DPMT 2005]
64. The number of neutrons in the parent nucleus (a) Alpha and beta rays simultaneously
which gives N 14 on  – emission is [Pb.CET 2004] (b) Beta and gamma rays simultaneously
(a) 7 (b) 14 (c) Gamma and alpha rays
(c) 6 (d) 8 (d) Gamma rays only
65. The nuclear binding energy for Ar (39.962384 2  
72 X 
74. 180    Z X  . Z and A are[DPMT 2005]
A
amu) is: (given mass of proton and neutron are
(a) 69, 172
1.007825 amu and 1.008665 amu respectively) [Pb.CET 2002] (b) 172, 69
(a) 343 .81 MeV (b) 0.369096 MeV (c) 180, 70 (d) 182, 68
(c) 931 MeV (d) None of these 75. Loss of a beta particle is equivalent to [J & K 2005]
(a) Increase of one neutron only
66. The number   and  - particles emitted
respectively during the transformation of (b) Decrease of one neutron only
232
Th to 208
Pb is (c) Both (a) and (b)
90 82
(d) None of these
[Kerala PMT 2004]
(a) 3, 6 (b) 6, 3 Rate of decay and Half-life
(c) 4, 6 (d) 6, 4
1. The half-life period of a radioactive substance is 8
(e) 6, 8
years. After 16 years, the mass of the substance
67. Consider the following nuclear reactions, will reduce from starting 16 .0 g to [MP PMT 1999]
92 M  y N  2 2 He
238 x 4
(a) 8.0 g (b) 6.0 g

x
y N A
BL  2 (c) 4.0 g (d) 2.0 g
2.
The number of neutrons in the element L is [AIEEE 2004] The atomic mass of an element is 12.00710 amu.
(a) 140 (b) 144 If there are 6 neutrons in the nucleus of the atom
of the element, the binding energy per nucleon of
(c) 142 (d) 146
the nucleus will be
68. The number of   and   particles emitted when [MP PMT 1999]
232 220
a radioactive element 90 E changes into 86 G (a) 7.64 MeV (b) 76.4 MeV
will be (c) 764 MeV (d) 0.764 MeV
[MP PET 2004] ( e  =0.00055 amu, p =1.00814 amu, n =1.00893
(a) 5 and 4 (b) 2 and 3 amu)
(c) 3 and 2 (d) 4 and 1 3. Half-life period of a metal is 20 days. What
69. The disintegration constant of radium with half- fraction of metal does remain after 80 days[BHU 1996]
life 1600 years is [MHCET 2004] (a) 1 (b) 1/16
(a) 2.12  10 4 year 1 (b) 4.33  10 4 year 1 (c) 1/4 (d) 1/8
 Nuclear Chemistry
277
4. In the radioactive decay 92 X 232  89 Y 220 , how many [NCERT 1980; CPMT 1999; KCET 2000; Pb.CET 2001]

 and  - particles are ejected from X to form Y (a) 12 gm (b) 24 gm

(c) 36 gm (d) 48 gm
[CBSE 1999]
(a) 3 and 3  (b) 5 and 3  14. C 14 is radioactive. The activity and the
disintegration product are
(c) 3 and 5  (d) 5 and 5 
(a)  -active, N 14 (b)  - active, Be 10
5. Which of the following does not take place by  - 7 7

decay (c) Positron active, 5 B14 (d)  - active, C 14

[MP PMT 1996] 15.
Radioactivity of a radioactive element remains
(a) 92 U 238
 90 Th 234
(b) 90 Th 232
 88 Ra 228
1
of the original radioactivity after 2.303
10
(c) 88 Ra 226
 86 Rn 222
(d) 83 Bi 213
 84 Po 213
seconds. The half-life period is
6. 1 .0 g of a radioactive isotope was found to reduce to (a) 2.303 (b) 0.2303
125 mg after 24 hours. The half-life of the isotope is[MP PET 1996]
(c) 0.693 (d) 0.0693
(a) 8 hours (b) 24 hours 16. A radioactive substance has t1 / 2 60 minutes. After
(c) 6 hours (d) 4 hours 3 hrs, what percentage of radioactive substance
7. A radioactive element decays at such a rate that will remain
after 15 minutes only 1/10 of the original amount [BHU 1995]
is left. How many more minutes will be needed (a) 50% (b) 75%
when only 1/100 of the original amount will be
(c) 25% (d) 12.5%
left
17. A freshly prepared radioactive source of half-life
(a) 1.5 minutes (b) 15.0 mintues
2 hours emits radiations of intensity which is 64
(c) 16.5 minutes (d) 30 minutes times the permissible safe level. The minimum
8. The radioactive decay of 35 X 88 by a beta emission time after which it would be possible to work
produces an unstable nucleus which safely with this source is
spontaneously emits a neutron. The final product [IIT 1988]
is [MNR 1995; CBSE 2001] (a) 6 hours (b) 12 hours
(a) 37 X 88 (b) 35 Y 89 (c) 24 hours (d) 128 hours
88 87 18. During a negative  -decay [MNR 1990; IIT 1985]
(c) 34 Z (d) 36 W
(a) An atomic electron is ejected
9. What is the half-life of a radioactive substance if
75% of a given amount of the substance (b) An electron which is already present within
disintegrates in 30 minutes the nucleus is ejected
(c) A neutron in the nucleus decays emitting an
(a) 7.5 minutes (b) 25 minutes
electron
(c) 20 minutes (d) 15 minutes
(d) A part of the binding energy of the nucleus is
10. In radioactive decay which one of the following converted into an electron
moves the fastest [MP PET/PMT 1998]
19. The decay constant of a radioactive sample is '  ' .
(a)  -particle (b)  -particle The half-life and mean life of the sample are
(c)  -rays (d) Positron respectively
[MNR 1990; IIT 1989]
11. The half-life of a radionuclide is 69.3 minutes.
What is its average life (in minutes) 1 ln 2 ln 2 1
(a) , (b) ,
(a) 100 (b) 10 2    

(c) (69 .3)1 (d) 0 .693  69 .3 1  1

(c)  ln 2, (d) ,
 ln 2 
12. 10 gm of a radioactive substance is reduced to
1 .25 gm after 15 days. Its 1kg mass will reduce (in 20. The half-life of a radio isotope is 20 hours. After
how many days) to 500 gm in 60 hours, how much amount will be left behind
[MP PMT 1991]
(a) 500 days (b) 125 days
(a) 1/8 (b) 1/4
(c) 25 days (d) 5 days
(c) 1/3 (d) 1/2
13. A radioactive isotope having a half-life of 3 days
was received after 12 days. It was found that 21. Half-life period of a zero order reaction is
there were 3 gm of the isotope in the container. [AMU (Engg.) 1999]
The initial weight of the isotope when packed was (a) Inversely proportional to the concentration
 278 Nuclear Chemistry
(b) Independent of the concentration (a) 2g (b) 600 mg
(c) Directly proportional to the initial (c) 1 g (d) 1.5 g
concentration 32. The binding energy of 8O
16
is 127 MeV. Its
(d) Directly proportional to the final binding energy per neutron is
concentration (a) 0.794 MeV (b) 1.5875 MeV
22. If 12 g of sample is taken, and 6 g of a sample (c) 7.94 MeV (d) 15.875 MeV
decays in 1 hr. The amount of sample showing
33. If the half-life period of a first order reaction is
decay in next hour is
138.6 minutes, then the value of decay constant for
[AMU (Engg.) 1999] the reaction will be
(a) 3 g (b) 1 g [MH CET 1999]
(c) 2 g (d) 6 g (a) 5 minute–1 (b) 0.5 minute–1
23. What will be half-life period of a nucleus if at the (c) 0.05 minute–1 (d) 0.005 minute–1
end of 4.2 days, N  0.798 N 0 [MP PET 2000] 34. Half-life of 10 gm of radioactive substance is 10
(a) 15 days (b) 10 days days. The half-life of 20 gm is
(c) 12.83 days (d) 20 days (a) 10 days (b) 20 days
24. If 2.0 g of a radioactive substance has half-life of (c) 25 days (d) Infinite
7 days. The half-life of 1 g sample is [MP PET 2000] 35. 8 gm of the radioactive isotope, cesium-137 were
(a) 7 days (b) 14 days collected on February 1 and kept in a sealed tube.
On July 1, it was found that only 0 .25 gm of it
(c) 28 days (d) 35 days
90
remained. So the half-life period of the isotope is[KCET 19
25. The half-life of 38 Sr is 20 years. If its sample
(a) 37.5 days (b) 30 days
having initial activity of 8000 dis/min is taken, (c) 25 days (d) 50 days
what would be its activity after 80 years [MP PMT 2000]
36. The half-life of radium (226) is 1620 years. The
(a) 500 dis/min (b) 800 dis/min time taken to convert 10 grams of radium to 1.25
(c) 1000 dis/min (d) 1600 dis/min grams is
26. Na 24
half-life is 15 hours. On heating it will [MP PET 1994; UPSEAT 2001]
11
(a) 810 years (b) 1620 years
(a) Reduce (b) Remain unchanged
(c) 3240 years (d) 4860 years
(c) Depend on temperature (d) Become double 37. Half-life of a radioactive substance is 120 days.
27. In a radioactive decay, an emitted electron comes After 480 days, 4 gm will be reduced to[EAMCET 1993]
from (a) 2 (b) 1
[CBSE 1994; Pb. PET 1999]
(c) 0.5 (d) 0.25
(a) Nucleus of the atom
38. The half-life of Co 60 is 7 years. If one gm of it
(b) Inner orbital of the atom
decays, the amount of the substance remaining
(c) Outermost orbit of the atom after 28 years is
(d) Orbit having principal quantum number one [EAMCET 1992]
28. What is the value of decay constant of a (a) 0.25 gm (b) 0.125 gm
compound having half-life time T1 / 2  2.95 days[AFMC 1997]
(c) 0.0625 gm (d) 0.50 gm
(a) 2.7  10 5 s 1 (b) 2.7  10 6 s 1 39. A radioactive isotope decays at such a rate that
(c) 2.7  10 6 s 1 (d) 3  10 5 s 1 1
after 96 minutes only th of the original amount
29. What kind of radioactive decay does not lead to 8
the formation of a daughter nucleus that is an remains. The half-life of this nuclide in minutes is[KCET 19
isobar of the parent nucleus [JIPMER
(a) 121999] (b) 24
(a) -rays (b) -rays (c) 32 (d) 48
(c) Positron (d) Electron capture 40. C  14 has a half-life of 5760 years. 100 mg of a
30. The half-life of 6 C 14 if its K or  is 2.31  10 4 is sample containing C  14 is reduced to 25 mg in
[BHU 1999] [Bihar CEE 1992; AMU 2002; MHCET 1999]

(a) 2  10 yrs 2
(b) 3  10 yrs 3 (a) 11520 years (b) 2880 years
(c) 1440 years (d) 17280 years
(c) 3.5  10 4 yrs (d) 4  10 3 yrs
41. Half-life of a radioactive element is 100 yrs. The
31. A radioactive isotope has a half-life of 10 days. If time in which it disintegrates to 50% of its mass,
today 125 mg is left over, what was its original will be
weight 40 days earlier [KCET 2005] [MP PMT 1995]
 Nuclear Chemistry
279
(a) 50 yrs (b) 200 yrs 51. The half-life of 92 U 238 is 4 .5  10 9 years. After how
(c) 100 yrs (d) 25 yrs many years, the amount of U 238 will be reduced
92
42. The average life period of a radioactive element is to half of its present amount [CPMT 1990; MP PET 1999]
the reciprocal of its [MP PET 1995]
(a) 9 . 0  10 9 years (b) 13 .5  10 9 years
(a) Half-life period
(b) Disintegration constant (c) 4 .5  10 years
9
(d) 4 .5  10 4.5 years
(c) Number of atoms present at any time 52. Radium has atomic weight 226 and a half-life of
1600 years. The number of disintegrations
(d) Number of neutrons
produced per second from 1 gm are [BHU 1990]
43. The half-life period of a radioactive element is 30
minutes. One sixteenth of the original quantity of (a) 4 .8  10 10 (b) 9 . 2  10 6
the element will remain unchanged after [CPMT 1983; MP PMT 3.7  10
(c)1994] 10
(d) Zero
(a) 60 minutes (b) 120 minutes 53. The half-life of a radioactive element is 6 months.
(c) 70 minutes (d) 75 minutes The time taken to reduce its original
44. For a radioactive substance with half-life period concentration to its 1/16 value is
500 years, the time for complete decay of 100 [MP PET 1991]
milligram of it would be (a) 1 year (b) 16 years
[MADT Bihar 1984] (c) 2 years (d) 8 years
(a) 1000 years (b) 100  500 years 54. In the case of a radio isotope the value of T1 / 2 and
(c) 500 years (d) Infinite time  are identical in magnitude. The value is [KCET 2002]
45. A substance of which one gram is taken, after
(a) 0 . 693 (b) (0.693 )1 / 2
half-life time what fraction of it is left ? [MADT Bihar 1983]
1 1 (c) 1/0.693 (d) (0.693 )2
(a) (b)
4 8 55. A radioactive element has half-life of one day.
1 1 After three days, the amount of the element left
(c) (d)
2 32 will be
46. The half-life of the radio element Bi 210 is 5 [MNR 1985; UPSEAT 2000, 01; MH CET 2002]
83

days. Starting with 20 g of this isotope, the (a) 1/2 of the original amount
amount remaining after 15 days is (b) 1/4 of the
[BHU original amount
1987]
(a) 10 g (b) 5 g (c) 1/8 of the original amount
(c) 2.5 g (d) 6.66 g (d) 1/16 of the original amount
47. In radioactive decay of X into Y below, Z Y m is 56. The radioactivity due to C 14 isotope (half-life
3 
6000 years) of a sample of wood from an ancient
6 X 14   Z Y m tomb was found to be nearly half that of fresh
(a) Y 15 (b) Y 17 wood, the tomb is therefore about
6 7
[NCERT 1980, 81; MP PET 1989]
(c) 9 Y 14 (d) 8 Y 14
(a) 3000 years old (b) 6000 years old
48. 75% of the first order reaction was completed in (c) 9000 years old (d) 1200 years old
32 minutes. When was 50% of the reaction
57. The decay of a radioactive element follows first
completed
order kinetics, as a result [
[MNR 1983; MP PET 1997; EAMCET 1998]
(a) Half-life period = constant / k , where k is the
(a) 24 minutes (b) 16 minutes
decay constant
(c) 8 minutes (d) 4 minutes
(b) Rate of decay is independent of temperature
49. If 2.0 g of a radioactive isotope has a half-life of
(c) Rate can be changed by changing chemical
20 hr, the half-life of 0 . 5 g of the same substance conditions
is (d) The element will be completely transformed
[MP PMT 1990; MNR 1992] into a new element after expiry of two half-
(a) 20 hr (b) 80 hr life period
(c) 5 hr (d) 10 hr 58. Half-life of a radioactive substance which
50. Radioactive lead Pb 201 has a half-life of 8 hours. disintegrates by 75 % in 60 minutes, will be [MP PMT 2002
82

Starting from one milligram of this isotope, how (a) 120 min (b) 30 min
much will remain after 24 hours [MP PMT 1990] (c) 45 min (d) 20 min
(a) 1 / 2 mg (b) 1 / 3 mg
(c) 1 / 8 mg (d) 1 / 4 mg
 280 Nuclear Chemistry
59. 87.5% decomposition of a radioactive substance 70. If 8.0 of a radioactive isotope has a half-life of 10
complete in 3 hours. What is the half-life of that hrs. The half-life of 2.0 g of the same substance is [UPSEAT 2
substance [MP PMT 2003] (a) 2.5 hrs. (b) 5 hrs.
(a) 2 hours (b) 3 hours (c) 10 hrs. (d) 40 hrs.
(c) 90 minutes (d) 1 hours 71. If the disintegration constant is 6 .93  10 6 , then
60. Tritium undergoes radioactive decay giving half-life of 6 C 14 will be [KCET 2001]
[CPMT 1976; NCERT 1978]
2 3
(a)  -particles (b)  -particles (a) 10 yrs (b) 10 yrs
4
(c) Neutrons (d) None of these (c) 10 yrs (d) 10 5 yrs

61. Given that a radioactive species decays according to 72. The decay constant of Ra 226 is 1.37  10 11 sec1 . A
exponential law N  N 0 e  t . The half-life of the sample of Ra 226 having an activity of 1.5
millicurie will contain ...... atoms
species is
[Kerala (Med.) 2003] (a) 4 .1  10 18 (b) 3.7  10 17
(a)  (b) No (c) 2 .05  10 15 (d) 4.7  10 10
(c) /ln 2 (d) ln 2/ 73. Amount of 53 I128 (t1 / 2  25 min) left after 75 minutes
62. Half-life of a radioactive disintegration (A  B) is
1 [DCE 2002]
having rate constant 231 sec is [CPMT 1988]
(a) 1 / 6 (b) 1 / 4
(a) 3 .0  10 2 sec (b) 3 .0  10 3 sec
(c) 1 / 8 (d) 1 / 9
(c) 3 .3  10 2 sec (d) 3 .3  10 3 sec 74. The half-life of a radioisotope is four hours. If the
63. The amount of 53 I 128 t1 / 2  25 minutes) left after initial mass of the isotope was 200 g, the mass
50 minutes will be [AIIMS 1982; DPMT 1982, 83] remaining after 24 hours undecayed is
(a) One – half (b) One – third (a) 3.125 g (b) 2.084 g
(c) One – fourth (d) Nothing (c) 1.042 g (d) 4.167 g
64. If 3/4 quantity of a radioactive element 75. An artificial radioactive isotope gave 147 N after
disintegrates in two hours, its half-life would be [MP PMT 1989;
twoCPMT 1984]
successive   particle emissions. The
(a) 1 hour (b) 45 minutes number of neutrons in the parent nucleus must be
(c) 30 minutes (d) 15 minutes (a) 9 (b) 14
65. Radioactive decay is a [MP PMT 1989, 97] (c) 5 (d) 7
(a) Second order reaction (b)First order reation 76. If the half-life of an isotope X is 10 years, its
(c) Zero order reaction (d) Third order reaction decay constant is
66. The half-life of a radioactive element depends [DCE 2004]
1 1
upon (a) 6 . 932 yr (b) 0 . 6932 yr
[EAMCET 1980] 1
(c) 0 . 06932 yr (d) 0 .006932 yr 1
(a) The amount of the element
77. A radioactive isotope decays at such a rate that
(b) The temperature
after 192 minutes only 1 / 16 of the original
(c) The pressure amount remains. The half-life of the radioactive
(d) None of these isotope is
67. The activity of radio isotope changes with[MNR 1986] [Kerala CET 2004]
(a) Temperature (b) Pressure (a) 32 min (b) 48 min
(c) Chemical environment (d) None of these (c) 12 min (d) 24 min
68. A certain nuclide has a half-life of 25 minutes. If 78. In the given reaction,
  
one starts with 100 g of it, how much of it will 92 U
235

( A) (B) (C ) isotope are
remain at the end of 100 minutes [DPMT 1982] [Pb. CET 2000]
(a) 1.0 g (b) 4.0 g 235
(a) A and C (b) 92 U and C
(c) 6.25 g (d) 12.50 g
(c) A and B (d) A, B and C
69. If U 235 is bombarded with neutrons, atom will
79. Rate constant for a reaction is  . Average life is
split into
representative by [Orissa JEE 2004]
[CPMT 1981]
(a) 1 /  (b) In 2 / 
(a) Sr + Pb (b) Cs + Rb
(c) Kr + Cd (d) Ba + Kr
 Nuclear Chemistry
281
 0 .693 5. Artificial elements have been prepared by
(c) (d)
2  bombardment reactions in high energy
accelerators. What is the mass number of the
80. For a reaction, the rate constant is 2 . 34 sec 1 . The element X produced in the following nuclear
half-life period for the reaction is 249
reaction 95 Cf  15
7 N 105 X  4 0 n [AMU (Engg.) 2002]
1

(a) 0.30 sec (b) 0.60 sec

(a) 261 (b) 264
(c) 3.3 sec (d) Data is insufficient
(c) 260 (d) 257
81. T1 / 2 of C 14 isotope is 5770 years. time after
6. Radioactive carbon dating was discovered by
which 72% of isotope left is [Orissa JEE 2005]
[MP PET 2001]
(a) 2740 years (b) 274 years
(a) W.F. Libby (b) G.N. Lewis
(c) 2780 years (d) 278 years
(c) J. Willard Gibbs (d) W. Nernst
82. A radioactive substance takes 20 min to decay
7. The nuclear
25%. How much time will be taken to decay 75% [Orissa JEE 2005] reaction
29 Cu  2 He  17 Cl  14 1 H  16 0 n is referred to as
63 4 37 1 1
(a) 96.4 min (b) 68 min
(c) 964 min (d) 680 min [MP PET 2002]
83. A radioactive sample is emitting 64 times (a) Spallation reaction (b) Fusion reaction
radiations than non hazardous limit. if its half life (c) Fission reaction (d) Chain reaction
is 2 hours, after what time it becomes non-
8. The carbon dating is based on [MP PMT 2001]
hazardous [DPMT 2005]
15 14
(a) 16 hr (b) 12 hr (a) 6 C (b) 6 C
13 11
(c) 8 hr (d) 4 hr (c) 6 C (d) 6 C
84. If 8.0 g of a radioactive substance has a half-life 9. A possible material for use in the nuclear reactors
of 10 hrs., the half life of 2.0 g of the same as a fuel is
substance is [J & K 2005]
[DPMT 1986]
(a) 2.6 hr (b) 5 hr
(a) Thorium (b) Zirconium
(c) 10 hr (d) 40 hr
(c) Beryllium (d) Plutonium
Artificial transmutation 10. Heavy water freezes at [UPSEAT 2001]
(a) 0 C (b) 3 .8 C
1. The age of most ancient geological formation is
(c) 38 C (d)  0.38 C
estimated by
[NCERT 1981; MP PET/PMT 1988; CBSE 1989; 11. To determine the masses of the isotopes of an
MP PET 1997; MP PMT 2002]
element which of the following techniques is
useful
(a) Potassium – Argon method
[NCERT 1978; MNR 1979]
(b) Carbon – 14 dating method (a) The acceleration of charged atoms by an
(c) Radium – Silicon method electric field and their subsequent deflection
(d) Uranium – Lead method by a variable magnetic field
(b) The spectroscopic examination of the light
2. The equation 3 Li 6  1 H 2  2 2 He 4  energy
emitted by vaporised elements subjected to
represents electric discharge
(a) Synthesis of helium (b) Transmutation of (c) The photographing of the diffraction patterns
element which arise when X-rays are passed through
(c) Fusion reaction (d) Nuclear fission crystals
3. The phenomenon of radioactivity arises from the (d) The bombardment of metal foil with alpha
[Kerala (Med.) 2002] particles
(a) Binary fission 12. The radioisotope, tritium (13 H ) has a half-life of
(b) Nuclear fusion 12.3 years. If the initial amount of tritium is 32 mg.
How many milligrams of it would remain after
(c) Stable nuclei
49.2 years [CBSE 2003]
(d) Decay of unstable nuclei (a) 8 mg (b) 1 mg
4. The first artificial disintegration of an atomic (c) 2 mg (d) 4 mg
nucleus was achieved by [Kerala (Engg.) 2002] 13. Neutron is used as a [CPMT 1988]
(a) Geiger (b) Wilson (a) Reducing agent (b) Moderator
(c) Madame curie (d) Rutherford (c) Tracer (d) In biological
(e) Soddy programme
 282 Nuclear Chemistry
14. Hydrogen bomb is based on the phenomenon of (c) Radioactivity
[EAMCET 1980; CPMT 1984, 96; (d) Fusion and fission both
MP PMT 1993, 95, 2002; RPET 1999]
25. Who observed that when the nucleus of uranium
(a) Nuclear fission (b) Nuclear fusion atom was bombarded with fast moving neutrons,
(c) Nuclear explosion (d) Disintegration it becomes so very unstable that it is immediately
15. In the nuclear reactors the speed of the neutrons broken into two nuclei of nearly equal mass
is slowed down by [CPMT 1983, 84] besides other fragments
(a) Heavy water (b) Ordinary water (a) J.J. Thomson (b) Chadwick
(c) Zinc rods (d) Molten caustic soda
(c) Einstein (d) Hahn and
16. By which law, energy produced in nuclear
Strassmann
reaction is given
[MP PET 2000]
26. When a radioactive substance is subjected to
vacuum, the rate of disintegration per second
(a) Graham’s law (b) Charle’s law
[DPMT 1985; NCERT 1972]
(c) Gas Lussac’s Law (d) Einstein’s law
17. If two light nuclei are fused together in nuclear (a) Increases considerably
reaction the average energy per nucleon [Pb. PMT 2001] (b) Increases only if the products are gaseous
(a) Increases (b) Cannot be (c) Is not affected
determined (d) Suffers a slight decrease
(c) Remains same (d) Decreases
27. A radio isotope will not emit [KCET 2002]
18. A wood piece is 11460 years old. What is the fraction
(a) Gamma and alpha rays simultaneously
of 14 C activity left in the piece? (Half-life period of
(b) Gamma rays only
14
C is 5730 years)
(c) Alpha and beta rays simultaneously
[MP PMT 2000]
(d) Beta and gamma rays simultaneously
(a) 0.12 (b) 0.25 56
28. What is the packing fraction of Fe
(c) 0.50 (d) 0.75 26

19. When nuclear energy is intended to be harnessed (Isotopic mass = 55.92066) [

for generation of electricity, potentially (a) 14 .167 (b) 173 .90
destructive neutron released in a nuclear reactor
(c) 14 .187 (d) 73 .90
are absorbed by
[MH CET 2001] 29. The energy released in an atom bomb explosion is
mainly due to [BVP 2003]
(a) Long rods of Cd (b) Heavy water
(c) Cubical blocks of steel (d) Both (a) and (c) (a) Release of neutrons
20. The proper rays for radiocarbon dating are [MP PET 2002] (b) Release of electrons
(a) UV-rays (b) IR-rays (c) Greater mass of products than initial material
(c) Cosmic rays (d) X-rays (d) Lesser mass of products than initial material
21. 1H
2
 1 H  2 He  0 n . Above nuclear reaction is
2 3 1 30. C 14 is [KCET 2002]
called (a) A natural radioactive isotope
[UPSEAT 2001] (b) A natural non-radioactive isotope
(a) Nuclear fission (c) An artificial radioactive isotope
(b) Nuclear fusion (d) An artificial non-radioactive isotope
(c) Artificial transmutation 31. A radioactive isotope has a half-life of 10 years.
(d) Spontaneous disintegration What percentage of the original amount of it
22. Which of the following is used as a moderator in a remain after 20 years
nuclear reactor [AIIMS 2001] [KCET 2001]
(a) D2 O (b) N 2 O (a) 0 (b) 12.5

(c) H 2 O (d) NaOH (c) 8 (d) 25

32. In a chain reaction, uranium atom gets fissioned
23. The fuel of atomic pile is [NCERT 1973; AFMC 1989] forming two different materials. The total weight
(a) Thorium (b) Sodium of these put together is [EAMCET 1986]
(c) Uranium (d) Petroleum (a) More than the weight of parent uranium atom
24. Atom bomb is based on the principle of (b) Less than the weight of parent uranium atom
[CPMT 1982; BHU 1985] (c) More or less depends upon experimental
(a) Nuclear fusion conditions
(b) Nuclear fission (d) Neither more nor less
 Nuclear Chemistry
283
33. A substance used as a moderator in nuclear 42. D2 O is used in [CPMT 1997]
reactors is (a) Industry (b) Nuclear reactor
[MP PET 1995]
(c) Medicine (d) Insecticide
(a) Cadmium (b) Uranium-235
43. India conducted an underground nuclear test at
(c) Lead (d) Heavy water [KCET 1998]
34. Equation 17 Cl 37  1 H 2  18 Ar 38  0 n 1 is[MP PMT 1989] (a) Tarapur (b) Narora
(a) Nuclear fission (c) Pokhran (d) Pushkar
(b) Nuclear fusion 44. Energy required to separate neutron and proton
(c) Transformation of chlorine from the nucleus is called [RPMT 1999]
(d) Synthesis of argon (a) Bond energy (b) Nuclear energy
35. 1.0 gm radioactive sodium on decay becomes (c) Chemical energy (d) Radiation energy
0.25 gm in 16 hours. How much time 48 gm of 45. Liquid sodium finds use in nuclear reactors. Its
function is
same radioactive sodium will need to become
(a) To collect the reaction products
3.0 gm
(b) To act as a heat exchanger or coolant
(a) 48 hours (b) 32 hours
(c) To absorb the neutrons in order to control the
(c) 20 hours (d) 16 hours chain reaction
36. Large energy released in an atomic bomb (d) To act as a moderator which slows down the
explosion is mainly due to [CPMT 1972, 73, 81, 90] neutrons
(a) Products having a lesser mass than initial 46. Which is least effective for artificial
substance transmutation
(b) Conversion of heavier to lighter atoms [DPMT 2000]
(c) Release of neutrons (a) Deuterons (b) Neutrons
(d) Release of electrons (c) -particles (d) Protons
37. The reaction 1H
2
 1 H 3  2 He 4  0 n 1  energy 47. A piece of wood was found to have C 14 /C 12 ratio
represents 0.7 times that in a living plant. The time period
[MP PMT 1990; CPMT 1990; KCET 1992]
when the plant died is (Half-life of C 14  5760 yrs ) [Pb. PMT
(a) Nuclear fission
(a) 2770 yrs (b) 2966 yrs
(b) Nuclear fusion
(c) 2980 yrs (d) 3070 yrs
(c) Artificial disintegration
48. When a slow neutron goes sufficiently close to a
(d) Transmutation of element
U 235 nucleus, then the process which takes place
38. Carbon-14 dating method is based on the fact that is [AFMC 2000]
[CBSE 1997]
(a) Fusion of U 235 (b) Fission of U 235
(a) Carbon-14 fraction is the same in all objects
(c) Fusion of neutron (d) First (a) then (b)
(b) Carbon-14 is highly insoluble
49. Al 28 when radiated by suitable projectile gives
(c) Ratio of carbon-14 and carbon-12 is constant 13

(d) All of these 15 P 31 and neutron. The projectile used is

39. Half-life period of a radioactive element is 10.6 [MP PMT/PET 1988; CPMT 1985, 82]
yrs. How much time will it take in its 99% (a) Proton (b) Neutron
decomposition (c) Alpha particle (d) Deuteron
[RPET 1999]
50. Which of the following statements about
(a) 7046 yrs (b) 7.046 yrs radioactivity of an element is incorrect
(c) 704.6 yrs (d) 70.4 yrs (a) It is a nuclear property
40. Deuterium resembles hydrogen in chemical (b) It does not involve any rearrangement of
properties but reacts [JIPMER 2001] electrons
(a) More vigorously than hydrogen (c) Its rate is affected by change in temperature
(b) Faster than hydrogen and/or pressure
(c) Slower than hydrogen (d) It remains unaffected by the presence of other
(d) Just as hydrogen element or elements chemically combined
with it
41. Which of the following is heavy water [AFMC 1997]
51. Radioactive iodine is being used to diagnose the
(a) H 2 O18 (b) H 2 O16
disease of
(c) H 2 O3 (d) D2 O [MP PET 1996]
 284 Nuclear Chemistry
(a) Bones (b) Kidneys (a) Loses only some elementary nuclear particles
(c) Blood cancer (d) Thyroid from another nucleus
52. C  14 is used in carbon dating of dead objects (b) Captures some elementary nuclear particles
because from another nucleus
[DPMT 1996] (c) Breaks up into several smaller nuclei
3 (d) Breaks up into two smaller nuclei with the
(a) Its half-life is 10 years
loss of same elementary nuclear particles
4
(b) Its half-life is 10 years
62. The huge amount of energy which is released
(c) It is found in nature abundantly and in during atomic fission is due to [CPMT 1990]
definite ratio
(a) Loss of mass (b) Loss of electrons
(d) It is found in dead animals abundantly
(c) Loss of protons (d) Loss of  -particles
53. A radioactive element resembling iodine in
properties is 63. The measure of binding energy of a nucleus is the
[Kurukeshetra CEE 1998] [CPMT 1982; Kurukshetra CEE 1998]
(a) Astatine (b) Lead (a) Mass defect (b) Energy of protons
(c) Radium (d) Thorium (c) Energy of neutrons (d) Total energy of
54. For artificial transmutation of nuclei, the most nucleons
effective one is 64. The first controlled artificial disintegration of an
[MP PMT 1996] atomic nucleus was achieved by [BHU 1987]
(a) Proton (b) Deuteron (a) Geiger (b) Wilson
(c) Helium nuclei (d) Neutron (c) Cockcroft (d) Rutherford
55. Which of the following cannot be accelerated [KCET 2005]
65. Artificial radioactivity was first discovered by
(a)  -particle (b)  -particle [CPMT 1972; BHU 1984; KCET 1999]
(c) Protons (d) Neutrons (a) Seaberg (b) Rutherford
56. For the fission reaction (c) Einstein (d) Irene Curie & Juliot
92 U
235
 0 n1  56 Ba40  y E x  2 0 n1 66. The half-life period of a radioactive element is
140 days. After 560 days, one gram of the element
The value of x and y will be
will reduce to
(a) x  93 and y  34 (b) x  92 and y  35 [CPMT 1989; IIT 1986; EAMCET 1992;
(c) x  89 and y  44 (d) x  94 and y  36 MP PET 1997; UPSEAT 1999]
57. Heavy water is used as (a) 1 / 2 g (b) 1 / 4 g
[Bihar MEE 1996; UPSEAT 1999, 2000, 02] (c) 1 / 8 g (d) 1 / 16 g
(a) Control rods (b) Moderator
67. A device used for the measurement of
(c) Fuel (d) Coolant
radioactivity is
(e) None of these
[BHU 1979]
58. Unit for radioactive constant is [MP PET 1990]
(a) Mass spectrometer (b) Cyclotron
(a) Time -1 (b) Time (c) Nuclear reactor (d) G.M. counter
(c) Mole  time 1 (d) Time  mole 1 68. In a nuclear reactor, chain reaction is controlled
59. Which of the following is used in dating by introducing [EAMCET 1984]
archeological findings or In a method of absolute (a) Iron rod (b) Cadmium rod
dating of fossils a radioactive element is used. It
(c) Graphite rod (d) Platinum rod
is
[CPMT 1983, 85; NCERT 1978; BHU 1981;
69. In atomic reactors, graphite is used as a
MP PMT 1993; AFMC 1997] [NCERT 1980; MP PET 1989]
(a) Lubricant
(a) 92 U 235 (b) 6 C 14
(b) Moderator to slow down neutrons
(c) 6 C 12 (d) 20 Ca 40 (c) Fuel
60. A radioactive isotope has a half-life of 20 days. If (d) Liner of the reactor
100 gm of the substance is taken, the weight of 70. The modern basis of atomic weight is
the isotope remaining after 40 days is [NCERT 1979] [MP PET 1989; CPMT 1993]
(a) 25 gm (b) 2.5 gm
(a) Isotope H 1  1 .000 (b) Oxygen = 16.000
(c) 60 gm (d) 40 gm
(c) Isotope O 16
 16 .000 (d) Isotope C 12  12 .000
61. In a fission reaction the nucleus of an element
[NCERT 1977]
 Nuclear Chemistry
285
71. Which radioactive carbon has been helpful in (d) 13 Al 27  2 He 4  15 P 30  0 n 1
understanding the mechanism of photosynthesis
in plants 79. The C 14 to C 12 ratio in a wooden article is 13%
14 13 that of the fresh wood. Calculate the age of the
(a) 6C (b) 6C
wooden article. Given that the half-life of C 14 is
12 15
(c) 6C (d) 6C 5770 years [Pb.CET 2004]
72. Artificial transmutation was discovered by[Pb.CET 2003] (a) 16989 years (b) 16858 years
(a) Pauli (b) Rutherford (c) 15675 years (d) 17700 years
(c) Soddy (d) Curie
80. Hydrogen bomb is based on the principle of [AIEEE 2005]
73. Which of the following is an example of nuclear
fusion (a) Nuclear fission (b) Natural radioactivity
[MP PMT 1989; DCE 2004] (c) Nuclear fusion (d) Artificial
radioactivity
(a) 1 H  1 H  2 He  energy
2 2 4

81. Match List –I and List-II and choose right one by

(b) 92 U 235  o n 1  56 Ba 141  36 Kr 92  30 n
1
 energy using code given in list [Kerala CET 2005]
(c) 13 Al 27  1 H 1  12 Mg 24  2 He 4 List – I List –II
(d) None of these Nuclear reactor Used substance
74. The radioactivity isotope 60
Co which is used in Component
27

the treatment of cancer can be made by (n, p) 1. Moderator (A) Uranium

2. Control rods
reaction. For this reaction the target nucleus is[CBSE PMT 2004] (B) Graphite
(a) 60 (b) 60 3. Fuel rods (C) Boron
28 Ni 27 Co
4. Coolent (D) Lead
(c) 59
28 Ni (d) 59
27 Co (E) Sodium
75. Fusion bomb involves [AFMC 2004] Code :
(a) Combination of lighter nuclei into bigger 1 2 3 4
nucleus (a) B A C E
(b) Destruction of heavy nucleus into smaller (b) B C A E
nuclei (c) C B A E
(c) Combustion of oxygen (d) C D A B

(d) Explosion of TNT (e) D C B A

76. The element used for dating the ancient remains

is Isotopes-Isotones and Nuclear isomers
[AFMC 2004]
1. Substances which have identical chemical
(a) Ni (b) C-14 properties but differ in atomic weights are called
(c) C-12 (d) Rd [EAMCET 1980, 83; DPMT 1985; MNR 1982]
77. If radium and chlorine combine to from radium (a) Isothermals (b) Isotopes
chloride the compound is [Kerala PMT 2004] (c) Isentropus (d) Elementary particles
(a) No longer radioactive 2. Tritium is an isotope of [DPMT 1985]

(b) Twice as radioactive as radium (a) Hydrogen (b) Titanium

(c) Tantalum (d) Tellurium
(c) Half as radioactive as radium
3. O – 18 isotope of oxygen will have [CPMT 1972, 79]
(d) As radioactive as radium
(a) 18 protons
(e) Thrice as radioactive as radium (b) 9 protons and 9 neutrons
78. Which of the following is an example of nuclear (c) 8 neutrons and 10 protons
fission (d) 10 neutrons and 8 protons
[Pb. CET 2002] 4. Which of the following is an isobaric pair [CPMT 1987, 93]
(a) 1H
2
 1 H  2 He  
2 4
(a) 6C
13
, 7 N 13 (b) 6C
13
, 7 N 14
(b) A  B  C  energy (c) 7 N 14 , 8 O 15 (d) 7 N 13 , 8 O 15
(c) 92 U 235  0 n 1  56 Ba 141  36 Kr 92  3 0 n 1  energy 5. Isotopes are atoms having the same
[EAMCET 1978, 79; MP PMT 1980; CPMT 1973;
 286 Nuclear Chemistry
BHU 2001; AFMC 2003] (c) Isomers (d) Isotones
(a) Atomic mass (b) Mass number 16. Which one of the following pairs represents
(c) Atomic number (d) Number of neutrons isobars
6. Successive emission of an  -particle and two  - [CPMT 1988]
3 4
particles by an atom of an element results in the (a) 2 He and 2 He
formation of its 24 25
(b) 12 Mg and 12 Mg
[MP PMT/PET 1988; BHU 1979]
40
(a) Isobar (b) Isomorph (c) 19 K and 40
20 Ca
(c) Isotope (d) Isomer 39 40
(d) 19 K and 19 K
7. In treatment of cancer, which of the following
17. Nuclei of isotopes differ in[CPMT 1986, 90; MP PMT 1987]
isotope is used[DPMT 1985; BHU 1995; KCET 1999; AMU 1999;
Pb.CET 2001; MP PET 2002; Kurukshetra CET 2002] (a) The number of protons
(a) 53 I131 (b) 15 P 32 (b) The number of neutrons
60 2 (c) The number of protons and neutrons both
(c) 27 Co (d) 1H
(d) None of these
8. Elements having different nuclear charge but the
18. An isotope of ‘parent’ is produced, when its
same mass number are called[NCERT 1974; MP PMT 1991;
nucleus loses
CBSE PMT 1991; CPMT 1989; EAMCET 1992]
[CPMT 1987; MP PET 1991]
(a) Isotopes (b) Isobars
(a) One  -particle
(c) Isomers (d) Isotones
(b) One  -particle
9. Which isotope on bombardment with  -particles
will give 17
and 1 H 1 (c) One  and two  -particles
8O [NCERT 1983]
16 (d) One  and two  - particles
(a) 8O (b) 7 N 14
19. Which of the following isotopes is likely to be
(c) 7 N 15 (d) 6C
14
most stable
10. Emission of  -particle by an atom of an element [EAMCET 1982]
results in the formation of its[BHU 1979; DPMT 1985; KCET 1999]
(a) 30 Zn 71 (b) 30 Zn 66
(a) Isotope (b) Isomer 64
(c) 30 Zn (d) None of these
(c) Isomorph (d) Isobar
20. Which of the following statement is false
11. Radioactive isotopes that have an excessive
[Manipal MEE 1995]
neutron/proton ratio generally exhibit
(a) e  emission (b) 4
emission (a) In chlorine gas, the ratio of Cl 35 and Cl 37 is 1
2 He
:3
(c) e  emission (d) K -electron capture (b) The hydrogen bomb is based on the principle
12. Atomic weights of carbon, nitrogen and oxygen of nuclear fusion
are 12, 14 and 16 respectively. An atom of atomic (c) The atom bomb is based on the principle of
weight 14 and nuclear charge + 6 is an isotope of nuclear fission
(a) Oxygen (b) Carbon (d) The penetrating power of a proton is less than
(c) Nitrogen (d) None of these that of an electron
13. Isotopes of an element have [MNR 1985] 21. Isotones are elements having
(a) Similar chemical properties but different [Bihar MEE 1996; Bihar CEE 1995]
physical properties (a) Same mass number but different neutrons
(b) Similar chemical and physical properties (b) Same atomic number but different neutrons
(c) Similar physical properties but different (c) Same atomic number, mass number and
chemical properties neutrons
(d) Different chemical and physical properties (d) Different atomic and mass number but same
14. Whose number is common in isotopes [AIIMS 1988] neutrons
(a) Proton (b) Neutron 22. Isobaric atoms may contain
(c) Proton and neutron (d) Nucleon (a) Same number of p  and different number of
15. In the following radioactive transformation n 0
  
R  X  Y  Z ; the nuclei R and Z are
(b) Same number of n 0 and different number of
[BHU 1987] 
p
(a) Isotopes (b) Isobars
 Nuclear Chemistry
287
(c) Same number of both p  and n 0 [EAMCET 1987; NCERT 1971; CPMT 1976; MP PET 1994]
 0 (a) Mass
(d) Different numbers of both p and n
(b) Atomic number
23. 20 X 40 and 21 X 40 are [CPMT 1996] (c) General chemical reactions
(a) Isobars (b) Isotopes (d) Number of electrons
(c) Isotones (d) Isostereomers 34. The isotope U 235 decays in a number of steps to
92
24. Which property is different for neutral atoms of
an isotope of lead Pb 207 . The groups of particles
the two isotopes of the same element [JIPMER 2001] 82

(a) Number of protons (b) Atomic number emitted in this process will be
(c) Number of neutrons (d) None of these (a) 4, 7  (b) 6, 4 
25. Which of the following species is isotonic with (c) 7, 4  (d) 10 , 8 
86
37 Rb 35. Addition of two neutrons in an atom A would[AMU 1984]
[BHU 2001] (a) Change the chemical nature of A
(a) 36 Kr 84 (b) 37 Rb 85 (b) Produce an isobar of A
(c) 87
(d) 89 (c) Produce an isotope of A
38 Sr 39 Y
(d) Produce another element
26. The maximum sum of the number of neutrons and
protons in an isotope of hydrogen is [Pb. PMT 2001] 36. Atomic weight of the isotope of hydrogen which
contains 2 neutrons is the nucleus would be[CPMT 1980]
(a) 4 (b) 5
(c) 6 (d) 3 (a) 2 (b) 3
35 37 (c) 1 (d) 4
27. Difference in 17 Cl and 17 Cl is of [AFMC 2000]
37. If a radioactive isotope with atomic number A and
(a) Atomic number (b) Number of protons
mass number M emits an  -particle, the atomic
(c) Number of neutrons (d) Number of electrons number and mass number of that new isotope will
28. Which of the following is an isotonic pair become
[AMU (Engg.) 2000] [NCERT 1980]
40 40 39
(a) 19 K, 20 Ca (b) 19 K , 40
20 Ca (a) A – 2, M – 4 (b) A – 2, M
33
(c) 18 Ar, 40
18 Ar (d) 40
18 Ar, 4020 Ca (c) A, M – 2 (d) A – 4, M – 2
38. Which character is different of the two isotopes of
29. 6 C 11 and 5 B 11 are referred as [NCERT 1978]
an element[NCERT 1971; EAMCET 1980, 92; CPMT 1992]
(a) Nuclear isomers (b) Isobars (a) Atomic mass (b) Atomic number
(c) Isotopes (d) Fission products (c) Number of electrons (d) Number of protons
30. The atomic number of bromine is 35 and its
39. The symbol of an isotope is 32 X 65 , this reveals
atomic weight is 79. Two isotopes of bromine are
present in equal amounts. Which of the following that
statements represents the correct number of [MP PET 1991]
neutrons [NCERT 1983] (a) Its atomic number is 32 and atomic weight is
First isotope Second isotope 65
(a) 34 36 (b) Its atomic number is 65
(b) 44 46 (c) It has 65 electrons
(c) 45 47 (d) It has 32 neutrons
(d) 79 81 40. Two atoms have the same atomic mass but
31. Isotopes are those which contain [RPMT 1997]
different atomic numbers. Such atoms are called
as
(a) Same number of neutrons
[NCERT 1971, 76; IIT 1983]
(b) Same physical properties
(a) Isotopes (b) Isobars
(c) Same chemical properties
(c) Isomer (d) Isoelectronic
(d) Different atomic mass 40 40 40
41. Ar , 20 Ca and K are
32. An element ' A ' emits an  -particle and forms 18 19

' B'. ' A' and ' B ' are [DPMT 1990] [MNR 1983; DPMT 1991; EAMCET 1992;

(a) Isotopes (b) Isobars RPMT 1997; Pb.CET 2000]

(c) Isotones (d) Isodiasphere (a) Isomers (b) Isotopes

33. Which of the following properties are different (c) Isobars (d) Isotones
for neutral atoms of isotopes of the same element 42. Atoms in hydrogen gas have preponderance of
 288 Nuclear Chemistry
[CPMT 1972] 53. Isotopes were discovered by[AMU 1983; AFMC 1995]
1
(a) 1H atoms (a) Aston (b) Soddy
(b) Deuteron atoms (c) Thomson (d) Millikan
(c) Tritium atoms 54. Which of the following are iso-electronic [CBSE 2002]
(d) All the three (a), (b) and (c) are in equal (a) CO2 and NO (b) SO 2 and CO2
proportion (c) CN and CO (d) NO2 and CO2
43. Positron emission results from the transformation 55. Which of the following are pairs of isotopes
of one nuclear proton into neutron. The isotope
[Bihar CEE 1982]
thus produced possesses [MP PMT 1990]

(a) 2
1H and 3
1H (b) 3
1H and 4
H
(a) Same mass number (b) Higher nuclear 2

charge (c) 3
2 He and 4
2 He (d) 12
6 C and 14
7 N
(c) Intense radioactivity (d) No radioactivity 56. Which among the following isotope is not found in
44. An isotope of oxygen has mass number 18. Other natural uranium [Orissa JEE 2002]
isotopes of oxygen will have the same 234 235
(a) 92 U (b) 92 U
[MP PMT 1985; MADT Bihar 1981]
238 239
(a) Mass number (b) Atomic weight (c) 92 U (d) 92 U

(c) Number of neutrons (d) Number of protons 57. An isotone of 76

32 Ge is (one or more are correct)
45. Two nuclei which are not identical but have the [IIT 1984; MADT Bihar 1995; MP PMT 1995]
same number of nucleons represent 77 77
(a) 32 Ge (b) 33 As
(a) Isotopes (b) Isobars
77 78
(c) Isotones (d) None of the three (c) 34 Se (d) 34 Se

46. The  -decay of 11 Na 24 produces an isotope of

[NCERT 1978]
(a) Mg (b) Na
(c) Al (d) Ne
47. Isotopes differ in [NCERT 1973]
(a) Number of protons (b) Valency
23
(c) Chemical reactivity (d) Number of neutrons 1. 11 Na is the more stable isotope of Na. Find out
48. The isobars are atoms with the same number of the process by which 24
11 Na can undergo
[DPMT 1982; CPMT 1994] radioactive decay
(a) Protons (b) Neutrons [IIT Screening 2003]
(c) Protons and neutrons (d) Nucleons (a)   emission (b)  emission
49. Radioactive isotope of hydrogen is
(c)   emission (d) K electron capture
[MP PMT 2001; MPPET 2003]
(a) Tritium (b) Deuterium 2. Oxygen contains 90% of O 16 and 10% of O 18 . Its
atomic mass is [KCET 1998]
(c) Para hydrogen (d) Ortho hydrogen
(a) 17.4 (b) 16.2
50. Isotopes of same elements have the same number
of (c) 16.5 (d) 17
[BHU 1984; DPMT 1983; CPMT 1972, 78; AFMC 2000, 01] 3. The missing particle in the reaction,
92 U  0 n  56 Ba  ...  3 10 n is
235 1 146
(a) Protons (b) Neutrons
87 89
(c) Deutrons (d) None (a) 32 Ge (b) 35 Br
35 37
51. In chlorine gas, ratio of Cl and Cl is (c) 87
Kr (d) 86
Br
36 35
[BHU 1984; CPMT 1977, 80]
4. Sulphur-35 (34.96903 amu) emits a   particle
(a) 1 : 3 (b) 3 : 1
but no   rays, the product is chlorine-35
(c) 1 : 1 (d) 1 : 4
(34.96885 amu). The maximum energy emitted by
52. An ordinary oxygen contains [NCERT 1977] the   particle is
(a) Only O  16 isotopes [DPMT 2004]
(b) Only O  17 isotopes (a) 0.016767 MeV (b) 1.6758 MeV
(c) A mixture of O  16 and O  18 isotopes (c) 0.16758 MeV (d) 16.758 MeV
(d) A mixture of O – 16, O  17 and O  18 5. A radioactive substance has a constant activity of
isotopes 2000 disintegration/minute. The material is
 Nuclear Chemistry
289
separated into two fractions, one of which has an (a) 2.5  10 3 yrs (b) 1.832  10 3 yrs
initial activity of 1000 disintegrations per second
while the other fraction decays with t1 / 2 = 24 (c) 2.275  10 3 yrs (d) 8.825  10 2 yrs
hours. The total activity in both samples after 48 14. 8 gms of a radioactive substance is reduced to
hours of separation is [JIPMER 2000] 0.5 g after 1 hour. The t1 / 2 of the radioactive
(a) 2000 (b) 1250 substance is [DCE 2000]
(c) 1000 (d) 1500 (a) 15 min (b) 30 min
6. How many alpha particles are emitted per second (c) 45 min (d) 10 min
by 1 microgram of radium
15. A first order nuclear reaction is half completed in
(a) 3.62  10 4 / sec (b) 0.362  10 4 / sec 45 minutes. How long does it need 99.9% of the
(c) 362  10 4 / sec (d) 36 .2  10 4 / sec reaction to be completed [KCET 2001]

7. If 1 microgram of radium has disintegrated for (a) 5 hours (b) 7.5 hours
500 years, how many alpha particles will be (c) 10 hours (d) 20 hours
emitted per second 16. Number of --particles emitted per second by a
(a) 2.92  10 4 / sec (b) 292  10 4 / sec radioactive element falls to 1/32 of its original
value in 50 days. The half-life-period of this
(c) 0.292  10 4 / sec (d) 29 .2  10 4 / sec
elements is [AMU 2001]
8. A radioactive nucleide X decays at the rate of
(a) 5 days (b) 15 days
1 .00  10 5 disintegration s 1 g 1 . Radium decays at
(c) 10 days (d) 20 days
the rate of 3.70  10 10 disintegration s 1 g 1 . The
17. What is the half-life of a radioactive substance if
activity of X in millicuries g 1 (m ci g 1 ) is [MP PET 2001]
87.5% of any given amount of the substance
(a) 0.027 (b) 0.270  10 5 disintegrates in 40 minutes [Kerala CET 1996]

(c) 0.00270 (d) 0.000270 (a) 160 min (b) 10 min

9. If 92 U
235
nucleus absorbs a neutron and (c) 20 min (d) 13 min 20 sec
disintegrates in Xe 139
, 94
and X, then what 18. A radioactive isotope has a t1 / 2 of 10 days. If
54 38 Sr

will be the product X today 125 gm of it is left, what was its weight 40
[CBSE 2002] days earlier
(a) -particle (b) -particle [EAMCET 1991]

(c) 2-neutrons (d) 3-neutrons (a) 600 gm (b) 1000 gm

10. The half-life of a radioactive isotope is 3 hours. (c) 1250 gm (d) 2000 gm
Value of its disintegration constant is [BHU 2002]
14
19. The half-life of 6C , if its decay constant is
(a) 0.231 per hr (b) 2.31 per hr
4
(c) 0.2079 per hr (d) 2.079 per hr 6.31  10 is
11. The activity of carbon-14 in a piece of an ancient [CBSE PMT 2001]
wood is only 12.5%. If the half-life period of (a) 1098 yrs (b) 109.8 yrs
carbon-14 is 5760 years, the age of the piece of
(c) 10.98 yrs (d) 1.098 yrs
wood will be (log 2  0.3010 )
20. A radioactive sample has a half-life of 1500
[MP PMT 1999]
years.A sealed tube containing 1 gm of the sample
(a) 17 .281  10 2 years (b) 172 .81  10 2 years will contain after 3000 years[MNR 1994; UPSEAT 2001, 02]
(c) 1.7281  10 2 years (d) 1728 .1  10 2 years (a) 1 gm of the sample
12. The radium and uranium atoms in a sample of
(b) 0 .5 gm of the sample
uranium mineral are in the ratio of 1 : 2 .8  10 6 . If
half-life period of radium is 1620 years, the half- (c) 0 .25 gm of the sample
life period of uranium will be (d) 0 .00 gm of the sample
[MP PMT 1999]
21. The half-life of a radioactive isotope is three
(a) 45 .3  10 9 years (b) 45 .3  10 10 years hours. If the initial mass of the isotope were 256
(c) 4 .53  10 9 years (d) 4 .53  10 10 years g, the mass of it remaining undecayed after 18
13. Half-life of radium is 1580 yrs. Its average life hours would be
will be [AIEEE 2003]
[AIIMS 1999; AFMC 1999; CPMT 1999] (a) 4.0 g (b) 8.0 g
 290 Nuclear Chemistry
(c) 12.0 g (d) 16.0 g 14
6 C is 5000 years) and a freshly cut wood gives
15 15 counts/min/gm of carbon
22. th of a radioactive sample decays in 40 days
16 [AMU (Engg.) 2002]
half-life of the sample is [DCE 2001]
(a) 5.78  10 years 4
(b) 9 .85  10 4 years
(a) 100 days (b) 10 days
(c) 7.85  10 3 years (d) 0 .85  10 4 years
(c) 1 day (d) loge 2 days
30. 92 U 235  n  fission product+neutron  3 .20  10 11 J .
23. A radioactive element with half-life 6.5 hrs has
48  10 19 atoms. Number of atoms left after 26 hrs The energy released when 1g of 92 U 235

[BHU 2003] undergoes fission is

[CBSE PMT 1997]
(a) 24  10 19 (b) 12  10 19
(a) 12 .75  10 kJ 8
(b) 18 .60  10 9 kJ
(c) 3  10 19 (d) 6  10 19
(c) 8 .21  10 7 kJ (d) 6 .55  10 6 kJ
24. The half-life of 1 gm of radioactive sample is 9
hours. The radioactive decay obeys first order 31. The triad of nuclei that is isotonic is
kinetics. The time required for the original [IIT 1988; DCE 2000;MP PMT 2004]
sample to reduce to 0.2 gm is 14 15
(a) 6 C , 7N , 9 F 17
[AMU (Engg.) 2002]
(a) 15.6 hours (b) 156 hours (b) 6 C 12 , 7 N 14 , 9 F 19

(c) 20.9 hours (d) 2.09 hours (c) 6 C 14 , 7 N 14 , 9 F 17

25. The half-life period of a radioactive substance is
(d) 6 C 14 , 7 N 14 , 9 F 19
140 days. After how much time 15 g will decay
from 16 g sample of it 32. The relative abundance of two isotopes of atomic
[AFMC 2002] weight 85 and 87 is 75% and 25% respectively.
The average atomic weight of element is[DCE 2003]
(a) 140 days (b) 560 days
(a) 75.5 (b) 85.5
(c) 280 days (d) 420 days
(c) 40.0 (d) 86.0
26. Percentage of a radioactive element decayed after
20 sec when half-life is 4 sec [BHU 2003]
(a) 92.25 (b) 96.87
(c) 50 (d) 75
27. Consider an -particle just in contact with a
238
92 U nucleus. Calculate the coulombic repulsion
energy (i.e. the height of the coulombic barrier Read the assertion and reason carefully to mark the
between U238 and alpha particle) assuming that correct option out of the options given below :
the distance between them is equal to the sum of (a) If both assertion and reason are true and the
their radii [UPSEAT 2001] reason is the correct explanation of the assertion.
(b) If both assertion and reason are true but reason is
(a) 23.8517× 10 4 eV
not the correct explanation of the assertion.
(b) 26 .147738  10 4 eV (c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
(c) 25.3522  10 eV
4
(e) If assertion is false but reason is true.
(d) 20 .2254  10 4 eV
1. Assertion : Mass number of an atom is equal to
28. The half-life period of Pb 210 is 22 years. If 2 gm of
Pb 210 is taken, then after 11 years how much of total number of nucleons present in
Pb 210 will be left the nucleus.
[KCET 2001] Reason : Mass number defines the identity of
(a) 1.414 gm (b) 2.428 gm an atom.
(c) 3.442 gm (d) 4.456 gm 2. Assertion : 1
, 1 H 2 and 1H
3
are isotopes of
1H
29. A wood specimen from an archeological centre
hydrogen.
shows a 14
6 C activity of 5.0 counts/min/gm of
Reason : Nuclides of the same element of
carbon. What is the age of the specimen (t1 / 2 for
different mass numbers are called
isotopes of that element.
 Nuclear Chemistry
291
3. Assertion : The activity of 1 g pure uranium- Reason : They require very low temperature
235 will be greater than the same to overcome electrostatic repulsion
amount present as U3 O8 . between the nuclei.

Reason : In the combined state, the activity 12. Assertion : The archeological studies are based
of the radioactive element on the radioactive decay of carbon-
decreases. 14 isotope.
Reason : The ration of C-14 to C-12 in the
4. Assertion : Nuclear forces are called short
animals and plants is same as that
range forces.
in the atmosphere.
Reason : Nuclear forces operate over very
13. Assertion : Photochemical smog is produce by
small distance i.e., 10 15 m or 1
nitrogen oxides.
fermi.
Reason : Vehicular pollution is a major
5. Assertion : An example of K-capture is
sources of nitrogen oxides.
133
56 Ba  e  133
55 Cs  X  ray.
14. Assertion : A nuclear binding energy per
Reason : The atomic number decreases by nucleon is in the order
one unit as result of K-capture. 9
4 Be 73 Li  42 He .
6. Assertion : Radioactive heavy nuclei decay by a Reason : Binding energy per nuclear
series of   and / or   emission, increases linearly with difference in
to form a stable isotope of lead. number of neutrons and protons.
Reason : Radioactivity is a physical 15. Assertion : Nuclear fission is always
phenomenon. accompanied by release of energy.
7. Assertion : Actinium series is so called because Reason : Nuclear fission is a chain process.
it starts with an isotope of [AIIMS 1994]
actinium. 16. Assertion : Protones are more effective than
Reason : Actinium is formed in the nature as neutrons of equal energy in causing
such and is not formed from the artificial disintegration of atoms.
disintegration of any other Reason : Neutrons are neutral they penetrate
radioisotope. the nucleus. [AIIMS 1998]
8. Assertion : For maximum stability N/P ratio 17. Assertion : A beam of electrons deflects more
must be equal to 1. than a beam of  -particles in an
Reason : Loss of   and   particles has no electric field.
role in N/P ratio. Reason : Electrons possess negative charge
while  -particles possess positive
9. Assertion : The neutrons are better initiators of
nuclear reactions, than the charge.
protons, deutrons or - particles of [AIIMS 2002]
the same energy. 22 22
18. Assertion : 11 Na emits a position giving 12 Mg .
Reason : Neutrons are uncharged particles
and hence, they are not repelled by Reason : In  emission neutron is
positively charged nucleus. transformed into proton.[AIIMS 1994]
10. Assertion : Breeder reactor produces fissile
94 Pu 239 from non-fissile uranium.

Reason : A breeder reactor is one that

produces more fissionable nuclei
that it consumes.
11. Assertion : The activation energies for fusion
reactions are very low. Nucleus (Stability and Reaction)
 292 Nuclear Chemistry
Rate of decay and Half-life
1 b 2 b 3 a 4 a 5 b
6 d 7 b 8 c 9 c 10 d 1 c 2 a 3 b 4 a 5 d

11 b 12 c 13 c 14 c 15 c 6 a 7 d 8 d 9 d 10 c

16 c 17 d 18 c 19 a 20 b 11 a 12 d 13 d 14 a 15 c

21 b 22 a 23 b 24 d 25 c 16 d 17 b 18 c 19 b 20 a

26 c 27 b 28 c 29 b 30 a 21 b 22 a 23 c 24 a 25 a

31 c 32 d 33 b 34 d 35 c 26 b 27 a 28 c 29 a 30 b

36 b 37 b 38 a 39 a 40 a 31 a 32 c 33 d 34 a 35 b

41 b 42 b 43 a 44 d 45 b 36 d 37 d 38 c 39 c 40 a

46 d 47 b 48 a 49 b 50 d 41 c 42 b 43 b 44 d 45 c

51 d 52 a 53 b 54 c 55 d 46 c 47 c 48 b 49 a 50 c

56 b 57 b 58 d 59 b 60 c 51 c 52 c 53 c 54 b 55 c

61 b 62 d 63 d 64 d 65 a 56 b 57 a 58 b 59 d 60 b

66 b 67 a 68 a 61 d 62 b 63 c 64 a 65 b
66 d 67 d 68 c 69 d 70 c

Radioactivity and ,  and - rays 71 d 72 a 73 c 74 a 75 a

76 c 77 b 78 b 79 a 80 a
1 c 2 d 3 a 4 b 5 c 81 a 82 a 83 b 84 c
6 b 7 c 8 c 9 b 10 b
11 a 12 a 13 a 14 b 15 c Artificial transmutation
16 c 17 a 18 a 19 c 20 b
1 b 2 c 3 d 4 d 5 c
21 a 22 c 23 d 24 b 25 c
6 a 7 a 8 b 9 d 10 b
26 d 27 d 28 c 29 c 30 a
11 a 12 c 13 c 14 b 15 a
31 d 32 c 33 a 34 b 35 a
16 d 17 d 18 b 19 a 20 c
36 c 37 a 38 acd 39 a
21 b 22 a 23 c 24 b 25 d
26 c 27 b 28 a 29 d 30 a
Causes of radioactivity and Group displacement law
31 d 32 b 33 d 34 c 35 b

1 b 2 d 3 d 4 d 5 c 36 a 37 b 38 c 39 d 40 c

6 c 7 c 8 a 9 b 10 a 41 d 42 b 43 c 44 b 45 b

11 a 12 c 13 d 14 b 15 a 46 c 47 b 48 b 49 c 50 c

16 a 17 a 18 a,b,c 19 c 20 c 51 d 52 c 53 a 54 d 55 d

21 b 22 d 23 d 24 a 25 b 56 d 57 b,d 58 a 59 b 60 a
61 d 62 a 63 a 64 d 65 d
26 d 27 b 28 b 29 b 30 a
66 d 67 d 68 b 69 b 70 d
31 a 32 a 33 c 34 b 35 a
71 a 72 b 73 a 74 a 75 a
36 b 37 c 38 b 39 c 40 d
76 b 77 d 78 c 79 a 80 c
41 a 42 b 43 c 44 c 45 d
81 b
46 b 47 b 48 d 49 a 50 d
51 a 52 a 53 d 54 d 55 b Isotopes-Isotones and Nuclear isomers
56 a 57 d 58 c 59 c 60 a
61 a 62 c 63 d 64 d 65 a 1 b 2 a 3 d 4 a 5 c
66 d 67 b 68 c 69 b 70 a 6 c 7 c 8 b 9 b 10 d
71 c 72 c 73 d 74 a 75 b 11 a 12 b 13 a 14 a 15 a
 Nuclear Chemistry
293
16 c 17 b 18 c 19 c 20 a
21 d 22 d 23 a 24 c 25 c
26 d 27 c 28 b 29 b 30 b
31 cd 32 d 33 a 34 c 35 c
36 b 37 a 38 a 39 a 40 b
41 c 42 a 43 a 44 d 45 b
46 a 47 d 48 d 49 a 50 a
51 b 52 d 53 b 54 c 55 ac
56 d 57 bd

Critical Thinking Questions

1 a 2 b 3 c 4 a 5 a
6 a 7 a 8 b 9 d 10 a
11 b 12 c 13 c 14 a 15 b
16 c 17 d 18 d 19 a 20 c
21 a 22 b 23 c 24 c 25 b
26 b 27 b 28 a 29 c 30 c
31 a 32 b

Assertion & Reason

1 c 2 a 3 d 4 a 5 b
6 c 7 d 8 c 9 a 10 a
11 d 12 a 13 b 14 d 15 b
16 e 17 b 18 d

Nucleus (Stability and Reaction)

1. (b) Protons + Neutrons = Nucleons

2. (b) A deutron (1 H 2 ) contains a neutron and a
proton
3. (a) Low binding energy causes radioactivity.
4. (a) 7 N 14  2 He 4  8 O 17  1 H 1
5. (b) Follow Einstein mass-energy relation.
6. (d) Mass (weight) of positron and electron is
9 .11  10 31 kg .
 Nuclear Chemistry 291
7. (b) Li 6  0 n 1  2 He 4  1 H 3 42. (b) Equate mass number and atomic number on
3
both sides.
8. (c) 7 N 14  0 n1  6 C 14  1 H 1 43. (a) Due to mass decay.
9. (c) 17 Cl
37
 1 H 2  18 Ar 38  0 n 1 44. (d) Mesons () have 200-300 times mass of
electron and + ve, 0 or – ve charges.
10. (d) Because of its high unstability.
o
  45. (b) 1 e is positron.
12. (c) 90 Th
234

 91 X 234 
 92 Y 234 

 90 Z 230 .
46. (d) Pb is the most stable atom.
13. (c) Isotopes of an element have similar chemical
47. (b) Anderson discovered positron in 1932.
properties but different physical properties.
48. (a) Even-Even are most stable
14. (c) A nuclear reaction must be balanced in terms
Odd- Odd are most unstable
of mass and energy.
49. (b) The atom which have lower value of packing
15. (c) 52 Te
130
1 H 2  53 I131  0 n1 fraction is stable.
16. (c) The emission of positron takes place. 50. (d) Number of neutrons in 88 Ra 226  226  88  138 .
18. (c) An ion is electrically charged atom or a group
51. (d) Nuclear reactions involves exchange of
of atoms.
nuclear energy.
19. (a) Charge on positron and proton is about
52. (a) Na 23  1 H 1  12 Mg 23  0 n 1
 1.602  10 19 C .
11

53. (b) U 235 is radioactive because it is most

20. (b) 12 Mg 24  2 He 4  o n 1  14 Si 27 92

unstable.
21. (b) The radioactive isotope 6 C 14 is produced in 54. (c) Equate atomic no. and mass no.
the atmosphere by the action of cosmic ray 57. (b) Be 9  2 He 4  6 C 12  o n 1
4
neutrons on 7 N 14
58. (d) According to group displacement law.
N 14  0 n1 6 C 14 1 H 1 59. (b) 9
Be  1 H 1  63 Li  4
7 4 2 He
23. (b) Tritium is the isotope. ( p) (  particle )
40
24. (d) 21 Sc 45 (n, p ) 20 Ca 45 according to Beath’s notation 60. (c) 18 Ar having 40 – 18 = 22 neutrons

N 14  1 H 1  8 O 15  
40
25. (c) 7
While 21 Sc having 40 – 21 = 19 neutrons.

26. (c) Np 239  94 Pu 239  1 e o 61. (b) Nuclear reactivity depends upon the number
93
of protons and neutrons.
27. (b) Equate atomic no. and mass no.
63. (d) 29 Cu
64
 28 Ni 64  1 e
0
28. (c) Magic no. are 2, 8, 20, 28, 50 and 82 protons
in nucleus or 2, 8, 20, 28, 50, 82, 126 65. (a) 24
12 Mg  1 D 2  2 He 4  11
22
Na
neutrons in nucleus. These numbers imparts 66. (b) Equate atomic no. and mass no.
stability to nucleus.
67. (a) 96 X 227  Y  4  5 
n 126
30. (a) of 82 Pb 208   1 .53 On equating mass number
p 82
227 = y + 4 × 4 + 0, y  211
n 126
of 83 Bi 209   1 .51 On equating atomic number
p 83
96 = y + 2 × 4 – 5, y = 93.
31. (c) According to Beath’s notation
27
68. (a) Meson was discovered by Yukawa
13 Al (n, p ) 12 Mg 27 .
32. (d) Azimuthal quantum no. is related to angular Radioactivity and ,  and - rays
momentum.
238  218 20 1. (c)   rays does not contain material particles.
33. (b) The value of n    5 1  4
4 4 2. (d)  -rays are neutral energy packet.
34. (d) Mass number increases by one unit. 3. (a) The order of penetrating power is :  <  < -
36. (b) Equal atomic number and mass number. rays. It is due to lower mass and high speed.
37. (b) 1 amu = 931.478 MeV. 1
4. (b) -rays travel with a velocity which is th to
38. (a) Positron is anti-particle of electron. 10
39. (a) Isotopes are formed by the emission of one  - 1
th of that of light.
and two  -particles respectively. 20
n n 5. (c) -rays have maximum penetrating power.
40. (a) The ratio of stable nucleoide is 1.
p p 6. (b) -particles are 4 time heavier than neutrons.
41. (b) Neutrino have no mass and no charge and 7. (c) 92 U
235
 0 n 1  56 Ba 145  36 Kr 88  3 10 n
thus known as ghost particles.
 292 Nuclear Chemistry
8. (c) Rutherford first of all used zinc sulphide (ZnS) In 90 Th 234 the mass no. division by four gives
as phosphor in the detection of -particles.
a residue of 2.
9. (b) -rays consist of a stream of He 2  . 2. (d) On emission of  -particles daughter element
10. (b) -rays are positively charged, -rays are shift 2 group to the left. On emission of  -
negatively charged, -rays carry no charge and particles daughter element shift 1 group to the
thus not deflected in field. right.
11. (a) -particle is identical with 2 He 4 helium 3. (d) Protons + Neutrons = Nucleons
nucleus. 4. (d) Radioactivity is characteristic property of
12. (a) -rays have maximum penetrating power. unstable nucleus.
13. (a) Henry Becquerel noticed the emission of 5. (c) Chemical change is extra nuclear
penetrating phenomenon.
rays from potassium uranyl sulphate and 8 
6. (c) 92U
238  82X206
Madam Curie named it as radioactivity. 6 

15. (c) Penetrating powers   rays    rays    rays Number of protons = 82; Number of neutrons
17. (a) -rays are positively charged, -rays are = 124
negatively charged, -rays carry no charge. Neutron/proton ratio in the product nucleus
(b) Deflection in  -rays is large. 124 62
20.  
82 41
21. (a) Penetrating power of  -rays are less than
X 218  84 Y 214  x  2 y 1 
4 0
 ,  and X-rays. 7. (c) 84

22. (c) Lead is a stable isotope. 218  214 4

no. of -particle =  1
23. (d) Neutrons carry no charge. 4 4
24. (b) -rays has least penetrating power. no. of -particle = 84  84  2  1  2 .
25. (c)  -rays carry no charge. 8. (a) When an -particle is emitted by any nucleus
26. (d) Proton is not emitted by radioactive than atomic weight decreases by four units
substances. and atomic number decreases by two units

27. (d) Due to it’s nature. 88 Ra 224 
 86 X 220

Ra 226 is radioactive because

n 231  207
28. (c) 88
p
ratio for it 9. (b) Number of -particles = 6
4
is 1.56 which is greater than 1.5. Number of -particles  89  82  2  6  5 .
30. (a) Cf – 98 belongs to actinid series. 10. (a) Th 228  83 Bi 212
90
31. (d) Photons are not carry any charge.
228  212 16
32. (c) 7 N 14  2 He 4 (  particle)  8 O 17  1 H 1 No. of  -particles =  4
4 4
33. (a) Definition of binding energy. No. of  -particles = 90  83  2  4  1 .
34. (b)   particle is 2 He 4 .
11. (a) 14
 7 N 14  0
6C 1 e
35. (a) Gamma ray doesn’t deviate from
No. of neutrons in C 14  14  6  8 .
electromagnetic field, the main reason of it is

that there is no charge on gamma rays. 12. (c) 92 X 238 
 90 Y 234
36. (c) Energy liberated = loss of mass  931 Number of neutrons = 234  90  144 .
 0 . 01864  931  17 .36 MeV 13. (d) A m  Z 1 B m  1e 0
Z
38. (acd) Beta emission causes increase in atomic 14. (b) r  . N
number by one unit.
15. (a) on
1
 1 P 1  1 e
0
(  -particle comes out)
39. (a) Mass loss = mass of reactant – mass of
product. 16. (a) Element 57 to 71 are placed in III group.
 (2.014  3.016 )  (4.004  1.008 ) 2 
17. (a) 5 X 14   7 N 14 than no. of neutrons in
 5.030  5.012  0.018 amu X 14
 14  5  9 .
5

18. (a,b,c) An emission of -particle means that atomic

Causes of Radioactivity and number increases by 1 but mass number remains
Group Displacement Law unaffected and neutron- proton ratio decreases.
19. (c) Suppose the no. of -particles emitted = x and
1. (b) In 95 Am 241 the mass no. division by four gives the no. of -particles emitted = y, then
82 Pb 206  x  2 y 1 
238 4 0
a residue of 1. 92 U
 Nuclear Chemistry 293
Equating the mass number on both sides, we 40. (d) An element formed by losing one -particle
get occupies two position left to parent element,
32 Pb in IVA, thus Po should be in VIA.
238 = 206 + 4x + 0y or 4x = 32 or x  8
4 41. (a) According to group displacement law.
Hence 8 -particles will be emitted. 238  206
42. (b) Number of -particles = 8
20. (c) Pb is the end product of each natural 4
radioactive series. Number of -particles = 92  82  2  8  6 .

21. (b) The

n
ratio of 13 Al 29 places it above the belt 43. (c) 40 X 41 Y  1e 0 (-emission)
p
90 600
of stability and thus it emits  -particles. 44. (c) n   3  N  3  75 atoms .
30 2
22. (d) Y A X  Y 10 B X 32  m 2 He 4  n 1e 0 45. (d) Equate mass no. and atomic no.
X  ( X )  32 46. (b) U 236  90 X 232  2 He 4
8
92
Value of m =
4 X 232 have 90 protons and 142 neutrons.
90
Value of n = Y – Y – 10 – 2 × 8 = 6.
47. (b) -rays have high I.P. due to high kinetic
23. (d) During  -decay atomic mass is unaffected energy.
while atomic no. increases by one unit. 48. (d) Going two positions back from 2nd group gives
24. (a) Equate atomic number and mass no. zero group.
2 
25. (b) 90 X 232   92 Y 232  82 Z 212  x 2 He 4 49. (a) Ra belongs to (4 n  2) series. End product will
232  212 20 also belong to the same series.
No. of  -particles   5. 50. (d) Ra contaminated with uranium mineral shows
4 4
appreciable radioactivity.
 
26. (d) X 238 
 90 Y 234 
 91 Z 234
 82 Pb 206  x  2 y 1 
92 238 4 0
51. (a) 92 U
no. of neutrons = 234 – 91 = 143.
238  206
27. (b) Z A
M 
 
 Z  2 B M 4 
 Z 4 C M 8 . no. of -particles = 8
Gr.2 Gr. 18 Gr.16 4
28. (b) Equate atomic no. and mass no. no. of -particles = 92  82  2  8  6
29. (b) The mass no. on division by four gives a Total no. of particles = 8  6  14 .
residue of 2. 52. (a) According to Group displacement law.
30. (a) 53. (d) Rate =  × number of atoms.
 82 Pb 208  x 2 He 4  y 1 
Serie Name of the Parent End 54. (d) 232 0
90 Th
s series element stable
element Equating mass no.
4n Thorium series Th-232 Pb–208 232 = 208 + 4x + 0 y or 4x = 24 or x = 6
4n + 1 Neptunium Pu-241 Bi–209 Equating atomic no.
4n + series U-238 Pb–206 90 = 82 + 2x –y or 90 = 82 + 2 × 6 – y or
2 Uranium series y4
U-235 Pb–207
4n + Actinium series Hence 6 and 4 particles will be emitted.
3
55. (b) Z A m  Z 1 B m  1e 0
31. (a) 8O
16
 1 H 2  9 F 18
56. (a) The mass no. division by four gives a residue of
32. (a) 84 A 218  84 B
214
 2 He 4  2 1e 0 . 1

33. (c) It is also called Soddy and Fajan rule. 57. (d) AX
m

 A 1 Y
m

34. (b) 84 Po 215  82 Pb 211  2 He 4 58. (c) Suppose the no. of -particles emitted  x and
35. (a) 92 U 238
 90 Th 234
 2 He 4 the no. of  -particles emitted =y. Then
No 24 92 U
238
82 Pb 206  x 4 2  y 1 
0
36. (b) N  n
and n  3
2 8 equating the mass number on both sides, we
40 40 get
N   5
23 8 238 = 206 + 4x + 0 y or 4x = 32, x = 8
37. (c) 20 Ca
42
21 Sc 42  1e 0 equating the atomic number on both sides, we
 M 4
get
38. (b) X M 
 A2 Y
A 92 = 82 + 2x – y
23
39. (c) 24
Mg   11 Na  11 H. 92 = 82 + 2× 8 –y
12
y=6
 294 Nuclear Chemistry
Hence 8  and 6  are emitted. 74. (a) 180
72
2
X 
 172  
68 P  69 Q  69 X .
172 172

0.693 0.693
59. (c) k    0.000693  6.93  10 4 s 1 75. (b) Loss of beta particle is equivalent to decrease
t1 / 2 1000 s of one neutron only.
60. (a) Bi is a stable end product of Neptunium n  p  e  v .
series.
62. (c) Pb – 208 is the stable end product of thorium Rate of decay and Half-life
series.
63. (d) Definition of disintegration series. 16 N 16 .0 16 .0
 1. (c) n   2, N  no  2   4 .0 gm.
64. (d) 6 X 14
 6 1 N 14
8 2 2 4
2. (a) Mass of 6 neutrons = 6.05358 amu, Mass of 6
in 6 X 14 no. of neutrons 14 – 6 = 8.
protons = 6.04884 amu, Mass of n + Mass of p
65. (a) 18 Ar 40 =12.10242 amu
Mass defect = 12.10242 – 12.00710 = 0.09532
Total no of protons = 18
Binding energy = 0.09532  931 = 88.74292
Total no of neutrons = 22 MeV.
Mass defect  [m  p  m  n]  39 .962384 Binding energy per neucleon = 88.74292/12
 [1 .007825  18  1.008665  22 ]  39 .962384 =7.39 MeV
80
 [18 .14085  22 .19063 ]  39 .962384  0 . 369 3. (b) T  t1 / 2  n,  n  4
20
Binding energy = mass defect  931 1 1 1
 0.369  931  343 .62 MeV Amount left  n  4  .
2 2 16
66. (d) 90 Th 232  82 Pb 208 4. (a) 92 X 232  89 Y 220  x 2 He 4  y 1 e o
232  208 232  220
No. of  - particle  6 no. of  -particles = 3
4 4
No. of  - particle  82  [90  6  2]  4 no. of  -particles = 89 –[92 – 2 × 3] = 3.
5. (d) It is occurs by  -decay.
67. (b) 92 M 238  y N x  2 2 He 4 n n
1  1
 6. (a) N     N o = 125 mg =    1000 mg
y N  B L  2 
x A
 
2 2
N x (92 22) N (238 42)  88 N 230 1
n
125 1
   
y

2  2 1000 8
88 N 230  (882) L(230)  86 L230
n 3
1 1
Total no of neutrons in L330      , n  3, so number, of t1 / 2  3
  2
90
2
230  86  144 Total time = 24 hours, Half-life time
68. (c) E 232  86 G 220 24
90
  8 hours .
232  220 3
No. of  particle = 3 
4 8. (d) 35 X 88 
 36 W 88  36 W 87  o n 1
No. of  particle  86  [90  2  3]  2 9. (d) 75% of the substance disintegrates in two half
0 .693 0 .693 lives.
69. (b) K  
t1 / 2 1600 2 half lives = 30 min  t1 / 2  15 min .
4 1
 4 . 33  10 year 10. (c)  -rays are electromagnetic waves.
70. (a) 92 U
238
 90 Th 234
 91 Pa 234
11. (a) Average life
238  234 4 ( )  1.44 t1 / 2  1.44  69 .3  99 .7  100 minutes.
No. of  particle   1
4 4 n
1 
No. of  particle  91  90  1 12. (d) N     N o
2
0 .693
72. (c) K  n
t1 / 2 1 
1 .25     10
0 .693 0.693 2
t1 / 2    1.2 hrs n 3
K 0.58 1  1 .25 1 1 
73. (d) A radioisotope first emits  or  particles,  2   10  8   2  , n  3
   
then it becomes unstable and emits  -rays.
 Nuclear Chemistry 295
15 4
Half-life time =  5 days. 125 1 125
3  N0   , N0   2  2  2  2  2g
1000 2 1000
12
13. (d) n  4 32. (c) Binding energy per nucleon =
127
 7 .94 MeV .
3 16
 N o  N  2 n  3  2 4  48 g . 0.693 0.693
33. (d) k    0.005 min 1
t1 / 2 138 .6 min
14. (a) 6C
14
 7 N 14  1 e o , -active.
34. (a) Half-life period is independent of initial
2 .303 amount.
15. (c) 2 .303   t1 / 2 log 10
0 .693 35. (b) t = Feb 1 to July 1 = 28  31  30  31  30  150 days
No N 2 .303 8 2 .303 0 .693
 N   o  10 .  log  log 2 5  day 1
10 N 150 0.25 150 30
No 100 0 .693
16. (d) Amount left    12 .5 % t1 / 2   30 days .
23 8 0 .693 / 30
No N 2 .303  t1 / 2 No
17. (b) N   6o  n  6 36. (d) t  log
64 2 0 .693 N
Thus total time  2  6  12 hr . 480 N 4 4
37. (d) n   4 , N  no , N  4  = 0.25 gm.
120 2 2 16
18. (c) -decay occurs by the nuclear change
n  p  1 e 0 . 28 N 1 1
38. (c) n   4 , N  no , N  4   0.0625 gm.
7 2 2 16
log e 2 1
19. (b) t1 / 2  , Average life  2 . 303 [ N o ] 2 . 303 1
  39. (c)   log  log
t [N ] 96 1/8
No 60 1 1
20. (a) N  n
,n   3; N o  1g, then N  3  . 
2 .303
 0 .9  0 .0216
2 20 2 8 98
21. (b) t1 / 2 of zero order reaction is independent of 0 .693 0 .693
 t1 / 2    32 .0 min .
the concentration.  0 .0216
22. (a) Half-life is 1 hr and thus in each half-life, half n n 2
1  1  25 1 1 
of the sample decays. 40. (a) 25     100 ,      
2  2  100 4 2
2 . 303  t1 / 2 N
23. (c) t log o , N  0 . 798 N o n = 2, No. of half lives = 2
0 . 693 N
so time required = 2  5760  11520 yr.
24. (a) Half-life is independent of initial amount.
25. (a) 80 years = 4 half lives 41. (c) t1 / 2  100 years.
1 1
Activity after n half lives  n  a . 42. (b) Average life ( )  .
2 
26. (b) t1 / 2 is independent of all external factors and 1 1 1 1
43. (b)  or 4  n or n  4
is constant for a given species. 16 2 n 2 2
27. (a) In nucleus electrons formed by the following  Required time  4  t1 / 2  120 min .
decay. 0 n1 1 P1  1e 0
44. (d) The time required for complete decay (I
28. (c) t1 / 2  2.95 days order) is always infinite.
= 2.95 × 24 × 60 × 60s = 254880 45. (c) After half-life time the half of the substance
0.693 0.693 will be decayed.
   2.7  10 6 s 1 15 N 20 20
t1 / 2 254880 46. (c) n   3, N  no  3   2 .5 gm.
5 2 2 8
29. (a) When a radioactive element emits an -
3 
particle, the atomic no. of the resulting 47. (c) 6 X 14   9 Y 14
nuclide decreases by two units and atomic 25
mass decreases by 4 units. 48. (b) N  N o (at t  32 minutes)
100
0 .693 0 .693
30. (b) t1 / 2    0 .3  10 4 yrs Thus t 
2 . 303 N
 t1 / 2 log o
k 2 .31  10 4 0 . 693 N
 3.0  10 3 yrs. 49. (a) Half-life period is a characteristic of
n radioactive isotope which is independent of
1 40
31. (a) N  N 0   . n  4 initial concentration.
2 10
 296 Nuclear Chemistry
24 N 1 1 0 .693 0 .693
50. (c) n   3, N  no  3  mg . 71. (d) t1 / 2    0 .1  10 6  10 5 yrs .
8 2 2 8 k 6 .93  10  6
51. (c) Because t1 / 2  4 .5  10 9 years, so after 4 .5  10 9 72. (a) 1 milli curie = 3.7  10 7 dps
years the amount of 92 U
238
will be half 1.5 milli curie = 5.55  10 7 dps
decayed. 5 . 55  10 7
   1 . 37  10  11
0.693 No
52. (c) r   No
t1 / 2 T 75
3
N  1  t1 / 2 N  1  25 N 1 1
0 .693 6 .023  10 23 73. (c)   ;   ;   
  No  2  No  2  No  2  8
1600  365  24  60  60 226
T 24
= 3.7  10 10 dps . N  1  t1 / 2 N 1 4 N 1
6
74. (a)   ;   ;  
2 .303  t1 / 2 N 1 No  2  200  2  200  2 
53. (c) t  log o ; N 
0 .693 N 16 200
N  3.125 g
0 .693 64
54. (b) t1 / 2 
k or  75. (a) x
2
X y 
 7 N 14
3 N 1 X y 14  5 X 14
55. (c) n   3; N  3o  x 7  2
1 2 8
Total no. of neutrons =14 – 5 = 9
n
1 0 .693 0 .693
56. (b) N  N 0    76. (c) K  ; K  0 .0693 yr 1
2 t1 / 2 10
n
1 1 T 192 192
 1  ; n 1 N  1  t1 / 2  1   1  t1 / 2 1  1  t1 / 2
4
2 2 77. (b)   ;    ;    
No  2   16   2  2 2
t  n  t1 / 2  1  6000  6000 yrs.
t1 / 2  48 min
57. (a) For Ist order t1 / 2  0 .693 K 1 .   
78. (b) 92 U
235

 ( A) 
(B) 
(C )
58. (b) 75% of the substance disintegrates in two half
lives 2 half lives = 60 min.  t1 / 2  30 min . (i) 92  2 A 235 4  90 A 231

0.693 2.303 100 (ii) 90 A 231 
 (90 1) B (231 )  91 B 231
59. (d)   log
t1 / 2 180 12 .5 
(iii) 91 B 231 
 (91 1)C 231  92 C 231
0 . 693  180
t1 / 2   60 min  1 hr . Isotopes are 92 U 235 and C
2 . 303  3  0 . 3010
0 .693 0 .693
60. (b) Tritium (1 H 3  2 He 3  1 e 0 ) is a -emitter. 80. (a) t1 / 2    0 .296 sec
K 2 .34
61. (d) t1 / 2  ln 2 /  0.693 0.693
81. (a) K  
0.693 0.693 T1 / 2 5770
62. (b) t1 / 2    3.0  10  3 sec .
 231 sec1 2 .303 100 2 .303  5770 100
128
 t log  log
63. (c) The amount of 53 I left after 50 minutes will K 72 0 .693 72
be  19175 .05  (log 100  log 72 )
100 1 19175 .05  0.143  2742 .03 years.
= 25 minutes   .
25 4 82. (a) For 25% decay
25 2 .303 100 2 .303
64. (a) N  N o (at t  2 hr ) K log   0 .1249  0 .. 1438
100 20 75 20
2 . 303 N For 75% decay,
Thus t   t1 / 2 log o
0 . 693 N 2 .303 100
65. (b) Radioactive decay is a first order reaction. t log  96 .4 minute.
0 .01438 25
66. (d) t1/ 2 is independent of all external factors. n n
1 N 1
67. (d) Rate of decay of radioactive species is 83. (b) N  N 0     
 
2 N 0 2
independent of all external factors.
n 6 n
100 N 100 100 1 1 1 1
68. (c) n   4 , N  no  4   6 .25 gm . or       n6
25 2 2 16 64  2   
2 2
69. (d) 92 U
235
 0 n1  56 Ba 145  36 Kr 88  3 10 n T  t1 / 2  n  2  6  12 hours.
70. (c) Half-life is independent of initial amount. After 12 hours, sample became non-hazardous.
 Nuclear Chemistry 297
84. (c) Half-life of same substance remains same. No 1 1
N   N o   100 % of N o  25 .
22 4 4
Artificial transmutation 32. (b) Due to evolution of nuclear energy as a result
of mass decay.
1. (b) C  14 dating method is used in estimate the
33. (d) Heavy water (D2 O) is used as a moderator in
age of most ancient geological formation.
2. (c) Joining up of two lighter nuclei is fusion. nuclear reactor.
5. (c) Equate atomic no. and mass no. 34. (c) It is a transformation of chlorine.
6. (a) For studies on carbon dating, W. F. Libby was 35. (b) 48 gm of radioactive sodium will need 32
awarded a Nobel prize. hours to become 3.0 gm.
7. (a) Spallation reactions are similar to fission 36. (a) Mass decay occurs.
reactions. They brought about by high energy 37. (b) In hydrogen bomb, the following reaction is
bombarding particles or photons. occur,
9. (d) Uranium or Plutonium are atomic fuel.
1H
2
 1 H 3  2 He 4  10 n  energy .
11. (a) It is the required technique.
n 49 .2 / 12 .3 4 38. (c) A reason for the C-14 dating technique.
1 1 1
12. (c) N t  N o    32     32     2 . 2 . 303 a 99
2 2 2 39. (d) t  log , (a  x )   0 . 99 a
k 0 . 99 a 100
14. (b) In hydrogen bomb, the following reaction is
occur, 0.693 0.693
But k    0.0653 year–1
t1 / 2 10 .6
1H
2
 1 H  2 He
3 4
 10 n  energy .
2 . 303 1
15. (a) Heavy water is D2 O . t log  70 . 4 yrs .
0 . 0653 0 . 99
16. (d) Einstein’s law is E  mc 2 . 41. (d) D2 O is heavy water.
17. (d)
42. (b) D2 O is used as moderator in nuclear reactor.
18. (b) 11460 years = 2 half lives
Activity left = 25% = 0.25. 45. (b) Liquid sodium use in nuclear reactors as heat
19. (a) The control rods used in nuclear reactor are exchanger or coolant.
made up of Cd – 113 or B -10. They can absorb 46. (c) Due to heavy mass -particles can not easily
neutrons. pass through solid matter so they are less
14
20. (c) The radioactive isotope 6C is produced in effective for artificial transmutation.
the atmosphere by the action of cosmic ray 47. (b) Given N o  1, N t  0.70 and t1 / 2  5760 yrs.
neutrons on 7 N 14 0.693 0.693
k  .
22. (a) Heavy water (D2 O) is used as a moderator in a t1 / 2 5760
nuclear reactor. It slows down the speed of 2 . 303 N 0 .693
neutrons. It also acts as a coolant. We also know, k  log 0 .
t N t 5760
23. (c) Uranium or Plutonium are atomic fuel.
2 . 303  5760  0 . 155
24. (b) atom bomb is based on the principal of or t   2966 yrs .
nuclear fission. 0 . 693
25. (d) Hahn and Strassmann discovered the 48. (b) The splitting of a heavier atom like that of U-
phenomenon of nuclear fission in 1939. 235 into a number of fragments of much
26. (c) Rate of disintegration is not affected by smaller mass by suitable bombardment with
environmental conditions. sub-atomic particles with liberation of huge
27. (b) It is believed that when an  or  -particle is amount of energy is called nuclear fission.
emitted, the nucleus becomes excited i.e. has 49. (c) Al 28  2 He 4  15 P 31  0 n1
13
higher energy and emits the excess energy in
the from of radiation which form  -rays. 50. (c) Rate of radioactivity is independent of all
external factors.
28. (a) Packing fraction  Isotopic mass  Massnumber  10 4
Massnumber 51. (d) I131 is used for goitre therapy, i.e. iodine
30. (a) C 14 is a natural radioactive isotope of C 12 . deficiency.
31. (d) t1 / 2  10 yrs, t  20 yrs. 52. (c) C-14 is found in nature abundantly and in
definite ratio.
t 20
n   2 53. (a) Astatine (At) is resembles in properties with
t1 / 2 10
iodine.
 298 Nuclear Chemistry
56. (d) Equate mass number and atomic number. 6. (c) Z A m z B m  4  2 He 4  2 1 e 0
57. (b,d) D2 O is used as moderator in nuclear
7. (c) Co 60 is used in radiotherapy of cancer.
reactor.
8. (b) Atoms of different elements having different
58. (a) The rate of disintegration is expressed in atomic no. but same mass no. are called
terms of the number of disintegrations per isobars.
second. 9. (b) N 14  2 He 4  8 O 17 1 H 1
7
14
59. (b) 6C is used in dating archeological findings.
10. (d) 1 H 3 2 He 3  1e 0
40
60. (a) n  2 1H
3
and 2 He 3 are isobars (same mass no.)
20
N 0 100 11. (a) The isotopes having an excessive n/p ratio
 Amount left  2  25 gm
exhibit e  -emission.
2n 2
14
61. (d) The definition of nuclear fission. 12. (b) 6C is an isotope of carbon (6 C 12 ) .
62. (a) The huge amount of energy released during 14. (a) Isotopes differ in number of neutrons but
atomic fission is due to loss of mass. have same number of protons.
63. (a) Mass defect is the measure of binding energy 15. (a) Z A m  z B m  4  2 He 4  2 1 e o
of a nucleus. 16. (c) Atoms of different elements having different
65. (d) Irene curie and Juliot studied the artificial atomic no. but same mass no. are called
radioactivity. isobars.
No 560 1 1 17. (b) Isotopes differ in number of neutrons but
66. (d) N  and n   4; N  4  gm.
2n 140 2 16 have same number of protons.
67. (d) G.M counter is used to determine rate of 18. (c) z A m  Z B m  4  2 He 4  2 1 e o
decay. n
68. (b) Cd and boron rods are control rods used in 19. (c) is minimum for this isotope.
p
reactors.
20. (a) In chlorine gas ratio of Cl 35 and Cl 37 is 3 : 1.
69. (b) Graphite is used as moderator to slow down
the speed of neutrons in atomic reactors. 21. (d) Isotones have the same number of neutrons
but different number of nucleons (n  p ) . e.g.,
70. (d) Isotope C 12 is the modern basis of atomic 39 40
Ar , 19 K.
weight. 18

14 22. (d) Isobars have different no. of protons and

71. (a) 6C is used to determine the mechanism of
neutrons.
photosynthesis.
23. (a) Atoms of different elements having different
74. (a) 28 Ni 60  0 n 1  28 Ni 61  27 Co 60  1 p 1 atomic no. but same mass no. are called
14 isobars.
76. (b) 6C used for dating process.
24. (c) Isotopes differ in mass no. and hence in the
T T
number of neutrons.
N  1  t1 / 2 13 1  5770
79. (a)      25. (c) Isotones are the species which have same
No  2  100  2 
number of neutrons and different number of
13 T nucleons (p + n).
Taking log  log  log 1 / 2  16989 yrs
100 5770 26. (d) In 13 H their are 1 proton and 2 neutrons.
27. (c) Isotopes differ in mass number, and hence in
Isotopes-Isotones and Nuclear isomers the number of neutrons.
28. (b) In isotones have same number of neutrons.
1. (b) The definition of Isotopes. 29. (b) Atoms of different elements having different
1 atomic no. but same mass no. are called
2. (a) Isotopes of hydrogen is 1H , 1 H 2 , 1 H 3 known as
isobars.
protium, deuterium and tritium respectively.
30. (b) Two isotopes of bromine are 35 Br 79 , 35 Br
81
18
3. (d) 8O isotope of oxygen have 10 neutrons and
No. of neutrons in 35 Br 79 = 79  35  44
8 protons.
No. of neutrons in Br 81 = 81  35  46 .
4. (a) Atoms of different elements having different 35

atomic no. but same mass no. are called 31. (c,d) Isotopes have same atomic number but
isobars. different mass number and same chemical
5. (c) Isotopes have same atomic number but properties.
different mass number. 33. (a) Isotopes have same atomic number but
different mass number.
 Nuclear Chemistry 299
 82 Pb 207  x 2 He 4  y 1 
235 0 n
34. (c) 92 U 1. (a) 23
 ratio  12 / 11
11 Na
p
235  207 28
no. of -particles =   7
4 4 n
24
11 Na  ratio  23 / 11
no. of  -particles = 92  82  2  7  4  . p

35. (c) z A m  2 o n1  Z A m  2 , an isotope of A. so decrease in

n
ratio gives out  -particle
p
36. (b) Atoms of different elements having different
atomic no. but same mass no. are called n  p  e (  ) .
isobars.

2. (b) Oxygen have 90% O 16 and 10% O 18
M 4
37. (a) AX
M

 A  2Y
 90 10 
38. (a) Isotopes have same atomic number but Atomic mass =   16   18 
 100 100 
different mass number.
1440  180 1620
39. (a) In isotope X 65 , 32 is atomic number and 65 =   16 . 2 .
32 100 100
is atomic weight. 3. (c) It is a neutron induced fission reaction.
40. (b) Atoms of different elements having different 4. (a) Mass defect = mass of sulphur – mass of
atomic no. but same mass no. are called chlorine
isobars.  34 . 96903  34 . 96885  0.00018 g
41. (c) Atoms of different elements having different
Binding energy =mass defect  931
atomic no. but same mass no. are called
isobars.  0 . 00018  931
43. (a) Mass no. will remain same as proton is  0.1675 MeV
replaced by neutron. 5. (a) The problem refers that rate is constant.
44. (d) Isotopes differ in number of neutrons but 6. (a) 1 C = Activity of 1 g of Ra 226  3.7  10 10 dps
have same number of protons.
Activity of 1g of Ra 226  3.7  10 4 dps
45. (b) Atoms of different elements having different
atomic no. but same mass no. are called So, the no. of  -particles are emitted per
isobars. second by 1g of Ra is
46. (a) 11 Na 24  12 Mg 24  1 e 0 (-particle comes out). 3 .7  10 4 dps  3 .62  10 4 / sec
47. (d) Isotopes differ in number of neutrons but 7. (a) 2 .92  10 4 -particles will be emitted per
have same number of protons. second.
48. (d) Atoms of different elements having different dx 1
atomic no. but same mass no. are called 8. (b)  N 1 , 1  10 5  N 1
dt
isobars.
dx 2
49. (a) 1H
3
 2 He 3  1 e
o
 N 2 , 3 . 7  10 10  N 2
dt
50. (a) Isotopes of same elements have the same
N1 1  10 5 1  10 5
number of protons but different number of    0 . 27  10  5 .
neutrons. N2 3 . 7  10 10 3 .7
x  37  (100  x )35 3500  2 x 9. (d) 92 U
235
 o n1 54 X e139  38 Sr 94  3 o n1
51. (b) 35.5 =  35 . 5 
100 100
0.693 0.693
2 x  50  x  25  Ratio 75 : 25 = 3 : 1 10. (a) k    0.231 per hrs.
t1 / 2 3hr.
52. (d) An ordinary oxygen contains a mixture of O-16
(99.8%), O-17(0.037%), O-18(0.204%) 0 .693
11. (b) t1 / 2 of C–14 = 5760 year,   ,
isotopes. 5760
54. (c) They are isosters i.e, Number of atoms = same 2 . 303 14
C original
Now t  log
Number of e  = same ;Physical properties =  14
C after time t
same
2 . 303  5760 100 2 . 303  5760  0 . 9030
55. (ac) Isotopes have same  log 
0 . 693 12 . 5 0 . 693
atomic number but different mass number.
57. (bd) Both have 34 neutrons; = 17281= 172.81 × 10 2 years.
Isotones have same number of neutrons. 12. (c) According to radioactive equilibrium
A N A  B N B
Critical Thinking Questions
0 .693  N A 0 .693  N B  0 .693 
or    
t1 / 2 ( A) t1 / 2 (B)  t1 / 2 
 300 Nuclear Chemistry
Where t1 / 2 ( A) and t1 / 2 (B) are half periods of A 40
one half-life =  10 days.
and B respectively 4
n 26 / 6 .5
NA NB N t ( A) 1 1
  or A  1 / 2 23. (c) N t  N o    48  10 19  
t1 / 2 ( A) t1 / 2 (B) NB t1 / 2 (B) 2 2
 At equilibrium A and B are present in the 1
4

ratio of their half lives 1 1620  48  10 19    3  10 19 .

 2
2.8  10 6 Half life of uranium
0 . 693 2 . 303 1
 Half-life of uranium 24. (c)  log
9 t 1  0 .2
= 2.8  10 6  1620  4.53  10 9 years.
0 . 693 2 . 303 16
13. (c) Average life period = 1.44  t1 / 2 25. (b)  log  560 days
140 t 16  15
1.44  1580  2275 .2  2.275  10 3 yrs. 20 N 1 1
5
26. (b) n   5, t     ,  decayed
14. (a) N o  8gms, N = 0.5g and t = 1 hr. = 60 min. 4 No  2  32
2 .303  t1 / 2 N  1 
find t1 / 2 by t  log o .  1 –   100 
31
 100  96 .87 .
0 .693 N  32  32
0 .693 2.303 a
15. (b) k   log 27. (b) rnucleus  1.3  10 -13  ( A)1 / 3 , where A is mass
0 .75 hr t a  0 .999 a
number
2 . 303
 log 10 3  7 . 5 hrs .
t rU 238  1 .3  10 13  (238 )1 / 3  8 .06  10 13 cm.
1
16. (c) T = 50 days, t1/ 2 = ?, N o  1, N  , rHe 4  1 .3  10 13  (4 )1 / 3  2 .06  10 13 cm.
32
n n Total distance in between uranium and 
1 1 1
N  No    or  1  , nuclei
2 32 2
5 n
= 8. 06× 10 13 + 2.06 × 10 13 = 10.12 × 10 13 cm
1 1
or      or n = 5 Now repulsion energy =
2 2
Q1 Q 2 92  4.8  10 10  2  4.8  10 10
 erg
T  t1 / 2  2 , or t1 / 2 
50
 10 days. r 10 .12  10 13
5
 418 .9  10 7 erg = 418 .9  10 7  6 .242  10 11 eV
2 .303 a 2 .303
17. (d) K  log  log 8
40 a  0 .875 a 40 = 26 .147738  10 4 eV .
 0.05199 min 1 t1 / 2 = 0.693/0.05199 1
2
28. (a) N t  N o   [  t1 / 2 = 22 years, T = 11 years,
= 13.33 min. = 13 min 20 sec. 2
18. (d) t1 / 2  10 days, N  125 N o =2, N t =?]

2 .303  t1 / 2 N 11 1
Calculate as, t  log o . T  t1 / 2  n, 11= 2 × n or n  
0 .693 125 22 2
0 .693 0 .693 1/2
19. (a) t1 / 2    0 .1098  10 4  1098 yrs . 1
k 6 .31  10 4  N t  2 gm     1 . 414 gm .
2
20. (c) T  t1 / 2  n,  3000  1500  n n = 2
2 . 303 15
1 1 29. (c) t   5000  log
 Amount left    0 .25 g . 0 . 693 5
22 4
2 . 303
1
n
1
18 / 3
1
6
  5000  log 3  7927  7 . 92  10 3 yrs .
21. (a) N t  N o   , N t  256    256    4 . 0 . 693
2 2 2
6.023  10 23
15 30. (c) 1g U-235  atoms
22. (b) Quantity of radioactive element decayed  235
16
15 1 6.023  10 23
Quantity left = 1    energy released  3.2  10 11  J  8 .21  10 10 J
16 16 235
n 4 n
1 1 1 1  8 .2  10 7 kJ .
 1    or     
16 2 2 2
31. (a) Isotones have same number of neutrons.

32. (b) Average atomic weight of element
85  3  87  1
  85 .5
3 1
Assertion & Reason
1. (c) Atomic number defines identity of an atom
because each atom has a definite number of
protons in its nucleus.
3. (d) The activity of 1 g of pure U  235 and that in
U3 O8 is same. Activity does not depend upon
the state of combination.
5. (b) In some nuclides, the nucleus may capture an
electron from the K -shell and the vacancy
created is filled by electrons from higher
levels giving rise to characteristic X -rays.
This process is known as K -electron capture
or simply K -capture.
6. (c) Radioactivity of an element is independent of
its physical state its chemical environment or
temperature, suggesting that it is a property
of nucleus i.e., nuclear phenomenon.
7. (d) At onetime, it was believed that actinium
series starts with Ac  227 but now it is well
known that it starts with U  235 and Ac  227
is one of the main products.
 
9. (a) 92 U 238  0 n 1  92 U 239 
 93 Np 239 
 94 Pu 239
In breeder reactors, the neutrons produced
from fission of U  235 are partly used to
carry on the fission of U  235 and partly used
to produce some other fissionable material.
10. (a) The activation energies for fusion reactions
are very high. They require very high
temperature ( 10 6 ) to over come electrostatic
repulsion between the nuclei.
12. (c) Loss of  or  -particle is to change N / P
ratio so that it lies with in the stability belt.
Loss of  -particle increases N / P ratio while
loss of  -particle decreases N / P ratio.
13. (b) It is correct that photochemical smog is
produced by nitrogen oxide and it is also fact
that vehicular pollution is a major source of
nitrogen oxide but it is not correct
explanation.
14. (d) Binding energy per nucleon of 3 Li 7 (5.38 MeV)
is lesser than 2 He 4 (7.08 MeV) as helium is
found to be more stable than Li . As the
atomic mass number increases, the binding
energy per nucleon decreases. As the atomic
number and the atomic mass number increase,
the repulsive electrostatic forces with in the
nucleus increase due to the greater number of
protons in the heavy elements. To over come
this increased repulsion, the proportion of
neutrons in the nucleus must increase to
Nuclear Chemistry 301
maintain stability. This increase in the
neutron to proton ratio only partially
compensates for the growing proton – proton
repulsive force in the heavier, naturally
occurring elements.
Because the repulsive forces are increasing
less energy must be supplied, on the average,
to remove a nucleon from the nucleus. The
BE/A has decreased. The BE/A of a nucleus is
an indication of its degree of stability.
Generally, the more stable nuclides have
higher BE/A than the less stable ones. The
increase in BE/A as the atomic mass number
decreases from 260 to 60 is the primary
reason for the energy liberation in the fission
process. The increase in the BE/A as the
atomic mass number increases from 1 to 60 is
the reason for the energy liberation in the
fusion process, which is the opposite reaction
of fission.
15. (b) It is correct that during nuclear fission energy
is always released and it is also true that
nuclear fission is a chain prouss.
16. (e) Neutrons are more effective than protons of
equal energy in causing artificial
disintegration of atoms. neutrons are neutral
they penetrate the nucleus and do not exert
any repulsive force like positive charged
protons.
17. (b) It is true that abeam of electrons deflects
more than a beam of  -particles in am
electric field. It is also true that electrons
have –ve while  -particles have +ve charge.
Here both are true but reason is not a correct
explanation.
Na 22  12 Mg 22  1 
0
18. (d) 11 .
Thus this change involves a  -particle
emission and not a positron. Also, proton
emission convert proton into neutron as :
1P 
1
 0 n 1  1  0
 Nuclear Chemistry 301

1. When Li 7 are bombarded with protons,  -rays (b) One electron decreases
3

are produced. The nuclide formed is [CPMT 1987] (c) One proton increases
(d) No change
(a) 3 Li 8 (b) 4 Be 8
(e) None of these
9 9
(c) 3B (d) 4 Be 8. Emission is caused by the transformation of one
2. Nuclides [BVP 2003] neutron into a proton. This results in the
formation of a new element having
(a) Have specific atomic numbers
(a) Same nuclear charge
(b) Have same number of protons
(b) Very lower nuclear charge
(c) Have specific atomic number and mass
(c) Nuclear charge higher by one unit
numbers
(d) Nuclear charge lower by one unit
(d) Are isotopes
9. The end product of 4 n series is [MNR 1983]
3. In the following nuclear reactions
208 207
(a) 82 Pb (b) 82 Pb
7 N 14  2 He 4  8 O 17  X 1 and 13 Al 27  1 D 2 14 Si 28  X 2
(c) 82 Pb 209 (d) 83 Bi 204
X 1 and X 2 are respectively [MP PMT 1999]
10. 92 U 235 belongs to group III B of periodic table. If
1 1 1 1
(a) 1H and 0n (b) 0 n and 1H
it loses one  -particle, the new element will
4 1 1 4 belong to group
(c) 2 He and 0n (d) 0n and 2 He
[MNR 1984; CPMT 2001]
4. Gamma rays are
(a) I B (b) I A
[NCERT 1978; MNR 1990; UPSEAT 1999, 2000]
(c) III B (d) V B
(a) High energy electromagnetic waves
11. Radioactive disintegration differs from a chemical
(b) High energy electrons
change in being [UPSEAT 2000, 01, 02]
(c) High energy protons
(a) An exothermic change
(d) Low energy electrons
(b) A spontaneous process
27
5. Which particle can be used to change 13 Al into
(c) A nuclear process
30
15 P (d) A unimolecular first order reaction
[MP PMT 2003] 12. Half-life is the time in which 50% of radioactive
(a) Neutron (b) -particle element disintegrates. Carbon-14 disintegrates
50% in 5770 years. Find the half-life of carbon-14[DPMT 1
(c) Proton (d) Deuteron
(a) 5770 years
6. Which of the following does not characterise X-
rays (b) 11540 years
[UPSEAT 2001] (c) 5770 years
(a) The radiation can ionise gases
(d) None of the above
(b) It causes ZnS to fluorescence
14
13. The half-life of C is about [MP PET 1996]
(c) Deflected by electric and magnetic field
(a) 12.3 years
(d) Have wavelengths shorter than ultraviolet
rays (b) 5730 years
7. During emission of  -particle [Bihar MEE 1996] (c) 4 .5  10 9 years
(a) One electron increases
 302 Nuclear Chemistry
(d) 2 . 52  10 5 years 20. The half-life period of a radioactive material is 15
minutes. What % of radioactivity of that material
14. Half-life for radioactive C 14 is 5760 years. In how
will remain after 45 minutes
many years 200 mg of C 14 sample will be reduced
(a) 10 % (b) 12.5%
to 25 mg
(c) 15% (d) 17.5%
[CBSE PMT 1995]
226
(a) 11520 years (b) 23040 years 21. Ra disintegrates at such a rate that after 3160

(c) 5760 years (d) 17280 years years only one-fourth of its original amount remains.
226
The half-life of Ra will be
15. The decay constant of a radioactive element is
3  10 6 min 1 . Its half-life is (a) 790 years (b) 3160 years
[MP PET 1993; Pb. CET 2002] (c) 1580 years (d) 6230 years
(a) 2 . 31  10 min
5
22. The ratio of the amount of two elements X and Y
(b) 2 . 31  10 min
6 at radioactive equilibrium is 1 : 2  10 6 . If the half-
life period of element Y is 4.9  10 4 days, then the
(c) 2 . 31  10 6 min
half-life period of element X will be
(d) 2 . 31  10 7 min
(a) 4.8  10 3 days (b) 245 days
16. A radioactive sample decays to half of its initial (c) 122.5 days (d) None of these
concentration in 6.93 minutes.It further decays
23. If half-life of a substance is 5 yrs, then the total
half in next 6.93 minutes. The rate constant for
amount of substance left after 15 years, when
the reaction is
initial amount is 64 grams is [AIEEE 2002]
[RPET 2000]
(a) 16 grams (b) 2 grams
(a) 0.10 min–1 (b) 0.01 min–1
(c) 32 grams (d) 8 grams
(c) 1.0 min–1 (d) 0.001 min–1
24. An element has half-life 1600 years. The mass left
17. The half-life of an isotope is 10 hrs. How much after 6400 years will be [AFMC 2003]
will be left behind after 4 hrs in 1 gm sample[BHU 1997]
(a) 1/16 (b) 1/12
(a) 45 .6  10 23
atoms (c) 1/4 (d) 1/32

(b) 4.56  10 23 atoms 25. Wooden artitact and freshly cut tree are 7.6 and
15 . 2 min 1 g 1 of carbon ( t1 / 2  5760 years)
(c) 4 .56  10 21 atoms
respectively. The age of the artitact is [AIIMS 1980]
(d) 45 .6  10 21 atoms (a) 5760 years
18. The half-life period t1 / 2 of a radioactive element 15 .2
(b) 5760  years
is N years. The period of its complete decay is[KCET 1998] 7 .6

(a) N 2 years (b) 2 N years 7 .6

(c) 5760  years
15 .2
1 2
(c) N years (d) Infinity
2 (d) 5760  (15 .2  7.6) years

19. A radioactive element has a half-life of 20 26. An element has two main isotopes of mass
minutes. How much time should elaspe before the numbers 85 and 87. In nature they occur in the
1 ratio of 75% and 25% respectively. The atomic
element is reduced to th of the original mass[EAMCET 1990]
weight of the element will be approximately
8
(a) 86.0 (b) 86.5
(a) 40 minutes
(c) 85.5 (d) 85.75
(b) 60 minutes
27. A sample of rock from moon contains equal
(c) 80 minutes number of atoms of uranium and lead ( t1 / 2 for
(d) 160 minutes U  4 .5  10 9 years). The age of the rock would be[MNR 1988
(a) 9 . 0  10 9 years
 Nuclear Chemistry 303
(b) 4 .5  10 9 years (a) 3.7  10 5 (b) 3.7  10 7
(c) 13 .5  10 9 years (c) 3.7  10 4 (d) 3.7  10 10
(d) 2 . 25  10 9 years 29. The sum of the number of neutrons and proton in
28. The value of one microcurie = ....... the radio isotope of hydrogen is [IIT 1986]
disintegrations / second (a) 6 (b) 5
[EAMCET 1982] (c) 4 (d) 3

(SET -7)

1. (b) 3 Li 7  1 H 1  4 Be 8   19. (b) t1 / 2  20 minute, N 

1
No
9
2. (d) The isotopes of an element is represented by
writing the symbol of the element and 2 . 303 N
Use, t   t1 / 2 log o .
representing the atomic number and mass 0 . 693 N
number as subscript and superscript No 45
respectively are called nuclides. 20. (b) N  and n  3
2n 15
3. (a) Equate atomic no. and mass no.
100
4. (a) -rays are designated by hv. Also use N o  100 than N   12 .5 % .
23
5. (b) Al 27  2 He 4  15 P 30  o n1
13
***
6. (c) x-rays do not carry any charge and hence are
not deflected by electric and magnetic fields. 21. (c) For an element to disintegrate
7. (c) During  -particle emission one proton 1
n

increases. N  No   …..(i), t = n × t1/ 2 …..(ii)

2
8. (c) on
1
  1 p 1  1 e o (-particle comes out).
N 1
For Ra 226  , from eq. (i)
208 No 4
9. (a) The end product of 4n series is 82 Pb .
n n 2 n
10. (c) Elements 89 to 103 are placed in III group. 1 1 1 1 1
   or   or      , n  2 ; from eq. (ii)
11. (c) Chemical reaction is not nuclear reaction, but 4 2 2 2 2
radioactivity is nuclear distingration. t 3160
T1 / 2    1580 yrs.
12. (a) t1 / 2  5770 years. n 2

13. (b) t1 / 2 of C 14 = 5730 years. NX t (X ) 4 . 9  10 4

22. (b)  1/2 , t1 / 2 ( X )   245 days.
n n 3
NY t1 / 2 (Y ) 2  10  6
1  1  25 1 1 
14. (d) 25     200 ,      
 
2  
2 200 8 2
23. (d) t1 / 2  5 yrs., t  15 yrs
n = 3, Number of half lives = 3
so time required = 3 × 5760 = 17280 yrs. t 15
n   3
t1 / 2 5
0 .693 0 .693
15. (a) t1 / 2    2 .31  10 5 min .
 3  10  6 min 1 No No 1 1
Now N    N o   64  8 grams.
0.693 0.693 2n 23 8 8
16. (a) k    0.10 min 1
t1 / 2 6.93 24. (a) T1 / 2  1600 yrs. , N o  1, N  ?, T  6400 yrs.
23
17. (b) 4.56 × 10 atoms will be left behind after 6400
4 hrs in 1 gm. sample. T  t1 / 2  n, or n  4
1600
18. (d) The t1 / 2 of a radioactive element = N years
n 4
1 1 1
 The period of its complete decay is infinity. N  No    , N  1    , N  .
 
2  
2 16
 Nuclear Chemistry 291
2 .303 ro
25. (a) ro  15 .2 and r  7.6,  t  log .
 r
26. (c) Isotopes have 75% and 25% respectively.

 75 25 
 Atomic mass =   85   87 
 100 100 
6375  2175
=  85 . 5 .
100

N0 2 .303  t1 / 2 N
27. (b) N  , use t  log o
2n 0 .693 N

28. (c) 1 Ci = 3.7  10 10 dps or 3.7  10 10 Bq.

1mCi = 3.7  10 4 dps .

29. (d) Tritium (1 H 3 ) consist of 1 proton and 2

neutrons.
 304 Chemical Equilibrium
Whenever we hear the word Equilibrium immediately a picture
arises in our mind an object under the influence of two opposing
forces. For chemical reactions also this is true. A reaction also can
exist in a state of equilibrium balancing forward and backward
reactions.
Reversible and Irreversible reactions
A chemical reaction is said to have taken place when the
concentration of reactants decreases, and the concentration of the
products increases with time. The chemical reactions are classified on
the basis of the extent to which they proceed, into the following two
classes;
(1) Reversible reactions : Reaction in which entire amount of
the reactants is not converted into products is termed as reversible
reaction.
(i) Characteristics of reversible reactions
(a) These reactions can be started from either side,
(b) These reactions are never complete,
(c) These reactions have a tendency to attain a state of
equilibrium, in which Free energy change is zero (G = 0),
(d) This sign (⇌) represents the reversibility of the reaction,
(ii) Examples of reversible reactions
(a) Neutralisation between an acid and a base either of which
or both are weak e.g.,
CH 3 COOH  Na OH ⇌ CH 3 COONa  H 2 O
(b) Salt hydrolysis, e.g.,
Fe Cl3  3 H 2 O ⇌ Fe OH 3  3 HCl
(c) Thermal decomposition, e.g.,
PCl 5 ( g ) ⇌ PCl3 (g )  Cl2 (g ) Q
(d) Esterification, e.g.,
Chapter
8
Chemical Equilibrium
CH 3 COOH  C2 H 5 OH ⇌ CH 3 COOC 2 H 5  H 2 O
(e) Evaporation of water in a closed vessel, e.g.,
H 2 O(l) ⇌ H 2 O(g) Q
(2) Irreversible reactions : Reaction in which entire amount of
the reactants is converted into products is termed as irreversible
reaction.
(i) Characteristics of irreversible reactions
(a) These reactions proceed only in one direction (forward
direction),
(b) These reactions can proceed to completion,
(c) In an irreversible reaction, G < 0,
(d) The arrow () is placed between reactants and products,
(ii) Examples of irreversible reactions
(a) Neutralisation between strong acid and strong base e.g.,
NaOH  HCl  NaCl  H 2 O 13 .7 kcal
(b) Double decomposition reactions or precipitation reactions
e.g.,
BaCl 2 (aq )  H 2 SO 4 (aq )  BaSO 4 (s)  2 HCl (aq )
(c) Thermal decomposition, e.g.,
MnO 2 ,
2 KClO3 (s)   2 KCl(s)  3O 2 
(d) Redox reactions, e.g.,
SnCl 2(aq )  2 FeCl3 (aq )  SnCl 4 (aq )  2 FeCl2(aq )
Equilibrium and Its dynamic nature
 Chemical Equilibrium 305
“Equilibrium is the state at which the concentration of kf [C ]c [D]d
reactants and products do not change with time. i.e. concentrations of  Kc 
kb [ A]a [B]b
reactants and products become constant.”
Where, K c is called equilibrium constant.
Products In terms of partial pressures, equilibrium constant is denoted by
K p and
Concentration

PCc PDd
Kp 
PAa PBb
Reactants
In terms of mole fraction, equilibrium constant is denoted by
K x and
Time Equilibrium state
The important characteristics of equilibrium state are, ( X C )c ( X D )d
Kx 
(1) Equilibrium state can be recognised by the constancy of ( X A )a ( X B )b
certain measurable properties such as pressure, density, colour, Relation between Kp, Kc and Kx
concentration etc. by changing these conditions of the system, we can K p  Kc (RT )n
control the extent to which a reaction proceeds.
K p  K x (P)n
(2) Equilibrium state can only be achieved in close vessel.
n = number of moles of gaseous products – number of moles
(3) Equilibrium state is reversible in nature.
of gaseous reactants in chemical equation.
(4) Equilibrium state is also dynamic in nature. As a general rule, the concentration of pure solids and pure
(5) At equilibrium state, liquids are not included when writing an equilibrium equation.
Rate of forward reaction = Rate of backward reaction Value of Relation between Kp Units of Kp Units of Kc
(6) At equilibrium state, G = 0, so that H = TS. n and Kc
0 Kp = K c No unit No unit
>0 Kp > K c (atm)n (mole l–1)n
Rate of reaction

<0 Kp < K c (atm)n (mole l–1)n

G= 0
Equilibrium state
Time
Law of mass action and Equilibrium constant
On the basis of observations of many equilibrium reactions, two
Norwegian chemists Goldberg and Waage suggested (1864) a
quantitative relationship between the rates of reactions and the
concentration of the reacting substances. This relationship is known as
law of mass action. It states that
“The rate of a chemical reaction is directly proportional to the
product of the molar concentrations of the reactants at a constant
temperature at any given time.”
The molar concentration i.e. number of moles per litre is also called
active mass. It is expressed by enclosing the symbols of formulae of the
substance in square brackets. For example, molar concentration of A is
expressed as [A].
Consider a simple reversible reaction
aA  bB ⇌ cC  dD (At a certain temperature)
According to law of mass action
Rate of forward reaction  [ A] [B]  k f [ A] [B]
a b a b
Characteristics of equilibrium constant
(1) The value of equilibrium constant is independent of the
original concentration of reactants.
(2) The equilibrium constant has a definite value for every
reaction at a particular temperature. However, it varies with change
in temperature.
(3) For a reversible reaction, the equilibrium constant for the
forward reaction is inverse of the equilibrium constant for the
backward reaction.
1
In general, Kforward reaction 
K backward reaction
(4) The value of an equilibrium constant tells the extent to
which a reaction proceeds in the forward or reverse direction.
(5) The equilibrium constant is independent of the presence of
catalyst.
(6) The value of equilibrium constant changes with the change
of temperature. Thermodynamically, it can be shown that if K1 and
K 2 be the equilibrium constants of a reaction at absolute temperatures
T1 and T2 . If H is the heat of reaction at constant volume, then
 H  1 1
log K 2  log K1     (Van’t Hoff equation)
2 .303 R  T2 T1 

Rate of backward reaction  [C ]c [D]d  k b [C ]c [D]d The effect of temperature can be studied in the following three
cases
At equilibrium ,
(i) When H  0 i.e., neither heat is evolved nor absorbed
Rate of forward reaction = Rate of backward reaction
k f [ A]a [B]b  k b [C]c [D]d log K2  log K1  0 or log K 2  log K1 or K 2  K1
 306 Chemical Equilibrium
Thus, equilibrium constant remains the same at all [ X ][Y ]
Concentration quotient, Q  .
temperatures. [ A][ B]
(ii) When H = +ve i.e., heat is absorbed, the reaction is
It may be noted that Q becomes equal to equilibrium constant
endothermic. The temperature T2 is higher than T1 .
(K) when the reaction is at the equilibrium state. At equilibrium,
log K 2  log K1  ve or log K 2  log K1 or K2  K1 Q  K  K c  K p . Thus,
The value of equilibrium constant is higher at higher (i) If Q > K, the reaction will proceed in the direction of
temperature in case of endothermic reactions. reactants (reverse reaction).
(iii) When H = – ve, i.e., heat is evolved, the reaction is
(ii) If Q < K, the reaction will proceed in the direction of the
exothermic. The temperature T2 is higher than T1 .
products (forward reaction).
log K 2  log K1  ve or log K1  log K 2 or K1  K2 (iii) If Q = K, the reaction mixture is already at equilibrium.
The value of equilibrium constant is lower at higher Thus, a reaction has a tendency to form products if Q < K and
temperature in the case of exothermic reactions. to form reactants if Q > K.
(7) The value of the equilibrium constant depends upon the
stoichiometry of the chemical equation.
For the reaction
2SO 3 (g) ⇌ 2SO 2 (g)  O2 (g) and SO 3 (g) ⇌ SO 2 (g)  1 / 2O2 (g) Q Kc Kc
Q Kc Q
[SO 2 ]2 [O 2 ] [SO 2 ][O 2 ]1 / 2
K 2
and K  
[SO 3 ] [SO 3 ]
Reactants  Products Equilibrium Reactants  Products
K  K or (K )1 / 2 Q<K Q=K Q>K
(Forward reaction) (At equilibrium) (Reverse reaction)
(i) Similarly, if a particular equation is multiplied by 2, the
equilibrium constant for the new reaction (K) will be the square of the Fig. 8.1

equilibrium constant (K) for the original reaction i.e., K   K 2
(ii) If the chemical equation for a particular reaction is written
in two steps having equilibrium constants K1 and K 2 , then the
equilibrium constants are related as K  K1  K 2
Applications of equilibrium constant
(1) Judging the extent of reaction
(i) If K c  10 3 , products predominate over reactants. If K c is
very large, the reaction proceeds almost all the way to completion.
(ii) If K c  10 3 , reactants predominate over products. If K c
is very small, the reaction proceeds hardly at all.
3 3
(iii) If K c is in the range 10 to 10 , appreaciable
concentration of both reactants and products are present.
Kc
Types of equilibria
The equilibrium between different chemical species present in
the same or different phases is called chemical equilibrium. There are
two types of chemical equilibrium.
(1) Homogeneous equilibrium : The equilibrium reactions in
which all the reactants and the products are in the same phase are
called homogeneous equilibrium reactions.
C 2 H 5 OH (l)  CH 3 COOH (l) ⇌ CH3COOC 2 H5 (l)  H2O(l)
N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g)
2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g)
(2) Heterogeneous equilibrium : The equilibrium reactions in
which the reactants and the products are present in different phases are
called heterogeneous equilibrium reactions.

Reaction proceeds 2 NaHCO3 (s) ⇌ Na2 CO3 (s)  CO2 (g)  H 2 O (g)
Reaction proceeds to
hardly at all 10–3 103 completion
Both reactants and Ca(OH )2 (s)  H 2 O (l) ⇌ Ca 2  (aq )  2 OH  (aq )
products are present at
equilibrium
(2) Predicting the direction of reaction : The concentration CaCO3 (s) ⇌ CaO(s)  CO2 (g)
ratio, i.e., ratio of the product of concentrations of products to that of
reactants is also known as concentration quotient and is denoted by Q. H 2 O (l) ⇌ H 2 O (g)

Table : 8.1 Homogeneous equilibria and equations for equilibrium constant (Equilibrium pressure is P atm in a V L flask)
n  0 ; K p  Kc n  0 ; K p  Kc n  0; K p  Kc

H 2 + I2 ⇌ 2 HI N 2  3 H 2 ⇌ 2 NH 3 2 SO 2  O 2 ⇌ 2 SO 3 PCl 5 ⇌ PCl 3  Cl 2
(g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (g)
(g)
 Chemical Equilibrium 307
Initial mole 1 1 0 1 3 0 2 1 0 1 0 0
Mole at (1–x) (1– x) 2x (1–x) (3–3x) 2x (2–2x) (1–x) 2x (1–x) x x
Equilibrium
Total mole at 2 (4 – 2x) (3 – x) (1 + x)
equilibrium

1  x  1  x   1  x   1  x   2x   2  2x   1  x   2x  1  x  x x
Active masses 2x
      3               
 V   V  V  V   V   V   V   V   V   V  V V
Mole fraction
1  x  1  x  2x 1 x 31 x 
 
x  2  2x   1  x   2x  1 x   x   x 
               
 2   2  2 2 2  x  2  2  x  ( 2  x)  3x  3 x 3 x 1  x  1  x  1  x 
Partial  1  x   1  x   2x   1  x   3(1  x )  Px  2  2x  1x   2x  1 x   x   x 
pressure p  p  p  P   P 
  P  P   P  P  P  P 
 2   2   2   2(2  x ) _   2(2  x )  (2  x )  3x  3  x 3 x 1  x  1  x  1  x 
Kc 4x2 4 x 2V 2 x 2V x2
1  x  2
27 1  x  4
1  x  3
1  x  V
Kp 4x2 16 x 2 2  x  2 x 2 3  x  Px 2
1  x  2
27 1  x  P 4 2
P 1  x  3
1 x2 
Table : 8.2 Heterogeneous equilibria and equation for equilibrium constant (Equilibrium pressure is P atm)

NH 4 HS (s) ⇌ NH 3 (g) + H 2S (g) C(s)  CO2 (g) ⇌ 2CO (g) NH2CO2 NH4 (s) ⇌ 2 NH3 (g)  CO2 (g)

Initial mole 1 0 0 1 1 0 1 0 0
Mole at equilibrium (1–x) x x (1–x) (1–x) 2x (1–x) 2x x
Total moles at equilibrium 2x (1+x) 3x
(solid not included)
Mole fraction x 1 1 1  x   2x  2 1
    
2x 2 2 1  x  1  x  3 3
Partial pressure P P 1  x   2x  2P P
P  P 
2 2 1  x  1  x  3 3

Kp P2 4P x2 4 P3
4 (1  x 2 ) 27

Relationship between equilibrium constant and G° Le-Chatelier's principle

G for a reaction under any condition is related with G° by Le-Chatelier and Braun (1884), French chemists, made certain
the relation, G  G  2.303 RT log Q generalizations to explain the effect of changes in concentration,
Standard free energy change of a reaction and its equilibrium temperature or pressure on the state of system in equilibrium. When a
constant are related to each other at temperature T by the relation, system is subjected to a change in one of these factors, the equilibrium
G o  2 . 303 RT log K gets disturbed and the system readjusts itself until it returns to
equilibrium. The generalization is known as Le-Chatelier's principle.
For a general reaction aA  bB ⇌ cC  dD
It may be stated as :
(aC )c (a D )d
K “Change in any of the factors that determine the equilibrium
(a A )a (a B )b
conditions of a system will shift the equilibrium in such a manner to
Where a represent the activity of the reactants and products. It reduce or to counteract the effect of the change.”
is unit less.
For pure solids and liquids: a  1 . The principle is very helpful in predicting qualitatively the
For gases: a  pressure of gas in atm. effect of change in concentration, pressure or temperature on a system
For components in solution: a  molar concentration. in equilibrium.

Table : 8.3 The effect of varying conditions on the equilibrium a A + b B ⇌ c C + d D, n = (c + d) – (a + b)

Change imposed on the system Equilibrium position moves Equilibrium constant Any other points
in equilibrium
Conc. of A and/or B increased To right No change No change
Conc. of C and /or D increased To left No change No change
 308 Chemical Equilibrium
Pressure increased To right if (c  d )  (a  b) , i.e. n  ve No change Very little effect, if any, on reactions
No change in liquid solution.
To left if (c  d )  (a  b) , i.e. n  ve
No change
No change if (c  d )  (a  b) , i.e. n  0
Temperature increased To left if H  ve (exothermic) Value decreased Equilibrium achieved faster
To right if H  ve (endothermic) Value increased

Addition of catalyst No change No change Equilibrium achieved faster

(In this reaction volume is decreased from 1.09 c.c. to 1.01
Application of Le-Chatelier's principle c.c. per gm.)
The Le-Chateliers principle has a great significance for the (a) At high temperature more water is formed as it absorbs heat.
chemical, physical systems and in every day life in a state of (b) At high pressure more water is formed as it is accompanied
equilibrium. by decrease in volume.
(1) Applications to the chemical equilibrium (c) At higher pressure, melting point of ice is lowered, while
(i) Synthesis of ammonia (Haber’s process) boiling point of water is increased.
N 2  3H 2 ⇌ 2 NH 3  23 kcal (exothermic) (ii) Melting of sulphur : S (s) ⇌ S (l)  x kcal
1 vol 3 vol 2 vol
(This reaction accompanies increase in volume.)
(a) High pressure (n  0 ) (a) At high temperature, more liquid sulphur is formed.
(b) Low temperature (b) At higher pressure, less sulphur will melt as melting
(c) Excess of N 2 and H 2 increases volume.
(c) At higher pressure, melting point of sulphur is increased.
(d) Removal of NH 3 favours forward reaction.
(iii) Boiling of water (water- water vapour system)
(ii) Formation of sulphur trioxide Water ⇌ Water Vapours  x kcal
(Low volume)
2 SO 2  O 2 ⇌ 2 SO 3  45 kcal (exothermic)
(Higher volume)

2 vol 1 vol 2 vol (It is accompanied by absorption of heat and increase in

(a) High pressure (n  0 ) volume.)
(a) At high temperature more vapours are formed.
(b) Low temperature
(b) At higher pressure, vapours will be converted to liquid as it
(c) Excess of SO 2 and O 2 , favours the reaction in forward decreases volume.
direction. (c) At higher pressure, boiling point of water is increased
(iii) Synthesis of nitric oxide (principle of pressure cooker).
N 2  O2 ⇌ 2 NO  43 .2 kcal (endothermic ) (iv) Solubility of salts : If solubility of a salt is accompanied by
1 vol 1 vol 2 vol absorption of heat, its solubility increases with rise in temperature;
(a) High temperature e.g., NH4 Cl, K2 SO4 , KNO3 etc.

(b) Excess of N 2 and O 2 KNO3(s)  (aq)  KNO3(aq )  x kcal

(c) Since reaction takes place without change in volume i.e., On the other hand if it is accompanied by evolution of heat,
n  0 , pressure has no effect on equilibrium. solubility decreases with increase in temperature; e.g., CaCl2 ,
(iv) Formation of nitrogen dioxide Ca(OH )2 , NaOH, KOH etc.
2 NO  O 2 ⇌ 2 NO 2  27 .8 Kcal Ca(OH )2( s)  (aq)  Ca(OH )2 (aq )  x kcal
2 vol 1 vol 2 vol

(a) High pressure Relation between vapour density and

(b) Low temperature Degree of dissociation
(c) Excess of NO and O 2 favours the reaction in forward
In the following reversible chemical equation.
direction. A ⇌ yB
(v) Dissociation of phosphours pentachloride Initial mol 1 0
PCl 5 ⇌ PCl 3  Cl 2  15 kcal At equilibrium (1–x) yx x = degree of dissociation
1 vol 1 vol 1 vol Number of moles of A and B at equilibrium
(a) Low pressure or high volume of the container, n  0 (b)  1  x  yx  1  x (y  1)
High temperature (c) Excess of PCl5 . If initial volume of 1 mole of A is V, then volume of
equilibrium mixture of A and B is,  [1  x (y  1)]V
(2) Applications to the physical equilibrium
Molar density before dissociation,
(i) Melting of ice (Ice – water system) molecular weight m
D 
Ice ⇌ Water  x kcal volume V
(Greater Volume) (Lesser Volume)
 Chemical Equilibrium 309
Molar density after dissociation, 2. Which of the following is a characteristic of a reversible
m D Dd reaction [AFMC 1993]
d ;  [1  x (y  1)] ; x 
[1  x (y  1)]V d d (y  1) (a) Number of moles of reactants and products are equal
y is the number of moles of products from one mole of (b) It can be influenced by a catalyst
(c) It can never proceed to completion
D
reactant. is also called Van’t Hoff factor. (d) None of the above
d 3. The reaction CaCO3 ⇌ CaO  CO 2 (g) goes to completion
M m
In terms of molecular mass, x  in lime kiln because
(y  1) m [MP PMT/PET 1988; CPMT 1990]
Where M  Initial molecular mass, (a) Of the high temperature
m  molecular mass at equilibrium (b) CaO is more stable than CaCO3
Thus for the equilibria
(c) CaO is not dissociated
(I) PCl5(g) ⇌ PCl3(g)  Cl 2(g) , y  2 (d) CO2 escapes continuously
(II) N 2 O 4 ( g ) ⇌ 2 NO 2(g) , y  2 4. In the given reaction N 2  O2 ⇌ 2 NO , equilibrium means
1 that
(III) 2NO 2 ⇌ N 2 O 4 , y  [MADT Bihar 1984]
2 (a) Concentration of reactants is changing where as
Dd 2(d  D) concentration of products is constant
 x (for I and II) and x  (for III) (b) Concentration of all substances is constant
d d
(c) Concentration of reactants is constant where as
Also D  2  Molecular weight (theoretical value)
concentration of products is changing
d  2  Molecular weight (abnormal value) of the mixture.
(d) Concentration of all substances is changing
5. Which of the following reactions is reversible
[MADT Bihar 1980]
(a) H 2  I 2  2 HI
(b) H 2 SO 4  Ba (OH )2  BaSO 4  2H 2O
(c) NaCl  AgNO 3  NaNO 3  AgCl
 Pure ice can be made to melt at a temperature slightly below (d) Fe  S  FeS
0°C by increasing the pressure. As the water so obtained on 6. All reactions which have chemical disintegration
melting is below 0°C, it refreezes when pressure is reduced. It [MP PMT 1990]
is called regelation of ice.
(a) Is reversible
 Increase in external pressure always increases the boiling point (b) Is reversible and endothermic
and vice-versa.
(c) Is exothermic
 If the reaction is multipled by 2, the equilibrium constant is (d) Is reversible or irreversible and endothermic or exothermic
squared.
7. Amongst the following chemical reactions the irreversible
 When a bottle of coca or beer is opened, the pressure is reaction is [MP PMT 1999]
decreased and dissolved CO2 gas escapes out with a fizze. (a) H 2  I2 ⇌ HI
 Increase in pressure favours melting of ice into water
(b) AgNO3  NaCl ⇌ AgCl  NaNO3
 Flash evaporation is a technique generally used for concentrating
certain aqueous solutions which cannot be concentrated by normal (c) CaCO3 ⇌ CaO  CO 2
boiling. (d) O2  2SO 2 ⇌ 2SO 3
 Freeze drying is a technique where water is made to sublime off
at a temperature below 0°C.

Reversible and Irreversible reaction

1. A reversible reaction is one which

[MP PET 1986]
(a) Proceeds in one direction
(b) Proceeds in both directions
(c) Proceeds spontaneously
(d) All the statements are wrong
 310 Chemical Equilibrium
Equilibrium state 7. For the reaction PCl3 (g)  Cl2 (g) ⇌ PCl5 (g) the
position of equilibrium can be shifted to the right
1. In any chemical reaction, equilibrium is supposed by [MP PMT 2004]
to be establish when (a) Increasing the temperature
[CPMT 1974, 80, 89; EAMCET 1975, 77, 79; (b) Doubling the volume
MP PMT 1990; NCERT 1980; MP PET 1995] (c) Addition of Cl2 at constant volume
(a) Mutual opposite reactions undergo (d) Addition of equimolar quantities of PCl3 and
(b) Concentration of reactants and resulting PCl5
products are equal
8. If a system is at equilibrium the rate of forward
(c) Velocity of mutual reactions become equal
to the reverse reaction is [UPSEAT 2004]
(d) The temperature of mutual opposite reactions
(a) Less (b) Equal
become equal
(c) High (d) At equilibrium
2. Which of the following conditions represents an
9. Chemical equilibrium is dynamic in nature
equilibrium
because
(a) Freezing of ice in a open vessel, temperature
[IIT 1977]
of ice is constant
(a) Equilibrium is maintained rapidly
(b) Few drops of water is present along with air
(b) The concentration of reactants and products
in a balloon, temperature of balloon is
become same at equilibrium
constant
(c) The concentration of reactants and products
(c) Water is boiling in an open vessel over stove,
are constant but different
temperature of water is constant
(d) Both forward and backward reactions occur at
(d) All the statements (a), (b) and (c) are correct
all times with same speed
for the equilibrium
10. The number of gram molecules of a substance
3. When rate of forward reaction becomes equal to present in unit volume is termed as [MP PMT 1993]
backward reaction, this state is termed as
(a) Activity (b) Normal solution
[NCERT 1975, 80; CPMT 1973, 74, 77]
(c) Molar concentration (d) Active mass
(a) Chemical equilibrium (b) Reversible state
(c) Equilibrium (d) All of these Law of mass action
4. In chemical reaction A ⇌ B , the system will be
known in equilibrium when[MP PMT 1990; NCERT 1977] 1. According to law of mass action rate of a chemical
reaction is proportional to [AFMC 2005]
(a) A completely changes to B
(a) Concentration of reactants
(b) 50% of A changes to B
(b) Molar concentration of reactants
(c) The rate of change of A to B and B to A on both
the sides are same (c) Concentration of products
(d) Only 10% of A changes to B (d) Molar concentration of products
5. A chemical reaction is at equilibrium when 2. In a reaction the rate of reaction is proportional
to its active mass, this statement is known as [IIT 1979]
[NCERT 1975; CPMT 1974; MP PMT 1996;
KCET 1993; IIT 1978; Manipal MEE 1995; Pb. PMT 2002]
(a) Law of mass action
(a) Reactants are completely transformed into (b) Le-chatelier principle
products (c) Faraday law of electrolysis
(b) The rates of forward and backward reactions (d) Law of constant proportion
are equal 3. The active mass of 64 gm of HI in a two litre flask
(c) Formation of products is minimised would be
(d) Equal amounts of reactants and products are [CPMT 1979]
present (a) 2 (b) 1
6. In the chemical reaction N 2  3H 2 ⇌ 2NH 3 at (c) 5 (d) 0.25
equilibrium point, state whether [NCERT 1977] 4. Under a given set of experimental conditions,
with increase in the concentration of the
(a) Equal volumes of N 2 and H 2 are reacting
reactants, the rate of a chemical reaction
(b) Equal masses of N 2 and H 2 are reacting (a) Decreases
(c) The reaction has stopped (b) Increases
(d) The same amount of ammonia is formed as is (c) Remains unaltered
decomposed into N 2 and H 2 (d) First decreases and then increases
5. The law of mass action was enunciated by[MP PMT 1995]
 Chemical Equilibrium 311
(a) Guldberg and Waage (b) Bodenstein [ A]3 [B]2 [C]
(c) (d)
(c) Birthelot (d) Graham [C ] [ A]3 [B]2
6. Theory of ‘active mass’ indicates that the rate of
In the reversible reaction A  B ⇌ C  D , the
2. 1990]
chemical reaction is directly proportional to the[MP PET
concentration of each C and D at equilibrium was
(a) Equilibrium constant
0.8 mole/litre, then the equilibrium constant K c
(b) Properties of reactants
will be [MP PET 1986]
(c) Volume of apparatus
(a) 6.4 (b) 0.64
(d) Concentration of reactants
(c) 1.6 (d) 16.0
7. The rate at which substances react depends on
their 3. 4 moles of A are mixed with 4 moles of B. At
[MP PMT 1997] equilibrium for the reaction A  B ⇌ C  D , 2 moles
(a) Atomic weight (b) Molecular weight of C and D are formed. The equilibrium constant for
the reaction will be [CPMT 1992]
(c) Equivalent weight (d) Active mass
1 1
8. Which is false [AMU 1999] (a) (b)
4 2
(a) The greater the concentration of the
substances involved in a reaction, the lower (c) 1 (d) 4
the speed of the reaction 4. On a given condition, the equilibrium
(b) The point of dynamic equilibrium is reached concentration of HI, H 2 and I2 are 0.80, 0.10 and
when the reaction rate in one direction just 0.10 mole/litre. The equilibrium constant for the
balances the reaction rate in the opposite reaction H 2  I2 ⇌ 2 HI will be [MP PET 1986]
direction
(a) 64 (b) 12
(c) The dissociation of weak electrolyte is a (c) 8 (d) 0.8
reversible reaction
5. In which of the following, the reaction proceeds
(d) The presence of free ions facilitates chemical towards completion [MNR 1990]
changes
(a) K  10 3 (b) K  10 2
9. Chemical equations convey quantitative
information on the (c) K  10 (d) K  1
[Orissa JEE 2002] 6. A reversible chemical reaction having two
(a) Type of atoms/molecules taking part in the reactants in equilibrium. If the concentrations of
reaction the reactants are doubled, then the equilibrium
constant will
(b) Number of atoms/molecules of the reactants
[CPMT 1982, 90; MP PMT 1990,2004; MNR 1992;
and products involved in the reaction
UPSEAT 2002; KCET 1999; Pb. CET 2004]
(c) Relative number of moles of reactants and
(a) Also be doubled (b) Be halved
products involved in the reaction
(c) Become one-fourth (d) Remain the same
(d) Quantity of reactant consumed and quantity of
product formed 7. The equilibrium constant in a reversible reaction
at a given temperature [AIIMS 1982]
10. In the thermal decomposition of potassium
(a) Depends on the initial concentration of the
chlorate given as 2 K ClO 3  2 KCl  3 O 2 , law of
reactants
mass action
(b) Depends on the concentration of the products at
[MADT Bihar 1983]
equilibrium
(a) Cannot be applied
(c) Does not depend on the initial concentrations
(b) Can be applied
(d) It is not characteristic of the reaction
(c) Can be applied at low temperature
8. Pure ammonia is placed in a vessel at temperature
(d) Can be applied at high temp. and pressure where its dissociation constant ( ) is
appreciable. At equilibrium
Law of equilibrium and Equilibrium constant [IIT 1984; Kurukshetra CEE 1998]
(a) K p does not change significantly with
1. For the system 3 A  2 B ⇌ C , the expression for
equilibrium constant is pressure
[NCERT 1981; CPMT 1989; MP PMT 1990; (b)  does not change with pressure
RPMT 1999; Pb. PMT 2002; Pb. CET 2002] (c) Concentration of NH 3 does not change with
[3 A][2 B] [C ] pressure
(a) (b)
C [3 A][2 B] (d) Concentration of H 2 is less than that of N 2
 312 Chemical Equilibrium
9. For the system A(g)  2 B(g) ⇌ C(g) , the equilibrium 15. Unit of equilibrium constant for the reversible
concentrations are (A) 0.06 mole/litre (B) 0.12 reaction H 2  I2 ⇌ 2 HI is [
mole/litre (C) 0.216 mole/litre. The K eq for the 1 2
(a) mol litre (b) mol litre
reaction is
[CPMT 1983] (c) mol litre 1 (d) None of these
(a) 250 (b) 416 16. The decomposition of N 2 O4 to NO2 is carried out
3
(c) 4  10 (d) 125 at 280 K in chloroform. When equilibrium has
10. The equilibrium constant for the given reaction been established, 0.2 mol of N 2 O4 and 2  10 3
H 2  I2 ⇌ 2 HI is correctly given by expression mol of NO2 are present in 2 litre solution. The
[CPMT 1984] equilibrium constant for reaction N 2 O4 ⇌ 2NO 2
[H 2 ][I 2 ] [H 2 ][I 2 ] is
(a) K c  (b) K c  [AIIMS 1984]
[HI ] [2 HI ] 2
(a) 1  10 (b) 2  10 3
2
[H 2 ][I 2 ] [HI ]
(c) K c  (d) K c  (c) 1  10 5 (d) 2  10 5
[HI ]2 [H 2 ][ I 2 ]
17. Concentration of a gas is expressed in the
11. Partial pressures of A, B, C and D on the basis of following terms in the calculation of equilibrium
gaseous system A  2 B ⇌ C  3 D are A = 0.20; B = constant [EAMCET 1982]
0.10; C = 0.30 and D = 0.50 atm. The numerical (a) No. of molecules per litre
value of equilibrium constant is [CPMT 1987]
(b) No. of grams per litre
(a) 11.25 (b) 18.75
(c) No. of gram equivalent per litre
(c) 5 (d) 3.75
(d) No. of molecules equivalent per litre
12. For the reaction A  2 B ⇌ C , the expression for 18. The unit of equilibrium constant K for the
equilibrium constant is
reaction A  B ⇌ C would be [CPMT 1987]
[MNR 1987; MP PMT 1999; UPSEAT 2002] 1 1
(a) mol litre (b) litre mol
[ A][ B] 2 [ A ][ B ]
(a) (b) (c) mol litre (d) Dimensionless
[C ] [C ]
[C ] [C ] 19. In a reaction A  B ⇌ C  D , the concentrations of
(c) (d)
[ A][ B] 2 2[ B ][ A ] A, B, C and D (in moles/litre) are 0.5, 0.8, 0.4 and
1.0 respectively. The equilibrium constant is[BHU 1981]
13. 2 moles of PCl5 were heated in a closed vessel of
(a) 0.1 (b) 1.0
2 litre capacity. At equilibrium, 40% of PCl5 is (c) 10 (d) 
dissociated into PCl3 and Cl2 . The value of
20. In a chemical equilibrium A  B ⇌ C  D , when
equilibrium constant is one mole each of the two reactants are mixed, 0.6
[MP PMT 1989; RPMT 2000; UPSEAT 2004; mole each of the products are formed. The
Kerala CET 2005] equilibrium constant calculated is
(a) 0.266 (b) 0.53 [CBSE PMT 1989]

(c) 2.66 (d) 5.3 (a) 1 (b) 0.36

(c) 2.25 (d) 4/9
14. For which of the following reactions does the
equilibrium constant depend on the units of 21. For the reaction N 2( g )  3 H 2( g ) ⇌ 2 NH 3( g ) , the
concentration correct expression of equilibrium constant K is
[AIIMS 1983] [CPMT 1984, 2000]
2
1 1
⇌ N 2( g )  O 2( g ) [ NH 3 ] [ N 2 ][ H 2 ]3
(a) NO(g ) (a) K  (b) K 
2 2 [ N 2 ][ H 2 ] 3
[ NH 3 ]2
(b) Zn(s)  Cu(2aq ) ⇌ Cu(s)  Zn(2aq ) 2[ NH 3 ] [ N 2 ]  3[H 2 ]
(c) K  (d) K 
(c) [ N 2 ]  3[H 2 ] 2[ NH 3 ]
C 2 H 5 OH (l)  CH 3 COOH (l) ⇌ 22. The suitable expression for the equilibrium
CH 3 COOC 2 H 5(l)  H 2 O(l) (Reaction carried in an constant of the reaction 2 NO(g)  Cl 2(g) ⇌ 2 NOCl ( g )
inert solvent) is
[CPMT 1983, 87]
(d) COCl 2(g ) ⇌ CO(g)  Cl 2 (g)
[2 NOCl ] [ NOCl ] 2
(a) K c  (b) K c 
[2 NO][Cl 2 ] [ NO] 2 [Cl 2 ]
 Chemical Equilibrium 313

[ NOCl ]2 [ NOCl ]2 27 . 54 g of NH 3 . The approximate value of K c for

(c) K c  2
(d) K c  2 2 2
[ NO][Cl 2 ] [ NO] [Cl 2 ] the above reaction can be (in mole litre 2 )[CBSE PMT 1990

23. A + B ⇌ C + D. If finally the concentration of A (a) 75 (b) 50

and B are both equal but at equilibrium (c) 25 (d) 100
concentration of D will be twice of that of A then 31. The equilibrium concentration of X, Y and YX 2
what will be the equilibrium constant of reaction.[BHU 2005]are 4, 2 and 2 moles respectively for the
(a) 4 / 9 (b) 9 / 4 equilibrium 2 X  Y ⇌ YX 2 . The value of K c is [EAMCET 199
(c) 1 / 9 (d) 4 (a) 0.625 (b) 0.0625
24. If in the reaction N 2 O4  2 NO2 , is that part of (c) 6.25 (d) 0.00625
N 2 O4 which dissociates, then the number of 32. An amount of solid NH 4 HS is placed in a flask
moles at equilibrium will be[MP PET 1990; MH CET 2001; KCET 2005] containing ammonia gas at a certain
already
(a) 3 (b) 1 temperature and 0.50 atm. pressure. Ammonium
(c) (1   )2 (d) (1   ) hydrogen sulphide decomposes to yield NH 3 and
H 2 S gases in the flask. When the decomposition
25. In the gas phase reaction, C 2 H 4  H 2 ⇌ C2 H 6 , the
reaction reaches equilibrium, the total pressure in
equilibrium constant can be expressed in units of
the flask rises to 0.84 atm. The equilibrium
[CBSE PMT 1992; Pb. PMT 1999] constant for NH 4 HS decomposition at this
1 1 1
(a) litre mole (b) litre mole temperature is
2
(c) mole litre 2
(d) mole litre 1 [AIEEE 2005]
(a) 0.30 (b) 0.18
26. For the reaction 2SO 2  O2 ⇌ 2SO 3 , the units of
(c) 0.17 (d) 0.11
K c are 33. In the reaction A  2 B ⇌ 2 C , if 2 moles of A, 3.0
[CPMT 1990] moles of B and 2.0 moles of C are placed in a
1
(a) litre mole (b) mol litre 1 2.0 l flask and the equilibrium concentration of C
is 0.5 mole/ l . The equilibrium constant (K c ) for
(c) (mol litre 1 )2 (d) (litre mole 1 2
)
the reaction is [KCET 1996]
27. A quantity of PCl5 was heated in a 10 litre vessel
(a) 0.073 (b) 0.147
at 250 o C ; PCl5 (g) ⇌ PCl3 (g)  Cl2 (g) . At (c) 0.05 (d) 0.026
equilibrium the vessel contains 0.1 mole of 34. In a 500 ml capacity vessel CO and Cl2 are mixed
PCl5 0.20 mole of PCl3 and 0.2 mole of Cl2 . The to form COCl 2 . At equilibrium, it contains 0.2
equilibrium constant of the reaction is
moles of COCl 2 and 0.1 mole of each of CO and
[KCET 1993, 2001; MP PMT 2003]
CO2 . The equilibrium constant Kc for the
(a) 0.02 (b) 0.05
reaction CO  Cl 2 ⇌ COCl 2 is
(c) 0.04 (d) 0.025
[CBSE PMT 1998]
28. A mixture of 0.3 mole of H 2 and 0.3 mole of I2 is
(a) 5 (b) 10
allowed to react in a 10 litre evacuated flask at
(c) 15 (d) 20
500 o C . The reaction is H 2  I2 ⇌ 2 HI , the K is
35. A reaction is A  B  C  D . Initially we start with
found to be 64. The amount of unreacted I2 at
equal concentration of A and B . At equilibrium
equilibrium is [KCET 1990] we find the moles of C is two times of A . What is
(a) 0.15 mole (b) 0.06 mole the equilibrium constant of the reaction[BHU 1998; KCET 2
(c) 0.03 mole (d) 0.2 mole (a) 4 (b) 2
29. In a chemical equilibrium, the rate constant of the (c) 1 / 4 (d) 1 / 2
backward reaction is 7.5  10 4 and the 36. 4.5 moles each of hydrogen and iodine heated in a
equilibrium constant is 1.5. So the rate constant of sealed ten litre vessel. At equilibrium, 3 moles of
the forward reaction is [KCET 1989] HI were found. The equilibrium constant for H 2 (g)  I2 (g) ⇌
(a) 5  10 4 (b) 2  10 3 [EAMCET 1998]
(c) 1 .125  10 3 (d) 9.0  10 4 (a) 1 (b) 10
30. 28 g of N 2 and 6 g of H 2 were kept at 400 o C in (c) 5 (d) 0.33
1 litre vessel, the equilibrium mixture contained 37. An equilibrium mixture of the reaction
2 H 2 S (g) ⇌ 2 H 2 (g)  S 2 (g) had 0.5 mole H 2 S , 0.10
 314 Chemical Equilibrium
mole H 2 and 0.4 mole S 2 in one litre vessel. The (a) 2.4 (b) 18
value of equilibrium constant (K ) in mole litre-1 is (c) 4.8 (d) 9
[AIIMS 1998; IIT 1992; AFMC 1999; UPSEAT 2001] 46. 15 moles of H 2 and 5.2 moles of I2 are mixed and
(a) 0.004 (b) 0.008 allowed to attain equilibrium at 500 o C . At
(c) 0.016 (d) 0.160 equilibrium, the concentration of HI is found to
38. At 3000 K the equilibrium pressures of CO2, CO be 10 moles. The equilbrium constant for the
and O2 are 0.6,0.4 and 0.2 atmospheres formation of HI is
respectively. K p for the reaction, 2CO2 ⇌ 2CO  O2 [KCET 2005]
is [JIPMER 1999] (a) 50 (b) 15
(a) 0.089 (b) 0.0533 (c) 100 (d) 25
(c) 0.133 (d) 0.177 47. In a chemical reaction equilibrium is established
39. The rate constant for forward and backward when
reactions of hydrolysis of ester are 1 .1  10 2 and [MP PET 2001]
1 .5  10 3 per minute respectively. Equilibrium (a) Opposing reaction ceases
constant for the reaction is
(b) Concentration of reactants and products are
CH 3 COOC 2 H 5  H 2 O ⇌ CH 3 COOH C2 H 5 OH equal
[AIIMS 1999] (c) Velocity of opposing reaction is the same as
(a) 4.33 (b) 5.33 that of forward reaction
(c) 6.33 (d) 7.33 (d) Reaction ceases to generate heat
40. At a certain temp. 2HI ⇌ H2 + I2 Only 50% HI is 48. For the reaction H 2  I2  2 HI ,the equilibrium
dissociated at equilibrium. The equilibrium
concentration of H 2 , I2 and HI are 8.0, 3.0 and
constant is
[DCE 1999] 28.0 mol per litre respectively, the equilibrium
(a) 0.25 (b) 1.0 constant of the reaction is
(c) 3.0 (d) 0.50 [BHU 2000; CBSE PMT 2001]
41. When 3 mole of A and 1 mole of B are mixed in 1 (a) 30.66 (b) 32.66
litre vessel the following reaction takes place (c) 34.66 (d) 36.66
A(g)  B(g) ⇌ 2C( g ) . 1.5 moles of C are formed. The 49. Change in volume of the system does not alter the
equilibrium constant for the reaction is[MP PMT 2000] number of moles in which of the following
(a) 0.12 (b) 0.25 equilibrium
(c) 0.50 (d) 4.0 [AIEEE 2002]
42. A 1 M solution of glucose reaches dissociation (a) N 2(g)  O 2(g) ⇌ 2 NO(g)
equilibrium according to equation given below
6 HCHO ⇌ C6 H12O6 . What is the concentration of (b) PCl5 ( g ) ⇌ PCl3(g)  Cl2(g)

HCHO at equilibrium if equilibrium constant is (c) N 2(g)  3 H 2(g) ⇌ 2 NH 3( g )

6  10 22 [MP PMT 2000] (d) SO 2 Cl2(g) ⇌ SO 2(g)  Cl2(g)
(a) 1.6  10 8 M (b) 3.2  10 6 M
50. The rate of forward reaction is two times that of
(c) 3.2  10 4 M (d) 1.6  10 4 M reverse reaction at a given temperature and
43. Equilibrium concentration of HI , I2 and H2 is identical concentration. Kequilibrium is [KCET 2002]
0.7, 0.1 and 0.1 M respectively. The equilibrium (a) 2.5 (b) 2.0
constant for the reaction I2  H 2 ⇌ 2 HI is [JIPMER 2000]
(c) 0.5 (d) 1.5
(a) 36 (b) 49 51. Write the equilibrium constant K for
(c) 0.49 (d) 0.36 CH 3 COOH  H 2 O  H 3 O   CH 3 COO 
44. For the equilibrium N 2  3H 2 ⇌ 2 NH 3 , Kc at 1000K [Kerala (Med.) 2002]
is 2.37  10 3 . If at equilibrium [H 3 O  ][ H 2 O ]
(a)
[N 2 ]  2 M,[H 2 ]  3 M , the concentration of NH 3 is [JIPMER 2000] K 
[CH 3 COO  ][CH 3 COOH ]
(a) 0.00358 M (b) 0.0358 M
[H 3 O  ][CH 3 COO  ]
(c) 0.358 M (d) 3.58 M (b) K 
[H O ][CH COOH ]
2 3
45. In the reaction, A  B ⇌ 2 C , at equilibrium, the
[H 3 O  ][ H 2 O ]
concentration of A and B is 0 . 20 mol l 1 each and (c) K 
[CH 3 COOH ][CH 3 COO  ]
that of C was found to be 0 .60 mol l 1 . The
equilibrium constant of the reaction is [MH CET 2000]
 Chemical Equilibrium 315

[H 2 O ][CH 3 COO  ] (a) 3 .3  10 2 mol litre 1 (b) 3  10 1 mol litre 1

(d) K 
[H 2 O ][CH 3 COOH ] (c) 3  10 3 mol litre 1 (d) 3  10 3 mol litre 1
52. The equilibrium constant (Kc) for the reaction 59. 3.2 moles of hydrogen iodide were heated in a
HA  B ⇌ BH   A is 100. If the rate constant for sealed bulb at 444 o C till the equilibrium state
the forward reaction is 105, then rate constant for was reached. Its degree of dissociation at this
the backward reaction is [CBSE PMT 2002] temperature was found to be 22%. The number of
(a) 10 7 (b) 10 3 moles of hydrogen iodide present at equilibrium
are [BHU 1982]
(c) 10 3 (d) 10 5
(a) 2.496 (b) 1.87
53. 9.2 grams of N 2 O4 (g) is taken in a closed one litre
(c) 2 (d) 4
vessel and heated till the following equilibrium is 60. 56 g of nitrogen and 8 g hydrogen gas are heated
reached N 2 O4 (g) ⇌ 2 NO 2( g ) . in a closed vessel. At equilibrium 34 g of ammonia
At equilibrium, 50% N 2 O4 (g) is dissociated. What are present. The equilibrium number of moles of
nitrogen, hydrogen and ammonia are respectively
is the equilibrium constant (in mol litre–1) [KCET 2004]
(Molecular weight of N 2 O 4  92) [MP PET 2003]
(a) 1,2,2 (b) 2,2,1
(a) 0.1 (b) 0.4 (c) 1,1,2 (d) 2,1,2
(c) 0.2 (d) 2
61. The reaction, 2 SO 2(g)  O2(g) ⇌ 2 SO 3( g ) is carried out
54. Two moles of NH 3 when put into a previously
evacuated vessel (one litre), partially dissociate in a 1 dm 3 vessel and 2 dm 3 vessel separately. The
into N 2 and H 2 . If at equilibrium one mole of ratio of the reaction velocities will be [KCET 2004]
NH3 is present, the equilibrium constant is (a) 1 [MP
: 8 PET 2003] (b) 1 : 4
(a) 3/4 mol 2 litre 2 (b) 27/64 mol 2 litre 2 (c) 4 : 1 (d) 8 : 1
(c) 27/32 mol 2 litre 2 (d) 27/1 mol 2 litre 2 62. The compound A and B are mixed in equimolar
proportion to form the products, A  B ⇌ C  D .
55. In a reaction, reactant ‘A’ decomposes 10% in 1
At equilibrium, one third of A and B are
hour, 20% on 2 hour and 30% in 3 hour. The unit
consumed. The equilibrium constant for the
of rate constant of this reaction is [MP PET 2003]
reaction is [KCET 2004]
(a) sec 1 (b) mol litre 1 sec 1
(a) 0.5 (b) 4.0
(c) litre mol 1 sec 1 (d) litre 2 mol 2 sec 1 (c) 2.5 (d) 0.25
56. In the reaction PCl5 ( g ) ⇌ PCl3( g ) Cl2( g ) . 63. Calculate the partial pressure of carbon monoxide
The equilibrium concentrations of PCl5 and PCl3 from the following

are 0.4 and 0.2 mole/litre respectively. If the CaCO3(s)  CaO(s)  CO2  ; K p  8  10 2
value of K c is 0.5 what is the concentration of Cl2
CO2(g)  C(s)  2CO(g) ; K p  2 [Orissa JEE 2004]
in moles/litre [EAMCET 2003]
(a) 2.0 (b) 1.5 (a) 0.2 (b) 0.4
(c) 1.0 (d) 0.5 (c) 1.6 (d) 4
57. In Haber process 30 litres of dihydrogen and 30 64. The equilibrium constant for the reaction
litres of dinitrogen were taken for reaction which N 2(g )  O2(g ) ⇌ 2 NO(g ) at temperature T is 4  10 4 .
yielded only 50% of the expected product. What
will be the composition of gaseous mixture under The value of K c for the reaction
the aforesaid condition in the end 1 1
NO(g ) ⇌ N 2( g )  O2( g ) at the same temperature is
[CBSE PMT 2003] 2 2
(a) 20 litres ammonia, 25 litres nitrogen, 15 litres [AIEEE 2004]
hydrogen (a) 4  10 4
(b) 50
(b) 20 litres ammonia, 20 litres nitrogen, 20 litres
hydrogen (c) 2 . 5  10 2
(d) 0.02
(c) 10 litres ammonia, 25 litres nitrogen, 15 litres 65. What is the equilibrium expression for the
hydrogen reaction P4 (s)  5 O2(g) ⇌ P4 O10 (s)
(d) 20 litres ammonia, 10 litres nitrogen, 30 litres
hydrogen (a) K c  [O 2 ]5 (b) Kc  [P4 O10 ] / 5[P4 ][O2 ]
58. For the reaction equilibrium N 2 O4 ⇌ 2 NO 2( g ) , the (c) K c  [P4 O10 ] /[ P4 ][O2 ]5 (d) K c  1 /[O 2 ]5
concentrations of N 2 O4 and NO2 at equilibrium
66. In the reaction, H 2  I2 ⇌ 2 HI . In a 2 litre flask 0.4
are 4.8  10 2 and 1 . 2  10 2 mol litre 1 respectively. moles of each H2 and I2 are taken. At
The value of K c for the reaction is [AIEEE 2003]
 316 Chemical Equilibrium
equilibrium 0.5 moles of HI are formed. What x2 (1  x )2
will be the value of equilibrium constant, K c (a) [CPMT 2004] (b)
(1  x )
2
(1  x )2
(a) 20.2 (b) 25.4
x2 x2
(c) 0.284 (d) 11.1 (c) (d)
(2  x )2 1  x2
67. Ammonia carbonate when heated to 200°C gives a
mixture of NH 3 and CO2 vapour with a density of 73. 0.6 mole of NH3 in a reaction vessel of 2dm3
13.0. What is the degree of dissociation of capacity was brought to equilibrium. The vessel
was then found to contain 0.15 mole of H2 formed
ammonium carbonate
by the reaction
[Kerala PMT 2004]
(a) 3 / 2 (b) 1 / 2 2 NH 3(g)  N 2(g)  3 H 2(g)

(c) 2 (d) 1 Which of the following statements is true[KCET 1999]

(e) 5 / 2
(a) 0.15 mole of the original NH3 had dissociated
68. 2 mol of N 2 is mixed with 6 mol of H 2 in a closed at equilibrium
vessel of one litre capacity. If 50% of N 2 is
(b) 0.55 mole of ammonia is left in the vessel
converted into NH 3 at equilibrium, the value of
(c) At equilibrium the vessel contained 0.45 mole
K c for the reaction N 2(g)  3 H 2(g) ⇌ 2 NH 3( g ) is [Kerala PMT 2004]
of N 2
(a) 4 / 27 (b) 27 / 4
(d) The concentration of NH3 at equilibrium is
(c) 1 / 27 (d) 24
0.25 mole per dm3
(e) 9
74. 5 moles of SO2 and 5 moles of O2 are allowed to
69. For a reaction H 2  I2 ⇌ 2 HI at 721K, the value of
react to form SO3 in a closed vessel. At the
equilibrium constant is 50. If 0.5 mols each of equilibrium stage 60% of SO2 is used up. The total
H 2 and I2 is added to the system the value of number of moles of SO2, O2 and SO3 in the vessel
equilibrium constant will be now is [KCET 2001]
[DCE 2004] (a) 10.0 (b) 8.5
(a) 40 (b) 60 (c) 10.5 (d) 3.9
(c) 50 (d) 30
Kp & Kc Relationship and Characteristics of K
70. What is the effect of halving the pressure by
doubling the volume on the following system at
1. In which of the following reaction, the value of
500°C
K p will be equal to K c [MP PMT 1995]
H 2(g)  I2(g) ⇌ 2 HI(g) [UPSEAT 2004]
(a) H 2  I2 ⇌ 2 HI (b) PCl5 ⇌ PCl3  Cl2
(a) Shift to product side (c) 2NH 3 ⇌ N 2  3H 2 (d) 2SO 2  O2 ⇌ 2SO 3
(b) Shift to product formation 2. Equilibrium constants K1 and K 2 for the following
(c) Liquefaction of HI equilibria
(d) No effect 1 K1
NO (g)  O 2 NO2 (g)
71. When NaNO3 is heated in a closed vessel, O 2 is 2
liberated and NaNO2 is left behind. At equilibrium and 2 NO2 (g) K2 2 NO(g)  O2 (g) are related as
[CBSE PMT 2005]
[IIT 1986; Roorkee 1995]
1
(a) Addition of NaNO3 favours forward reaction (a) K 2  (b) K 2  K12
K1
(b) Addition of NaNO2 favours reverse reaction K1 1
(c) K 2  (d) K 2 
(c) Increasing pressure favours reverse reaction
2 K12

(d) Increasing temperature favours forward 3. For the reaction PCl3 (g)  Cl2 (g) ⇌ PCl5 (g) at
reaction o
250 C , the value of K c is 26, then the value of
72. For the reaction : H 2(g)  CO2(g) ⇌ CO(g)  H 2O(g) , if K p on the same temperature will be [MNR 1990; MP PET
the initial concentration of [H 2 ]  [CO2 ] and x
(a) 0.61 (b) 0.57
moles/litre of hydrogen is consumed at
(c) 0.83
equilibrium, the correct expression of K p is[Orissa JEE 2005] (d) 0.46
 Chemical Equilibrium 317
4. The relation between equilibrium constant K p
and K c is 10. In which of the following equilibria, the value of
K p is less than K c [MP PMT 1993]
[IIT 1994; MP PMT 1994; CPMT 1997; AMU 2000;
RPMT 2000, 02;MP PET 2002; Kerala PMT 2002] (a) H 2  I2 ⇌ 2 HI
n n
(a) K c  K p (RT ) (b) K p  Kc (RT ) (b) N 2  3H 2 ⇌ 2NH 3
n
K  (c) N 2  O2 ⇌ 2 NO
(c) K p   c  (d) K p  K c  (RT )n
 RT 
(d) CO  H 2 O ⇌ CO2  H 2
5. CH 3 COOH (l)  C 2 H 5 OH (l) ⇌ CH 3 COOC 2 H 5 (l)  H 2 O(l)
1
In the above reaction, one mole of each of acetic 11. Two gaseous equilibria SO 2(g )  O 2(g ) ⇌ SO 3( g )
2
acid and alcohol are heated in the presence of
and 2 SO 3(g ) ⇌ 2SO 2(g)  O 2(g) have equilibrium
little conc. H 2 SO 4 . On equilibrium being attained
constants K1 and K2 respectively at 298 K .
[CPMT 1985; MP PET 1992]
(a) 1 mole of ethyl acetate is formed Which of the following relationships between K 1

(b) 2 mole of ethyl acetate are formed and K 2 is correct

(c) 1/2 moles of ethyl acetate is formed [CPMT 1988; CBSE PMT 1989; MP PET 1993, 95;
(d) 2/3 moles of ethyl acetate is formed RPMT 1999; MP PMT 2001]

6. If the equilibrium constant of the reaction 2 HI ⇌ (a) K1  K 2 (b) K 2  K 12

H 2  I2 is 0.25, then the equilibrium constant of
1 1
the reaction H 2  I2 ⇌ 2 HI would be[MP PMT 1989, 95] (c) K 2  (d) K 2 
K 12 K1
(a) 1.0 (b) 2.0
(c) 3.0 (d) 4.0
12. H 2  I2 ⇌ 2 HI

7. For N 2  3H 2 ⇌ 2NH 3  heat In the above equilibrium system if the

o
[CPMT 1990; MP PMT 1997; RPMT 1999; concentration of the reactants at 25 C is
MP PET 2000; KCET 2001]
increased, the value of K c will

(a) K p  K c (RT ) (b) K p  K c (RT ) [BHU 1979; CPMT 1990; CBSE PMT 1990]
(a) Increase
(c) K p  K c (RT )2 (d) K p  K c (RT )1
(b) Decrease
8. In the reaction N 2 (g)  3 H 2 ⇌ 2 NH 3 (g) , the value
(c) Remains the same
of the equilibrium constant depends on
[CPMT 1990; AIIMS 1991; MP PET 1996] (d) Depends on the nature of the reactants

(a) Volume of the reaction vessel 13. At a given temperature, the equilibrium constant

(b) Total pressure of the system for reaction PCl5 (g) ⇌ PCl3 (g)  Cl2 (g) is 2.4  10 3 .

(c) The initial concentration of nitrogen and At the same temperature, the equilibrium
hydrogen constant for reaction PCl3 (g)  Cl2 (g) ⇌ PCl5 (g) is[KCET 199
(d) The temperature (a) 2.4  10 3 (b)  2 .4  10 3
9. For the chemical equilibrium, CaCO3 (s) ⇌ (c) 4 .2  10 2 (d) 4.8  10 2
CaO (s)  CO 2 (g), H r can be determined from which 14. For the reaction C(s)  CO2 (g) ⇌ 2CO (g) , the
one of the following plots [AIIMS 2005] partial pressure of CO2 and CO are 2.0 and 4.0
atm respectively at equilibrium. The K p for the
pCO2/p°

pCO2/p°
log10

log10

reaction is [Roorkee 1990]

(a) (b)
(a) 0.5 (b) 4.0
1/T T (c) 8.0 (d) 32.0
15. K for the synthesis of HI is 50. K for
ln pCO2/p°

pCO2/p°

dissociation of HI is [Roorkee 1990]

(c) (d) (a) 50 (b) 5

log10T
(c) 0.2 (d) 0.02
1\T
 318 Chemical Equilibrium
16. In which one of the following gaseous equilibria (c) K p  K e
K p is less than K c [EAMCET 1989; MP PET 1994; Pb. PMT 2000;
(d) Whether K p is greater than, less than or
KCET 2001; CBSE PMT 2002] equal to Kc depends upon the total gas
(a) N 2 O4 ⇌ 2NO 2 (b) 2 HI ⇌ H 2  I2 pressure

(c) 2SO 2  O2 ⇌ 2SO 3 (d) N 2  O2 ⇌ 2 NO 24. In equilibrium CH 3 COOH  H 2 O ⇌ CH 3 COO  H 3 O

The equilibrium constant may change when
17. For which of the following reactions K p  K c
(a) CH 3 COO  are added (b) CH 3 COOH is added
[KCET 1991; IIT 1991; EAMCET 1992;
(c) Catalyst is added (d) Mixture is heated
AIIMS 1996; KCET 2000; AMU 2000]
25. For reaction 2NOCl(g) ⇌ 2 NO(g)  Cl2 (g) , KC at
(a) 2 NOCl (g) ⇌ 2 NO(g)  Cl2 (g)
427°C is 3  10 6 L mol 1 . The value of K P is nearly [AIIMS 2
(b) N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g)
(a) 7.50  10 5 (b) 2.50  10 5
(c) H 2 (g)  Cl2 (g) ⇌ 2 HCl (g)
(c) 2.50  10 4 (d) 1.75  10 4
(d) N 2 O4 (g) ⇌ 2 NO2 (g) 26. For which one of the following reactions K p  K c
18. For the reaction H 2 (g)  I2 (g) ⇌ 2 HI (g) at 721 K the [MP PET 1997]
value of equilibrium constant (K c ) is 50. When (a) N 2  3H 2 ⇌ 2NH 3 (b) N 2  O2 ⇌ 2 NO
the equilibrium concentration of both is 0.5 M , (c) PCl5 ⇌ PCl3  Cl2 (d) 2SO 3 ⇌ 2SO 2  O2
the value of K p under the same conditions will be 27. The equilibrium constant for the reversible
[CBSE PMT 1990] reaction, N 2  3H 2 ⇌ 2NH 3 is K and for the
(a) 0.002 (b) 0.2 1 3
reaction N 2  H 2 ⇌ NH 3 the equilibrium
(c) 50.0 (d) 50 / RT 2 2
19. In which of the following reaction K p  K c [AFMC 1995] constant is K  . K and K  will be related as

(a) N 2  3H 2 ⇌ 2NH 3 (b) H 2  I2 ⇌ 2 HI (a) K  K  (b) K   K

(c) PCl3  Cl2 ⇌ PCl5 (d) 2SO 3 ⇌ O2  2SO 2 (c) K  K  (d) K  K   1

28. The equilibrium constant (K p ) for the reaction
20. For the reaction PCl5 (g) ⇌ PCl3 (g)  Cl2 (g)
PCl5 (g)  PCl3 (g)  Cl2 (g) is 16. If the volume of the
[MP PET 1996]
container is reduced to one half its original
(a) K p  K c (b) K p  K c (RT )1
volume, the value of K p for the reaction at the
(c) K p  K c (RT ) (d) K p  K c (RT )2 same temperature will be
21. The equilibrium constant of the reaction [KCET 1996]
H 2 (g)  I2 (g) ⇌ 2 HI (g) is 64. If the volume of the (a) 32 (b) 64
container is reduced to one fourth of its original (c) 16 (d) 4
volume, the value of the equilibrium constant will 29. 2NO 2 ⇌ 2 NO  O 2 ; K  1 .6  10 12
be [MP PET 1996] 1
(a) 16 (b) 32 NO  O 2 ⇌ NO2 K   ? [CPMT 1996]
2
(c) 64 (d) 128
1 1
22. For the following gaseous reaction H 2  I2 ⇌ 2 HI , (a) K   (b) K  
K2 K
the equilibrium constant[MP PMT 1996; MP PET/PMT 1998] 1
(a) K p  K c (b) K p  K c (c) K   (d) None of these
K
(c) K p  K c (d) K p  1 / K c
30. The value of Kp for the following reaction
23. For the reaction
2 H 2 S (g) ⇌ 2 H 2 (g)  S 2 (g) is 1 .2  10 2 at 106 . 5 o C .
2 NO 2( g ) ⇌ 2 NO(g)  O2(g)
The value of K c for this reaction is
(K c  1 . 8  10 6 at 184 C)
[EAMCET 1997; AIIMS 1999; AFMC 2000; KCET 2001]
(R  0.0831 kJ / (mol . K)) (a) 1 . 2  10 2 (b)  1 .2  10 2
When K p and K c are compared at 184°C it is (c) 83 (d)  1 .2  10 2
found that 31. Which statement for equilibrium constant is true
[AIEEE 2005]
for the reaction A  B ⇌ C [CPMT 1997]
(a) K p is greater than K c
(a) Not changes with temperature
(b) K p is less than K c (b) Changes when catalyst is added
(c) Increases with temperature
 Chemical Equilibrium 319
(d) Changes with temperature 38. At 490°C, the equilibrium constant for the
32. The equilibrium constant for the reaction synthesis of HI is 50, the value of K for the
N 2  3H 2 ⇌ 2NH 3 is K , then the equilibrium dissociation of HI will be
[KCET 2000]
1 3
constant for the equilibrium NH 3 ⇌ N 2  H 2 is (a) 20.0 (b) 2.0
2 2
[CBSE PMT 1996; UPSEAT 2001] (c) 0.2 (d) 0.02
39. In which of the following case Kp is less than Kc
(a) 1 / K (b) 1 / K 2
[AFMC 1997; Pb. PMT 2000]
1
(c) K (d) (a) H 2  Cl2 ⇌ 2 HCl (b) 2SO 2  O2 ⇌ 2SO 3
K
(c) N 2  O2 ⇌ 2 NO (d) PCl5 ⇌ PCl3  Cl2
33. Which of the following statements regarding a
chemical equilibrium is wrong 40. 3(s) ⇌ CaO
CaCO[JIPMER (s)  CO 2( g )
1999] which of the following
(a) An equilibrium can be shifted by altering the expression is correct [MH CET 2000]
temperature or pressure
(a) K P  (PCaO  PCO 2 / PCaCO 3 )
(b) An equilibrium is dynamic
(c) The same state of equilibrium is reached (b) K P  PCO 2
whether one starts with the reactants or the (c) K P  (PCaO  PCO 2 ).PCaCO 3
products
K p [CaO][CO 2 ]
(d) The forward reaction is favoured by the (d)
addition of a catalyst [CaCO3 ]
34. The reaction between N 2 and H 2 to form 41. If Kc is the equilibrium constant for the
ammonia has K c  6  10 2 at the temperature formation of NH 3 , the dissociation constant of
500°C. The numerical value of Kp for this ammonia under the same temperature will be[DPMT 2001]
reaction is [UPSEAT 1999] (a) K c (b) Kc
(a) 1.5  10 5 (b) 1 .5  10 5 (c) K c2 (d) 1 / Kc
6
(c) 1.5  10 (d) 1 .5  10 6
42. 3.2 moles of hydrogen iodide were heated in a
35. For the gaseous phase reaction scaled bulb at 444°C till the equilibrium was
2NO ⇌ N 2  O2 H    43 . 5 kcal mol 1 reached. The degree of dissociation of HI at this
Which statement is correct temperature was found to be 22%. The number of
[MH CET 1999]
moles of hydrogen iodide present at equilibrium
(a) K varies with addition of NO
are [MH CET 2001]
(b) K decrease as temperature decreases
(a) 1.87 (b) 2.496
(c) K Increases as temperature decreases
(d) K is independent of temperature (c) 4.00 (d) 2.00
36. For the reversible reaction, 43. The K c for H 2(g)  I2(g) ⇌ 2 HI(g) is 64. If the volume
N 2(g)  3 H 2(g) ⇌ 2 NH 3( g ) of the container is reduced to one-half of its
original volume, the value of the equilibrium
at 500°C, the value of K P is 1.44  10 5 when constant will be [JIPMER 2001]
partial pressure is measured in atmospheres. The (a) + 28 (b) 64
corresponding value of K c with concentration in
(c) 32 (d) 16
mole litre-1, is
44. A reversible reaction H 2  Cl2 ⇌ 2 HCl is carries out
[IIT Screening 2000; Pb. CET 2004]
in one litre flask. If the same reaction is carried
(a) 1.44  10 5 / 0 .082  500 
2
out in two litre flask, the equilibrium constant
(b) 1.44  10 5 / 8 .314  773 
2
will be [JIPMER 2001]

(c) 1.44  10 5 / 0 . 082  773 

2 (a) Decreased (b) Doubled
(c) Halved (d) Same
(d) 1.44  10 5 / 0 .082  773 
2
45. For the reaction
37. A chemical reaction is catalyzed by a catalyst X. 2 NO 2( g ) ⇌ 2 NO(g)  O2(g) , K c  1 . 8  10 6 at 185°C. At
Hence X
1
[AIIMS 2000] 185°C the Kc for NO(g ) + O 2( g ) ⇌ NO 2( g ) is
(a) Reduces enthalpy of the reaction 2
[JIPMER 2001]
(b) Decreases rate constant of the reaction
(c) Increases activation energy of the reaction (a) 1 .95  10 3 (b) 1.95  10 3
(d) Does not affect equilibrium constant of (c) 7.5  10 2 (d) 0 .9  10 6
reaction
 320 Chemical Equilibrium

46.
1
If for H 2 ( g )  S 2(S ) ⇌ H 2 S (g) and (c) k / 2 (d) k 1
2
H 2(g)  Br2(g) ⇌ 2 HBr( g ) 53. For the reaction, PCl3( g ) + Cl 2( g ) ⇌ PCl5 ( g ) , the value

The equilibrium constants are K1 and K2 of K c at 250°C is 26. The value of K p at this
respectively, the reaction temperature will be
1 [UPSEAT 1999, 2000, 02]
Br2(g)  H 2 S (g) ⇌ 2 HBr ( g )  S 2(S ) would have
2 (a) 0.61 (b) 0.57
equilibrium constant [MP PMT 2001]
(c) 0.83 (d) 0.46
(a) K1  K2 (b) K1 / K2
54. A tenfold increase in pressure on the reaction
(c) K2 / K1 (d) K 22 / K1 N 2( g ) 3 H 2( g ) ⇌ 2 NH 3( g ) at equilibrium, makes K p
47. Some solid NH 4 HS is placed in a flask containing [MP PET 2003]
0.5 atm of NH 3 , what would be pressures of NH 3 (a) Unchanged (b) Two times
and H 2 S when equilibrium is reached (c) Four times (d) Ten times
NH 4 HS (g) ⇌ NH 3(g)  H 2 S (g) , K p  0 .11 [UPSEAT 2001] 55. If equilibrium constant for reaction
(a) 6.65 atm (b) 0.665 atm 2 AB ⇌ A2  B2 , is 49, then the equilibrium
(c) 0.0665 atm (d) 66.5 atm 1 1
constant for reaction AB ⇌ A 2  B 2 , will be
48. In which of the following reactions, increase in 2 2
the volume at constant temperature don’t affect [EAMCET 1998; MP PMT 2003]
the number of moles at equilibrium. [AIEEE 2002]
(a) 7 (b) 20
(a) 2NH 3 ⇌ N 2  3H 2
(c) 49 (d) 21
1
(b) C(g )  O2(g)  CO(g ) 56. In the manufacture of ammonia by Haber's
2 process,
(c) H 2( g ) + O2(g)  H 2 O 2(g)
N 2(g)  3H 2 ⇌ 2 NH 3(g)  92 .3kJ ,
(d) None of these
which of the following conditions is unfavourable
49. A chemical reaction was carried out at 300 K and
[KCET 2004]
280 K. The rate constants were found to be K1 and
K2 respectively. The energy of activation is (a) Increasing the temperature
1.157  10 4 cal mole 1 and R  1.987 cal . Then (b) Increasing the pressure
[KCET 2002]
(a) K2  0.25 K1 (b) K 2  0.5 K1 (c) Reducing the temperature
(d) Removing ammonia as it is formed
(c) K 2  4K1 (d) K 2  2K1
57. The chemical equilibrium of a reversible reaction
50.  n , the change in the number of moles for the
is not influenced by [KCET 2004]
reaction,
(a) Pressure
C12 H 22 O11 (s) 12 O2(g) ⇌ 12 CO 2( g) 11 H 2 O(l)
(b) Catalyst
at 25°C is [Pb. PMT 2002]
(c) Concentration of the reactants
(a) 0 (b) 2
(c) 4 (d) – 1 (d) Temperature
51. Value of K p in the reaction 58. Of the following which change will shift the
reaction towards the product
MgCO3(s) ⇌ MgO(s)  CO 2(g) is
I2 (g) ⇌ 2 I(g), H r0 (298 K )  150 kJ [AIIMS 2004]
[CBSE PMT 2000; RPMT 2002]
(a) K P  PCO 2 (a) Increase in concentration of l
(b) Decrease in concentration of I2
Pco 2  PMgO
(b) K P  Pco 2  (c) Increase in temperature
PMgCO 3
(d) Increase in total pressure
Pco 2  PMgO
(c) K P  59. For the reaction, CO(g)  Cl2(g) ⇌ COCl 2(g ) the
PMgCO 3
K p / K c is equal to [AIEEE 2004]
PMgCO 3
(d) K P  (a) RT (b) RT
PCO 2  PMgO
(c) 1 / RT (d) 1 .0
52. For N 2  3H 2 ⇌ 2NH 3 equilibrium constant is k
60. Consider the following reversible reaction at
then equilibrium constant for 2N2 + 6H2 ⇌ 4NH3 is equilibrium, 2 H 2 O(g) ⇌ 2 H 2(g)  O 2(g) ; H  241 .7 kJ
[RPMT 2002]
Which one of the following changes in conditions
(a) k (b) k 2 will lead to maximum decomposition of H 2 O( g ) [Kerala PMT
 Chemical Equilibrium 321
(a) Increasing both temperature and pressure (c) 0.01 (d) 0.025
(b) Decreasing temperature and increasing 68. A(g)  3 B(g) ⇌ 4 C(g) . Starting concentration of A is
pressure equal to B, equilibrium concentration of A and C
(c) Increasing temperature and decreasing are same. Kc 
pressure
[Kerala CET 2005]
(d) Increasing temperature at constant pressure (a) 0.08 (b) 0.8
61. For reaction, 2 A(g) ⇌ 3 C(g)  D(s) , the value of (c) 8 (d) 80
K c will be equal to [Pb. CET 2003] (e) 1/8
(a) K p (RT ) (b) K p / RT 69. NH 4 COONH 2(s) ⇌ 2 NH 3(g)  CO 2(g) if equilibrium

(c)  K p (d) None of these pressure is 3 atm for the above reaction K p for
the reaction is [
62. In the reaction, A2 (g)  4 B2 (g) ⇌ 2 AB4 (g)
(a) 4 (b) 27
H  0 the formation of AB4 is will be favoured at (c) 4/27 (d) 1/27
[IIT Screening 1990; MP PET 2004]
(a) Low temperature, high pressure Activation energy, Standard free energy and
(b) High temperature, low pressure Degree of dissociation and Vapour density
(c) Low temperature, low pressure
(d) High temperature, high pressure
1. The vapour density of completely dissociated
63. The formation of SO 3 takes place according to the
NH 4 Cl would be [NCERT 1974]
following reaction, 2SO 2  O2 ⇌ 2SO 3 ;
(a) Slight less than half that of NH 4 Cl
H  45 .2 kcal
(b) Half that of NH 4 Cl
The formation of SO 3 is favoured by[UPSEAT 2004]
(c) Double that of NH 4 Cl
(a) Increasing in temperature
(b) Removal of oxygen (d) Determined by the amount of solid NH 4 Cl in
(c) Increase of volume the experiment
(d) Increasing of pressure 2. In an equilibrium reaction for which G 0  0 , the
64. What is the effect of increasing pressure on the equilibrium constant K  [
dissociation of PCl5 according to the equation (a) 0 (b) 1
PCl5 ( g ) ⇌ PCl3(g)  Cl2(g)  x cal [UPSEAT 2004] (c) 2 (d) 10
(a) Dissociation decreases 3. For a system in equilibrium G  0 under
(b) Dissociation increases conditions of constant [KCET 1992, 2005]

(c) Dissociation does not change (a) Temperature and pressure

(d) None of these (b) Temperature and volume
65. If equilibrium constants of reaction, N 2  O2 ⇌ (c) Energy and volume
1 1 (d) Pressure and volume
2 NO is K1 and N 2  O 2 ⇌ NO is K 2 , then[BHU 2004]
2 2 4. A reaction attains equilibrium when the free
(a) K1  K 2 (b) K 2  K1 energy change accompanying it is [KCET 1989]
(a) Positive and large (b) Zero
1
(c) K1  2K 2 (d) K1  K 2 (c) Negative and large (d) Negative and small
2
66. For the following reaction in gaseous phase 5. G (HI, g)  1 .7 kJ .
0
What is the equilibrium
1
CO  O 2  CO 2 ; K p / K c is [DCE 2002]
constant at 25 C for 2 HI (g)  H 2 (g)  I2 (g) [KCET 1992]
o

2
(a) 24.0 (b) 3.9
(a) (RT )1 / 2 (b) (RT )1 / 2
(c) 2.0 (d) 0.5
(c) (RT ) (d) (RT )1 6. The standard state gibbs free energy change for
67. For the reaction N 2(g)  O 2(g) ⇌ 2 NO( g) , the value of the given isomerization reaction cis-2-pentene ⇌
o trans –2 -pentene is 3.67 kJ / mol at 400 K . If more
K c at 800 C is 0.1. When the equilibrium
trans-2-pentene is added to the reaction vessel,
concentrations of both the reactants is 0.5 mol,
then
what is the value of K p at the same temperature [KCET 2005]
[CBSE PMT 1995; BHU 1999; AFMC 2000]
(a) 0.5 (b) 0.1
 322 Chemical Equilibrium
(a) More cis –2–pentene is formed (b) The speed of forward and backward reaction
(b) Equilibrium is shifted in the forward direction decreases
(c) Equilibrium remains unaffected (c) Only the speed of that reaction increases
(d) Additional trans–2–pentene is formed which nullifies the factor causing increase of
7. In a reversible reaction, the catalyst [KCET 2003] speed
(a) Increases the activation energy of the (d) No difference
backward reaction 4. Which of the following reactions proceed at low
(b) Increases the activation energy of the forward pressure
reaction [MP PET 1985; CPMT 1984; MP PMT 1995; RPMT 1997]
(c) Decreases the activation energy of both,
(a) N 2  3H 2 ⇌ 2NH 3 (b) H 2  I2 ⇌ 2 HI
forward and backward reaction
(d) Decreases the activation energy of forward (c) PCl5 ⇌ PCl3  Cl2 (d) N 2  O2 ⇌ 2 NO
reaction
5. Le-chatelier principle is applicable
8. For the reaction H 2 (g)  I2 (g) ⇌ 2 HI (g) , the
(a) Both for physical and chemical equilibrium
equilibrium constant changes with
(b) Only for chemical equilibrium
[IIT 1981; MNR 1983, 85; NCERT 1984; MP PMT 1987, 97;
MP PET/PMT 1988; CPMT 1976, 90; UPSEAT 2000]
(c) Only for physical equilibrium

(a) Total pressure (d) Neither for (b) nor for (c)
(b) Catalyst 6. In the following reversible reaction
(c) The amounts of H 2 and I2 taken 2SO 2  O2 ⇌ 2SO 3  Q Cal
(d) Temperature Most suitable condition for the higher production
9. Calculate G  for conversion of oxygen to ozone of SO 3 is
3 / 2 O2 (g)  O3 (g) at 298 K, if K p for this conversion [NCERT 1974; DPMT 1983, 89; IIT 1981; MP PET 1992;
29 MP PMT 1990, 91, 94, 99; CPMT 1973, 77, 84, 89, 94, 99]
is 2.47  10 [DPMT 2004]
1 (a) High temperature and high pressure
(a) 163 kJ mol (b) 2 . 4  10 kJ mol 1
2

(b) High temperature and low pressure

(c) 1 .63 kJ mol 1 (d) 2 .38  10 6 kJ mol 1 (c) Low temperature and high pressure

Le-Chaterlier principle and It’s application (d) Low temperature and low pressure
7. When the pressure is applied over system ice ⇌
1. When in any system at equilibrium state pressure, water what will happen ?
temperature and concentration is changed then [MP PMT 1990; CPMT 1983; NCERT 1978; DPMT 2002]
the equilibria shifted to such a direction which (a) More water will form
neutralize the effect of change. This is known as (b) More ice will form
[MP PMT/PET 1988; DPMT 1985] (c) There will be no effect over equilibrium
(a) First law of thermodynamics (d) Water will decompose in H 2 and O 2
(b) Le-chatelier's principle 8. The reaction A  B ⇌ C  D +heat has reached
(c) Ostwald's rule equilibrium. The reaction may be made to proceed
forward by
(d) Hess's law of constant heat summation
[IIT 1978]
2. N 2  O2 ⇌ 2 NO  Q cals (a) Adding more C
In the above reaction which is the essential (b) Adding more D
(c)
condition for the higher production of NO [CPMT 1971, 89; MP Decreasing
PMT 1985] the temperature
(a) High temperature (b) High pressure (d) Increasing the temperature
9. On the velocity in a reversible reaction, the
(c) Low temperature (d) Low pressure
correct explanation of the effect of catalyst is[MP PMT 198
3. A reversible reaction is in equilibrium. If a factor (a) It provides a new reaction path of low
is changed which affect it, then activation energy
(a) The speed of forward and backward reaction (b) It increases the kinetic energy of reacting
increases molecules
(c) It displaces the equilibrium state on right side
 Chemical Equilibrium 323
(d) It decreases the velocity of backward reaction (c) Increase in the concentration of one or more
10. Select the correct statement from the following products
[MP PMT 1985] (d) None of these
(a) Equilibrium constant changes with addition of 17. In the formation of SO 3 by contact process, the
catalyst conditions used are [CPMT 1984]
(b) Catalyst increases the rate of forward reaction (a) Catalyst, optimum temperature and higher
concentration of reactants
(c) The ratio of mixture at equilibrium is not
changed by catalyst (b) Catalyst, optimum temperature and lower
concentration of reactants
(d) Catalyst are active only in solution
(c) Catalyst, high temperature and higher
11. According to Le-chatelier principle, if heat is concentration of reactants
given to solid-liquid system, then [MNR 1990]
(d) Catalyst, low temperature and lower
(a) Quantity of solid will reduce concentration of reactants
(b) Quantity of liquid will reduce 18. Given reaction is 2 X (gas )  Y(gas ) ⇌ 2 Z(gas )  80 kcal
(c) Increase in temperature
Which combination of pressure and temperature
(d) Decrease in temperature gives the highest yield of Z at equilibrium [
12. In the reaction A(g)  2 B(g) ⇌ C(g)  Q kJ , greater (a) 1000 atm and 500 C o

product will be obtained or the forward reaction

(b) 500 atm and 500 o C
is favoured by
[MNR 1988; MP PMT 1989, 97] (c) 1000 atm and 100 o C
(a) At high temperature and high pressure (d) 500 atm and 100 o C
(b) At high temperature and low pressure 19. Consider the reaction HCN (aq ) ⇌ H (aq )  CN (aq ) . At
(c) At low temperature and high pressure 
equilibrium, the addition of CN (aq ) would[NCERT 1979]
(d) At low temperature and low pressure
(a) Reduce HCN (aq ) concentration
13. Following gaseous reaction is undergoing in a

vessel C 2 H 4  H 2 ⇌ C2 H 6 ; H  32 .7 Kcal (b) Decrease the H (aq ) ion concentration

Which will increase the equilibrium concentration (c) Increase the equilibrium constant
of C2 H 6 (d) Decrease the equilibrium constant
[IIT 1984; MP PET/PMT 1988; MADT Bihar 1995]
20. In the gaseous equilibrium H 2 X 2  heat ⇌ 2 HX ,
(a) Increase of temperature the formation of HX will be favoured by[CPMT 1977]
(b) By reducing temperature (a) High pressure and low temperature
(c) By removing some hydrogen (b) High temperature and low pressure
(d) By adding some C2 H 6 (c) Low temperature and low pressure
14. The effect of increasing the pressure on the (d) High temperature and high pressure
equilibrium 2 A  3 B ⇌ 3 A  2 B is[EAMCET 1980; MP PMT
21. Raising the temperature of an equilibrium system
1991]
(a) Forward reaction is favoured [MP PMT 1987]
(b) Backward reaction is favoured (a) Favours the exothermic reaction only
(c) No effect (b) Favours the endothermic reaction only
(d) None of the above (c) Favours both the exothermic and endothermic
15. For the equilibrium 2 NO2 (g) ⇌ N 2O4 (g) 14 .6 kcal reactions
the increase in temperature would [CPMT 1974, 78] (d) Favours neither the exothermic nor
(a) Favour the formation of N 2 O4 endothermic reactions
22. Reaction in which yield of product will increase
(b) Favour the decomposition of N 2 O4
with increase in pressure is [
(c) Not alter the equilibrium
(a) H 2(g)  I 2(g) ⇌ 2 HI ( g )
(d) Stop the reaction
16. Which of the following factors will favour the (b) H 2 O(g)  CO(g) ⇌ CO 2(g)  H 2(g)
reverse reaction in a chemical equilibrium [AIIMS 1982]
(c) H 2 O(g)  C(s) ⇌ CO(g)  H 2(g)
(a) Increase in the concentration of one of the
reactants (d) CO(g)  3 H 2(g) ⇌ CH 4 (g)  H 2 O(g)
(b) Removal of at least one of the product at
regular time intervals
 324 Chemical Equilibrium
23. In reaction N 2(g)  3 H 2(g) ⇌ 2 NH 3(g) ; H  93 .6 kJ , 29. In which of the following equilibrium reactions,
the equilibrium would shift to the right, if total
the yield of ammonia does not increase when[CPMT 1988]
pressure is increased [KCET 1993]
(a) Pressure is increased
(a) N 2  3H 2 ⇌ 2NH 3 (b) H 2  I2 ⇌ 2 HI
(b) Temperature is lowered
(c) H 2  Cl2 ⇌ 2 HCl (d) N 2 O4 ⇌ 2 NO
(c) Pressure is lowered
(d) Volume of the reaction vessel is decreased 30. In which of the following gaseous equilibrium an
increase in pressure will increase the yield of the
24. The equilibrium which remains uneffected by products
change in pressure of the reactants is
[EAMCET 1988]
[CPMT 1987; KCET 1991; EAMCET 1992;
(a) 2 HI ⇌ H 2  I2 (b) 2SO 2  O2 ⇌ 2SO 3
MP PET 1992, 95; MP PMT 1999]
(c) H 2  Br2 ⇌ 2 HBr (d) H 2 O  CO ⇌ H 2  CO 2
(a) N 2(g)  O 2(g) ⇌ 2 NO( g)
31. In the reaction A(g)  B(g) ⇌ C(g) , the backward
(b) 2SO 2(g)  O 2(g) ⇌ 2 SO 3(g )
reaction is favoured by [EAMCET 1986]
(c) 2O 3( g ) ⇌ 3 O 2( g ) (a) Decrease of pressure (b) Increase of pressure
(c) Either of the two (d) None of the two
(d) 2 NO 2( g ) ⇌ N 2 O 4 ( g )
32. The formation of NO2 in the reaction
25. The endothermic reaction (M  N  P ) is allowed
2 NO  O 2 ⇌ 2NO 2 + heat is favoured by
to attain an equilibrium at 25 o . Formation of P
[Rookee Qualifying 1998]
can be increased by [BHU 1981]
(a) Low pressure (b) High pressure
(a) Raising temperature
(c) Low temperature (d) Reduction in the
(b) Lowering temperature mass of
(c) Keeping temperature constant 33. For the reaction PCl5 (g) ⇌ PCl3 (g)  Cl2 (g) , the
(d) Decreasing the concentration of M and N forward reaction at constant temperature is
26. According to Le-chatelier's principle, an increase favoured by
in the temperature of the following reaction will [IIT 1991; AMU 2001]
N 2  O2 ⇌ 2 NO  43,200 kcal [MP PMT 1985, 93] (a) Introducing an inert gas at constant volume
(a) Increase the yield of NO (b) Introducing chlorine gas at constant volume
(c) Introducing an inert gas at constant pressure
(b) Decrease the yield of NO
(d) Decreasing the volume of the container
(c) Not effect the yield of NO
34. Which of the following conditions is favourable
(d) Not help the reaction to proceed in forward
for the production of ammonia by Haber's process[MP PET
direction
(a) High concentration of reactants
27. In the manufacture of NH 3 by Haber's process,
the condition which would give maximum yield is (b) Low temperature and high pressure
N 2  3H 2 ⇌ 2 NH 3  Q kcal (c) Continuous removal of ammonia
[NCERT 1978; EAMCET 1980; MNR 1987; AFMC 1999; (d) All of these
CPMT 1983, 84, 86, 94; MP PMT 1999] 35. According to Le-chatelier's principle, which of the
(a) High temperature, high pressure and high following factors influence a chemical system[MP PMT 199
concentrations of the reactants
(a) Concentration only
(b) High temperature, low pressure and low
concentrations of the reactants (b) Pressure only
(c) Low temperature and high pressure (c) Temperature only
(d) Low temperature, low pressure and low (d) Concentration, pressure and temperature
concentration of H 2
36. If pressure increases then its effect on given
28. Suppose the reaction PCl5 (s) ⇌ PCl3(s)  Cl 2(g) is in a equilibrium C(s)  H 2 O(g) ⇌ CO(g)  H 2 (g) it is
closed vessel at equilibrium stage. What is the satisfied in
effect on equilibrium concentration of Cl 2( g ) by [BCECE 2005]
adding PCl5 at constant temperature[MP PMT 1992] (a) Forward direction (b) Backward direction
(a) Decreases (c) No effect (d) None of these
(b) Increases
37. The exothermic formation of ClF3 is represented
(c) Unaffected
by the equation
(d) Cannot be described without the value of K p
 Chemical Equilibrium 325
Cl2(g)  3 F2(g) ⇌ 2ClF3(g) ; H  329 kJ (c) N 2 (g)  3 H 2 (g)  2 NH 3 (g)

Which of the following will increase the quantity (d) PCl5 (g) ⇌ PCl3 (g)  Cl2 (g)
of ClF3 in an equilibrium mixture of Cl2 , F2 and 44. Which of the following information can be
ClF3 [AIEEE 2005] obtained on the basis of Le-chatelier's principle
[AIIMS 1998; Pb. PMT 1999; BHU 2000; DPMT 2004]
(a) Increasing the temperature
(a)Entropy change in a reaction
(b) Removing Cl2
(b)Dissociation constant of a weak acid
(c) Increasing the volume of the container (c)Equilibrium constant of a chemical reaction
(d) Adding F2 (d)Shift in equilibrium position on changing
value of a constant
38. What would happen to a reversible reaction at
45. The equilibrium 2 SO 2(g)  O 2(g) ⇌ 2 SO 3(g ) shifts
equilibrium when an inert gas is added while the
pressure remains unchanged forward,
[MP if
PMT 1997]
[CPMT 1988]
(a) More of the product will be formed
(a) A catalyst is used
(b) Less of the product will be formed (b) An adsorbent is used to remove SO 3 as soon
(c) More of the reactants will be formed as it is formed
(d) It remains unaffected (c) Low pressure
39. Formation of SO 3 takes place according to the (d) Small amounts of reactants are used
reaction 2SO 2  O2  2SO 3 ; H  45 .2 kcal 46. The equilibrium SO 2 Cl2(g) ⇌ SO 2(g)  Cl2(g) is
attained at 25°C in a closed container and an inert
Which of the following factors favours the
gas helium is introduced which of the following
formation of SO 3
statement is correct
[MP PET/PMT 1998] [MP PMT 2000]
(a) Increase in temperature (a) More chlorine is formed
(b) Increase in pressure (b) Concentration of SO 2 is reduced

(c) Removal of oxygen (c) More SO 2 Cl2 is formed

(d) Increase in volume (d) Concentration of SO 2 Cl2 , SO 2 and Cl2 does not

3 X (g)  Y (g) ⇌ X 3 Y (g) ,

change
40. For the chemical reaction
47.
Which of the following equilibria will shift to
the amount of X 3 Y at equilibrium is affected by [IIT 1999]
right side on increasing the temperature[MP PMT 2000]
(a) Temperature and pressure (a) CO(g)  H 2 O(g) ⇌ CO 2 (g)  H 2 (g)
(b) Temperature only (b) 2SO 2 (g)  O2 (g) ⇌ 2SO 3 (g)
(c) Pressure only 1
(c) H 2 O(g) ⇌ H 2 ( g )  (O 2 )( g )
(d) Temperature, pressure and catalyst 2
41. In N 2  3H 2 ⇌ 2NH 3 reversible reaction, increase (d) 4 HCl(g)  O2 (g) ⇌ 2 H 2 O(g)  2Cl2 (g)
in pressure will favour [DPMT 1996]
48. Sodium sulphate dissolves in water with evolution
(a) Reaction in forward direction of heat. Consider a saturated solution of sodium
(b) Reaction in reverse direction sulphate. If the temperature is raised, then
(c) Will not exert any effect according to Le-Chatelier principle
(d) In backward and forward direction equally (a) More solid will dissolve
42. In the reaction N 2  3 H 2  2 NH 3 , the product (b) Some solid will precipitate out from the
increases on solution
[Bihar MEE 1996]
(a) Increasing temperature (c) The solution will become supersaturated
(b) Increasing pressure (d) Solution concentration will remain unchanged
(c) Increasing temperature and pressure both 49. Consider the equilibrium
(d) Decreasing temperature and pressure both N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g) ;  H = – 93.6 KJ. The
(e) None of these maximum yield of ammonia is obtained by
43. In which of the following system, doubling the [UPSEAT 1999; AMU 2000]
volume of the container cause a shift to the right[AIIMS 1996]
(a) Decrease of temp. and increase of pressure
(a) H 2 (g)  Cl2 (g)  2 HCl(g)
(b) Increase of temp. and decrease of pressure
(b) 2CO(g)  O2 (g)  2CO2 (g) (c) Decrease of both the temp. and pressure
 326 Chemical Equilibrium
(d) Increase of both the temp. and pressure [Pb. PMT 2001]

50. In the equilibrium AB ⇌ A  B ; if the equilibrium (a) The reaction remains unaffected
concentration of A is doubled, the equilibrium (b) Forward reaction is favoured
concentration of B would become: [AMU 2000] (c) The reaction halts
(a) Twice (b) Half (d) Backward reaction is favoured
(c) 1/4th (d) 1/8th
58. Le-Chatelier principle is not applicable to[MH CET 2001]
51. Le-Chatelier’s principle is applicable only to a
(a) H 2(g)  I2(g) ⇌ 2 HI(g)
[MP PET/PMT 1988; KCET 1999; AFMC 2000;
Pb. CET 2002] (b) Fe(S )  S (S ) ⇌ FeS (S )
(a) System in equilibrium (b)Irreversible reaction (c) N 2(g)  3 H 2(g) ⇌ 2 NH 3( g )
(c) Homogeneous reaction (d)Heterogeneous reaction
(d) N 2(g)  O2(g) ⇌ 2 NO(g )
52. In a vessel containing SO 3 , SO 2 and O2 at
equilibrium, some helium gas is introduced so 59. For the reaction: A + B + Q ⇌ C + D, if the
that the total pressure increases while temperature is increased, then concentration of
temperature and volume remain constant. the products will
According to Le–Chatelier principle the
[AFMC 2001]
dissociation of SO 3
(a) Increase (b) Decrease
[UPSEAT 2000]
(c) Remain same (d) Become Zero
(a) Increases (b) Decreases
60. H 2( g ) + I2(g) ⇌ 2 HI(g)
(c) Remains unaltered (d) Changes
unpredictably In this reaction when pressure increases, the
53. H 2(g)  I2(g) ⇌ 2 HI(g) H  q cal, then formation of reaction direction [RPMT 2002]

HI: (a) Does not change (b) Forward

[AMU 2000] (c) Backward (d) Decrease
(a) Is favoured by lowering the temperature 61. The rate of reaction of which of the following is
(b) Is favoured by increasing the pressure not affected by pressure [MP PMT 2002]

(c) Is unaffected by change in pressure (a) PCl3  Cl2 ⇌ PCl5 (b) N 2  3H 2 ⇌ 2NH 3
(d) Is unaffected by change in temperature (c) N 2  O2 ⇌ 2NO (d) 2SO 2  O2 ⇌ 2SO 3
54. In which of the following equilibrium systems is
the rate of the backward reaction favoured by 62. In the equilibrium N2 + 3H2 ⇌ 2NH3 + 22 kcal, the
increase of pressure formation of ammonia is favoured by[MP PET 2000, 02]
[KCET 2001] (a) Increasing the pressure
(a) PCl5 ⇌ PCl3  Cl2 (b) 2SO 2  O2 ⇌ 2SO 3 (b) Increasing the temperature
(c) Decreasing the pressure
(c) N 2  3H 2 ⇌ 2NH 3 (d) N 2  O2 ⇌ 2 NO
(d) Adding ammonia
55. Which of the following equilibrium is not shifted
by increase in the pressure 63.[MP
The
PMTreaction
2001] 2SO 2  O2 ⇌ 2SO 3 ; H = – ve is

(a) H 2 (g)  I2 (g) ⇌ 2 HI(g)
(b) N 2(g)  3 H 2(g) ⇌ 2 NH 3 (g)
(c) 2CO(g)  O 2 (g) ⇌ 2CO 2 (g)
(d) 2C(S )  O 2(g) ⇌ 2CO( g )
56. According to Le–Chatelier’s principal adding heat
to a solid and liquid in equilibrium with
endothermic nature will cause the [JIPMER 2000; MP PET 2001]
(a) Temperature to rise
(b) Temperature to fall
(c) Amount of solid to decrease
(d) Amount of liquid to decrease
57. On addition of an inert gas at constant volume to
the reaction N 2  3H 2 ⇌ 2NH 3 at equilibrium
favoured by [CPMT 2002; Pb. PMT 2001]
(a) Low temperature, low pressure
(b) Low temperature, high pressure
(c) High temperature, high pressure
(d) High temperature, low pressure
64. Which of the following will favour the reverse
reaction in a chemical equilibrium[Kerala (Med.) 2002]
(a) Increasing the concentration of the reactants
(b) Removal of at least one of the products at
regular intervals
(c) Increasing the concentration of one or more of
the products
(d) Increasing the pressure
(e) None of these
 Chemical Equilibrium 327
65. Under what conditions of temperature and of Le-Chatelier’s principle, the condition
pressure the formation of atomic hydrogen from favourable for the forward reaction is
molecular hydrogen will be favoured most[UPSEAT 2000, 01, (a)
02] Lowering of temperature as well as pressure
(a) High temperature and high pressure (b) Increasing temperature as well as pressure
(b) Low temperature and low pressure (c) Lowering the temperature and increasing the
pressure
(c) High temperature and low pressure
(d) Any value of temperature and pressure
(d) Low temperature and high pressure
66. The formation of nitric oxide by contact process
N 2  O2 ⇌ 2NO.  H = 43.200 kcal is favoured by[AMU 2002]
(a) Low temperature and low pressure
(b) Low temperature and high pressure
(c) High temperature and high pressure
(d) High temperature and excess reactants 1. If dissociation for reaction, PCl5 ⇌ PCl3  Cl2
concentration
67. The chemical reaction: BaO2(S ) ⇌ BaO(s) O 2( g ) ’  H Is 20% at 1 atm. pressure. Calculate K c

= + ve. In equilibrium condition, pressure of O2 [Kerala (Med.) 2003]

depends upon (a) 0.04 (b) 0.05
[CBSE PMT 2002]
(c) 0.07 (d) 0.06
(a) Increase mass of BaO
(b) Increase mass of BaO2 2. Ammonia under a pressure of 15 atm at 27°C is
heated to 347°C in a closed vessel in the presence
(c) Increase in temperature
of a catalyst. Under the conditions, NH 3 is
(d) Increase mass of BaO2 and BaO both
partially decomposed according to the equation,
68. The yield of product in the reaction
A2(g) + 2 Bg  ⇌ C(g ) + Q.kJ. would be high at 2NH 3 ⇌ N 2  3H 2 .The vessel is such that the
[UPSEAT 2002] volume remains effectively constant where as
pressure increases to 50 atm. Calculate the
(a) High temperature and high pressure
percentage of NH 3 actually decomposed. [IIT 1981; MNR 19
(b) High temperature and low pressure
(c) Low temperature and high pressure (a) 65% (b) 61.3%
(d) Low temperature and low pressure (c) 62.5% (d) 64%
69. Which reaction is not effected by change in
pressure 3. Kp for the following reaction at 700 K is 1 .3  10 3
[UPSEAT 2003] atm-1. The Kc at same temperature for the reaction
2SO 2  O2  2SO 3 will be [AIIMS 2001]
(a) H 2  I2 ⇌ 2HI (b) 2C  O2 ⇌ 2CO
(c) N 2  3H 2 ⇌ 2NH 3 (d) PCl5 ⇌ PCl3  Cl2 (a) 1 .1  10 2 (b) 3 . 1  10 2

70. The gaseous reaction A + B ⇌ 2C + D; + Q is most (c) 5 .2  10 2 (d) 7 .4  10 2

favoured at [Karnataka CET 2003]
4. For the reaction 2 NO 2 ( g ) ⇌ 2 NO(g)  O 2 (g)
(a) Low temperature and high pressure
(b) High temperature and high pressure K c  1 .8  10 6 at 185°C. At 185°C, the value of K c
(c) High temperature and low pressure
1
(d) Low temperature and low pressure for the reaction NO g   O 2 ⇌ NO 2  g  is[UPSEAT 2000]
2 g 
71. For a reaction if K p  K c , the forward reaction is
favoured by [RPET 2003] (a) 0 . 9  10 6 (b) 7.5  10 2
(a) Low pressure (b) High pressure (c) 1 .95  10 3 (d) 1.95  10 3
(c) High temperature (d) Low temperature
5. 2SO 3 ⇌ 2SO 2  O2 . If Kc  100 ,   1 , half of the
72. A2(g)  B2(g) ⇌ 2 AB( g ) ; H  ve [BHU 2003]
reaction is completed, the concentration of SO 3
(a) Unaffected by pressure and SO 2 are equal, the concentration of O 2 is [CPMT 1996
(b) It occurs at 1000 pressure
(c) It occurs at high temperature 1
(a) 0.001 M (b) SO 2
(d) It occurs at high pressure and high 2
temperature (c) 2 times of SO 2 (d) Data incomplete
73. Consider the reaction equilibrium,
2 SO 2( g ) + O2(g) ⇌ 2 SO 3( g ) ; H  = –198kJ. On the basis
 328 Chemical Equilibrium
6. At 700 K, the equilibrium constant K p for the 11. At constant temperature, the equilibrium constant
3 (Kp) for the decomposition reaction N 2 O4 ⇌ 2NO2
reaction 2 SO 3( g ) ⇌ 2SO 2(g)  O2(g) is 1 . 80  10 and
Jk-1 mol–1). (4 x 2 P )
kPa is 14, (R = 8.314 The numerical is expressed by K P  ,
value in moles per litre of K c for this reaction at (1  x 2 )
the same temperature will be where P  pressure, x  extent of decomposition.
[AFMC 2001] Which one of the following statements is true
(a) 3 . 09  10 7 mol-litre (b) 5 . 07  10 8 mol-litre [IIT Screening 2001]
(a) Kp increases with increase of P
(c) 8 . 18  10 9 mol-litre (d) 9 .24  10 10 mol-litre
(b) Kp increases with increase of x
7. 0.1 mole of N 2 O4 (g) was sealed in a tube under one
(c) Kp increases with decrease of x
atmospheric conditions at 25°C. Calculate the
number of moles of NO 2( g ) present, if the (d) Kp remains constant with change in P and x

equilibrium N 2 O4 (g) ⇌ 2 NO 2( g ) (K p  0 .14 ) is reached

after some time
[UPSEAT 2001]

(a) 1 . 8  10 2
(b) 2 . 8  10 2

(c) 0.034 (d) 2 . 8  10 2

8. The partial pressures of CH 3 OH , CO and H 2 in the Read the assertion and reason carefully to mark the
equilibrium mixture for the reaction correct option out of the options given below :
(a) If both assertion and reason are true and the
CO  2H 2 ⇌ CH 3 OH reason is the correct explanation of the assertion.
at 427°C are 2.0, 1.0 and 0.1 atm respectively. The (b) If both assertion and reason are true but reason is
value of K P for the decomposition of CH 3 OH to not the correct explanation of the assertion.
(c) If assertion is true but reason is false.
CO and H 2 is
(d) If the assertion and reason both are false.
[Roorkee 1999] (e) If assertion is false but reason is true.
(a) 1  10 2 atm (b) 2  10 2 atm 1 1. Assertion : The equilibrium constant is fixed
(c) 50 atm 2
(d) 5  10 3
atm 2 and is the characteristic of any
given chemical reaction at a
9. One mole of a compound AB reacts with one mole specified temperature.
of a compound CD according to the equation Reason : The composition of the final
equilibrium mixture at a particular
AB + CD ⇌ AD + CB.
temperature depends upon the
When equilibrium had been established it was starting amount of reactants.[AIIMS 2000]
3 2. Assertion : K p  Kc for all reaction.
found that mole each of reactant AB and CD had
4
Reason : At constant temperature, the
been converted to AD and CB. There is no change
pressure of the gas is proportional
in volume. The equilibrium constant for the
to its concentration.
reaction is [Kerala (Med.) 2003]
3. Assertion : The equilibrium constant for the
9 1 reaction
(a) (b)
16 9 CaSO 4 .5 H 2 O(s) ⇌ CaSO 4 .3 H 2 O(s)  2 H 2 O(g)
16 [CaSO 4 .3 H 2 O][H 2 O]2
(c) (d) 9 is KC 
9 [CaSO 4 .5 H 2 O]

10. For the reaction CO(g)  H 2 O(g) ⇌ CO2 (g)  H 2 (g) at Reason : Equilibrium constant is the ratio of
the product of molar concentration
a given temperature, the equilibrium amount of
of the substances produced to the
CO 2 (g) can be increased by [IIT 1998]
product of the molar concentrations
(a) Adding a suitable catalyst of reactants with each
concentrations term raised to the
(b) Adding an inert gas
power equal to the respective
(c) Decreasing the volume of the container stoichiometric constant.
(d) Increasing the amount CO (g) 4. Assertion : On cooling a freezing mixture,
colour of the mixture turns to pink
 Chemical Equilibrium 329
from deep blue for a reaction. 2 NH 3 (g) ⇌ N 2 (g) 3 H 2 (g) , the unit
Co(H 2O)62 (aq )  4 Cl (aq ) ⇌ of K p will be atm.
CoCl42 (aq )  6 H 2O(l) . Reason : Unit of K p is (atm)n .
Reason : Reaction is endothermic so on
13. Assertion : Effect of temperature of
cooling, the reaction moves to
Kc or K p depends on enthalpy
backward direction.
5. Assertion : If Qc (reaction change.
quotient)  KC (equilibrium Reason : Increase in temperature shifts the
equilibrium in exothermic direction
constant) reaction moves in
and decrease in temperature shifts
direction of reactants.
the equilibrium position in
Reason : Reaction quotient is defined in the
endothermic direction.
same way as equilibrium constant
at any stage of he reaction. 14. Assertion : For a gaseous reaction,
6. Assertion : NaCl solution can be purified by xA  yB ⇌ lC  mD , K p  KC .
passage of hydrogen chloride
Reason : Concentration of gaseous reactant
through brine.
is taken to be unity.
Reason : This type of purification is based on
Le-Chaterlier's principle. 15. Assertion : Ice ⇌water, if pressure is applied
7. Assertion : According to Le-Chatelier's principle water will evaporate.
addition of heat to an equilibrium Reason : Increase of pressure pushes the
solid ⇌ liquid results in decrease in equilibrium towards the side in
the amount of solid. which number of gaseous mole
decreases.
Reason : Reaction is endothermic, so on
1
heating forward reaction is 16. Assertion : SO 2 (g)  O2 (g) ⇌ SO 3 (g)  heat.
favoured. 2
8. Assertion : Equilibrium constant has meaning Forward reaction is favoured at
only when the corresponding high temperature and low pressure.
balanced chemical equation is Reason : Reaction is exothermic.
given. 17. Assertion : For a reaction H2 (g)  I2 (g) ⇌ 2 HI (g)
Reason : Its value changes for the new if the volume of vessel is reduced to
equation obtained by multiplying or half of its original volume,
dividing the original equation by a equilibrium constant will be
number. doubled.
9. Assertion : Equilibrium constant for the Reason : According to Le-Chatelier principle,
reverse reaction is the inverse of reaction shifts in a direction that
the equilibrium constant for the tends to undo the effect of the
reaction in the forward direction. stress.
Reason : Equilibrium constant depends upon
the way in which the reaction is
written.
10. Assertion : The value of K gives us a relative
idea about the extent to which a
reaction proceeds.
Reason : The value of K is independent of the
stochiometry of reactants and Reversible and Irreversible reaction
products at the point of
equilibrium. 1 b 2 c 3 d 4 b 5 a
11. Assertion : Catalyst affects the final state of
6 d 7 b
the equilibrium.
Reason : It enables the system to attain a
new equilibrium state by
Equilibrium state
complexing with the reagents.
12. Assertion : For the reaction, 1 c 2 b 3 a 4 c 5 b
6 d 7 c 8 b 9 cd 10 cd
 330 Chemical Equilibrium
Law of mass action Le-Chaterlier principle and It’s application

1 b 2 a 3 d 4 b 5 a 1 b 2 a 3 c 4 c 5 a

6 d 7 d 8 a 9 c 10 a 6 c 7 a 8 c 9 a 10 c
11 a 12 c 13 b 14 c 15 b
Law of equilibrium and Equilibrium constant 16 c 17 a 18 c 19 b 20 b
21 b 22 d 23 c 24 a 25 a
1 d 2 d 3 c 4 a 5 a
26 a 27 c 28 b 29 a 30 b
6 d 7 c 8 a 9 a 10 d
31 a 32 b,c 33 c 34 d 35 d
11 b 12 c 13 a 14 d 15 d
36 b 37 d 38 d 39 b 40 a
16 c 17 a 18 b 19 b 20 c
41 a 42 b 43 d 44 d 45 b
21 a 22 b 23 d 24 d 25 b
46 d 47 c 48 b 49 a 50 b
26 a 27 c 28 b 29 c 30 a
51 a 52 b 53 c 54 a 55 a
31 b 32 d 33 c 34 b 35 a
56 c 57 a 58 b 59 a 60 a
36 a 37 c 38 a 39 d 40 a
61 c 62 a 63 b 64 c 65 c
41 d 42 d 43 b 44 c 45 d
66 d 67 a 68 c 69 a 70 d
46 a 47 c 48 b 49 a 50 b
71 a 72 a 73 c
51 b 52 b 53 c 54 d 55 b
56 c 57 c 58 c 59 a 60 c Critical Thinking Questions
61 d 62 d 63 b 64 b 65 d
1 b 2 b 3 d 4 b 5 d
66 d 67 d 68 a 69 c 70 d
6 a 7 c 8 d 9 d 10 d
71 abcd 72 a 73 d 74 b
11 d
Kp & Kc Relationship and Characteristics of K
Assertion & Reason
1 a 2 d 3 a 4 b 5 d
1 c 2 e 3 e 4 a 5 e
6 d 7 c 8 d 9 a 10 b
6 c 7 b 8 a 9 a 10 c
11 c 12 c 13 c 14 c 15 d
11 d 12 e 13 c 14 d 15 e
16 c 17 c 18 c 19 d 20 c
16 e 17 e
21 c 22 c 23 a 24 d 25 d
26 b 27 b 28 c 29 c 30 b
31 d 32 d 33 d 34 a 35 b
36 d 37 d 38 d 39 b 40 b
41 d 42 b 43 b 44 d 45 c
46 c 47 b 48 d 49 a 50 a
51 a 52 b 53 a 54 a 55 a
56 a 57 b 58 c 59 c 60 c
61 b 62 a 63 d 64 a 65 b
66 b 67 b 68 c 69 b

Activation energy, Standard free energy and

Degree of dissociation and Vapour density

1 b 2 b 3 a 4 b 5 d
6 a 7 c 8 d 9 a
 Chemical Equilibrium 329
1. (d) Equilibrium constant for the reaction , 3A +
2B ⇌ C is
[C ]
K  .
[ A ]3 [ B ] 2
2. (d) Suppose 1 mole of A and B each taken then 0.8
mole/litre of C and D each formed remaining
Reversible and Irreversible reaction concentration of A and B will be (1 – 0.8) = 0.2
mole/litre each.
1. (b) Reversible reaction always attains equilibrium [C] [D] 0.8  0.8
Kc    16 .0
which proceeds both sides and never go for [ A] [B] 0.2  0.2
completion.
3. (c) AB ⇌ CD
2. (c) In a reversible reaction some amount of the
reactants remains unconverted into products. Initial conc. 4, 4 0 0
3. (d) In lime klin CO2 escaping regularly so After T time conc. (4-2) (4-2) 2 2
reaction proceeds in forward direction. [C] [D] 2  2
Equilibrium constant =  1
7. (b) The reaction is not reversible. [ A] [B] 2  2
4. (a) H 2  I2 ⇌ 2HI; [HI] = 0.80, [H 2 ]  0.10 ,
Equilibrium state
[I2 ]  0.10

1. (c) When rate of forward reaction is equal to the [HI ] 2 0 . 80  0 . 80

Kc    64
rate of backward reaction then equilibrium is [H 2 ] [I 2 ] 0 . 10  0 . 10
supposed to be established.
5. (a) Those reaction which have more value of K
2. (b) Equilibrium can be achieved only in closed
proceeds towards completion.
vessel.
4. (c) When rate of forward reaction is equal to rate of 6. (d) K c is a characteristic constant for the given
backward reaction the reaction is said to be in reaction.
equilibrium. 7. (c) Equilibrium constant is independent of
6. (d) At equilibrium rate of forward reaction is original concentration of reactant.
equal to the rate of backward reaction. 8. (a) K p is constant and does not change with
7. (c) According to Le-chatelier principle when
pressure.
concentration of reactant increases, the
equilibrium shift in favour of forward 9. (a) For reaction A + 2B ⇌ C
reaction. [C] 0.216
K   250 .
8. (b) At equilibrium, the rate of forward & [ A] [B]2 0.06  0.12  0 .12
backward reaction become equal.
11. (b) A + 2B ⇌C + 3D
Law of mass action
[ pC ] [ pD ]3 0 . 30  0 . 50  0 . 50  0 . 50
K   18 . 75
1. (b) According to law of mass-action, “at a given [ pA ] [ pB ]2 0 . 20  0 . 10  0 . 10
temperature, the rate of a reaction at a 13. (a) PCl5 ⇌ PCl3  Cl 2
particular instant is proportional to the 2 0 0
product of the active masses of the reactants at 2  60 2  40 2  40
that instant raised to powers which are
100 100 100
numerically equal to the numbers of their
respective molecules in the stoichiometric Volume of container = 2 litre.
equation describing the reaction”. 2  40 2  40

64 gm Kc  100  2 100  2  0 . 266 .
3. (d) [HI ]   0.25 2  60
128  2 litre
100  2
Active mass is the concentration in
moles/litre. 14. (d)  n = 1 for this change
8. (a) As we increase the concentration of So the equilibrium constant depends on the
substance, then speed of the reaction unit of concentration.
increases. 15. (d) Unit of K p  (atm)n
9. (c) Chemical reaction quantitatively depend on
the reactant and product molecule. Unit of K c  (mole / litre )n
 [mole / litre]0  0
Law of equilibrium and Equilibrium constant
 330 Chemical Equilibrium
2 6
 10 
3
No. of moles of H 2   3 mole
 2  2
[ NO 2 ]2  2  10  6
16. (c) K      10  5 . 27 .54
[N 2 O4 ]  .2  10 1 No. of moles of NH 3   1 .62 mole
2 17
 
[ NH 3 ]2 [1 . 62 ]2
19. (b) For A + B ⇌ C + D Kc  3
 =75
[ N 2 ] [H 2 ] [0 . 19 ] [0 . 57 ]3
[C] [D] 0 .4  1
K  1.
[ A] [B] 0.5  0.8 31. (b) K c 
[YX 2 ]

2

1
 0 . 0625 .
[ X ]2 [Y ] 4  4  2 16
20. (c) A+ B ⇌C+ D
32. (d) NH 4 HS ⇌ NH 3 ( g )  H 2 S ( g )
Initial 1 1 0 0 a 0 .5 atm
remaining at equilibrium 0.4 0.4 0.6 0.6 a x 0 . 5 x x
[C] [D] 0.6  0.6 36 Total pressure  0 . 5  2 x  0 . 84
K    2.25 .
[ A] [B] 0.4  0.4 16 i.e., x  0.17
[ NH 3 ] 2 K p  PNH 3 .PH 2 S  (0.67 ). (0.17 ) =0.1139
21. (a) K 
[ N 2 ] [ H 2 ]3
33. (c) A + 2B ⇌ 2C
23. (d) A + B ⇌ C + D Initial conc. 2 3 2
x x 0 0 at eqm. 2.5 4 1
2 .5 4 1
2x 2x Molar  1 .25 2  0 .5
2 2 2
[C][D] 2 x . 2 x
Kc   4 [0 .5]2
[ A][B] x.x K  0 .05
[1 .25 ]  [2]2
24. (d) N 2 O 4 ⇌ 2 NO 2
1 0 34. (b) CO  Cl2 ⇌ COCl 2
(1  ) 2
0 .1 0 .1 0 .2
total mole at equilibrium  (1   )  2  1   [CO]  , [Cl2 ]  , [COCl 2 ] 
0 .5 0 .5 0 .5
[C 2 H 6 ] [mole / litre] 0 .2
25. (b) K  
[C 2 H 4 ] [H 2 ] [mole / litre] [mole / litre] [COCl 2 ] 0 .5 2
 0   25  10
[CO ] [Cl2 ] 0 . 1 0 . 1 5
= litre/mole. or litre mole–1. 
0 .5 0 .5
0.2 0.2
 35. (a) A+ B ⇌ C+ D
[PCl3 ] [Cl2 ] 10 10
27. (c) K c    0 .04 .
[PCl5 ] 0.1 10  at equilibrium a a 2a 2a
2a  2a
K 4
[ HI ]2 x2 aa
28. (b) K c  ; 64 
[H 2 ] [I2 ] 0.03  0.03 36. (a) H 2  I2 ⇌ 2HI
x 2  64  9  10 4 Initial conc. 4.5 4.5 0
x x 2x
x  8  3  10 2  0.24 from question 2x = 3
x is the amount of HI at equilibrium amount of 3
I2 at equilibrium will be x   1 .5
2
0 .30  0 . 24  0 . 06 So conc. at eqm. 4 . 5  1 . 5 of H 2
Kf  4 . 5  1 . 5 of I2 and 3 of HI
29. (c) K c 
Kb [ HI ]2 33
K  1.
[I2 ] [H 2 ] 3  3
K f  K c  Kb  1.5  7.5  10 4  1 .125  10 3
[H 2 ]2 [S 2 ] [0 . 10 ]2 [0 . 4 ]
30. (a) N 2  3H 2 ⇌ 2NH 3 37. (c) K    0 . 016
[ H 2 S ]2 [0 . 5 ]2
Initial conc. 1 3 0
[PCO ]2 [PO2 ] [0 .4 ]2  [0 .2]
at equilibrium 1-0.81 3-2.43 1.62 38. (a) K p  2
  0 .0888 .
[PCO 2 ] [0 .6]2
0.19 0.57
39. (d) K f  1.1  10 2 ; K b  1 .5  10 3
28
No. of moles of N 2   1 mole
28 Kf 1 . 1  10 2
Kc    7 . 33 .
Kb 1 . 5  10  3
 Chemical Equilibrium 331
40. (a) 2 HI ⇌ H 2  I 2 [PCl3 ] [Cl2 ] 0.2  x
100 0 0
56. (c) K c    0.5 , x  1
50 25 25 [PCl5 ] 0.4
[H 2 ] [I2 ] 25  25 57. (c) N 2  3H 2 ⇌ 2NH 3
  0 . 25 .
[HI ]2 50  50 30 30 0
41. (d) A  B  2C 30-x 30-3x 2x
(3  0 .75 ) (1  0 .75 ) 1.5
10
[C ]2 (1 . 5 )2 2 . 25 2x = 10 ; x = 5
K    4 .0 . 2
[ A] [B] 2 . 25  0 .25 2 . 25  0 . 25
N 2  30  5  25 litre
K2 H 2  30  3  5  15 litre
42. (d) 6 HCHO C6 H12O6 forward reaction
NH 3  2  5  10 litre
K1
C6 H12O6 6 HCHO backward reaction 58. (c)
[ NO 2 ]2 [1 .2  10 2 ]2
 1 
16
 1 
16 K   0 .3  10 2  3  10 3
K2    ; K2   [N 2O4 ] [4 .8  10  2 ]
22 
 K1   6  10 
22
59. (a)  3 .2  0 .704
K 2  1 . 6  10 4 M 100
[HI ] 2 [0 . 7 ] 2  at equil. moles of HI =3.2–0.704 = 2.496
43. (b) K c    49 60. (c) N 2  3H 2 ⇌ 2NH 3 ….. (i)
[H 2 ] [I 2 ] [0 . 1] [0 . 1]
at t  0 56 gm 8 gm 0 gm
[ NH 3 ]2
44. (c) K c  = 2mole 4 mole 0 mole
[ N 2 ] [ H 2 ]3
at equilibrium 2  1 4  3 34 gm
x2 = 1 mole = 1 mole = 2 mole
2 . 37  10  3   x 2  0 . 12798
[2] [3]3 According to eq. (i) 2 mole of ammonia are
x = 0.358 M. present & to produce 2 mole of NH 3 , we need
45. (d) A  B ⇌ 2 C 1 mole of N 2 and 3 mole of H 2 hence 2  1  1
mole of N 2 and 4  3  1 mole of H 2 are
[C ]2 [0 . 6 ]2
Kc   9 present at equilibrium in vessel.
[ A] [B] [0 . 2] [0 . 2]
61. (d) 2SO 2 (g)  O2 (g) ⇌ 2SO 3 (g)
46. (a) H 2 + I2 ⇌ 2 HI
For 1dm 3 R  k [SO 2 ]2 [O 2 ]
15 5.2 0
2
(15–5) (5.2–5) 10  1  1 
R  K     1
[HI ] 2
10  10  T  1 
KC    50
[H 2 ][ I2 ] 10  0 . 2 2
1  1  1
47. (c) Rate of backward reaction = Rate of forward For 2dm 3 R  K     
2 2 8
reaction
So, the ratio is 8 : 1
[HI ]2 (28 )2
48. (b) K c    32 . 66 1 1
[H 2 ] [I2 ] 8  3 
[C][D] 3 3 1
62. (d) K     0 .25
49. (a) N 2(g)  O 2(g) ⇌ 2 NO(g) ; n  2  2  0 [ A][B] 2 2 4

50. (b) The rate of forward reaction is two times that 3 3
of reverse reaction at a given temperature and So, K  0 .25

identical concentration Kequilibriu m is 2 because 63. (b) Given, CaCO 3 (s)  CaO (s)  CO 2 (g) 

the reaction is reversible. So K 

K1 2
 2. C(s)  CO2 (g) ⇌ 2CO (g)
K2 1
[ pCO ]2
Kf 10 5 Kf Kp 2  ; pCO  [Kp1  Kp 2 ]
52. (b) K c  Kb    10 3 [ pCO 2 ]
Kb K c 100
pCO  [8  10 2  2]  16  10 2  4  10 1  0 .4
[ NO 2 ]2 4  (0.05 )2
53. (c) K c    4  0 .05  0 .2
[N 2O4 ] 0 .05 64. (b) N 2 (g)  O2 (g) ⇌ 2 NO (g)

[ N 2 ][ H 2 ]3 1  3 3 [ NO ]2
54. (d) 2 NH 3 ⇌ N 2  3H 2 ; K   27 Kc   4  10 4
initial 2 0 0 [ NH 3 ]2 1 [ N 2 ][O 2 ]
at. equil. 1 1 3
 332 Chemical Equilibrium

NO2 ⇌
1 1
N 2 (g )  O 2 (g )
pCO . p H 2 O x.x x2
Kp   
2 2 p H 2 . pCO 2 (1  x )(1  x ) (1  x )2
1/ 2 1/2
[ N 2 ] [O2 ] 1 1
Kc   
[ NO] Kc 4  10  4 Kp & Kc Relationship and Characteristics of K
1 100
 2
  50 1. (a) n p  nr then K p  K c
2  10 2
65. (d) P4 (s)  5O2 (g) ⇌ P4 O10 (s) where n p = no. of moles of product

[P4 O10 (s)] nr = no. of moles of reactant.

Kc  5
[P4 (s)][O 2 (g)] [ NO 2 ] [ NO] 2 [O 2 ]
2. (d) K 1  ; K2 
We know that concentration of a solid [ NO][O 2 ]1 / 2 [ NO 2 ] 2
1
component is always taken as unity K c  [ NO 2 ] 2 1 [ NO 2 ] 1
[O 2 ]5    
2
[ NO] [O 2 ] K2 [ NO ] [O 2 ]1 / 2 K2
66. (d) H2  I2 ⇌ 2HI
0.4 0.4 0 . 50 1 1
0.4 0.25  0.15 0.4 0.25  0.15 / 2 0 . 50 / 2  K1  ; K2  .
K2 K 12
2
 0 .5 
 2  3. (a) K p  Kc (RT )n  26 (0 . 0821  523 ) 1  0 .61 .
[HI ] 2
  0 .5  0 .5
Kc     11 .11 n g  1  2  1
[H 2 ][ I 2 ]  0 .15   0 . 15  0.15  0 .15
 2  2 
   5. (d) In presence of little H 2 SO 4 (as catalyst) about
67. (d) NH 2 COONH 4 ⇌ 2 NH 3  CO2 2/3 mole of each of CH 3 COOH and C2 H 5 OH
Dd react to form 2/3 mole of the product at
 where D is the density (initial) equilibrium.
(n  1) d
6. (d) K1 for reaction 2HI ⇌ H 2  I2 is 0.25 K 2 for
mol . wt 78
D   39 reaction H 2  I2 ⇌ 2HI will be
2 2
n  no. of product = 3 d  final density K2 
1

1
4
39  13 K1 0.25
  1 , so   1
(3  1)13 Because IInd reaction is reverse of Ist.
a b 0 9. (a) For the reaction,
68. (a) N 2  3 H 2 ⇌ 2 NH 3
(a  x ) (b 3 x ) (2 x ) CaCO3(g) ⇌ CaO(s) + CO2(g)
50% Dissociation of N 2 take place so, Kp = PCO 2 and KC = [CO2]
2  50 ( [CaCO3] = 1 and [CaO] = 1 for solids]
At equilibrium  1 ; value of x  1
100 According to Arrhenius equation we have
[ 2] 2 4 4 K  Ae  H r / RT
Kc   so, K c 
[1][3]3 27 27 Taking logarithm, we have
69. (c) The equilibrium constant does not change H ro
when concentration of reactant is changed as log K p  log A 
RT (2 .303 )
the concentration of product also get changed
accordingly. This is an equation of straight line. When log
Kp is plotted against 1 / T. we get a straight
70. (d) We know that PV  nRT
line.
1
P become P & V bcome 2 V so,
2 ( log K p  log pCO 2 )
1 log pCO 2
P  2 V  PV  nRT
2
So there is no effect in equation.
71. (abcd)All options are true for that equilibrium. 1/
72. (a) H 2(g)  CO2(g) ⇌ CO(g)  H 2O(l) The interceptTof this line = log A, slope = –∆H°r /
2.303 R
Initial conc. 1 1 0 0
Knowing the value of slope from the plot and
At equili (1– (1 – x) x x
universal gas constant R, ∆Hr° can be
x)
calculated.
 Chemical Equilibrium 333
(Equation of straight line : Y = mx + C. Here,  K  K1 / 2  K
H ro  1  (c) 2NO2 ⇌ 2 NO  O2
log K p      log A 29. ……(i)
2 . 303 R  T 
12
K  1 .6  10
Y m x C
1
NO  O 2 ⇌ NO2 ……(ii)
10. (b) K p  Kc (RT )n ; When n  2  (2  1)  1 , i.e. 2
negative, K p  K c . Reaction (ii) is half of reaction (i)
[ NO ]2 [O 2 ]
[SO 3 ] [SO 2 ]2 [O 2 ] 1 K ……(i)
11. (c) K1  12
and K 2  2
; K2  2 . [ NO 2 ]2
[SO 2 ] [O 2 ] [ SO 3 ] K1
[ NO 2 ]
13. (c) Reaction is reversed. Hence K'  ……(ii)
[ NO] [O 2 ]1 2
1
K  4.2  10 2 On multiplying (i) and (ii)
(2.4  10  3 )
[ NO ]2 [O 2 ] [ NO 2 ] [ NO ] [O 2 ]1 2 1
2
[Pco ] 44 K  K'  2
 1 2
  '
14. (c) K p   8 . [ NO 2 ] [ NO ] [O 2 ] [ NO 2 ] K
[PCO ] 2
2
1 1 1
K  K'  ; K ; K'  .
15. (d) Kc1 for H 2  I2 ⇌ 2HI is 50 K' K '2 K
K c2 for 2HI ⇌ H 2  I2 30. (b) K p  Kc (RT )n ; n  1
1 1 So K c will be less than K p .
K c2    0 .02
K c1 50
32. (d) K 1 for N 2  3H 2 ⇌ 2NH 3
16. (c) K p  Kc (RT )n 1 3
K 2 for NH 3 ⇌ N2  H2
n  1 for reaction 2SO 2  O2 ⇌ 2SO 3 2 2

So for this reaction K p is less than K c . [ NH 3 ]2 [ N 2 ]1 2 [H 2 ]3 2

K1  K 2  
[ N 2 ] [H 2 ]3 [ NH 3 ]
17. (c) K p  Kc (RT )n ; n  2  2  0
1 1
K1  K 2  ; K2 
18. (c) For the reaction H 2  I2 ⇌ 2HI K2 K1
n  0
34. (a) K p  Kc (RT )n ; n  2  4  2
So K p  K c 50.0
19. (d) For reaction 2SO 3 ⇌ O2  2SO 2 K p  6  10 2  (0.0812  773 )2

 n is + ve so K p is more than K c . 6  10 2
Kp   1 . 5  10  5 .
(0 . 0812  773 )2
By K p  Kc (RT )n
K 2 H [T2  T1 ]
20. (c)  n =2-1=1 35. (b) 2.303 log 
K1 R T1  T2
K p  Kc (RT )
H  +ve for the reaction
21. (c) For this reaction there is no change in 36. (d) N 2  3H 2 ⇌ 2NH 3
equilibrium constant by change of volume. 4 2

22. (c) If  n =0 then K p  K c n = 2 – 4 = – 2

23. (a) k p  k c (RT )n K p  Kc [RT ]n ; K p  Kc [RT ]2

n  3  2  1 ; k p  k c . Kp 1 .44  10 5
Kc  2

[RT ] [0 .082  773 ] 2
24. (d) Equilibrium constant depends upon
temperature. 37. (d) Catalyst does not affect equilibrium constant.
25. (d) 2NOCl(g) = 2NO(g) + Cl2(g) 38. (d) K for dissociation of HI =?
Kp = KC (RT)∆n H 2  I2 ⇌ 2HI
Kp = 3  10–6 (0.0821  700) = 172.41  10–6 1
= 1.72  10–4 Ka  50 , K b   0 . 02
50
27. (b) K   K n ; Hence n 
1 39. (b) 2 SO 2  O 2 ⇌ 2SO 3 for this reaction
2 3 2
 334 Chemical Equilibrium
 n = –1 ;  K c  K p 1 1
For reaction AB ⇌ A2  B2
2 2
40. (b) CaCO3(s) ⇌ CaO(s)  CO 2(g)
[ A 2 ]1 2 [B 2 ]1 2
Kc  ; Kc  K c  49  7 .
' '
K p  PCO 2
[ AB ]
Solid molecule does not have partial pressure 56. (a) For this reaction  n is negative & H is
so in calculation of K p only PCO 2 is applicable. positive so it take forward by decrease in
1 3 temperature.
41. (d) NH 3 ⇌ N2  H2
2 2 57. (b) Chemical equilibrium of reversible reaction is
1 2 3 2 not influenced by catalyst. It is affected by
[ N 2 ] [H 2 ] 1 3
Kc  and N 2  H 2 ⇌ NH 3 pressure, temperature & concentration of
NH 3 2 2 reactant.
[ NH 3 ] 58. (c) H is positive so it will shift toward the
Kc 
[ N 2 ]1 2 [H 2 ]3 2 product by increase in temperature.
1 59. (c) CO(g)  Cl2 (g) COCl 2 (g)
So for dissociation 
Kc n  1  2  1
22 Kp 1
42. (b) Given x  and a  3 .2 K p  K c [RT ]n ;   [RT ]1 
100 Kc RT
 22  60. (c) H is positive so reaction move forward by
[HI ]at equilibrium  3.2 1    2.496
 100  increase in temperature & value of
43. (b) K c does not depend upon initial concentration n  3  2  1 is positive so it forward with
decrease in pressure.
of reactants or product.
61. (b) 2 A(g) 3 C(g)  D(s)
44. (d) K p and K c are characteristic for a given
reaction if n  0 then there is no change. For this reaction, n g  3  2  1

[ NO ]2 [O 2 ] [ NO 2 ] Kp Kp
45. (c) K c1  2
 1 . 8  10  6  K c2   K p  K c [RT ]1 or  RT or K c 
[ NO 2 ] [ NO] [O 2 ]1 2 Kc RT
1 1 62. (a) According to Le-Chatelier principle
K c1  ; 1 . 8  10  6   K c2  7.5  10 2
K c22 K c2
2 exothermic reaction is forwarded by low
temperature, in forward direction number of
[H 2 S ] [HBr ]2 moles is less, hence pressure is high.
46. (c) K1  ; K 
[H 2 ] [S 2 ]1 2
2
[H 2 ] [Br 2 ] 63. (d) In this reaction H is negative so reaction
move forward by decrease in temperature
[HBr ]2  [S 2 ]1 2 K while value of n  2  3  1 i.e., negative so
K3  ; 2  K3
[Br2 ]  [H 2 S ] K1 the reaction move forward by increase in
pressure.
p2 p2
47. (b) K p  ; 0.11   p 2  0.44 64. (a) PCl5 (g) ⇌ PCl3 (g)  Cl2 (g)
4 4
or p  0.44  0.66444  0.665 atm For this reaction n  2  1  1
Value of  n is positive so the dissociation of
50. (a) C12 H 22 O11(s)  12 O2(g)  12 CO2(g)  11 H 2 O
PCl5 take forward by decrease in pressure &
n  12  12  0 by increase in pressure the dissociation of
51. (a) In this reaction gaseous molecule count PCl5 decrease.
MgCO3  MgO(s)  CO2(g) 65. (b) N 2  O2 ⇌ 2 NO …..(i)
K p  PCO 2 1 1
N 2  O 2 ⇌ NO ……(ii)
n 2 2
53. (a) K p  Kc [RT ] ; n  1, Kc  26
For equation number (i)
R  0.0812 , T  250  273  523 K
[ NO ]2
1 K1  ….. (iii)
K p  26 [0.0812  523 ]  0.605  0.61 [ N 2 ][O 2 ]

55. (a) 2 AB ⇌ A2  B2 For equation number (ii)

[ NO]
[ A 2 ] [B 2 ] K2  …... (iv)
Kc  [ N 2 ]1 / 2 [O 2 ]1 / 2
[ AB]2
From equation (iii) & (iv) it is clear that
 Chemical Equilibrium 335
K 2  (K1 )1 / 2  K1 ; Hence, K 2  K1 8. (d) Equilibrium constant changes with
temperature, pressure and the concentration
n g
66. (b) K p  K c [RT ] of either reactant or product.

n g  1  1.5  0.5 9. (a) As we know that, G o  2.303 RT log K p

Kp Therefore, G o  2 . 303  (8 . 314 )  (298 )

K p  K c [RT ]1 / 2   [RT ]1 / 2
Kc
(log 2 .47  10 29 )
67. (b) N 2(g)  O 2(g) ⇌ 2 NO(g)
G o  16 ,3000 J mol 1  163 KJ mol 1
n
K c  0.1, K p  K c (RT )
n  0, K p  K c  0.1 Le-Chaterlier principle and It’s application
68. (c)
2. (a) N 2  O2 ⇌ 2NO; Q cal
A + 3B ⇌ 4C
a b 0 The above reaction is endothermic so for
(a – x) (b – 4x higher production of NO, and the temperature
3x) should be high.
[C ]4 4 x .4 x .4 x .4 x 4. (c) At low pressure, reaction proceeds where
KC  
[ A][ B] 3
(a  x )(b  3 x ) volume is increasing. This is the favourable
Given a  b, a  x  4 x  a  5 x  b condition for the reaction. PCl5 ⇌ PCl3  Cl2 .

4 x .4 x .4 x .4 x 4 x .4 x .4 x .4 x 6. (c) Reaction is exothermic and volume is

KC   8.
(5 x  x )(5 x  3 x ) 4 x .2 x .2 x .2 x decreasing from left to right so for higher
production of SO 3 there should be low
69. (b) Equilibrium pressure = 3atm
temperature and high pressure.
NH 4 COONH 2(s) ⇌ 2 NH 3(g)  CO 2(g)
7. (a) Ice ⇌ Water
K p  p NH
2
3
. p CO 2  3 2 .3  27 more volume less volume

On increasing pressure, equilibrium shifts

Activation energy, Standard free energy and forward.
Degree of dissociation and Vapour density 8. (c) Exothermic reaction is favoured by low
temperature to proceed in forward direction.
Normal molecular weight
1. (b) =1+ 9. (a) Effect of catalyst is that it attains equilibrium
experiment al molecular wt.
quickly by providing a new reaction path of
NH 4 Cl ⇌ NH 3  HCl low activation energy. It does not alter the
   1 Experimental Molecular wt state of equilibrium.
nor.mol.wt . 11. (a) On increasing temperature equilibrium will
=
2 shift in forward direction due to decrease in
2. (b) If G o  0 intermolecular forces of solid.

G o  2.303 RT log K p 12. (c) Both  n and H are negative. Hence, high
pressure and low temperature will forward
log K p  0 ( log1  0) reaction.
Kp  1. 13. (b) Exothermic reaction, favoured by low
temperature.
5. (d) G o  2.303  8.314  10 3  298 log K p
14. (c) n  0 , No effect of pressure.
1.7  2.303  8.314  10 3  298  log K p
15. (b) The reaction is endothermic in reverse
K p  0.5 direction and hence increase in temperature
will favour reverse reaction.
6. (a) Equilibrium shifts backward by Le-chatelier’s
principle. 16. (c) A reaction is in equilibrium it will shift in
reverse or backward direction when we
7. (c) Decreases the activation energy of both
forward and backward reaction. increase the concentration of one or more
product (from Le chatelier’s principle).
 336 Chemical Equilibrium
17. (a) According to Le chatelier’s principle. In this reaction volume is increasing in the
18. (c) The reaction takes place with a reduction in forward reaction. So on increasing
number of moles (volume) and is exothermic. temperature reaction will proceed in forward
So high pressure and low temperature with direction.
favour the reaction in forward direction 48. (b) When temperature increases precipitation of
19. (b) At equilibrium, the addition of (CN ) would sodium sulphate takes place. Because reaction
is exothermic so reverse reaction will take
decrease the (H  ) ion concentration to produce
place.
more and more HCN to nullified the increase
49. (a) For high yield of ammonia low temperature,
of CN  aq .
high pressure and high concentration of the
20. (b) H 2 X 2  heat ⇌ 2HX. reactant molecule.
Reaction is endothermic and volume 53. (c) Since n  0 .
increasing in forward direction so according 54. (a) The rate of backward reaction favoured by
to Le chatelier’s principle for formation of HX, increase of pressure in the reaction as  n is
Temperature of the reaction should be high positive
and pressure should be low. PCl5 ⇌ PCl3  Cl2
21. (b) According to Le chatelier’s principle.
55. (a) H 2( g )  I2( g ) ⇌ 2HI
22. (d) In reaction CO  3H 2 ⇌ CH 4  H 2 O 2
2

Volume is decreasing in forward direction so n  0 ;  K c  K p

on increasing pressure the yield of product
will increase. 56. (c) Solid + liquid ⇌ Solution H =+ve

25. (a) In endothermic reaction rate of forward Increase in temperature favours forward
reaction can be increased by raising reaction.
temperature. 57. (a) Addition of an inert gas of constant volume
26. (a) Being endothermic, the forward reaction is condition to an equilibrium has no effect.
favoured by high temperature. 58. (b) Le chatelier principle is not applicable to
27. (c) According to Le chatelier’s principle. solid-solid equilibrium.
28. (b) On adding more PCl5 , equilibrium shifts 59. (a) A  B  Q ⇌ C  D
2 2
forward.
29. (a) According to Le chatelier’s principle. The reaction is endothermic so on increase
30. (b) Increase in pressure causes the equilibrium to temperature concentration of product will
shift in that direction in which no. of moles increase.
(volume) is less. 60. (a) In that type of reaction the state of
32. (b,c) According to Le-chatelier’s principle. equilibrium is not effected by change in
37. (d) By increasing the amount of F2 in the reaction volume (hence pressure) of the reaction
mixture.
the amount of ClF3 increases.
61. (c) N 2  O2 ⇌ 2 NO ; n  0
39. (b) According to Le chatelier’s principle when we
increase pressure reaction proceeds in that 65. (c) High temperature and low pressure.
direction where volume is decreasing. 66. (d) High temperature and excess concentration of
40. (a) Factors affecting equilibrium are pressure, the reactant concentration.
temperature and concentration of product or 68. (c) Low temperature and high pressure.
reactant.
69. (a) H 2  I2 ⇌ 2HI  n  2  2  0 .
42. (b) According to Le chatelier’s principle.
43. (d) Increase in volume, i.e., decrease in pressure 70. (d) Low temperature and low pressure.
shifts the equilibrium in the direction in 73. (c) It is an exothermic reaction hence low
which number of moles increases (n temperature and increasing pressure will
positive) favour forward reaction
46. (d) At constant volume. Three is no change in
concentration (closed container). Critical Thinking Questions
1
47. (c) H 2 O(g) ⇌ H 2( g )  O 2( g )
2
 Chemical Equilibrium 337
 20   20  (.1-) 2

[PCl 3 ][Cl 2 ]  100   100  ∵ P  0.1
1. (b) c
K  
[PCl5 ]  80 
 100  If V and T are constant (P0.1+ )
 
P  (0.1   ) / 0 .1
0 .2  0 .2 0 .04
   0 .05
0.8 0.8 [2 ]2  P  40  2
Kp    or K p   0 .14
2. (b) 2NH 3 ⇌ N 2  3H 2 [0 .1   ]  0 .1    [0 .1   ]

Initial mole a 0 0   0.017

Mole at equilibrium (a  2 x ) x 3x NO2  0.017  2  0.034 mole
Initial pressure of NH 3 of a mole = 15 atm at 8. (d) CH 3 OH  CO  2H 2
o
27 C
[H 2 ]2 [CO ] 0 . 1  0 . 1  1 0 . 01 10  10 3
The pressure of 'a' mole of NH 3  p atm at   
[CH 3 OH ] 2 2 2
347 o C
 5  10 3 .
15 p
 
300 620 9. (d) AB + CD ⇌ AD +
 p  31 atm CD

At constant volume and at 347 o C , mole  mole at t  0 1 1 0

0
pressure
a  31 (before equilibrium)  3  3 3
Mole at equilibrium 1   1   ⇌  
 4  4 4
 a  2 x  50 (after equilibrium)
3
a  2 x 50  
  4
a 31
0.25 0.25 ⇌ 0.75
19
 x a 0.75
62
0 .75  0 .75 0 .5625
 % of NH 3 decomposed 
2x
 100 Kc   9
a 0 .25  0 .25 0 .0625

2  19 a 10. (d) According to Le-chatelier’s principle.

  100  61 .33 %
62  a 11. (d) K p (equilibrium constant) is independent of

3. (d) K p  Kc (RT )n R = Gas constant pressure and concentration.

Kp 1 . 3  10 3 Assertion & Reason

Kc  n
  7 . 4  10  2
(RT ) (0 . 0821  700 )1
2. (e) Assertion is false but reason is true.
4. (b) Reaction is reversed and halved. K p  K c for all reaction.
6
K  1 1.8  10  7.5  10 2
K p  K c (RT )n
5. (d) Conc. is not known so we can’t calculate. n  number of moles of products – number of
6. (a) 2SO 3 ⇌ 2 SO 2  O 2 moles of reactants in the balanced chemical
2 3 equation.

n  3  2  1 ; K p  1.80  10 3 So, if for a reaction n  0 . Then K p  K c

3. (e) Assertion is false but reason is true.

[RT ]n  (8.314  700 )1
K c  [H 2 O ]2 , because concentration of solids is
3
Kp 1 . 8  10
Kc   taken to be unity.
(RT )n (8 . 314  700 )1
4. (a) Both assertion and reason are true and reason
 3 .09  10 7 mole-litre. is the correct explanation of assertion.

7. (c) N 2 O 4 ⇌ 2 NO 2 CO (H 2 O)62  (Pink) while CoCl 42  (blue). So, on

0 .1 0
 338 Chemical Equilibrium
Cooling because of Le-chatelier’s principle the
KC 
H 2 I2   1 .
reaction tries to over come the effect of HI 2 KC
temperature.
10. (c) The value of K depends on the stoichiometry
5. (e) Assertion is false but reason is true.
of reactants and products at the point of
[C ]c [ D]d
aA  bB ⇌ cC  dD , Qc  equilibrium. For e.g., if the reaction is
[ A ] a [ B ]b multiplied by 2, the equilibrium constant is
If Qc  K c , reaction will proceed in the squared.
direction of reactants. 11. (d) Catalyst does not affect the final state of the
If Qc  K c , reaction will move in direction of equilibrium. It enables the system to attain
products. equilibrium state earlier by providing an
If Qc  K c , the reaction mixture is already at alternative path which involve lower energy
equilibrium. of activation.

6. (c) Assertion is true but reason is false. This is p H3 2  p N 2 (atm)3 (atm)

12. (e) K p    (atm)2
based on common ion effect. p NH 3 (atm)2
   
NaCl ⇌ Na  Cl ; HCl ⇌ H  Cl or n  4  2  2 .

Concentration of Cl ions increases due to Unit of K p for given reaction  (atm)2 .
ionisation of HCl which increases the ionic
product [ Na  ][Cl  ] . This result in the 13. (c) According to Le-Chatelier's principle
precipitation of pure NaCl . endothermic reaction favours increase in
temperature. However exothermic reaction
7. (b) Both assertion and reason are true and reason
favours decrease in temperature.
is not the correct explanation of assertion,
solid+heat ⇌ liquid, so on heating forward 14. (d) K p  Kc (RT )n ; where n  (l  m )  (x  y)
reactions is favoured and amount of solid will
Concentration of solids and liquids is taken to
decrease.
be unity.
8. (a) aA  bB ⇌ cC  dD 15. (e) Increase in pressure favours melting of ice

KC 
C  D
C d into water because at higher pressure melting
A a B b point of ice is lowered.
16. (e) As assertion is exothermic, low temperature
For 2aA  2bB ⇌ 2 cC  2 dD
favours forward reaction. High pressure

KC 
C 2 c D2 d .
favours forward reaction as it is accompanied
A 2 a B 2b by decrease in the number of moles.

9. (a) H 2(g)  I2(g) ⇌ 2 HI(g) 17. (e) There is no change in number of gas
molecules. Therefore the expression for K is

KC 
HI 2 independent of volume. Hence K will remain
H 2 I2  same.

For reverse reaction 2 HI(g) ⇌ H 2(g)  I2(g)

 338 Chemical Equilibrium

1. One mole of SO 3 was placed in a litre reaction vessel at a 8. In the thermal dissociation of PCl5 , the partial pressure in the
certain temperature. The following equilibrium was established gaseous equilibrium mixture is 1.0 atmosphere when half of
2SO 3 ⇌ 2SO 2  O2 PCl5 is found to dissociate. The equilibrium constant of the
At equilibrium 0.6 moles of SO 2 were formed. The reaction (K p ) in atmosphere is [JIPMER 2002]
equilibrium constant of the reaction will be [MP PMT 1991] (a) 0.25 (b) 0.50
(a) 0.36 (b) 0.45 (c) 1.00 (d) 0.3
(c) 0.54 (d) 0.675 9. HI was heated in a closed tube at 440 o C till equilibrium is
2. For the following homogeneous gas reaction 4 NH 3  5O2 ⇌ obtained. At this temperature 22% of HI was dissociated. The
4 NO  6 H 2 O , the equilibrium constant K c has the equilibrium constant for this dissociation will be
dimension of [CPMT 1990; MP PET/PMT 1998] [MP PET 1988, 92; MNR 1987; UPSEAT 2000]
10 (a) 0.282 (b) 0.0796
(a) Conc (b) Conc 1
(c) 0.0199 (d) 1.99
(c) Conc 1 (d) It is dimensionless 10. The following equilibrium exists in aqueous solution
3. Consider the imaginary equilibrium
CH 3 COOH ⇌ CH 3 COO   H  . If dilute HCl is added
4A + 5B ⇌ 4X + 6Y without a change in temperature, then the [MNR 1987]
The equilibrium constant K c has the unit [RPMT 2000] 
(a) Concentration of CH 3 COO will increase
(a) Mole2 litre-2 (b) Litre mole-1
(b) Concentration of CH 3 COO  will decrease
(c) Mole litre-1 (d) Litre2 mole-2
(c) Equilibrium constant will increase
4. For the reaction CO(g)  2 H 2 (g) ⇌ CH 3 OH (g) , true
(d) Equilibrium constant will decrease
condition is
11. Which of the following is not favourable for SO 3 formation
(a) K p  Kc (b) K p  K c
2SO 2 (g)  O2 (g) ⇌ 2SO 3 (g); H  45 .0 kcal
(c) K p  Kc (d) K c  0 but K p  0
[IIT 1984; MP PET 1997]
1 Kp (a) High pressure
5. For the reaction CO(g)  O 2 (g) ⇌ CO 2 (g) ; is
2 Kc (b) High temperature
equivalent to [MP PET/PMT 1998; AIEEE 2002] (c) Decreasing SO 3 concentration
(a) 1 (b) RT (d) Increasing reactant concentration
1 1/ 2 12. 120 gm of urea are present in 5 litre solution, the active mass
(c) (d) (RT )
RT of urea is [MP PMT 1994]
6. 2 N 2 O 5  4 NO 2  O 2 what is the ratio of the rate of (a) 0.2 (b) 0.06
(g) (g) (g)
(c) 0.4 (d) 0.08
decomposition of N 2 O5 to rate of formation of NO2
13. For the system 2 A(g)  B(g) ⇌ 3 C(g) , the expression for
[DCE 2003]
equilibrium constant K is [NCERT 1973; DCE 1999]
(a) 1 : 2 (b) 2 : 1
(c) 1 : 4 (d) 4 : 1 [2 A]  [ B] [ A] 2  [ B]
(a) (b)
7. The reaction quotient (Q) for the reaction [3 C ] [C ]3
N 2(g)  3 H 2(g) ⇌ 2 NH 3( g ) [3 C ] [C ]3
(c) (d)
[2 A]  [ B] [ A] 2  [ B]
[ NH 3 ]2
is given by Q  . The reaction will proceed from 14. If concentration of reactants is increased by ' x ' , then K
[ N 2 ][ H 2 ]3
becomes [AFMC 1997]
right to left is [CBSE PMT 2003]
(a) ln ( K / x ) (b) K / x
(a) Q = 0 (b) Q = K c
(c) Kx (d) K
(c) Q < K c (d) Q > K c
Where K c is the equilibrium constant

(SET -8)
 Chemical Equilibrium 339

1. (d) 2 SO 3 ⇌ 2 SO 2  O 2 At equilibrium 0.5 0.5 0.5

(10 .6 ) (0 . 6 ) (0 . 3 )
Px 2
1  0 .5  0 .5 0 .5  0 .5 1
Kp      0 .3
[SO 2 ]2 [O 2 ] 0 . 6  0 . 6  0 . 3 (1  x 2 ) [1  (0 .5)2 ] 0 .75 3
Kc    0 . 675 .
[SO 3 ] 0 .4  0 .4
9. (c) 2HI ⇌ H 2  I2
2. (b) K has the units of (conc.)n , where n  10  9  1 Initial conc. 2 moles 0 0
3. (c) Unit of K c  (unit of concentration)n 22
at equilibrium  2 0.22 0.22
= (mole litre–1)n 100

n = 10 – 9 = 1  2  0 . 44  1 . 56

 K c  mol Litre–1. [H 2 ] [I 2 ] 0 . 22  0 . 22
K   0 .0199 .
[HI ]2 [1 . 56 ]2
4. (c) When nr  n p then K p  K c
10. (b) When adding HCl in CH 3 COOH solution the
where nr = no. of moles of reactant 
concentration of H is increased. So reaction is proceed
n p = no. of moles of product. in reverse direction and the concentration of CH 3 COO 
is decreased.
1
5. (c) For CO  O 2 ⇌ CO2 11. (b) The reaction is exothermic so high temperature will favour
2
backward reaction.
1 1
1 1  Kp 1
K p  K c (RT ) 2  K c (RT ) 2 ;  12. (c) Active mass 
moles
Kc RT litre
6. (b) 2 N 2 O5  HNO 2  O2 wt. in gm/molecular wt. 120 60 2
    .4
Rate of decomposition of N 2 O5 V in litre 5 5

1 K[ N 2 O 5 ] [C ]3
 . 13. (d) K  .
2 dt [ A]2 [ B]
1 d[ NO 2 ]
Rate of formation of NO 2  . 14. (d) There is no effect of change in concentration on
4 dt equilibrium constant.
 Ratio = 2 : 1
7. (d) If Q  Kc reaction will proceed right to left to decrease
concentration of product.

***

8. (d) PCl5 ⇌ PCl3  Cl2

Initial conc. 1 0 0
 340 Ionic Equilibrium
In chemical equilibrium we studied reaction
involving molecules only but in ionic equilibrium we
will study reversible reactions involving formation of
ions in water. When solute is polar covalent
compound then it reacts with water to form ions.
Electrical conductors
Substances, which allow electric current to pass
through them, are known as conductors or electrical
conductors. Conductors can be divided into two types,
(1) Conductors which conduct electricity without
undergoing any chemical change are known as metallic
or electronic conductors.
(2) Conductors which undergo decomposition (a
chemical change) when an electric current is passed
through them are known as electrolytic conductors or
electrolytes.
Electrolytes are further divided into two types on
the basis of their strengths,
(i) Substances which almost completely ionize
into ions in their aqueous solution are called strong
electrolytes. Degree of ionization for this type of
electrolyte is one i.e.,   1 .
For example :
HCl, H 2 SO 4 , NaCl, HNO3 , KOH, NaOH,
HNO3 , AgNO3 , CuSO4 etc. means all strong acids, bases
and all types of salts.
(ii) Substances which ionize to a small extent in
their aqueous solution are known as weak electrolytes.
Chapter
9
Ionic Equilibrium
Degree of ionization for this types of electrolytes is
  1 .
For example : H2O, CH3COOH , NH4 OH , HCN,
Liq. SO 2 , HCOOH etc. means all weak acids and bases.
Arrhenius theory of electrolytic dissociation
(1) Postulates of Arrhenius theory
(i) In aqueous solution, the molecules of an
electrolyte undergo spontaneous dissociation to form
positive and negative ions.
(ii) Degree of ionization ( )
Number of dissociate d molecules

Total number of molecules of electrolyt e before dissociati on
(iii) At moderate concentrations, there exists
an equilibrium between the ions and undissociated
molecules, such as, NaOH ⇌ Na   OH  ; KCl ⇌ K
 Cl 
This equilibrium state is called ionic equilibrium.
(iv) Each ion behaves osmotically as a molecule.
(2) Factors affecting degree of ionisation
(i) At normal dilution, value of  is nearly 1 for
strong electrolytes, while it is very less than 1 for weak
electrolytes.
(ii) Higher the dielectric constant of a solvent more
is its ionising power. Water is the most powerful
ionising solvent as its dielectric constant is highest.
 Ionic Equilibrium 341
1 1
(iii)    Ka  C  2 or  
Ka
…..(iii)
Con. of solution wt. of solution C
 Dilution of solution  Amount of solvent The degree of dissociation,  can therefore be
calcualted at a given concentration, C if K a is known.
(iv) Degree of ionisation of an electrolyte in
solution increases with rise in temperature. Furher, if V is the volume of the solution in litres
containing 1 mole of the electrolyte, C  1 / V . Hence we
(v) Presence of common ion : The degree of have
ionisation of an electrolyte decreases in the presence of
  Ka V …..(iv)
a strong electrolyte having a common ion.
Similarly, for a weak base like NH4 OH , we have
Ostwald's dilution law
The strength of an acid or a bas is experimentally   Kb / C  Kb V …..(v)
measured by determining its dissociation or ionisation The above equations lead to the following result
constant.
“For a weak electrolyte, the degree of ionisation is
When acetic acid (a weak electrolyte) is dissolved inversely proportional to the square root of molar
in water, it dissociates partially into H  or H 3 O  and concentration or directly proportional to the square root
CH 3 COO  ions and the following equilibrium is of volume containing one mole of the solute.”

obtained, This is called Ostwald’s dilution law.

 
CH3COOH  H 2O ⇌ CH 3 COO  H 3 O Dissociation constants of acids and Bases
Applying law of chemical equilibrium, (1) Dissociation constant for weak acid :
Consider an acid HA which, when dissolved in water
[CH 3 COO  ]  [ H 3 O  ]
K ionizes as,
[CH 3 COOH ]  [ H 2 O ]
HA ⇌ H   A 
In dilute solution, [H 2 O] is constant. The product
[H  ][ A  ]
of K and constant [H 2 O] is denoted as K a , the Applying the law of mass action, K a 
[HA ]
ionization constant or dissociation constant of the acid
Where, K a is the dissociation constant of the acid,
is,
HA . It has constant value at definite temperature and
[CH 3 COO  ]  [H 3 O  ]
Ka  …..(i) does not change with the change of concentration.
[CH 3 COOH ]
Dissociation Constant for polybasic acid :
The fraction of total number of molecules of an Polybasic acids ionise stepwise as, for example,
electrolyte which ionise into ions is known as degree of orthophosphoric acid ionises in three steps and each
dissociation/ionisation  . step has its own ionisation constant.
If ' C ' represents the initial concentration of the H 3 PO4 ⇌ H   H 2 PO 4 (I step)
1
acid in moles L and  the degree of dissociation,
H 2 PO 4 ⇌ H   HPO 42 (II step)
then equilibrium concentration of the ions (CH 3 COO 
HPO 42 ⇌ H  
PO 43 (III step)
and H 3 O  ) is equal to C  and that of the undissociated
Let K1 , K 2 and K 3 be the ionization constants of
acetic acid  C(1   ) i.e., we have
first, second and third steps respectively. Thus,
CH3COOH  H 2O ⇌ CH 3 COO   H 3 O 
Initial conc C 0 0 [H  ][ H 2 PO 4 ] [H  ][ HPO 42 ] [H  ][ PO 43 ]
K1  ; K2  ; K 
Conc. at eqb. C(1   ) C C [H 3 PO 4 ] [H 2 PO 4 ]
3
[HPO 4 2 ]
Substituting the values of the equilibrium In general, K1  K 2  K 3
concentrations in equation (i), we get
The overall dissociation constant (K ) is given by
C  .C  C 2 2 C 2
Ka    …..(ii) the relation,
C(1   ) C(1   ) 1  
K  K1  K2  K3
In case of weak electrolytes, the value of  is very
(2) Dissociation constant for weak base : The
small and can be neglected in comparison to 1 i.e.,
equilibrium of NH 4 OH (a weak base) can be
1   1 .
represented as,
Hence, we get
NH 4 OH ⇌ NH 4  OH 
 342 Ionic Equilibrium
[ NH 4 ][OH  ] [ A  ][B  ]
Applying the law of mass action, K b  Applying the law of mass action, K
[ NH 4 OH ] [ AB ]

K b is constant at a definite temperature and does Since the solution is saturated, the concentration
of unionised molecules of the electrolyte is constant at
not change with the change of concentration.
a particular temperature, i.e., [ AB ]  K   constant.
Common ion effect
Hence, [ A  ][B  ]  K[ AB]  KK   K sp (constant)
The degree of dissociation of an electrolyte (weak)
is suppressed by the addition of another electrolyte K sp is termed as the solubility product. It is
(strong) containing a common ion, this is termed as defined as the product of the concentration of ions in a
common ion effect. Acetic acid is a weak electrolyte and saturated solution of an electrolyte at a given
its ionisation is suppressed in presence of a strong acid temperature.
( H  ion as common ion) or a strong salt like sodium Consider, in general, the electrolyte of the type
acetate (acetate ion is a common ion). Similarly, the A x By which dissociates as, A x By ⇌ xA y   yB x 
addition of NH 4 Cl or NaOH to NH 4 OH solution will
[ A y  ]x [B x  ]y
suppress the dissociation of NH 4 OH due to common ion Applying law of mass action, K
[ A x By ]
either NH 4 or OH  .
When the solution is saturated, [ A x By ]  K 
 
CH 3 COOH ⇌ CH 3 COO  H NH 4 OH ⇌ NH 4  OH 
(constant) or

CH 3 COONa  CH 3 COO   Na  NH 4 Cl  NH 4  Cl  [ A y  ]x [B x  ]y  K[ A x By ]  KK   K sp (constant)

Common ion
As a result of common ion effect, the
concentration of the ion of weak electrolyte which is
not common in two electrolytes, is decreased. The use
of this phenomenon is made in qualitative analysis to
adjust concentration of S 2  ions in second group and
OH  ion concentration in third group.
Isohydric solution
If the concentration of the common ions in the
solution of two electrolytes , for example
concentration in HCl and HNO3
concentration in Ca(OH )2 and Ba(OH )2 is same, then on
mixing them there is no change in the degree of
dissociation of either of the electrolytes. Such solutions
are called isohydric solutions.
Consider two isohydric solutions of acids HA1
and HA 2 . Let V1 and V2 be their dilutions and 1 and
 2 be their degree of dissociation at the respective
dilution. Then,
1 2

V1 V2
Above equation is useful for calculating the
relative dilution of two acids at which they would be
isohydric.
Common ion Thus, solubility product is defined as the product
of concentrations of the ions raised to a power equal to
the number of times the ions occur in the equation
representing the dissociation of the electrolyte at a
given temperature when the solution is saturated.
(1) Difference between solubility product and
ionic product : Both ionic product and solubility
product represent the product of the concentrations of
the ions in the solution. The term ionic product has a
broad meaning since, it is applicable to all types of
solutions, either unsaturated or saturated and varies
H ion
accordingly.

or OH ion On the other hand, the term solubility product is
applied only to a saturated solution in which there
exists a dynamic equilibrium between the undissolved
salt and the ions present in solution. Thus the solubility
product is in fact the ionic product for a saturated
solution at a constant temperature.
(2) Different expression for solubility products
(i) Electrolyte of type AB (1 : 1 type salt) e.g.,
AgCl, BaSO 4
AgCl ⇌ Ag   Cl 
x x
K sp  [ Ag  ][Cl  ] ; Ksp  x 2 ; x  Ksp
(ii) Electrolytes of type AB2 (1:2 type salt)
e.g., PbCl2 , CaF2

Solubility product PbCl2 ⇌ Pb 2   2Cl 

x 2x
In a saturated solution of sparingly soluble electrolyte
K sp  [Pb 2  ][Cl  ]2 ; Ksp  [x ] [2 x ]2 ; K sp  4 x 3
two equilibria exist and can be represented as, AB ⇌
Solid
x  3 K sp / 4
AB ⇌ A  B
Unionised
(Dissolved ) ions
 Ionic Equilibrium 343
(iii) Electrolyte of type A2B (2 : 1 type salt) salt. HCl and NaCl dissociate into their respective ions
e.g., Ag2CrO4 , H2S as,

Ag 2CrO4 ⇌ 2 Ag   CrO42  NaCl ⇌ Na   Cl  ; HCl ⇌ H   Cl 

2x x
The concentration of Cl  ions increases
K sp  [ Ag  ]2 [CrO42  ] ; Ksp  [2 x ]2 [x ] ; K sp  4 x 3
considerably in solution due to ionisation of HCl and
K sp due to common ion effect, dissociation of NaCl is
x 3
4 decreased. Hence, the ionic product [ Na  ][Cl  ] exceeds
(iv) Electrolyte of type A2 B3 (2 : 3 type salt) the solubility product of NaCl and therefore pure NaCl
e.g., As2 S 3 , Sb 2 S 3 precipitates out from the solution.
(iv) Salting out of soap : From the solution, soap
As 2 S 3 ⇌ 2 As 3   3 S 2 
2x 3x is precipitated by the addition of concentrated solution
K sp  [ As 3  ]2 [S 2  ]3 ; K sp  [2 x ]2 [3 x ]3 ; K sp  4 x 2  27 x 3 of NaCl .

RCOONa ⇌ RCOO   Na  ; NaCl ⇌ Na   Cl 

K sp Soap
Ksp  108 x 5 ; x  5
108
Hence, the ionic product [RCOO–] [Na+] exceeds
(v) Electrolyte of type AB3 (1 : 3 type salt) the solubility product of soap and therefore, soap
e.g., AlCl3 , Fe(OH )3 precipitates out from the solution.

AlCl3 ⇌ Al     3Cl (v) In qualitative analysis : The separation and

x 3x
identification of various basic radicals into different
Ksp  [ Al 3 ][3Cl  ] ; Ksp  [x ] [3 x ]3 groups is based upon solubility product principle and
common ion effect.
K sp
Ksp  27 x 4 ; x  4 . (a) Precipitation of group first radicals (Pb+2, Ag+ ,
27
Hg+2) The group reagent is dilute HCl. [ Ag  ][Cl  ]  Ksp
(3) Criteria of precipitation of an electrolyte :
When Ionic product of an electrolyte is greater than its for AgCl.
solubility product, precipitation occurs. (b) Precipitation of group second radicals (Hg+2,
(4) Applications of solubility product Pb+2,Bi+3, Cu+2, Cd+2, As+3, Sb+3 and Sn+2) : The group
(i) In predicting the formation of a precipitate reagent is H2S in presence of dilute HCl .
Case I : When Kip  Ksp , then solution is [Pb 2 ][S 2 ]  K sp for PbS .
unsaturated in which more solute can be dissolved. i.e.,
(c) Precipitation of group third radicals (Fe+3, Al+3
no precipitation.
and Cr+3) The group reagent is NH 4 OH in presence of
Case II : When Kip  K sp , then solution is saturated
NH4 Cl .
in which no more solute can be dissolved but no ppt. is
fomed. [Fe 3 ][OH  ]3  K sp
Case III : When K ip  K sp , then solution is
(d) Precipitation of group fourth radicals (Co+2,
supersaturated and precipitation takes place. Ni+2, Mn+2 and Zn+2) : The group reagent is H 2 S in
When the ionic product exceeds the solubility presence of NH 4 OH .
product, the equilibrium shifts towards left-hand side,
i.e., increasing the concentration of undissociated [Co 2 ][S 2 ]  Ksp
molecules of the electrolyte. As the solvent can hold a
fixed amount of electrolyte at a definite temperature, (e) Precipitation of group fifth radicals (Ba+2, Sr+2,
the excess of the electrolyte is thrown out from the Ca+2) The group reagent is ammonium carbonate in
solutions as precipitate. presence of NH4 Cl and NH 4 OH . [Ba 2 ] [CO32 ]  Ksp
(ii) In predicting the solubility of sparingly soluble (vi) Calculation of remaining concentration
salts Knowing the solubility product of a sparingly after precipitation : Sometimes an ion remains after
soluble salt at any given temperature, we can predict precipitation if it is in excess. Remaining concentration
its solubility. can be determined,
(iii) Purification of common salt : HCl gas is
circulated through the saturated solution of common
 344 Ionic Equilibrium
K sp [ AB ] (i) Utility of Arrhenius concept : The Arrhenius
Example : [ A  ]left  ;
[B  ] concept of acids and bases was able to explain a
K sp [Ca (OH ) 2 ] number of phenomenon like neutralization, salt
[Ca 2  ]left  hydrolysis, strength of acids and bases etc.
[OH  ] 2
(ii) Limitations of Arrhenius concept
K sp [ A m B n ]
In general [ A n  ]mleft  (a) For the acidic or basic properties, the
[ B m  ]n
presence of water is absolutely necessary. Dry HCl
% precipitation of ion shall not act as an acid. HCl is regarded as an acid only
 Initial conc. - Remaining conc.  when dissolved in water and not in any other solvent.
=   100
 Initial conc.  (b) The concept does not explain acidic and basic
(vii) Calculation of simultaneous solubility : character of substances in non-aqueous solvents.
Solubility of two electrolytes having common ion; when (c) The neutralisation process is limited to
they are dissolved in the same solution, is called those reactions which can occur in aqueous solutions
simultaneous solubility. only, although reactions involving salt formation do
Calculation of simultaneous solubility is divided occur in absence of solvent.
into two cases. (d) It cannot explain the acidic character of
Case I : When the two electrolytes are almost certain salts such as AlCl3 in aqueous solution.
equally strong (having close solubility product).
(2) Bronsted–Lowry concept : According to this
e.g., AgBr (K sp  5  10 13 ) ; AgSCN (K sp  10 12 ) concept,

Here, charge balancing concept is applied. “An acid is defined as a substance which has the
tendency to give a proton (H+) and a base is defined as a
Charge of Ag  = Charge of Br  + Charge of substance which has a tendency to accept a proton. In
 other words, an acid is a proton donor whereas a base is
SCN
a proton acceptor.”
[ Ag  ] = [Br  ] + [SCN  ]
HCl  H 2 O ⇌ H 3 O   Cl  …..(i)
(a  b ) = a b Acid Base

Case II : When solubility products of two CH 3 COOH  H 2 O ⇌ H 3 O   CH 3 COO  …..(ii)

Acid Base
electrolytes are not close, i.e., they are not equally (i) HCl and CH 3 COOH are acids because they
strong.
donate a proton to H 2 O .(ii) NH 3 and CO 32  are bases
11 9
e.g., CaF2 (K sp  3.4  10 ) ; SrF2 (K sp  2.9  10 ) because they accept a proton from water.
In reaction (i), in the reverse process, H3O+ can
Most of fluoride ions come of stronger electrolyte.
give a proton and hence is an acid while Cl– can accept
Acid and Bases the proton and hence is a base. Thus there are two
(1) Arrhenius concept : According to Arrhenius acid-base pairs in reaction (i). These are HCl – Cl– and
H3O+– H2O. These acid-base pairs are called conjugate
concept all substances which give H+ ions when
acid-base pairs.
dissolved in water are called acids while those which
ionise in water to furnish OH– ions are called bases. Conjugate acid ⇌ Conjugate base  H 
Conjugate base of a strong acid is a weak base and
H   Cl  ; Na   OH 
H2O H2O
HCl NaOH vice a versa. Weak acid has a strong conjugate base and
( Acid ) (aq .) (aq .) (Base ) (aq .) (aq )
vice a versa.
Some acids and bases ionise almost completely in Levelling effect and classification of solvents :
solutions and are called strong acids and bases. Others In acid-base strength series, all acids above H3O+ in
are dissociated to a limited extent in solutions and are aqueous solution fall to the strength of H3O+. Similarly
termed weak acids and bases. HCl, HNO3 , H 2 SO 4 , HClO4 , the basic strength of bases above OH– fall to the
strength of OH–in aqueous solution. This is known as
etc., are examples of strong acids and levelling effect. Levelling effect of water is due to its
NaOH, KOH , (CH 3 )4 NOH are strong bases. Every high dielectric constant and strong proton accepting
tendency.
hydrogen compound cannot be regarded as an acid,
On the basis of proton interaction, solvents are of
e.g., CH4 is not an acid. Similarly, CH 3 OH , C2 H5 OH , four types,
etc., have OH groups but they are not bases.
 Ionic Equilibrium 345
(i) Protophilic solvents : Solvents which have (ii) It can explain the basic character of the
greater tendency to accept protons, i.e., water, alcohol, substances like Na2 CO3 , NH 3 etc.
liquid ammonia, etc.
(iii) It can explain the acid-base reactions in the
(ii) Protogenic solvents : Solvents which have the
non-aqueous medium or even in the absence of a
tendency to produce protons, i.e., water, liquid
solvent (e.g., between HCl and NH2).
hydrogen chloride, glacial acetic acid, etc.
Limitations of Bronsted lowry concept
(iii) Amphiprotic solvents : Solvents which act
(i) The protonic definition cannot be used to explain
both as protophilic or protogenic, e.g., water, ammonia,
the reactions occuring in non-protonic solvents such as
ethyl alcohol, etc.
COCl2, SO2, N2O4, etc.
(iv) Aprotic solvents : Solvents which neither
(ii) It cannot explain the reactions between acidic
donate nor accept protons, e.g., benzene, carbon
oxides like CO2 , SO 2 , SO 3 etc and the basic oxides like
tetrachloride, carbon disulphide, etc.
HCl acts as acid in H2O, stronger acid in NH3, CaO, BaO, MgO etc which take place even in the absence
weak acid in CH3COOH, neutral in C6H6 and a weak base of the solvent e.g.,
in HF. CaO  SO3  CaSO4
HCl  HF  H 2 Cl   F  There is no proton transfer in the above example.
Base Acid Acid Base
(iii) Substances like BF3, AlCl3 etc, do not have any
Utility of Bronsted – Lowry concept hydrogen and hence cannot give a proton but are known
(i) Bronsted – Lowry concept is not limited to to behave as acids.
molecules but includes even the ionic species to act as
acids or bases.
Table: 9.1 Conjugate acid-base pairs
Acid Conjugate base
HClO4 (Perchloric acid) ClO 4 (Perchlorate ion)
H 2 SO 4 (Sulphuric acid) HSO 4 (Hydrogen sulphate ion)
Increasing order of acidic strength

HCl (Hydrogen chloride)  (Chloride ion)

Cl
HNO 3 (Nitric acid) NO 3 (Nitrate ion)

Increasing order of basic strength

H 3O  (Hydronium ion) H 2O (Water)
HSO 4 (Hydrogen sulphate ion) SO 42  (Sulphate ion)
H 3 PO4 (Ortho phosphoric acid) H 2 PO 4 (Dihydrogen phosphate ion)
CH 3 COOH (Acetic acid) CH 3 COO  (Acetate ion)
H 2 CO3 (Carbonic acid) HCO 3 (Hydrogen carbonate ion)
H2S (Hydrogen sulphide) HS  (Hydrogen sulphide ion)
NH 4 (Ammonium ion) NH 3 (Ammonia)
HCN (Hydrogen cyanide)  (Cyanide ion)
CN
C6 H 5 OH (Phenol) C6 H 5 O  (Phenoxide ion)
H 2O (Water) OH  (Hydroxide ion)
C2 H 5 OH (Ethyl alcohol) C2 H 5O  (Ethoxide ion)
NH 3 (Ammonia) NH 2 (Amide ion)
CH 4 (Methane)  (Methyl carbanion)
CH 3

(3) Lewis concept : This concept was proposed by Lewis concept is more general than the Bronsted
G.N. Lewis, in 1939. According to this concept, “a base Lowry concept. All Bronsted bases are also Lewis bases
is defined as a substance which can furnish a pair of but all Bronsted acids are not Lewis acids. [e.g.,
electrons to form a coordinate bond whereas an acid is a HCl, H 2 SO 4 as they are not capable of accepting a pair of
substance which can accept a pair of electrons.” The acid electrons]
is also known as electron pair acceptor or electrophile
(i) Types of Lewis acids : According to Lewis
while the base is electron pair donor or nucleophile.
concept, the following species can act as Lewis acids.
A simple example of an acid-base is the reaction
(a) Molecules in which the central atom has
of a proton with hydroxyl ion, H   OH   HOH incomplete octet BF3 , BCl 3 , AlCl3 , BeCl 2 , etc.
Acid Base
 346 Ionic Equilibrium
(b) All cations are expected to act as Lewis acids of ionisation constant K a1 and K a2 respectively at the
since they are deficient in electrons. same concentration C , we have,
(c) Molecules in which the central atom has empty K a1
Acid strength of HA 1
d-orbitals. e.g., SiF4 , SnCl 4 , PF5 etc. 
Acid strength of HA 2 K a2
(d) Molecules having a multiple bond between
atoms of dissimilar electronegativity e.g., CO2 , SO 2 . Similarly, relative strengths of any two weak
bases at the same concentration are given by the ratio
(ii) Types of Lewis bases : The following species of the square-roots of their dissociation constants. i.e.,
can act as Lewis bases.
Basic strength of B OH 1 K b1
(a) Neutral species having at least one lone pair 
Basic strength of B O H 2 K b2
.. ..
of electrons : NH 3 ,  N H 2 , R  O  H (1) Relative strength of Inorganic acids
..
(i) Hydrides
(b) Negatively charged species or anions (a) The acidic strength increases with the increase
(iii) Hard and Soft principle of acids and bases : in the electronegativity of the element directly attached
Lewis acids and bases are classified as hard and soft with the hydrogen.
acids and bases. Hardness is defined as the property of H  F  H  OH  H  NH 2  H  CH 3
retaining valence electrons very strongly. Thus a hard HCI  H 2 S  PH 3  SiH 4
acid is that in which electron-accepting atom is small, (b) The acidic strength increases with the increase in
has a high positive charge and has no electron which atomic size,
can be easily polarised or removed e.g.,
HF  HCl  HBr  HI ; H 2 O  H 2 S  H 2 Se  H 2 Te
Li  , Na  , Be 2  , Mg 2 , Al 3 BF3 , SO3 etc.. On the contrary, a
(ii) Oxyacids
soft acid is that in which the acceptor atom is large,
(a) Among oxyacids of the same type formed by
carries a low positive charge or it has electrons in
different elements, acidic nature increases with
orbitals which are easily polarised or distorted
increasing electronegativity,
e.g., Pb 2 , Cd 2 , Pt 2 , Hg 2 , Ro  , Rs  , I2 etc.. HOI  HOBr  HOCl ; HIO4  HBrO 4  HClO4
A Lewis base which holds its electrons strongly is (b) In oxyacids of the same element, acidic nature
called hard base, e.g., OH  , F  , H 2 O, NH 3 , CH 3 OCH 3 , etc. increases with its oxidation number
on the other hand, a Lewis base in which the position of HOCl  HClO2  HClO3  HClO4 ; H 2 SO 3  H 2 SO 4
1 3 5 7
electrons is easily polarised or removed is called a soft
HNO 2  HNO 3
base e.g., I  , CO , CH 3 S  , (CH 3 )3 P , etc.
(c) The strength of oxyacids increases from left to
In general, hard acids prefer to bind to hard bases right across a period
and soft acids prefer to bind to soft bases. The bonding H 4 SiO4  H 3 PO4  H 2 SO 4  HClO4
between hard acids and hard bases is chiefly ionic and
that between soft bases and soft acids is mainly (d) For the same oxidation state and configuration
covalent. of the elements, acid strength decreases with increase in
size of the atom.
(iv) Utility of Lewis concept : Lewis concept is
HNO3  HPO3 ; H3 PO4  H3 AsO4
the most general of all the concepts and can explain the
acidic and basic nature of all those substances which HClO4  HBrO4  HIO4
could not be explained by the earlier concepts. (2) Relative strength of organic acids
Similarly, it can explain even those acid-base reactions (i) A compound is acidic in nature, if its conjugate
which could not be explained by the other concepts. base can stabilize through resonance. Thus phenol is
(v) Limitations of lewis concept : It does not acidic while ethanol is neutral because the conjugate base
explain behaviour of well known protonic acids, as of phenol (C 6 H 5 O  ) can be stabilized through resonance
HCl, H 2 SO 4 etc, as which do not form coordinate bonds while that of alcohol (C 2 H 5 O  ) can not.
with bases.
(ii) Hydrogen atom attached to sp-hybridized
It does not explain relative strengths of acids and
carbon is more acidic than that on sp 2 hybridized
bases. Many lewis acids do not posses catalytic
property. carbon which in turn is more acidic than that on sp 3
hybridized carbon.
Relative strength of acids and Bases
Thus, HC  CH  CH 2  CH 2  CH 3  CH 3
sp
In practice K a is used to define the strength only sp 2 sp 3

of those acids that are weaker than H 3 O  and Kb is (3) Relative strength of Inorganic bases
used to define the strength of only those bases that are
weaker than OH  . For two weak acids HA 1 and HA 2
 Ionic Equilibrium 347
(i) The basicity of a compound decreases with (1) Simple salts : The salt formed by the
increase in electronegativity of the atom holding the interaction between acid and base, is termed as simple
. . . . . . salt. These are of three types,
electron pair, N H 3  H 2 O :  H F :
. .
(i) Normal salts : the salts formed by the loss of
(ii) The larger the size of the atom holding the all possible protons (replaceable hydrogen atoms as
unshared electrons, the lesser is the availability of H  ) are called normal salts. Such a salt does not
electrons. contain either replacable hydrogen or a hydroxyl group.
F   Cl   Br   I  ; O 2  S 2 Examples : NaCl, NaNO3 , K 2 SO 4 , Ca3 (PO4 )2 , Na3 BO 3 ,
(iii) Presence of negative charge on the atom Na 2 HPO 3 (one H atom is not replaceable as H 3 PO2 is
holding the electron pair increases the basicity, while a dibasic acid) NaH2 PO2 (both H atoms are not
the presence of positive charge on the atom holding the
replaceable as H 3 PO2 is a monobasic acid) etc.
electron pair decreases the basicity.
(ii) Acidic salts : Salts formed by incomplete
OH   H 2 O  H 3 O 
neutralisation of poly-basic acids are called acidic salts.
(iv) Among alkali and alkaline earth hydroxides Such salts still contain one or more replaceable
(oxides) the basic nature increases with hydrogen atoms. These salts when neutralised by bases
electropositivity form normal salts.
LiOH  NaOH  KOH  RbOH  CsOH ; Examples : NaHCO3 , NaHSO 4 , NaH2 PO4 , Na2 HPO4 ,
Be(OH )2  Mg(OH )2  Ca(OH )2  Sr(OH )2  Ba(OH )2 etc.
(iii) Basic salts : Salts formed by incomplete
CsOH is the strongest known base
neutralisation of poly acidic bases are called basic
(v) On going down the group; basic nature
salts. Such salts still contain one or more hydroxyl
decreases with size of the central atom due to decrease
groups. These salts when neutralised by acids form
in the ability to donate the lone pair.
normal salts.
NH 3  PH 3  AsH 3  SbH 3  BiH3
Examples: Zn(OH )Cl, Mg(OH )Cl, Fe(OH )2 Cl, Bi(OH )2 Cl
(4) Relative strength of Organic bases (2) Double salts : The addition compounds
(i) Higher the electron density on nitrogen, more formed by the combination of two simple salts are
is the basic character of amine. termed double salts. Such salts are stable in solid state
(ii) A compound is basic in nature, if its conjugate only.
acid can be stabilized through resonance. Thus Examples : Ferrous ammonium sulphate, Potash
NH 2 alum and other alums.
|
guanidine ( NH 3  C  NH ) is as strong alkali as metal (3) Complex salts : These are formed by
combination of simple salts or molecular compounds.
NH 2

| These are stable in solid state as well as in solutions.
hydroxides because its conjugate acid (H 3 N  C  NH ) FeSO 4  6 KCN  K 4 [Fe (CN )6 ] K 2 SO 4
Simple salts Complex salt
is very much stabilised through resonance.
(4) Mixed salts : The salt which furnishes more
The acid-base neutralisation and Salt
than one cation or more than one anion when dissolved
The reaction between an acid and a base to form in water is called a mixed salt.
salt and water is termed neutralisation OCl Na Na
Examples : Ca / ; \ SO ; NH PO4
HCl(aq .)  NaOH(aq .) ⇌ NaCl(aq .)  H 2 O(l) \
Cl K
/ 4 4
H
Sodium Chloride
Salt
Ionic product of water
The process of neutralisation does not produce Water is a weak electrolyte and undergoes
the resulting solution always neutral; no doubt it selfionistion to a small extent.
involves the interaction of H  and OH  ions. The “The product of concentrations of H  and OH 
nature of the resulting solution depends on the ions in water at a particular temperature is known as
particular acid and the particular base involved in the ionic product of water.” It is designated as K w .
reaction.
H 2 O ⇌ H   OH  ; H  57 .3 kJM 1
Salts : Salts are regarded as compounds made up
[H  ][OH  ]
of positive and negative ions. The positive part comes K ; K[H 2 O]  [H  ][OH  ] ; K w  [H  ][OH  ]
[H 2 O ]
from a base while negative part from an acid. Salts are
ionic compounds.The salts can be classified into
following classes,
 348 Ionic Equilibrium
The value of K w increases with the increase of
temperature, i.e., the concentration H+ and OH– ions
increases with increase in temperature.
The value of K w at 25 o C is 1  10 14 mole/litre.
Since pure water is neutral in nature, H  ion
concentration must be equal to OH  ion concentration.
[H  ]  [OH  ]  x or [H  ][OH  ]  x 2  1  10 14 or
x  1  10 7 M or [H  ]  [OH  ]  1  10 7 mole litre 1
This shows that at 25 o C , in 1 litre only 10 7 mole
of water is in ionic form out of a total of approximately
55.5 moles.
Thus when, [H  ]  [OH  ] ; the solution is neutral
 
[H ]  [OH ] ; the solution is acidic
[H  ]  [OH  ] ; the solution is basic
Hydrogen ion concentration – pH scale
Sorensen, a Danish biochemist developed a scale
to measure the acidity in terms of concentrations of H 
in a solution. As defined by him, “pH of a solution is the
negative logarithm to the base 10 of the concentration of
H+ ions which it contains.”
1 negative logarithm of dissociation constant.
pH   log[H  ] or pH  log
[H  ]
Just as pH indicates the hydrogen ion
concentration, the pOH represents the hydroxyl ion
concentration, i.e.,
(i) pH values of the solutions do not give us
immediate idea of the relative strengths of the
solutions. A solution of pH =1 has a hydrogen ion
concentration 100 times that of a solution pH = 3 (not
three times). A 4  10 5 N HCl is twice concentrated of a
2  10 5 N HCl solution, but the pH values of these
solutions are 4.40 and 4.70 (not double).
(ii) pH value zero is obtained in 1 N solution of
strong acid. If the concentration is 2 N , 3 N, 10 N , etc. the
respective pH values will be negative.
(iii) A solution of an acid having very low
concentration, say 10 8 N , can not have pH 8, as shown
by pH formula but the actual pH value will be less than
7.
pK value : p stands for negative logarithm. Just as
H  and OH  ion concentrations range over many
negative powers of 10, it is convenient to express them
as pH or pOH, the dissociation constant (K) values also
range over many negative powers of 10 and it is
convenient to write them as pK. Thus, pK is the
pKa   log K a and pKb   log Kb
Weak acids have higher pK a values. Similarly
weak bases have higher pKb values

pOH   log[OH  ] For any conjugate acid-base pair in aqueous

Considering the relationship, solution, Ka  Kb  Kw
[H  ][OH  ]  K w  1  10 14 pKa  pKb  pKw  14 (at 298o K)
Taking log on both sides, we have 10 8 M HCl
Calculation of the pH of &
  14
log[ H ]  log[ OH ]  log K w  log( 1  10 ) or
10 8 M NaOH
  14
 log[ H ]  log[ OH ]   log K w   log( 1  10 )
If we use the relation pH   log[ H 3 O  ] we get pH
or pH  pOH  pKw  14
equal to 8, but this is not correct because an acidic
[H+] [OH–] pH pOH solution connot have pH greater than 7. In this
Acidic solution > 10–7 < 10–7 <7 >7 condition H  concentration of water cannot be
–7
Neutral 10 10–7 7 7 neglected.
solution
Basic solution < 10–7 > 10–7 >7 <7 Therefore, [H  ]total  H Acid
 
 H water
pH of some materials
Since HCl is strong acid and completely ionised,
Material pH Material pH
[H  ]HCl  1  10 8 , [H  ]H 2O  10 7
Gastric juice 1.4 Rain water 6.5
Lemon juice 2.1 Pure water 7.0
[H  ]total  [H  ]HCl  [H  ]H 2O  10 8  10 7  10 8 [1  10 ]
Vinegar 2.9 Human saliva 7.0
Soft drinks 3.0 Blood plasma 7.4  10 8  11
Beer 4.5 Tears 7.4 pH   log 10 8  log 11  6.958
Black coffee 5.0 Egg 7.8
Cow’s milk 6.5 Household ammonia 11.9
Similarly if NaOH concentration is 10 8 M
Then, [OH  ]total  [10 8 ]NaOH  [10 7 ]H 2O
Limitations of pH scale
[OH  ]  10 8  11 ; pOH  6.96 pH  7 . 04
 Ionic Equilibrium 349
Buffer solutions For acidic buffers, pH  pK a  log
[salt]
[acid ]
A solution whose pH is not altered to any great
extent by the addition of small quantities of either [salt]
When  10 , then, pH  1  pKa and
sirong acid (H+ ions) or a sirong base (OH– ions) is [acid ]
called the buffer solution. It can also be defined as a [salt ] 1
when  , then, pH  pKa  1
solution of reserve acidity or alkalinity which resists [acid ] 10
change of pH upon the addition of small amount of
So weak acid may be used for preparing buffer
acid or alkali. solutions having pH values lying within the ranges
(1) Types of buffer solutions : There are two pK a  1 and pKa  1 . The acetic acid has a pK a of about
types of buffer solutions,
4.8; it may, therefore, be used for making buffer
(i) Solutions of single substances : The solution solutions with pH values lying roughly within the
of the salt of a weak acid and a weak base. range 3.8 to 5.8.
Example : ammonium acetate (CH 3 COONH 4 ) , [salt ]
For basic Buffers, pOH  pK b  log
NH 4 CN act as a buffer. [base ]

(ii) Solutions of Mixtures : These are further of Knowing pOH , pH can be calculated by the
two types, application of formula, pH  pOH  14

(a) Acidic buffer : It is the solution of a mixture of
a weak acid and a salt of this weak acid with a strong
base.
Example : CH 3 COOH  CH 3 COONa
(b) Basic buffer : It is the solution of a mixture of
a weak base and a salt of this weak base with a strong
acid.
Example : NH 4 OH  NH 4 Cl
(2) Buffer action : Buffer action is the mechanism
by which added H+ ions or OH– ions are almost
neutralised; so that pH practically remains constant.
Reserved base of buffer neutralises the added H  ions
while the reserved acid of buffer neutralises the added
OH– ions.
(3) Examples of buffer solutions
(i) Phthalic acid + potassium hydrogen phthalate
(ii) Citric acid + sodium citrate.
(iii) Boric acid + borax (sodium tetraborate).
(iv) Carbonic acid (H 2 CO 3 ) + sodium hydrogen
carbonate (NaHCO3 ) . This system is found in blood and
helps in maintaining pH of the blood close to 7.4 ( pH
value of human blood lies between 7.36 – 7.42; a
change in pH by 0.2 units may cause death).
(v) NaH2 PO4  Na3 PO4
(vi) NaH2 PO4  Na2 HPO4
(vii) Glycerine + HCl
(viii) The pH value of gastric juice is maintained
between 1.6 and 1.7 due to buffer system.
(4) Henderson - Hasselbalch equation : pH of
an acidic or a basic buffer can be calculated by
Henderson- Hasselbalch equation.
pH of a buffer solution does not change with
dilution but it varies with temperature because value of
Kw changes with temperature.
(5) Buffer capacity : The property of a buffer
solution to resist alteration in its pH value is known as
[salt]
buffer capacity. It has been found that if the ratio
[acid]
[salt]
or is unity, the pH of a particular buffer does
[base ]
not change at all. Buffer capacity is defined
quantitatively as number of moles of acid or base added
in one litre of solution as to change the pH by unity,
i.e.,
Buffer capacity
Number of moles of acid or base added to 1 litre
( ) 
Change in pH
Thus greater the buffer capacity, the greater is
its capacity to resist change in pH value. Buffer
capacity is greatest when the concentration of salt and
weak acid/base are equal, or when pH  pKa or
pOH  pKb .
(6) Significance of buffer solutions
(i) Buffer solutions are used for comparing
colorimetrically the hydrogen ion concentration of
unknown solutions.
(ii) Acetic acid-sodium acetate is used in the
removal of phosphate radical during the qualitative
analysis of the mixture.
(iii) NH 4 Cl / NH 4 OH buffer is used for the
precipitation of hydroxides of third group of qualitative
analysis.
(iv) In industries, buffer solutions are used in the
alcoholic fermentation (pH 5 to 6.5), tanning of leather,
 350 Ionic Equilibrium
electroplating, manufacture of sugar, paper Indicators
manufacturing etc., An indicator is a substance, which is used to determine
(v) In bacteriological research culture media are the end point in a titration. In acid-base titrations,
generally buffered to maintain the pH required for the organic substance (weak acids or weak bases) are
growth of the bacteria being studied. generally used as indicators. They change their colour
(vi) In biological systems buffer system of within a certain pH range. The colour change and the
carbonic acid and sodium bicarbonate is found in our pH range of some common indicators are tabulated
blood. It maintains the pH of blood to a constant value
below
(about 7.4) inspite of various acid and base-producing
Table : 9.2 Colour changes of indicators with pH
reactions going on in our body.
Indicator pH range Colour
Salt hydrolysis
Acid Base
It is the reaction of the cation or the anion or both solution solution
the ions of the salt with water to produce either acidic Cresol red 1.2 – 1.8 Red Yellow
or basic solution. Hydrolysis is the reverse of Thymol blue 1.2 – 2.8 Red Yellow
neutralization. Methyl yellow 2.9 – 4.0 Red Yellow
Neutr No hydrolysis Methyl orange 3.1 – 4.4 Pink Yellow
Salt 2 Aqueous
H O al
Acidic Cationic Methyl red 4.2 – 6.3 Red Yellow
solution Basic hydrolysis
Anionic Litmus 5.0 – 8.0 Red Blue
hydrolysis
Bromothymol 6.0 – 7.6 Yellow Blue
(1) Hydrolysis constant : The general equation blue
for the hydrolysis of a salt (BA), BA  H 2 O ⇌ HA BOH Phenol red 6.4 – 8.2 Yellow Red
salt acid base
Thymol blue 8.1 – 9.6 Yellow Blue
Applying the law of chemical equilibrium, we get
(base)
[HA ][BOH ]
K, where K is the equilibrium Phenolphthalein 8.3 – 10.0 Colourless Pink
[BA][H 2 O]
Thymolphthalein 8.3 – 10.5 Colourless Blue
constant.
Alizarin yellow R 10.1 – 12.0 Blue Yellow
Since water is present in very large excess in the
Nitramine 10.8 – Colourless Orange,
aqueous solution, its concentration [H 2 O] may be 13.0 Brown
regarded as constant so,
Two theories have been proposed to explain the
[HA ][ BOH ]
 K[H 2 O]  K h change of colour of acid-base indicators with change in
[BA ]
pH.
where K h is called the hydrolysis constant.
(i) Ostwald’s Theory (ii) Quinonoid theory
(2) Degree of hydrolysis : It is defined as the
(1) Selection of suitable indicator or choice of
fraction (or percentage) of the total salt which is
indicator : In order to choose a suitable indicator, it is
hydrolysed at equilibrium. For example, if 90% of a
necessary to understand the pH changes in the
salt solution is hydrolysed, its degree of hydrolysis is
titrations. The change in pH in the vicinity of the
0.90 or as 90%. It is generally represented by ‘ h ’. equivalence point is most important for this purpose.
Number of moles of the salt hydrolysed
h The curve obtained by plotting pH as ordinate against
Total number of moles of the salt taken the volume of alkali added as abscissa is known as
Types of Exp. for Exp. for h Exp. for pH neutralisation or titration curve. The suitable
salt Kh indicators for the following titrations are,
(i) Salt of Kh=Kw / Ka 1
K  pH=– [log (i) Strong acid Vs strong base : Phenolphthalein
weak acid h  h  2
 C  (pH range 8.3 to 10.5), methyl red (pH range 4.4 – 6.5)
and strong   Kw+log Ka– log C]
base and methyl orange (pH range 3.2 to 4.5).
(ii) Salt of Kh=Kw / Kb 1 (ii) Weak acid Vs strong base : Phenolphthalein.
K  pH=– [log Kw–
strong acid h  h  2
 C  (iii) Strong acid Vs weak base : Methyl red and
and weak   log Kb+ log C]
base methyl orange.
(iii) Salt of Kw h  (K h ) 1 (iv) Weak acid vs. weak base : No suitable
Kh  pH=– [log Ka+
weak acid Ka Kb 2 indicator can be used for such a titration.
and weak log Kw– log Kb]
base Reason for use of different indicators for
(iv) Salts of strong acids and strong bases do not different systems : Indicators are either weak acids or
undergo hydrolysis (they undergo only ionization) weak bases and when dissolved in water their
hence the resulting aqueous solution is neutral. dissociated form acquires a colour different from that
 Ionic Equilibrium 351
of the undissociated form. Consider a weak acid not 3 times. (ii) A 4 × 10–5 M HCl solution is twice
indicator of the general formula HIn, where in concentrated as compared to 2 × 10–5 M HCl
represents indicator. The equilibrium established in solution but pH values of these solutions are 4.4
aqueous solution will be and 4.7 respectively and not double.
 pH can be zero in 1M HCl or it can be negative for
HIn(aq.) ⇌ H  (aq.)  In (aq.)
Red Green more concentrated solutions like 2M, 3M, 10M etc.
Let K In be the equilibrium constant  At the temperature of the human body which is
nearly 37°C, pH of neutral solution is 6.8.
[H  ][In ] [HIn] [H  ]  Buffer solutions have reserve acidity and reserve
K In  or 
[HIn]  K In
[In ] alkalinity.
The human eye can detect the change in colour if the  The greater the buffer capacity, the greater is its
ratio of the two forms of indicator ranges between 0.1 to capacity to resist change in pH value.
10.  Buffers cannot withstand the addition of large
[HIn] amounts of acids or alkalies. The addition of
If,  1 .0 , the colour visible will be yellow 0.1mol per litre of [H+] or OH– is about the
[In ]
maximum that any buffer can be expected to
[HIn] withstand.
 10 , the colour visible will be red.
[In ]
[HIn]
 0 . 1 , the colour visible will be green.
[In ]
In other words,
The colour visible will be red, when pH  pK In  1
The colour visible will be yellow, when pH  pK In
The colour visible will be green, when pH  pK In  1
Thus, our imaginary indicator will be red at any
pH which just falls below pK In  1 and green at any pH
which just exceeds pK In  1 . The indicator changes its
colour in the narrow pH range pK In  1 to pK In  1 from
red to (red-yellow, yellow, yellow-green) green. We can
therefore use this indicator to locate this narrow pH
range. In other words, in order to use the indicator
effectively in this range, we should have a solution for
which pH is very near to pK In of the indicator. The
colour change of an indicator can, therefore, be
summarised as,
First change of Mid point of Colour change
colour change complete
[H+] 10 KIn KIn 0.1 KIn
pH PKIn – 1 PKIn PKIn + 1

It is for this reason that we use different

indicators for different systems.

 pH of boiling water is 6.5625. It does not mean

that boiling water is not neutral. It is due to
greater dissociation of H2O into H+ and OH–.
 pH values of solutions do not give the exact idea of
their relative strengths e.g., (i) A solution with pH
= 1 had [H+] 100 times than that with pH = 3 and
 350 Ionic Equilibrium
9. Which one is strongest electrolyte in the
following
[CPMT 1990]
(a) NaCl (b) CH 3 COOH
(c) NH 4 OH (d) C6 H12O6
10. The equivalent conductance at infinite dilution of
Electrical conductors, Arrhenius theory and a weak acid such as HF [Pb. PMT 1998]
Ostwald's dilution law (a) Can be determined by measurement of very
dilute HF solution
1. Which of the following is non-electrolyte [CPMT 2001] (b) Can be determined by extrapolation of
measurements on dilute solutions of HCl, HBr
(a) NaCl (b) CaCl2
and HI
(c) C12H 22O11 (d) CH 3 COOH
(c) Can best be determined from measurements
2. Ammonium hydroxide is a [CPMT 1977] on dilute solutions of NaF, NaCl and HCl
(a) Strong electrolyte (d) Is an undefined quantity
(b) Weak electrolyte 11. If  is the degree of ionization, C the
(c) Both under different conditions concentration of a weak electrolyte and K a the
(d) Non-electrolyte acid ionization constant, then the correct
3. Ammonium hydroxide is a weak base because relationship between , C and K a is
[MP PET 2000]
[CET Pune 1998; Pb. PMT 1998; RPMT 2002]
(a) It has low vapour pressure
Ka C
(b) It is only slightly ionized (a)  2  (b)  2 
C Ka
(c) It is not a hydroxide of any metal
(d) It has low density Ka C
(c)   (d)  
4. Electrolytes when dissolved in water dissociate C Ka
into their constituent ions. The degree of
12. Theory of ionization was given by
dissociation of an electrolyte increases with [CPMT 1974]
[AMU 1983; DPMT 1985]
(a) Increasing concentration of the electrolyte
(a) Rutherford (b) Graham
(b) Decreasing concentration of the electrolyte
(c) Faraday (d) Arrhenius
(c) Decreasing temperature
13. An ionizing solvent has
(d) Presence of a substance yielding a common
(a) Low value of dielectric constant
ion
(b) High value of dielectric constant
5. An electrolyte [MP PMT/PET 1988; CPMT 1974]
(c) A dielectric constant equal to 1
(a) Gives complex ions in solution
(d) Has a high melting point
(b) Dissolves in water to give ions
14. The extent of ionization increases [MNR 1982]
(c) Is ionized in the solid state (a) With the increase in concentration of solute
(d) Generates ions on passing electric current (b) On addition of excess water to solution
6. A monoprotic acid in 1.00 M solution is 0.01% (c) On decreasing the temperature of solution
ionised. The dissociation constant of this acid is [BVP 2003] (d) On stirring the solution vigorously
15. Which is generally true about ionic compounds
(a) 1  10 8 (b) 1  10 4
[Pb. PMT 2002]
(c) 1  10 6 (d) 10 5 (a) Have low boiling point
7. Molten sodium chloride conducts electricity due (b) Have low melting point
to the presence of [BHU 2001] (c) Soluble in non polar solvents
(a) Free electrons (d) Conduct electricity in the fused state
(b) Free ions 16. At infinite dilution, the percentage ionisation for
(c) Free molecules both strong and weak electrolytes is [CPMT 1999]
(d) Atoms of sodium and chlorine (a) 1% (b) 20%
8. An example for a strong electrolyte is [KCET 2002] (c) 50% (d) 100%
(a) Urea (b) Ammonium 17. The degree of ionization of a compound depends
hydroxide on
[MNR 1980]
(c) Sugar (d) Sodium acetate
(a) Size of solute molecules
 Ionic Equilibrium 351
(b) Nature of solute molecules (c) 10 7 (d) 10 9
(c) Nature of vessel used 27. The hydrogen ion concentration in weak acid of
(d) Quantity of electricity passed dissociation constant K a and concentration c is
18. For a weak acid HA , Ostwald's dilution law is nearly equal to
represented by the equation [CBSE PMT 1989; RPMT 2000]
c  2c (a) Ka / c (b) c / K a
(a) K a  (b) K a 
1 2 1 
(c) K a c (d) Kac
Kac  2c
(c)   (d) K a 
1c 1 2 28. Degree of dissociation of 0.1 N CH 3 COOH is
19. Acetic acid is a weak electrolyte because[CPMT 1974] (Dissociation constant  1  10 5 ) [MP PET 1997]
(a) Its molecular weight is high 5 4
(a) 10 (b) 10
(b) It is covalent compound 3
(c) 10 (d) 10 2
(c) It does not dissociate much or its ionization is
29. Which of the following substance is an electrolyte
very less
[MADT Bihar 1980]
(d) It is highly unstable
(a) Chloroform
20. In which of the following dissociation of NH 4 OH
(b) Benzene
will be minimum [MP PET 2000]
(c) Toluene
(a) NaOH (b) H 2 O
(d) Magnesium chloride
(c) NH 4 Cl (d) NaCl 30. In weak electrolytic solution, degree of ionization
21. Vant hoff factor of BaCl2 of conc. 0 . 01 M is 1.98. (a) Will be proportional to dilution
Percentage dissociation of BaCl2 on this conc. (b) Will be proportional to concentration of
Will be electrolyte
[Kerala CET 2005] (c) Will be proportional to the square root of
(a) 49 (b) 69 dilution
(c) 89 (d) 98 (d) Will be reciprocal to the dilution
(e) 100 31. 0.2 molar solution of formic acid is ionized 3.2%.
Its ionization constant is [MP PMT 1991]
22. In which of the following solutions, ions are present
[NCERT 1981] (a) 9.6  10 3 (b) 2.1  10 4
(a) Sucrose in water (b) Sulphur in CS 2 (c) 1 .25  10 6 (d) 4.8  10 5
(c) Caesium nitrate in water (d) Ethanol in water 32. The best conductor of electricity is a 1.0 M
solution of
23. The following equilibrium exists inaqueous
[NCERT 1973]
solution, CH 3 COOH ⇄ CH 3 COO   H  if dil HCl is
(a) Boric acid (b) Acetic acid
added, without change in temperature, the [UPSEAT 2000, 02]
(c) Sulphuric acid (d) Phosphoric acid
(a) Concentration of CH 3 COO  will increase
33. The colour of an electrolyte solution depends on
(b) Concentration of CH 3 COO  will decrease [DPMT 1985]

(c) The equilibrium constant will increase (a) The nature of the anion

(d) The equilibrium constant will decrease (b) The nature of the cation

24. Which will not affect the degree of ionisation (c) The nature of both the ions
[MP PMT 1994] (d) The nature of the solvent
(a) Temperature (b) Concentration 34. Ionisation depends upon [CPMT 2004]

(c) Type of solvent (d) Current (a) Pressure (b) Volume

25. The addition of a polar solvent to a solid (c) Dilution (d) None of these
electrolyte results in [NCERT 1973] 35. The values of dissociation constants of some acids
(a) Polarization (b) Association (at 25 o C ) are as follows. Indicate which is the
(c) Ionization (d) Electron transfer strongest acid in water [MP PMT 1991]

26. The degree of dissociation of 0.1 M HCN solution is (a) 1 .4  10 2 (b) 1.6  10 4
0.01%. Its ionisation constant would be [RPMT 1999] (c) 4 .4  10 10 (d) 4.3  10 7
(a) 10 3 (b) 10 5
 352 Ionic Equilibrium
36. Concentration CN  in 0.1 M HCN is (c) SO 4   (d) NO 2 
[K a  4  10 10 ] 10. NaOH is a strong base because [AIIMS 2001]

[RPET 2000] (a) It gives OH ion (b) It can be oxidised
6 6 (c) It can be easily ionised (d) Both (a) and (c)
(a) 2.5  10 M (b) 4.5  10 M
6 6 11. Which one of the following can be classified as a
(c) 6.3  10 M (d) 9.2  10 M
Bronsted base [KCET 2001]
(a) NO 3 (b) H 3 O 
Acids and Bases
(c) NH 4 (d) CH 3 COOH
1. Which of the following is not a Lewis acid [MP PET 2002]
12. Which one of the following substance has the
(a) CO (b) SiCl4 highest proton affinity [AIEEE 2003]
(c) SO 3 (d) Zn 2  (a) H 2 O (b) H 2 S

2. Review the equilibrium and choose the correct (c) NH 3 (d) PH3
statement HClO4  H 2 O ⇄ H 3 O   ClO 4 [RPMT 2000] 13. Which of the following is the strongest Lewis acid
(a) HClO4 is the conjugate acid of H 2 O [EAMCET 1998]
(a) BI3 (b) BBr3
(b) H 3 O  is the conjugate base of H 2 O
(c) BCl3 (d BF3
(c) H 2 O is the conjugate acid of H 3 O 
14. An aqueous solution of ammonia consists of
(d) ClO 4 is the conjugate base of HClO4 [MP PET 2001]
 
3. A solution of FeCl3 in water acts as acidic due to (a) H (b) OH

[BVP 2003] (c) NH 4 (d) NH 4 and OH 
3
(a) Hydrolysis of Fe (b) Acidic impurities 15. Which of the following is not a Lewis acid
(c) Dissociation (d) Ionisation [CBSE PMT 1996]
4. A white substance having alkaline nature in (a) BF3 (b) FeCl3
solution is
[BVP 2003]
(c) SiF4 (d) C2 H 4
(a) NaNO3 (b) NH 4 Cl 16. The conjugate base of NH 2  is [EAMCET 1998]
(c) Na2CO3 (d) Fe2O3 2
(a) NH 3 (b) NH
5. Which of the following can act both as Bronsted
acid and Bronsted base[MP PET 1995; MP PET/PMT 1998] (c) NH 4 (d) N 3 
(a) Cl  (b) HCO 3 17. The strength of an acid depends on its tendency to
[MP PET 1996]
(c) H 3 O  (d) OH 
(a) Accept protons (b) Donate protons
6. Lewis acid [MP PMT 1987] (c) Accept electrons (d) Donate electrons
(a) Presence of H atom is necessary 18. Which is not a electrophile [RPET 1999]
(b) Is a electron pair donor
(a) AlCl3 (b) BF3
(c) Always a proton donor
(d) Is a electron pair acceptor (c) (CH 3 )3 C  (d) NH 3
7. For two acids A and B, pKa  1.2, pKb  2.8 19. Ammonia gas dissolves in water to give NH 4 OH .
respectively in value, then which is true [Bihar MEE 1998] In this reaction water acts as [CPMT 1990; MP PMT 1990]
(a) A and B both are equally acidic (a) An acid (b) A base
(b) A is stronger than B (c) A salt (d) A conjugate base
(c) B is stronger than A 20. In the equilibrium
(d) Neither A nor B is strong 
CH 3 COOH  HF ⇄ CH 3 COOH 2  F  [BHU 1987]
(e) None of these
8. Aq. solution of sodium cyanide is [BHU 1981] (a) F  is the conjugate acid of CH 3 COOH
(a) Acidic (b) Amphoteric (b) F  is the conjugate base of HF
(c) Basic (d) Netural (c) CH 3 COOH is the conjugate acid of
9. Which of the following is the strongest conjugate 
base CH 3 COOH 2
[MADT Bihar 1983; CBSE PMT 1999; KCET (Med.) 2001]
(a) Cl  (b) CH 3 COO 
 Ionic Equilibrium 353
(d) CH 3 COOH 2  is the conjugate base of 31. HNO 3 in liquid hydrogen fluoride behaves
CH 3 COOH (a) As an acid
(b) As a base
21. The compound that is not a Lewis acid is [IIT 1985]
(c) Neither as a base nor as an acid
(a) BF3 (b) AlCl3
(d) As a base and as an acid
(c) BeCl 2 (d) NH 3 32. Aqueous solution of CuSO 4 .5 H 2 O changes blue
22. Which of the following dissolves in water to give litmus paper to red due to [CPMT 1979; MP PMT 1989]
a neutral solution [Bihar MADT 1980]
(a) Presence of Cu   ions
(a) (NH 4 )2 SO 4 (b) Ba(NO3 )2
(b) Presence of SO 4   ions
(c) CrCl3 (d) CuSO 4
(c) Hydrolysis taking place
23. Which of the following is the strongest acid [AMU 1982] (d) Reduction taking place
(a) H 3 PO4 (b) H 2 SO 4 33. In the following reaction
 
(c) HNO 2 (d) CH 3 COOH HC 2 O4  PO4 ⇄ HPO 4    C 2 O4  
24. An example of a Lewis acid is Which are the two Bronsted bases [MP PMT 1991]
[MADT Bihar 1982; AMU 1982; MNR 1994;   
(a) HC 2 O4 and PO4 (b) HPO 4 and C 2 O4  
RPMT 1997; KCET 2000; Orissa JEE 2005]
(a) NaCl (b) MgCl2 (c) HC 2 O4  and HPO 4   (d) PO4    and C 2 O4  
(c) AlCl3 (d) SnCl 4 34. Which of the following is the weakest acid [CPMT 2001]
(a) HF (b) HCl
25. In the equilibrium HClO4+H2O ⇌ H2O++ ClO 4
(c) HBr (d) HI
[BHU 1981, 86] 35. The degree of dissociation in a weak electrolyte
(a) HClO4 is the conjugate acid of H 2 O increases
[CBSE PMT 1989; MP PMT 1997]
(b) H 2 O is the conjugate acid of H 3 O 
(a) On increasing dilution (b)On increasing pressure
(c) H 3 O  is the conjugate base of H 2 O (c) On decreasing dilution (d) None of these
(d) ClO 4 is the conjugate base of HClO4 36. H  is a [MADT Bihar 1983]

26. Which of the following would be expected to form (a) Lewis acid (b) Lewis base
ionic solution in water [CPMT 1976; Kurukshetra CEE 1998] (c) Bronsted-Lowry base (d) None of the above
(a) CCl (b) O 37. Dissociation of H 3 PO4 takes place in following
4 2

(c) NaBr (d) CHBr3 steps

[CPMT 1976; NCERT 1987]
27. A solution of sodium bicarbonate in water turns (a) 1 (b) 2
[NCERT 1971]
(c) 3 (d) 4
(a) Phenolphthalein pink (b)Methyl orange yellow 38. The aqueous solution of disodium hydrogen
(c) Methyl orange red (d) Blue litmus red phosphate is
28. Accepting the definition that an acid is a proton [MADT Bihar 1982]
donor, the acid in the following reaction (a) Acidic (b) Neutral
NH 3  H 2 O  NH 4  OH  is [Kerala (Med.) 2003] (c) Basic (d) None
(a) NH 3 (b) H  39. Which of the following is a conjugated acid-base
pair
(c) NH 4 (d) H 2 O [MADT Bihar 1984; DPMT 2001]
29. With reference to protonic acids, which of the (a) HCl, NaOH (b) NH 4 Cl, NH 4 OH
following statements is correct [CPMT 1990] (c) H 2 SO 4 , HSO 4  (d) KCN, HCN
(a) PH3 is more basic than NH 3
40. The solution of strong acid and weak base
(b) PH3 is less basic than NH 3 (FeCl3 ) is
(c) PH3 is equally basic as NH 3 [MADT Bihar 1981; CPMT 1979, 83, 84]
(d) PH3 is amphoteric while NH 3 is basic (a) Acidic (b) Basic
(c) Neutral (d) None of the above
30. NH 4 OH is weak base because [CPMT 1979]
41. The conjugate acid of HPO 32  is [EAMCET 1989]
(a) It has low vapour pressure
(a) H 3 PO4 (b) H 3 PO3
(b) It is only slightly ionized
(c) It is not a hydroxide of metal (c) H 2 PO 3 (d) PO 43 
(d) It has low density
 354 Ionic Equilibrium
42. What name is given to the reaction between 53. H 3 BO3 is [IIT Screening 2003]
hydrogen ion and hydroxyl ion [MP PMT 1990]
(a) Monobasic and weak Lewis acid
(a) Hydrogenation (b) Hydroxylation
(b) Monobasic and weak Bronsted acid
(c) Hydrolysis (d) Neutralization
(c) Monobasic and strong Lewis acid
43. Among the following, the weakest Lewis base is
[NCERT 1981] (d) Tribasic and weak Bronsted acid
(a) H 
(b) OH  54. In the reaction SnCl 2  2Cl   SnCl 4 , Lewis acid is
(c) Cl  (d) HCO 3 [EAMCET 1987]

44. The pKa for acid A is greater than pKa for acid B. (a) SnCl 2 (b) Cl
The strong acid is [DPMT 2000] (c) SnCl 4 (d) None of these
(a) Acid B (b) Acid A
55. Lewis base is [RPMT 1997]
(c) Both A and B (d) Neither A nor B
(a) CO2 (b) SO 3
45. The conjugate acid of NH 2 is[IIT 1985; Roorkee 1995;
EAMCET 1997;CBSE PMT PMT 2000; MP PET 1996,2000] (c) SO 2 (d) ROH
(a) NH 3 (b) NH 4 56. 10 ml of 1 M H 2 SO 4 will completely neutralise
(c) NH 2 OH (d) N 2 H 4 (a) 10 ml of 1 M NaOH solution
46. Correct statement is [CPMT 1985] (b) 10 ml of 2 M NaOH solution
(a) NH 4 Cl gives alkaline solution in water (c) 5 ml of 2 M KOH solution
(b) CH 3 COONa gives acidic solution in water
(d) 5 ml of 1 M Na2 CO3 solution
(c) CH 3 COOH is a weak acid
57. Which of the following compounds are diprotic
(d) NH 4 OH is a strong base [Pb. PMT 2000]
47. pKa of a weak acid is defined as [JIPMER 1999] (a) H 2 PO5 (b) H 2 S
1 (c) HClO3 (d) H 3 PO3
(a) log 10 Ka (b)
log10 K a
58. When 100 ml of 1M NaOH solution is mixed with
1 1 10 ml of 10 M H 2 SO 4 , the resulting mixture will
(c) log 10 (d) –log 10
Ka Ka be [AMU 2002]
48. A salt ' X ' is dissolved in water ( pH  7 ), the (a) Acidic (b) Alkaline
resulting solution becomes alkaline in nature. The (c) Neutral (d) Strongly alkaline
salt is made of
59. The pH indicators are [KCET 1996]
[CPMT 1983]
(a) A strong acid and strong base (a) Salts of strong acids and strong bases
(b) A strong acid and weak base (b) Salts of weak acids and weak bases
(c) A weak acid and weak base (c) Either weak acids or weak bases
(d) A weak acid and strong base (d) Either strong acids or strong bases
49. Which one is not an acid salt [MNR 1984] 60. Which of the following is not Lewis acid[BHU 1997]
(a) NaH2 PO2 (b) NaH2 PO3 (a) BF3 (b) AlCl3
(c) NaH2 PO4 (d) None (c) FeCl3 (d) PH3
50. A white substance was alkaline in solution. Which 61. A solution of sodium acetate in water will[MNR 1979]
of the following substances could it be [CPMT 1989] (a) Turn red litmus blue (b) Turn blue litmus red
(a) Fe2 O3 (b) Na2 CO3 (c) Not effect litmus (d) Decolourises litmus
(c) NH 4 Cl (d) NaNO3 62. Cl  is the conjugate base of
51. An aqueous solution of ammonium carbonate is [NCERT 1979; CPMT 1976; MP PET/PMT 1988]

[MP PMT 1989] (a) HClO4 (b) HCl

(a) Weakly acidic (b) Weakly basic (c) HOCl (d) HClO3
(c) Strongly acidic (d) Neither acidic nor 63. Which of the following behaves as both Lewis and
basic Bronsted base [MP PMT 2003]
52. 100 ml of 0.2 M H 2 SO 4 is added to 100 ml of
(a) BF3 (b) Cl 
0.2 M NaOH . The resulting solution will be[BHU 1996]
(c) CO (d) None of these
(a) Acidic (b) Basic 64. The conjugate acid of a strong base is a[EAMCET 1979]
(c) Neutral (d) Slightly basic (a) Strong acid (b) Weak acid
 Ionic Equilibrium 355
(c) Strong base (d) Weak base 76. Which of the anhydrous salts when come in
65. Which one is the weakest acid [DPMT 2002] contact with water turns blue [AMU 1981, 82]
(a) HNO3 (b) HClO4 (a) Ferrous sulphate (b) Copper sulphate
(c) Zinc sulphate (d) Cobalt sulphate
(c) H 2 SO 4 (d) HBr
77. The species among the following, which can act
66. Conjugate base of HPO 42  is [MP PMT 1995] as an acid and a base is [AIEEE 2002; KCET 2005]
(a) HSO 4 (b) SO 42 
(a) PO 43  (b) H 2 PO 4
(c) H 3 PO4 (d) H 4 PO3 (c) H 3 O  (d) Cl 
78. The strongest base from the following species is
67. Which of the following is not Lewis acid [RPET/PMT 2002]
[KCET 1996]
(a) FeCl3 (b) AlCl3
(a) NH 2  (b) OH 
(c) BCl3 (d) NH 3
(c) O 2  (d) S 2 
68. (i) A strong acid has a weak conjugate base 79. Which one is Lewis acid [CPMT 1997]
(ii) An acid is an electron pair acceptor (a) Cl  (b) Ag 
The above statements (i) and (ii)
(c) C2 H 5 OH (d) S 2 
(a) Correct
80. The conjugate acid of H 2 PO 4 is [MP PET 1990]
(b) Wrong
(c) (i) Correct and (ii) Wrong (a) H 3 PO4 (b) H 2 PO 4
(d) (i) Wrong and (ii) Correct (c) PO 43  (d) H 3 O 
69. The pH is less than 7, of the solution of
81. The conjugate acid of S 2 O 82  is [EAMCET 1984]
[Pb. PMT 2002; MP PMT 2003]
(a) FeCl3 (b) NaCN (a) H 2 S 2 O8 (b) H 2 SO 4

(c) NaOH (d) NaCl (c) HSO 4 (d) HS 2 O 8

70. In the reaction I2  I   I3  , the Lewis base is 82. In the reaction BCl3  PH3  Cl3 B  PH3 , Lewis
base is
[CPMT 1997; RPMT 2002; BCECE 2005]
[EAMCET 1986]
(a) I2 (b) I  (a) BCl3 (b) PH3
(c) I3  (d) None of these (c) Cl3 B  PH3 (d) None of these
71. The strength of an acid depends on its tendency to 83. Which of the following statement is true[MP PMT 1996]
[UPSEAT 2001] (a) The conjugate base of a strong acid is a strong
(a) Accept protons (b) Donate protons base
(b) The conjugate base of a weak acid is a strong
(c) Accept electrons (d) Donate electrons
base
72. In Lewis acid-base theory, neutralization reaction
(c) The conjugate base of a weak acid is a weak
may be considered as [NCERT 1977]
base
(a) Formation of salt and water (d) The base and its conjugate acid react to form a
(b) Competition for protons by acid and base neutral solution
(c) Oxidation reduction 84. What is the conjugate base of OH  [AIEEE 2005]
(d) Coordinate covalent bond formation (a) O 2 (b) H 2 O
73. The salt that forms neutral solution in water is
(c) O  (d) O 2 
[EAMCET 1981]
(a) NH 4 Cl (b) NaCl 85. Which of the following is a Lewis base [BHU 1995]
(c) Na2 CO3 (d) K3 BO3 (a) CH 4 (b) C2 H 5 OH

74. Which of the following cannot act as a Lewis or (c) Acetone (d) Secondary amine
Bronsted acid [DCE 2001] 86. The correct order of acid strength is [CBSE PMT 2005]
(a) BF3 (b) AlCl3 (a) HClO  HClO2  HClO3  HClO4
(c) SnCl 4 (d) CCl4 (b) HClO4  HClO  HClO2  HClO3
75. Which one of the following salts gives an acidic (c) HClO2  HClO3  HClO4  HClO
solution in water [MP PET 2002]
(d) HClO4  HClO3  HClO2  HClO
(a) CH 3 COONa (b) NH 4 Cl
(c) NaCl (d) CH 3 COONH 4 87. The strongest acid is [DPMT 2000]
(a) H3 AsO4 (b) H 3 AsO3
 356 Ionic Equilibrium
(c) H 3 PO3 (d) H 3 PO4 (c) Accepts a lone pair of electrons
88. Which of the following is the strongest base[Roorkee 2000] (d) Donates a lone pair of electrons
99. Water is a [KCET 2002]
(a) C 2 H 5 (b) C 2 H 5 COO 
(a) Amphoteric acid (b) Aprotic solvent
(c) C 2 H 5 O  (d) OH  (c) Protophobic solvent (d) None of these
89. The aqueous solution of which one of the 100. Conjugate base of NH 3 is [RPMT 2002]
following is basic
(a) NH 4 (b) NH 2
[MP PMT 2001]
(a) HOCl (b) NaHSO 4 (c) NH 2 (d) N 2

(c) NH 4 NO3 (d) NaOCl 101. Which of the following species is an acid and also
a conjugate base of another acid [NCERT 1981]
90. Which of the following is the weakest base [IIT 1980]
(a) HSO 4 (b) H 2 SO 4
(a) NaOH (b) Ca (OH )2

(c) OH (d) H 3 O 
(c) NH 4 OH (d) KOH
102. Which of the following is Lewis acid
91. The suitable indicator for strong acid and weak
[NCERT 1978; EAMCET 1987; MP PET 1994;
base is
CPMT 1990; AFMC 1997; RPMT 1999]
[RPMT 1997; UPSEAT 2002]
(a) BF3 (b) Cl 
(a) Methyl orange (b) Methyl red
(c) Phenol red (d) Phenolphthalein (c) H 2 O (d) NH 3
92. Among the following acids, the weakest one is 103. According to Bronsted-Lowry concept, base is a
[NCERT 1984] substance which is[NCERT 1982; RPMT 1997 AFMC 1999]
(a) HF (b) HCl (a) A proton donor
(c) HBr (d) HI (b) An electron pair acceptor
93. The compound HCl behaves as …. in the reaction, (c) A proton acceptor
HCl  HF  H 2 Cl  F  [JIPMER 2001] (d) An electron pair donor
104. Which of the following is known as hydronium ion
(a) Weak base (b) Weak acid
[NCERT 1976]
(c) Strong base (d) Strong acid
(a) H  (b) H 2 O 
94. The conjugate base of a strong acid is a[EAMCET 1978]
(a) Strong base (b) Strong acid (c) H 3 O  (d) H 2 O 2
(c) Weak acid (d) Weak base 105. An aqueous solution of aluminium sulphate would
95. Which among the following is strongest acid[BHU 2005] show
(a) H(ClO)O2 (b) H(ClO)O3 [NCERT 1977]

(c) H(ClO)O (d) H(ClO) (a) An acidic reaction

  (b) A neutral reaction
96. In the reaction 2 H 2 O ⇄ H 3 O  OH , water is
(c) A basic reaction
[MP PET 1989] (d) Both acidic and basic reaction
(a) A weak base 106. The aqueous solution of aluminium chloride is
(b) A weak acid acidic due to
(c) Both a weak acid and a weak base [MNR 1986, 88]
(d) Neither an acid nor a base (a) Cation hydrolysis
97. In the reaction HCl  H 2 O ⇌ H 3 O   Cl  (b) Anion hydrolysis
(c) Hydrolysis of both anion and cation
[NCERT 1978; EAMCET 1982, 89]
(d) Dissociation
(a) H 2 O is the conjugate base of HCl acid
107. HSO 4 is the conjugate base of [NCERT 1977]

(b) Cl is the conjugate base of HCl acid
(a) H  (b) H 2 SO 3
(c) Cl  is the conjugate acid of H 2 O base
2
(c) SO (d) H 2 SO 4
(d) H 3 O  is the conjugate base of HCl 4

108. An acid is a compound which furnishes (Bronsted-

98. According to Lewis concept, an acid is a substance
Lowry concept) [EAMCET 1975]
which
(a) An electron (b) A proton
[EAMCET 1981; NCERT 1981;
CPMT 1986; MP PMT 1987] (c) An electron and a proton (d) None of the above
(a) Accepts protons 109. The conjugate base of sulphuric acid is
(b) Donates protons [EAMCET 1974]
 Ionic Equilibrium 357
(a) Sodium hydroxide (b) Hydrochloric acid 121. The aqueous solution of AlCl3 is acidic due to the
(c) Bisulphate ion (d) Barium hydroxide hydrolysis of [UPSEAT 2001, 02]
110. Which is strongest Lewis base [CPMT 1994] (a) Aluminium ion
(a) SbH 3 (b) AsH 3 (b) Chloride ion
(c) PH3 (d) NH 3 (c) Both aluminium and chloride ion
(d) None of these
111. According to Bronsted principle, an aqueous
122. Which shows weak ionisation in water [MH CET 2001]
solution of HNO 3 will contain [MP PMT/PET 1988]
(a) H 2 SO 4 (b) NaCl
(a) NO 2 (b) NO 3
(c) HNO3 (d) NH 3
(c) NO 2 (d) NO  123. An organic dye, cosine used to detect end point of
112. Aqueous solution of an acid is characterised by precipitation titration by adsorption is called
the presence of [MH CET 1999]
[NCERT 1977] (a) Absorption indicator (b) Adsorption indicator
(a) H  ions (b) H 2 ions (c) Chemical indicator (d) None of these
124. The indicator used in the titration of iodine
(c) H 3 O  ions (d) H 4 O  ions against sodium thiosulphate is [AFMC 2002]
113. Ammonium ion is [RPMT 1999; KCET 2002] (a) Starch (b) K3 Fe(CN )6
(a) Neither an acid nor base (b)Both an acid and a base (c) K 2 CrO4 (d) Potassium
(c) A conjugate acid (d) A conjugate base 125. Phenolphthalein does not act as an indicator for
114. Aqueous solution of AlCl3 is [RPMT 2002] the titration between [Pb. PMT 2002]
(a) Acidic (b) Basic (a) NaOH and CH 3 COOH
(c) Amphoteric (d) None of these (b) H 2C2O4 and KMnO4
115. The species which acts as a Lewis acid but not a (c) Ba(OH )2 and HCl
Bronsted acid is [MP PMT 1999; Kurukshetra CET 2002]
(d) KOH and H 2 SO 4
(a) NH 2 (b) O 2 
126. Which is not example of Bronsted Lowry theory
(c) BF3 (d) OH  [AIEEE 2003]
116. Among the following, the weakest base is[MP PMT 2002] (a) AlCl3 (b) H 2 SO 4
(a) H  (b) CH 3 (c) SO 2 (d) HNO3

(c) CH 3 O  (d) Cl  127. An aqueous solution of sodium carbonate is

alkaline because sodium carbonate is a salt of [MP PET 20
117. Which of the following is not lewis base (a) Weak acid and weak base
[EAMCET 1975; RPMT 2002]
(b) Strong acid and weak base
(a) NH 3 (b) PH3
(c) Weak acid and strong base
(c) (CH 3 )3 N (d) HN 3 (d) Strong acid and strong base
118. pK a value of the strongest acid among the 128. The acid that results when a base accepts a proton
is called
following is
[Kerala (Med.) 2002]
[MP PMT 1990]
(a) Conjugate base of the acid
(a) 3.0 (b) 4.5
(b) Conjugate protonated base
(c) 1.0 (d) 2.0
(c) Lewis base
119. The most acidic compound in water is [CBSE PMT 2001]
(d) Conjugate acid of the base
(a) AlCl3 (b) BeCl 2
(e) None of these
(c) FeCl3 (d) None of these
129. Ammonia gas dissolves in water to form NH 4 OH .
120. BF3 is used as a catalyst in several industrial In this reaction water acts as[KCET (Engg./Med.) 1999]
processes due to its [Kerala (Med.) 2002] (a) A conjugate base (b) A non-polar solvent
(a) Strong reducing agent (c) An acid (d) A base
(b) Weak reducing agent 130. The conjugate base in the following reaction
(c) Strong Lewis acid nature H 2 SO 4  H 2O ⇄ H 3 O   HSO 4 [DCE 1999]
(d) Weak Lewis acid character
(a) H 2 O (b) HSO 4
 358 Ionic Equilibrium
(c) H 3 O  (d) SO 2 (b) Which provide H  ion in the solution
131. An aqueous solution of aluminium sulphate shows (c) Which give electron pair
[DPMT 2001] (d) Which accept OH  ion
(a) A basic nature 143. The conjugate base of HCO 3 is
(b) An acidic nature
(a) H 2 CO3 (b) CO 32 
(c) A neutral nature
(d) Both acidic and basic nature (c) CO2 (d) H 2 O
132. Neutralization of an acid with a base invariably 144. In the reaction NH 3  BF3 ⇌ NH 3  BF3 , BF3 is
results in the production of [CPMT 1983]
[MP PMT 1989; MHCET 2001]
(a) H 3 O  (b) OH  (a) Lewis acid
(c) H 2 O (d) H  and OH  (b) Lewis base
(c) Neither Lewis acid nor Lewis base
133. The conjugate acid of HPO 42  is
(d) Lewis acid and Lewis base both
[MP PMT 1987, 90, 91; EAMCET 1993]
145. The strongest Lewis base in the following
(a) H 2 PO 4 (b) PO 43  [MP PET/PMT 1988]
(c) H 3 PO4 (d) H 3 PO3  
(a) CH 3 (b) F
134. Which of the following is not used as a Lewis acid (c) NH 2  (d) OH 
[MP PET 2000]
146. The aqueous solution of CuSO 4 is [CPMT 1985]
(a) SnCl 4 (b) FeCl3
(a) Acidic (b) Basic
(c) KCl (d) BF3
(c) Neutral (d) Amphoteric
135. Orthoboric acid in aqueous medium is [AMU 2000]
147. The acid having the highest pKa value among the
(a) Monobasic (b) Dibasic
following is [JIPMER 2002]
(c) Tribasic (d) All are correct
(a) HCOOH (b) CH 3 COOH
136. According to Lewis concept which one of the
following is not a base[MP PET/PMT 1988; Pb. CET 2003] (c) ClCH2 COOH (d) FCH2COOH
(a) OH  (b) H 2 O 148. The indicator used in the titration of sodium
 carbonate with sulphuric acid is [DPMT 2001]
(c) Ag (d) NH 3
(a) Phenolphthalein
137. The aqueous solution of ammonium chloride is (b) Methyl orange
[CPMT 1987]
(c) Potassium ferrocynide
(a) Neutral (b) Basic
(d) Potassium ferricynide
(c) Acidic (d) Amphoteric
149. According to Bronsted law, water is a/an
138. In the process BCl3  PH3  BCl3 : PH3 The Lewis
[MP PET/PMT 1988]
acid is
(a) Base (b) Acid
[RPMT 2000]
(c) Acid and base both (d) Salt
(a) PH3 (b) BCl3
150. Which of the following can give base OH 
(c) Both (d) None
[MP PET/PMT 1988]
139. The conjugate acid of NH 3 is
(a) H 2 O (b) H 3 O 
[BHU Varanasi 1999; Pb. PMT 2004]
(c) H 2 (d) HCl
(a) NH 3 (b) NH 4
(c) N 2 H 4 (d) NH 2 OH 151. Conjugate base of HBr is [MP PET/PMT 1988]
 
140. Which halide of nitrogen is least basic [DPMT 2001] (a) H 2 Br (b) H

(a) NBr3 (b) NI3 (c) Br (d) Br 
(c) NCl3 (d) NF3 152. Molar heat of neutralization of NaOH with HCl
in comparison to that of KOH with HNO 3 is [MP PMT 1989
141. When FeCl3 gets soluble in water, then its
(a)1988]
solution represents which of the characteristics [MP PET/PMT Less (b) More
(a) Amphoteric (b) Acidic (c) Equal (d) Depends on pressure
(c) Basic (d) Neutral 153. Which of the following is not a Lewis acid [J & K 2005]
142. Lewis acid are those substances [MP PMT 1987] (a) BF3 (b) AlCl3
(a) Which accept electron pair (c) HCl (d) LiAlH4
 Ionic Equilibrium 359
154. The solvent which neither accepts proton nor 163. Strongest conjugate base is [DPMT 2004]
donates proton is called [RPMT 2000]  
(a) Cl (b) Br
(a) Amphoteric (b) Neutral 
(c) F (d) I 
(c) Aprotic (d) Amphiprotic
164. The conjugate base of H 2 PO 4 is [AIEEE 2004]
155. For the reaction in aqueous solution Zn 2   X  ⇄
(a) H 3 PO4 (b) P2 O 5
ZnX  , the K eq is greatest when X is [Pb. PMT 1998]
(c) PO 43  (d) HPO 42 
(a) F  (b) NO 3

(c) ClO 4 (d) I  165. Conjugate base of HSO 4 is [MH CET 2004]

156. Why are strong acids generally used as standard (a) SO 42  (b) H 2 SO 4
solutions in acid-base titrations [Pb. PMT 1998]
(c) H 3 SO 4 (d) None of these
(a) The pH at the equivalence point will always
be 7 Common ion effect, Isohydric solutions, Solubility
(b) They can be used to titrate both strong and product, Ionic product of water and Salt hydrolysis
weak bases
(c) Strong acids form more stable solutions than
1. The expression for the solubility product of
weak acids
Al2 (SO 4 )3 is
(d) The salts of strong acids do not hydrolysed
(a) K sp  [ Al 3  ] (SO 42  ] (b) K sp  [ Al 3  ]2 (SO 42  ]3
157. For an aqueous solution, the characteristic
species of acid is (c) K sp  [ Al 3  ]3 (SO 42  ]2 (d) K sp  [ Al 3  ]2 (SO 42  ]2
[RPMT 1999]
2. On addition of ammonium chloride to a solution
 
(a) H ion (b) H 3 O ion of ammonium hydroxide [CPMT 1976, 80, 81, 99;
NCERT 1976, 77; MP PMT 1989, 99; DPMT 1983]
(c) H 2  ion (d) H 4 O  ion (a) Dissociation of NH 4 OH increases
158. Which is a Lewis base [CPMT 1988; JEE Orissa 2004] (b) Concentration of OH  increases
(a) B2 H 6 (b) LiAlH4 (c) Concentration of OH  decreases
(c) AlH3 (d) NH 3 (d) Concentration of NH 4 and OH  increases
3.
159. For a weak acid, the incorrect statement is [Pb. PMT 2004] The solubility product of a salt having general
(a) Its dissociation constant is low formula MX 2 , in water is : 4  10 12 . The
(b) Its pKa is very low concentration of M 2  ions in the aqueous solution
of the salt is [AIEEE 2005]
(c) It is partially dissociated
(a) 2.0  10 6 M (b) 1 .0  10 4 M
(d) Solution of its sodium salt is alkaline in water
4
(c) 1 .6  10 M (d) 4 .0  10 10 M
160. Boron halides behave as Lewis acids, because of
their 4. In a saturated solution of electrolyte, the ionic
product of their concentration are constant at
[CBSE PMT 1996; BHU 2004]
constant temperature and this constant for
(a) Ionic nature (b) Acidic nature electrolyte is known as [CPMT 1983]
(c) Covalent nature (d) Electron deficient (a) Ionic product (b) Solubility product
nature (c) Ionization constant (d) Dissociation constant
161. Would gaseous HCl be considered as an Arrhenius 5. If the solubility product K sp of a sparingly soluble
acid
salt MX 2 at 25 C is 1 .0  10 11 , the solubility of
[UPSEAT 2004]
the salt in mole litre–1 at this temperature will be[RPMT 20
(a) Yes
(a) 2.46  10 14 (b) 1 .36  10 4
(b) No
(c) 2.60  10 7 (d) 1 .20  10 10
(c) Not known
6. The unit of ionic product of water Kw are
(d) Gaseous HCl does not exist
[UPSEAT 2001, 02]
162. Which one of the following is called amphoteric 1 1 2 2
(a) Mol L (b) Mol L
solvent
[UPSEAT 2004] (c) Mol 2 L1 (d) Mol 2 L2
(a) Ammonium hydroxide (b) Chloroform 7. A solution which is 10 3 M each in Mn 2  , Fe 2  , Zn 2 
(c) Benzene (d) Water and Hg 2  is treated with 10 16 M sulphide ion. If
 360 Ionic Equilibrium
K sp of MnS , FeS, ZnS and HgS are 10 15 , 10 23 , 10 20 (d) Both sulphides precipitate
54 16. Which of the following salts when dissolved in
and 10 respectively, which one will precipitate
water will get hydrolysed
first
[IIT Screening 2003] [MNR 1985; CPMT 1989; CBSE PMT 1989; MP PET 1999]
(a) FeS (b) MgS (a) NaCl (b) NH 4 Cl
(c) HgS (d) ZnS (c) KCl (d) Na2 SO 4
8. Let the solubility of an aqueous solution of 17. The aqueous solution of FeCl3 is acidic due to
Mg(OH )2 be x then its k sp is [AIEEE 2002]
[CPMT 1972, 79, 83, 84;
(a) 4 x 3 (b) 108 x 5 MP PET/PMT 1988; RPMT 2000]
(c) 27 x 4 (d) 9 x (a) Acidic impurities (b) Ionisation
9. The solubility product of BaSO4 at 25 C is (c) Hydrolysis (d) Dissociation
1 .0  10 9 . What would be the concentration of 18. A precipitate of AgCl is formed when equal
H 2 SO 4 necessary to precipitate BaSO4 from a volumes of the following are mixed. [ K sp for
solution of 0 .01 M Ba 2  ions AgCl  10 10 ] [KCET 2005]
[RPMT 1999]
(a) 10 4 M AgNO 3 and 10 7 M HCl
(a) 10 9 (b) 10 8
(c) 10 7 (d) 10 6 (b) 10 5 M AgNO 3 and 10 6 M HCl
10. The solubility in water of a sparingly soluble salt
(c) 10 5 M AgNO 3 and 10 4 M HCl
AB2 is 1 . 0  10 5 mol l 1 . Its solubility product
number will be (d) 10 6 M AgNO 3 and 10 6 M HCl
[AIEEE 2003] 19. The solubility of silver chromate in 0.01 M
(a) 4  10 15
(b) 4  10 10
K 2 CrO4 is 2  10 8 mol dm 3 . The solubility product
15
(c) 1  10 (d) 1  10 10 of silver chromate will be [
24 24
11. The solubility of CaF2 is a moles/litre. Then its (a) 8  10 (b) 16  10
solubility product is ….. [Orissa JEE 2002] (c) 1 . 6  10 18 (d) 16  10 18
(a) s 2 (b) 4 s 3 20. Some salts although containing two different
2 3
metallic elements give test for only one of them in
(c) 3s (d) s solution. Such salts are [MNR 1979]
12. On passing a current of HCl gas in a saturated (a) Double salts (b) Normal salts
solution of NaCl , the solubility of NaCl (c) Complex salts (d) Basic salts
[CPMT 1989; CBSE PMT 1989] N
21. What is the pH value of KOH solution
(a) Increases (b) Decreases 1000
(c) Remains unchanged (d) NaCl decomposes [CPMT 1975; MNR 1986, 91; Pb. CET 2004]
13. Which is the correct representation of the (a) 10 11 (b) 3
solubility product constant of Ag 2 CrO4 [NCERT 1974, 75] (c) 2 (d) 11
(a) [ Ag  ]2 [CrO 42 ] (b) [ Ag  ] [CrO 42 ] 22. Mohr's salt is a [MNR 1986]
(a) Normal salt (b) Acid salt
(c) [2 Ag  ] [CrO 42 ] (d) [2 Ag  ]2 [CrO 42 ] (c) Basic salt (d) Double salt
14. The solubility of CaF2 is 2  10 4 moles / litre. Its 23. Aqueous solution of sodium acetate is
[MNR 1978; CPMT 1971, 80, 81;
solubilily product (K sp ) is[NCERT 1981; BHU 1983, 86;
MADT Bihar 1982; MP PMT 1985;]
MP PET 1992; CBSE PMT 1999] (a) Neutral (b) Weakly acidic
4 3
(a) 2.0  10 (b) 4.0  10 (c) Strongly acidic (d) Alkaline
(c) 8 . 0  10 12
(d) 3 . 2  10 11 24. Which is the correct alternate for hydrolysis
25
constant of NH 4 CN [CBSE PMT 1989]
15. Solubility product of a sulphide MS is 3  10 and
that of another sulphide NS is 4  10 40 . In (a)
Kw
(b)
Kw
ammoniacal solution Ka K a  Kb
[NCERT 1981]
Kb Ka
(a) Only NS gets precipitated (c) (d)
c Kb
(b) Only MS gets precipitated
25. Which of the following salts undergoes hydrolysis
(c) No sulphide precipitates
[CPMT 1972, 74, 78; DPMT 1985]
 Ionic Equilibrium 361
(a) CH 3 COONa (b) KNO3 36. A white salt is readily soluble in water and gives a
(c) NaCl (d) K2 SO 4 colourless solution with a pH of about 9. The salt
would be
26. What will happen if CCl4 is treated with AgNO3
[Pb. PMT 1998]
[DPMT 1983] (a) NH 4 NO3 (b) CH 3 COONa
(a) A white ppt. of AgCl will form (c) CH 3 COONH 4 (d) CaCO3
(b) NO2 will be evolved
37. If acetic acid mixed with sodium acetate, then
(c) CCl4 will dissolve in AgNO3 H  ion concentration will be [Roorkee 1995]
(d) Nothing will happen (a) Increased (b) Decreased
27. The correct representation for solubility product (c) Remains unchanged (d) pH decreased
of SnS 2 is 38. Solubility of AgCl will be minimum in
[CPMT 1977; MP PET 1999;RPMT 2000] [CBSE PMT 1995]
4 2 2 2 2 2 (a) 0.001 M AgNO3 (b) Pure water
(a) [Sn ] [S ] (b) [Sn ] [S ]

(c) [Sn 2
] [2 S 2
] (d) [Sn 4
] [2 S 2 2
] (c) 0.01 M CaCl2 (d) 0.01 M NaCl
39. In absence of formation of complex ions by the
28. A precipitate of calcium oxalate will not dissolve
addition of a common ion, the solubility of a given
in
salt is [BHU 1979]
[CPMT 1971, 89; IIT 1986]
(a) Increased
(a) HCl (b) HNO 3
(b) Decreased
(c) Aquaregia (d) CH 3 COOH
(c) Unaffected
29. Baking soda is [RPMT 2000] (d) First increased and then decreased
(a) Basic salt (b) Acidic salt 40. At 298 K, the solubility product of PbCl2 is
(c) Complex salt (d) Double salt 1 .0  10 6 . What will be the solubility of PbCl2 in
30. Which one of the following substances will be a
moles/litre
mixed salt
[MP PMT 1990; CPMT 1985, 96]
[DPMT 1982; CPMT 1972]
3
(a) NaHCO3 (a) 6.3  10 (b) 1 .0  10 3
(b) Ca (OCl )Cl (c) 3.0  10 3 (d) 4 .6  10 14
(c) K2 SO 4 Al2 (SO 4 )3 .24 H 2 O 41. Solubility product is [CET Pune 1998]
(a) The ionic product of an electrolyte in its
(d) Mg (OH )Br
saturated solution
31. Solubility product of BaCl2 is 4  10 9 . Its (b) The product of the solubilities of the ions of
solubility in moles/litre would be the electrolyte
[AFMC 1982; Roorkee 1990; BHU 2000] (c) The product of solubilities of the salts
(a) 1  10 3
(b) 1  10 9 (d) The product of the concentration of the ions
27 42. Ionic product of water increases, if
(c) 4  10 (d) 1  10 27
[AMU 1983; MP PET 1986; MP PET/PMT 1988;
32. Which hydroxide will have lowest value of
JIPMER 2002]
o
solubility product at normal temperature (25 C) [IIT 1990; RPMT 1997] 
(a) Pressure is reduced (b) H is added
(a) Mg (OH )2 (b) Ca (OH )2
(c) OH  is added (d) Temperature
(c) Ba (OH )2 (d) Be (OH )2 increases
33. Which will not be hydrolysed [MP PMT 1989] 43. Which one is a mixed salt [DPMT 1985]
(a) Potassium nitrate (a) NaHSO 4 (b) NaKSO 4
(b) Potassium cyanide (c) K4 Fe(CN )6 (d) Mg (OH )Cl
(c) Potassium succinate
44. If K sp for HgSO 4 is 6 .4  10 5 , then solubility of
(d) Potassium carbonate
34. Which pair will show common ion effect the salt is
[MP PMT 1990, 99; Pb. PMT 2001] [AFMC 1997; KCET 2000; CPMT 2000; JIPMER 2001]
(a) BaCl2  Ba (NO3 )2 (b) NaCl  HCl (a) 8  10 3 (b) 8  10 6
(c) NH 4 OH  NH 4 Cl (d) AgCN  KCN (c) 6.4  10 5 (d) 6.4  10 3
45. The solubility of BaSO4 in water is
35. Which is least soluble in water [UPSEAT 1999]
3
(a) AgCl (b) AgF 2 . 33  10 gm / litre. Its solubility product will be
(c) AgI (d) Ag 2 S (molecular weight of BaSO 4  233 ) [AIIMS 1998]
 362 Ionic Equilibrium
(a) 1  10 5 (b) 1  10 10 54. The addition of HCl will not suppress the
15 20 ionization of
(c) 1  10 (d) 1  10
[MP PET 1993]
46. The solubility of AgCl in 0.2 M NaCl solution
(a) Acetic acid (b) Benzoic acid
(K sp for AgCl  1.20  10 10 ) is [MP PET 1996] (c) H 2 S (d) Sulphuric acid
10
(a) 0.2 M (b) 1 . 2  10 M 55. On the addition of a solution containing
2
(c) 0 . 2  10 10
M (d) 6 . 0  10 10
M CrO4 ions to the solution of Ba 2  , Sr 2  and
2
47. The solubility of AgI in NaI solution is less than Ca ions, the precipitate obtained first will be of
that in pure water because [UPSEAT 2001] [MP PMT 1993]
(a) AgI forms complex with NaI (a) CaCrO4 (b) SrCrO4
(b) Of common ion effect (c) BaCrO4 (d) Mixture of (a), (b),
(c) Solubility product of AgI is less than that of (c)
NaI 56. The solubility product of a sparingly soluble salt
(d) The temperature of the solution decreases AB at room temperature is 1 .21  10 6 . Its molar
48. The solubility product of BaSO4 is 1 .5  10 9 . The solubility is
precipitation in a 0.01 M Ba 2  solution will start, [CPMT 1987; MP PET 2001]
6
on adding H 2 SO 4 of concentration [CPMT 1988] (a) 1 .21  10 (b) 1 .21  10 3
(c) 1 .1  10 4 (d) 1 .1  10 3
(a) 10 9 M (b) 10 8 M
57. The precipitation occurs if ionic concentration is
(c) 10 7 M (d) 10 6 M
[AFMC 1995; J & K 2005]
49. At 20 o C, the Ag  ion concentration in a saturated (a) Less than solubility product
solution of Ag 2 CrO4 is 1 . 5  10 4 mole / litre. At (b) More than solubility product
o
20 C, the solubility product of Ag 2 CrO4 would be (c) Equal to solubility product
[MP PET 1997; MP PMT 1999]
(d) None of these
58. If S and K sp are respectively solubility and
(a) 3.3750  10 12 (b) 1.6875  10 10
solubility product of a sparingly soluble binary
(c) 1.6875  10 12 (d) 1.6875  10 11 electrolyte, then
50. The solubility of PbCl2 is [MP PMT 1995; DCE 1999] [CPMT 1988; MP PMT 1999]

(a) K sp (b) 3
K sp (a) S  K sp (b) S  K sp
2

1
3 K sp (c) S  K sp (d) S  K sp
(c) (d) 8 K sp 2
4
59. Any precipitate is formed when
51. The solubility product of AgCl is 1.44  10 4
[AIIMS 1982; DPMT 1985; KCET 1999; MP PMT 2004]
at 100 o C . The solubility of silver chloride in (a) Solution becomes saturated
boiling water may be
(b) The value of ionic product is less that than the
[MP PMT 1994; Bihar MEE 1998]
value of solubility product
(a) 0 . 72  10 4 M (b) 1 .20  10 2 M (c) The value of ionic product is equal than the
(c) 0 . 72  10 2 M (d) 1 . 20  10 4 M value of solubility product
52. If the solubility of a sparingly soluble salt of the (d) The value of ionic product is greater than the
type BA 2 (giving three ions on dissociation of a value of solubility product
molecule) is x moles per litre, then its solubility 60. The solubility product of AgCl is 4 . 0  10 10 at
product is given by [BHU 1987] 298 K. The solubility of AgCl in 0.04 m CaCl2 will
(a) x 2 (b) 2x 3 be
[KCET 1996]
(c) 4 x 2 (d) 4 x 3
5 4
(a) 2 .0  10 m (b) 1 . 0  10 m
53. The solubility product of Ag 2 CrO4 is 32  10 12 .
9 4
What is the concentration of CrO 4 ions in that (c) 5 . 0  10 m (d) 2 .2  10 m
solution 61. Hydrolysis of sodium acetate will give [MNR 1978]
[BHU 1997; DPMT 2004] (a) Acidic solution (b) Basic solution
(a) 2  10 4 m / s (b) 16  10 4 m / s (c) Neutral solution (d) Normal solution
62. If the solubility product of BaSO4 is 1 .5  10 9 in
(c) 8  10 4 m / s (d) 8  10 8 m / s
water, its solubility in moles per litre, is
 Ionic Equilibrium 363
[BHU 1995; MP PET 1995; UPSEAT 204] 71. The solubility of PbCl2 at 25 o C is
9 5
(a) 1 .5  10 (b) 3.9  10 3
6.3  10 mole/litre. Its solubility product at that
(c) 7.5  10 5 (d) 1 .5  10 5 temperature is
63. On passing H 2 S gas through a highly acidic [NCERT 1979; CPMT 1985]
2 3 3
solution containing Cd ions, CdS is not (a) (6.3  10 )  (6.3  10 )
precipitated because
(b) (6.3  10 3 )  (12 .6  10 3 )
(a) Of common ion effect
(b) The solubility of CdS is low (c) (6.3  10 3 )  (12 .6  10 3 )2
(c) Cd 2  ions do not form complex with H 2 S (d) (12 .6  10 3 )  (12 .6  10 3 )
(d) The solubility product of CdS is low 72. Which of the following cannot be hydrolysed
64. Which of the following will occur if a 0.1 M [MP PMT 1996]
solution of a weak acid is diluted to 0.01 M at (a) A salt of weak acid and strong base
constant temperature (b) A salt of strong acid and weak base
[UPSEAT 2001, 02]
(c) A salt of weak acid and weak base
(a) [H  ] will decrease to 0.01 M (d) A salt of strong acid and strong base
(b) pH will decrease 73. pH of water is 7. When a substance Y is dissolved
(c) Percentage ionization will increase in water, the pH becomes 13. The substance Y is a
(d) K a will increase salt of
65. If solubility of calcium hydroxide is 3 , then its [MP PMT 1997]
solubility product will be (a)CET
[MH Strong
2002]acid and strong base
(a) 27 (b) 3 (b) Weak acid and weak base
(c) 9 (d) 12 3 (c) Strong acid and weak base
66. When NH 4 Cl is added to NH 4 OH solution, the (d) Weak acid and strong base
dissociation of ammonium hydroxide is reduced. 74. Which is a basic salt [MP PMT 1985]
It is due to (a) PbS (b) PbCO3
[MP PMT 1993] (c) PbSO4 (d) 2PbCO3 .Pb(OH )2
(a) Common ion effect (b) Hydrolysis
(c) Oxidation (d) Reduction 75. The saturated solution of Ag 2 SO 4 is 2 . 5  10 2 M .
67. At 298 K, the solubility of PbCl2 is 2  10 2 mol /lit , Its solubility product (K sp ) is [NCERT 1980]

then k sp  [RPMT 2002] (a) 62 .5  10 6 (b) 6 .25  10 4

(a) 1  10 7 (b) 3.2  10 7 (c) 15 .625  10 6 (d) 3.125  10 6
5 5
(c) 1  10 (d) 3.2  10 76. K sp for sodium chloride is 36 mol 2 / litre 2 . The
68. The solubility product of silver sulphide is solubility of sodium chloride is [BHU 1981]
3.2  10 11 . Its solubility at the experimental
1 1
temperature is (a) (b)
36 6
(a) 2  10 4 moles per litre
(c) 6 (d) 3600
(b) 6  10 6 moles per litre
77. Sodium chloride is purified by passing hydrogen
(c) 1 .2  10 5 moles per litre chloride gas in an impure solution of sodium
(d) 8  10 4 moles per litre chloride. It is based on
69. The solubility of CaCO3 in water is [MP PMT 1996]
4
3.05  10 moles / litre. Its solubility product will be [MP PMT 1997]
(a) Buffer action (b) Common ion effect
4 (c) Association of salt (d) Hydrolysis of salt
(a) 3.05  10 (b) 10
(c) 6.1  10 4
(d) 9.3  10 8 78. If the concentration of lead iodide in its saturated
3
70. Solubility of BaF2 in a solution Ba(NO3 )2 will be solution at 25 o
C be 2  10 moles per litre, then
its solubility product is [CPMT 1984]
represents by the concentration term 6 12
[UPSEAT 2001, 02; CPMT 2002]
(a) 4  10 (b) 8  10
(c) 6  10 9 (d) 32  10 9
(a) [Ba   ] (b) [ F  ]
79. The precipitate of CaF2 (Ksp  1.7  10 10 ) is
1 
(c) [F ] (d) 2 [ NO 3 ] obtained when equal volumes of the following are
2
mixed
 364 Ionic Equilibrium
[IIT 1992; UPSEAT 2000] (a) Acidic (b) Alkaline
4 2 4 
(a) 10 M Ca  10 MF (c) Neutral (d) None of these
88. In which of the following salt hydrolysis takes
(b) 10 2 M Ca 2   10 3 M F 
place
(c) Both [CPMT 1974, 78]
(d) None of these (a) KCl (b) NaNO3
80. In the reaction: H 2 S ⇄ 2 H   S   , when NH 4 OH (c) CH 3 COOK (d) K2 SO 4
is added, then [KCET (Med.) 1999; AFMC 2000] 89. At 90 C pure water has [H 3 O  ]  10 6 M , the value
o

(a) S   is precipitate of Kw at this temperature will be

(b) No action takes places [IIT 1981; MNR 1990; CBSE PMT 1993; UPSEAT 1999]
(c) Concentration of S   decreases (a) 10 6 (b) 10 12

(d) Concentration of S increases (c) 10 14 (d) 10 8
81. What is the minimum concentration of SO 42  90. Solubility of MX 2 type electrolyte is
4
required to precipitate BaSO4 in a solution 0 . 5  10 mole /litre . The value of K sp of the
4 2
containing 1 . 0  10 mol Ba ? ( K sp for BaSO4 is electrolyte is [CBSE PMT 2002]

4  10 10
) (a) 5  10 13 (b) 25  10 10
13
[MP PMT 2000] (c) 1 .25  10 (d) 5  10 12
(a) 4  10 10 M (b) 2  10 7 M 91. According to the reaction PbCl 2  Pb 2  2 Cl  , the
6 3 solubility coefficient of PbCl2 is [MP PET/PMT 1988]
(c) 4  10 M (d) 2  10 M
82. Solubility product for salt AB2 is 4  10 12
. (a) [Pb 2  ][Cl  ]2 (b) [Pb 2  ][Cl  ]
Calculate solubility [RPET 2003] (c) [Pb 2  ]2 [Cl  ] (d) None of these
3
(a) 1  10 gm mol / litre 92. K sp value of Al (OH )3 and Zn (OH )2 are
5
(b) 1  10 gm mol / litre 8 . 5  10 23
and 1 . 8  10 14
respectively. If NH 4 OH is
4
(c) 1  10 gm mol / litre added in a solution of Al 3  and Zn 2  , which will
(d) 1  10 2 gm mol / litre precipitate earlier
[MP PMT 1989; CPMT 1989]
83. Solubility product of a salt AB is 1  10 8 in a (a) Al (OH )3 (b) Zn (OH )2
solution in which concentration of A is 10 3 M . (c) Both together (d) None
The salt will precipitate when the concentration 93. Why pure NaCl is precipitated when HCl gas is
of B becomes more than passed in a saturated solution of NaCl
[MP PET 1990; KCET 2003] [NCERT 1977; MP PMT 1987; CPMT 1974, 78, 81]
4
(a) 10 M (b) 10 7 M (a) Impurities dissolves in HCl
(c) 10 6 M (d) 10 5 M (b) The value of [ Na  ] and [Cl  ] becomes smaller
84. At equilibrium, if to a saturated solution of than K sp of NaCl
NaCl, HCl is passed, NaCl gets precipitated
(c) The value of [ Na  ] and [Cl  ] becomes greater
because [RPMT 1999]
than K sp of NaCl
(a) HCl is a strong acid
(b) Solubility of NaCl decreases (d) HCl dissolves in the water
(c) Ionic product of NaCl becomes greater than 94.
Pure NaCl is prepared by saturating a cold
its K sp saturated solution of common salt in water with
HCl gas. The principle used is
(d) HCl is a weak acid (a) Le Chatelier principle (b) Displacement law
85. The solubility product of BaSO4 is 1 .3  10 9 . The (c) Common ion effect (d) Fractional
solubility of this salt in pure water will be[MP PET 2002] distillation
9
(a) 1 . 69  10 mol litre 1 18
(b) 1 . 69  10 mol litre 1 95. What is the solubility of calcium fluoride in a
saturated solution, if its solubility product is
(c) 3 .6  10 18 mol litre 1 (d) 3 . 6  10 5 mol litre 1 3 . 2  10 11
86. The solubility product of AgCl under standard [CPMT 1997]
4
conditions of temperature is given by [Kerala (Med.) 2003] (a) 2 .0  10 mole / litre (b) 12 . 0  10 3 mole / litre
(a) 1 .6  10 5 (b) 1.5  10 8 (c) 0 .2  10 4 mole / litre (d) 2  10 3 mole / litre
(c) 3 . 2  10 10 (d) 1 . 5  10 10 96. The following equilibrium exists in an aqueous
87. An aqueous solution of CH 3 COONa will be solution of hydrogen sulphide :
[MP PET 2001]
 Ionic Equilibrium 365
H 2 S ⇄ H   HS  (c) PbS (d) ZnS
If dilute HCl is added to an aqueous solution of 106. The concentration of which ion is to be decreased,
H 2 S without any change in temperature[NCERT 1989] when NH 3 solution is added [RPMT 1997]

(a) The equilibrium constant will change (a) OH  (b) NH 4

(b) The concentration of HS  will increase (c) H 3 O  (d) O 2
(c) The concentration of undissociated H 2 S will
107. The compound insoluble in acetic acid is [IIT 1986]
decrease
(a) Calcium oxide
(d) The concentration of HS  will decrease
(b) Calcium carbonate
97. Solubility of a salt M 2 X 3 is y mol dm 3 . The
(c) Calcium oxalate
solubility product of the salt will be
(d) Calcium hydroxide
[IIT 1990, 97; AFMC 1991; RPMT 1999;
MP PET 2001; MP PMT 2003; Orissa JEE 2005] 108. A saturated solution of Ag 2 SO 4 is 2.5  10 2 M; The
(a) 6y 4 (b) 64 y 4 value of its solubility product is [Pb.CET 2004]
6 4
(c) 36 y 5
(d) 108 y 5
(a) 62 .5  10 (b) 6.25  10
6
98. Which one of the following is most soluble (c) 15 .625  10 (d) 3.125  10 6
[CBSE PMT 1994; RPMT 2000]
109. Solubility product of AgCl is 1  10 6 at 298 K. Its
(a) CuS (K sp  8  10 37 ) (b) MnS (K sp  7  10 16 )
solubility in mole litre 1 would be [
70 51
(c) Bi2 S 3 (K sp  1  10 ) (d) Ag 2 S (K sp  6  10 )
(a) 1  10 6 mol / litre
o
99. The solubility product of PbCl2 at 20 C is (b) 1  10 3 mol / litre
4
1 .5  10 . Calculate the solubility[Bihar CEE 1995; BHU 2002]
(c) 1  10 12 mol / litre
(a) 3.75  10 4 (b) 3.34  10 2
(d) None of these
(c) 3 .34  10 2 (d) None of these
110. A litre of solution is saturated with AgCl. To this
100. Which one of the following compounds is a Lewis
solution if 1.0  10 4 mole of solid NaCl is added,
acid
what will be the [ Ag  ] , assuming no volume
[EAMCET 1997]
(a) PCl3 (b) BCl3 change [UPSEAT 2004]
(a) More (b) Less
(c) NCl3 (d) CHCl 3
(c) Equal (d) Zero
101. Which one of the following salt is most acidic in
111. The concentration of KI and KCl in certain
water
solution containing both is 0.001M each. If 20 ml
[IIT 1995]
of this solution is added to 20 ml of a saturated
(a) NiCl2 (b) BeCl 2 solution of AgI in water? What will happen [MP PMT 2004
(c) FeCl3 (d) AlCl3 (a) AgCl will be precipitated
102. Which of the following aqueous solution will have (b) AgI will be precipitated
a pH less than 7.0 [MP PMT 1991, 92] (c) Both AgCl and AgI will be precipitated
(a) KNO3 (b) NaOH (d) There will be no precipitated
(c) FeCl3 (d) NaCN 112. The solubility product of a sparingly soluble salt
103. Hydrolysis constant for a salt of weak acid and AX 2 is 3 .2  10 11 . Its solubility (in moles / litres)
weak base would be [RPMT 1999] is
Kw Kw [CBSE PMT 2004]
(a) Kh  (b) Kh  4
Ka Kb (a) 2  10 (b) 4  10 4
6
Kw (c) 5.6  10 (d) 3.1  10 4
(c) Kh  (d) None of these
K a Kb 113. 0.5 M ammonium benzoate is hydrolysed to 0.25
104. Which salt will give basic solution on hydrolysis percent, hence its hydrolysis constant is[MH CET 2004]
[RPMT 1997] (a) 2.5  10 5 (b) 1.5  10 4
(a) KCN (b) KCl (c) 3.125  10 6 (d) 6.25  10 4
(c) NH 4 Cl (d) CH 3 COONH 4 114. The solubility of Sb 2 S 3 in water is 1 .0  10 5 mol /
105. Which of the following sulphides has the lowest litre at 298 K. What will be its solubility product [CPMT 20
solubility product [KCET 1996]
(a) 108  10 25 (b) 1 . 0  10 25
(a) FeS (b) MnS
 366 Ionic Equilibrium
(c) 144  10 25 (d) 126  10 24 (c) pH will remain the same
o
115. The ionic product of water at 25 C is 10 . The 14 (d) Electrical conductivity will not change
ionic product at 90 o C will be [CBSE PMT 1996] 8. pH of a 10 3 M solution of hydrochloric acid will
be
(a) 1  10 20 (b) 1  10 12
[MP PET 2000]
(c) 1  10 14 (d) 1  10 16
(a) 1.3 (b) 2.0
116. In hydrolysis of a salt of weak acid and strong
(c) 3.0 (d) 4.5
base, A   H 2 O ⇄ HA  OH  , the hydrolysis
o
9. The pH of water at 25 C is nearly
constant (Kh ) is equal to.… [Orissa JEE 2002]
[CPMT 1986, 89, 90, 93; CBSE PMT 1989;
Kw Kw MADT Bihar 1995]
(a) (b)
Ka Kb (a) 2 (b) 7
Ka Kw (c) 10 (d) 12
(c) (d)
C K a  Kb 10. pH of a solution is 5. Its hydroxyl ion
concentration is
[JIPMER 1999]
Hydrogen ion concentration- pH scale and (a) 5 (b) 10
Buffer solution 5
(c) 10 (d) 10 9

1. The pH of blood does not appreciably change by a 11. The pH of a solution in which the [H  ]  0.01, is
small addition of an acid or a base because blood [MADT Bihar 1980]
[CBSE PMT 1995] (a) 2 (b) 1
(a) Contains serum protein which acts as buffer (c) 4 (d) 3
(b) Contains iron as a part of the molecule 12. At 25°C, the dissociation constant of a base BOH is
(c) Can be easily coagulated 1 .0  10 12 . The concentration of Hydroxyl ions in
(d) It is body fluid 0.01 M aqueous solution of the base would be[CBSE PMT 2
2. The pH of a 0.001 M NaOH will be (a) 2 . 0  10 6 mol L1 (b) 1 .0  10 5 mol L1
[MP PMT 1995; UPSEAT 2001]
(c) 1 . 0  10 6 mol L1 (d) 1 .0  10 7 mol L1
(a) 3 (b) 2
13. Aqueous solution of HCl has the pH  4 . Its
(c) 11 (d) 12
molarity would be [RPMT 1999]
3. pH value of a solution, whose hydronium ion
(a) 4 M (b) 0.4 M
concentration is 6 . 2  10 9 mol / l, is [AFMC 1999; AIIMS 2000]
(c) 0.0001 M (d) 10 M
(a) 6.21 (b) 7.21
14. Which is a buffer solution
(c) 7.75 (d) 8.21
[CPMT 1985, 88; AIIMS 1980; MP PMT 1994; AFMC 2004]
4. 0.1 mole of CH3NH2 (Kb = 5  104) is mixed with
(a) CH 3 COOH  CH 3 COONa
0.08 mole of HCl and diluted to one litre. What
+
will be the H concentration in the solution? [IIT 2005] (b) CH 3 COOH  CH 3 COONH 4
(a) 8  102 M (b) 8  1011 M (c) CH 3 COOH  NH 4 Cl
(c) 1.6  1011 M (d) 8  105 M
(d) NaOH  NaCl
5. What will be the sum of pH and pOH in an
15. The addition of solid sodium carbonate to pure
aqueous solution ? [MP PET/PMT 1998]
water causes
(a) 7 (b) pkw
[NCERT 1973]
(c) Zero (d) 1 (a) An increase in hydronium ion concentration
6. Hydrogen ion concentration in mol/L in a solution (b) An increase in alkalinity
of pH  5 .4 will be [AIEEE 2005]
(c) No change in acidity
(a) 3 .98  10 8 (b) 3 .88  10 6 (d) A decrease in hydroxide ion concentration
6 6
(c) 3.68  10 (d) 3.98  10 16. The aqueous solution of which of the following
7. When solid potassium cyanide is added in water salt has the lowest pH [CBSE PMT 2002]
then (a) NaClO (b) NaClO2
[CPMT 2002; BHU 2002]
(c) NaClO3 (d) NaClO4
(a) pH will increase
17. The pH of a 10 10 M NaOH solution is nearest to
(b) pH will decrease
 Ionic Equilibrium 367
[UPSEAT 2001, 02] (c) pH of A and B increase
(a) 10 (b) 7 (d) pH of B and A decrease
(c) 4 (d) 10 28. The compound whose 0.1 M solution is basic is
18. Which will have maximum pH [NCERT 1979] [IIT 1986; MP PMT 1991]
(a) Distilled water (a) Ammonium acetate
(b) 1 M NH 3 (b) Calcium carbonate
(c) Ammonium sulphate
(c) 1 M NaOH
(d) Sodium acetate
(d) Water saturated by chlorine 29. The following reaction is known to occur in the
19. pH of a solution is 9.5. The solution is[MH CET 2000] body CO2  H 2 O ⇌ H 2 CO3 ⇌ H   HCO 3 . If
(a) Neutral (b) Acidic CO2 escapes from the system[NCERT 1973; RPMT 1997]
(c) Basic (d) Amphoteric (a) pH will decrease
20. The pH of a 10 9 M solution of HCl in water is (b) Hydrogen ion concentration will decrease
[UPSEAT 2000, 02] (c) H 2 CO3 concentration will be unaltered
(a) 8 (b) – 8 (d) The forward reaction will be promoted
(c) Between 7 and 8 (d) Between 6 and 7 30. For preparing a buffer solution of pH 6 by mixing
21. pH  pOH equal to [NCERT 1975] sodium acetate and acetic acid, the ratio of the
(a) Zero (b) Fourteen concentration of salt and acid should be (K a  10 5 ) [MP PET
(c) A negative number (d) Infinity (a) 1 : 10 (b) 10 : 1
22. Which of the following 0.1M solution will contain (c) 100 : 1 (d) 1 : 100
the largest concentration of hydronium ions[NCERT 1971, 73]
31. Which is incorrect for buffer solution [CPMT 1985]
(a) NaHCO3 (b) NH 4 Cl
(a) It contains weak acid and its conjugate base
(c) HCl (d) NH 3 (b) It contains weak base and its conjugate acid
23. Which one has pH 12 [Roorkee 1995] (c) In this there is very less change is pH value
(a) 0.01 M KOH (b) 1 N KOH ml when very less amount of acid and base is
mixed
(c) 1 N NaOH ml (d) 1 N Ca(OH )2 ml
(d) None of the above
24. What is the correct relationship between the pHs
32. pH values of HCl and NaOH solutions each of
of isomolar solutions of sodium oxide (pH1 ) ,
N
sodium sulphide (pH 2 ), sodium selenide (pH 3 ) and strength will be respectively [MP PMT 1999]
100
sodium telluride (pH4 ) ? [CBSE PMT 2005] (a) 2 and 2 (b) 2 and 12
(a) pH1  pH 2  pH 3  pH 4 (c) 12 and 2 (d) 2 and 10
(b) pH1  pH 2  pH 3  pH 4 33. When rain is accompained by a thunderstorm, the
collected rain water will have a pH value[AIEEE 2003]
(c) pH1  pH 2  pH 3  pH 4
(a) Slightly lower than that of rain water without
(d) pH1  pH 2  pH 3  pH 4 thunderstorm
25. Given pH of a solution A is 3 and it is mixed with (b) Slightly higher than that when the
another solution B having pH 2. If both mixed thunderstorm is not there
then resultant pH of the solution will be[BHU 2005] (c) Uninfluenced by occurrence of thunderstorm
(a) 3.2 (b) 1.9 (d) Which depends on the amount of dust in air
(c) 3.4 (d) 3.5 34. Which of the following is the buffer solution of
26. On adding solid potassium cyanide to water strong acidic nature [MP PET 2002]
[MP PMT 1989] (a) HCOOH  HCOO 
(a) pH will increase
(b) CH 3 COOH  CH 3 COO 
(b) pH will decrease
(c) pH will not change (c) H 2 C 2 O 4  C 2 O 42 
(d) Electrical conductance will not change (d) H 3 BO 3  BO 33 
27. A is an aqueous acid; B is an aqueous base. They
35. The dissociation constant of an acid HA is 1  10 5 .
are diluted separately, then [KCET 2002]
The pH of 0.1 molar solution of the acid will be
(a) pH of A increases and pH of B decreases
[KCET (Engg./Med.) 1999]
(b) pH of A increases and pH of B decreases till
(a) Five (b) Four
pH in each case is 7
(c) Three (d) One
 368 Ionic Equilibrium
36. The pH value of 1 .0  10 8 M HCl solution is less 46. The hydrogen ion concentration of 0.1 N solution
than 8 because of CH 3 COOH , which is 30% dissociated, is [JIPMER 2002]
(a) HCl is completely ionised at this (a) 0.03 (b) 3.0
concentration (c) 0.3 (d) 30.0
(b) The ionization of water is negligible 47. What is the pH of 0.1 M NH 3 [RPET 2000]
(c) The ionization of water cannot be assumed to (a) 11.27 (b) 11.13
be negligible in comparison with this low
(c) 12.0 (d) 9.13
concentration of HCl
48. By adding a strong acid to the buffer solution, the
(d) The pH cannot be calculated at such a low
pH of the buffer solution [DPMT 1996]
concentration of HCl
(a) Remains constant (b) Increases
37. What is the pH for a neutral solutions at the
(c) Decreases (d) Becomes zero
normal temperature of the human body[JIPMER 2000]
49. The pH of 0.1 M NaOH is [MP PET 2003]
(a) 7.2 (b) 14.0
(c) 6.8 (d) 6.0 (a) 11 (b) 12
38. 1 M NaCl and 1 M HCl are present in an aqueous (c) 13 (d) 14
solution. The solution is [AIEEE 2002] 50. pH of human blood is 7.4. Then H  concentration
(a) Not a buffer solution with pH < 7 will be
[RPMT 2002]
(b) Not a buffer solution with pH > 7
8 8
(c) A buffer solution with pH < 7 (a) 4  10 (b) 2  10
4
(d) A buffer solution with pH > 7 (c) 4  10 (d) 2  10 4
39. A solution has pH  5 , it is diluted 100 times, 51. Assuming complete ionisation, the pH of
then it will become [NCERT 1978; AFMC 2005] 0.1 M HCl, is 1. The molarity of H 2 SO 4 with the
(a) Neutral (b) Basic same pH is
[Pb. PMT 2002]
(c) Unaffected (d) More acidic
(a) 0.1 (b) 0.2
40. 0.02 M monobasic acid dissociates 2% hence, pH
(c) 0.05 (d) 2.0
of the solution is [MH CET 2000]
52. Highest pH 14 is given by [DCE 1999]
(a) 0.3979 (b) 1.3979
(a) 0.1 M H 2 SO 4 (b) 0.1 M NaOH
(c) 1.699 (d) 3.3979
41. Components of buffer solution are 0.1 M HCN and (c) 1 N NaOH (d) 1 N HCl
0.2 M NaCN . What is the pH of the solution[RPET 2000]53. What will be the pH of a 10 8 M HCl solution
(a) 9.61 (b) 6.15 [MP PET/PMT 1998; RPET 1999;MP PMT 2000]
(c) 2.0 (d) 4.2 (a) 8.0 (b) 7.0
42. pH of a solution of 10 ml . 1N sodium acetate and (c) 6.98 (d) 14.0
50 ml 2N acetic acid (K a  1 . 8  10 5 ), is 54. When 10 ml of 0.1 M acetic acid (pKa  5.0) is
approximately titrated against 10 ml of 0.1M ammonia solution
[MP PMT 2003] (pKb  5.0) , the equivalence point occurs at pH[AIIMS 2005
(a) 4 (b) 5 (a) 5.0 (b) 6.0
(c) 6 (d) 7 (c) 7.0 (d) 9.0
43. By adding 20 ml 0.1 N HCl to 20 ml 0.001 N KOH , 55. Which on reaction with water will have pH less
the pH of the obtained solution will be [KCET 2000] than 7
(a) 2 (b) 1.3 [MH CET 2001]
(c) 0 (d) 7 (a) BaO (b) CaO
44. The pH of the solution containing 10 ml of a (c) Na2O (d) P2O5
0.1 N NaOH and 10 ml of 0.05 N H 2 SO 4 would be 56. A solution of MgCl2 in water has pH
[Pb. PMT 2002, 04]
[MP PMT 2002]
(a) 1 (b) 0
(a) < 7 (b) > 7
(c) 7 (d) > 7
(c) 7 (d) 14.2
45. The pH of 10 7 M NaOH is [MP PMT 2001]
57. pH of completely dissociated 0.005 M H 2 SO 4 is
(a) 7.01 (b) Between 7 and 8 [RPET 2003]
(c) Between 9 and 10 (d) Greater than 10 (a) 3 (b) 4
(c) 2 (d) 5
 Ionic Equilibrium 369
58. The pKa of a weak acid is 4.8. What should be the 68. To obtain a buffer which should be suitable for
ratio of [Acid]/[Salt] of a buffer if pH  5 .8 is maintaining a pH of about 4  5, we need to have
required in solution, a mixture of
[MP PET 2003] (a) A strong base + its salt with a weak acid
(a) 10 (b) 0.1 (b) A weak base + its salt with a strong acid
(c) A strong acid + its salt with a weak base
(c) 1 (d) 2
(d) A weak acid + its salt with a strong base
59. Which of the following salt is acidic
[CPMT 1979, 81; NCERT 1979, 81; 69. The concentration of NaOH solution is 10 8 M .
MP PET 1990; JIPMER 2002] Find out the (OH  ) concentration [CPMT 1993]
(a) Na2 SO 4 (b) NaHSO 3 (a) 10 8

(c) Na2 SO 3 (d) Na2 S (b) Greater than 10 6

60. 20 ml of 0.5 N HCl and 35 ml of 0.1N NaOH are (c) 10 6
mixed. The resulting solution will [KCET 2005] (d) Lies between 10 6 and 10 7
(a) Be neutral 70. The pH of 0.0001 N solution of KOH will be
(b) Be basic [BHU 1997; CET Pune 1998]
(c) Turn phenolphthalein solution pink (a) 4 (b) 6
(d) Turn methyl orange red (c) 10 (d) 12
71. Given that the dissociation constant for H 2 O is
61. The pH of a 0.02 M solution of hydrochloric acid
is K w  1  10 14 mole 2
litre 2 , what is the pH of a
[MP PMT 1993] 0.001 molar KOH solution
(a) 2.0 (b) 1.7 [MP PET 1995; MP PET/PMT 1998]
(c) 0.3 (d) 2.2 (a) 10 11 (b) 3
62. A sample of Na2 CO3 .H 2 O weighing 0.62 g is added (c) 14 (d) 11
to 100 ml of 0.1 N (NH 4 )2 SO 4 solution. What will 72. An acidic buffer solution can be prepared by
mixing solution of [MNR 1983]
be the resulting solution [BHU 1997]
(a) Ammonium acetate and acetic acid
(a) Acidic (b) Neutral (b) Ammonium chloride and hydrochloric acid
(c) Basic (d) None of these (c) Sulphuric acid and sodium sulphate
63. The pH of the solution is 4. The hydrogen ion (d) Acetic acid and sulphuric acid
concentration of the solution in mol/litre is[UPSEAT 2000] (e) NaCl and NaOH
(a) 9.5 (b) 10 4 73. Which of the following mixtures forms an acid
buffer
(c) 10 4 (d) 10 2 [MP PMT 1993; IIT 1981; CPMT 1989; CBSE PMT 1989]
64. NaOH (aq ) , HCl(aq ) and NaCl(aq ) concentration of each (a) NaOH  HCl
is 10 3 M . Their pH will be respectively [BHU 2003] (b) CH 3 COOH  CH 3 COONa
(a) 10, 6, 2 (b) 11, 3, 7 (c) NH 4 OH  NH 4 Cl
(c) 10, 2, 6 (d) 3, 4, 7 (d) H 2 CO3  (NH 4 )2 CO3
65. The pH of 10 5 M aqueous solution of NaOH is 74. A buffer solution has equal volumes of
[MP PET 1996] 0.2 M NH 4 OH and 0.02 M NH 4 Cl . The pK b of the
(a) 5 (b) 7 base is 5. The pH is
(c) 9 (d) 11 [CBSE PMT 1989; KCET 2005]
66. The pH of 0.05 M solution of dibasic acid is (a) 10 (b) 9
[MH CET 2002] (c) 4 (d) 7
(a) 1 (b) 1 75. The pH of a simple sodium acetate buffer is given
(c)  2 (d)  2 [Salt ]
67. A buffer solution contains 0.1 M of acetic acid by pH  pK a  log
[ Acid ]
and 0.1 M of sodium acetate. What will be its
K a of acetic acid  1 .8  10 5
pH , if pK a of acetic acid is 4.75 [MP PMT 1996]
If [Salt] = [Acid] = 0.1 M, the pH of the solution
(a) 4.00 (b) 4.75 would be about [BHU 1987]
(c) 5.00 (d) 5.25 (a) 7 (b) 4.7
(c) 5.3 (d) 1.4
 370 Ionic Equilibrium
76. Amongst the following solutions, the buffer 87. Which solution contains maximum number of
solution is H  ion
[MP PMT 1999]
(a) 0.1 M HCl (b) 0.1 M NH 4 Cl
(a) NH 4 Cl  NH 4 OH solution
(c) 0.1 M NaHCO3 (d) 0.1 M
(b) NH 4 Cl  NaOH solution
(c) NH 4 OH  HCl solution 88. A certain buffer solution contains equal
concentration of X  and HX . The K b for X  is
(d) NaOH  HCl solution
10 10 . The pH of the buffer is
77. The pH of solution having [OH  ]  10 7 is[AIIMS 1996]
[IIT 1984; RPMT 1997; CPMT 1996; DPMT 2004]
(a) 7 (b) 14
(c) Zero (d) 7 (a) 4 (b) 7
78. 50 ml water is added to a 50 ml solution of (c) 10 (d) 14
Ba(OH )2 of strength 0.01 M. The pH value of the 89. The defination of pH is [EAMCET 1980; UPSEAT 2001]
resulting solution will be [MP PMT 1999] 1
(a) pH  log (b) pH  log [H  ]
(a) 8 (b) 10 [H  ]
(c) 12 (d) 6 1 

79. pH of a solution can be expressed as (c) pH   log (d) pH   log[ H ]

[H  ]
[CPMT 1999; UPSEAT 2001]

90. Which of the following does not make any change
(a)  log e (H ) (b)  log 10 (H  ) in pH when added to 10 ml dilute HCl [NCERT 1975]
(c) log e (H  ) (d) log 10 (H  ) (a) 5 ml pure water (b) 20 ml pure water
80. The solution of sodium carbonate has pH [MP PET 2000] (c) 10 ml HCl (d) Same 20 ml dilute
(a) Greater than 7 (b) Less than 7 HCl
(c) Equal to 7 (d) Equal to zero
91. A compound whose aqueous solution will have the
81. The pH of 10 7 N HCl is [RPMT 2000] highest pH
(a) 6.0 (b) 6.97 [CPMT 1974, 75, 78; MP PET 1996; DPMT 1982, 83]
(c) 8.0 (d) 10.0 (a) NaCl (b) Na2 CO3
82. If the pH of a solution is 2, its normality will be
(c) NH 4 Cl (d) NaHCO3
[MADT Bihar 1982; MP PET 2000]
(a) 2N (b) 1
2
N 92. At 80 o C, distilled water has [ H 3 O  ] concentration
(c) 0.01 N (d) None of these equal to 1  10 6 mole / litre. The value of Kw at this
83. The buffer solution of 100 ml having a pH value temperature will be [CBSE PMT 1994; RPMT 2000;
4 when added to 1 ml dilute HCl , then the pH of AFMC 2001; AIIMS 2002; BHU 2002]
buffer solution (a) 1  10 6 (b) 1  10 9
[NCERT 1976, 77]
(c) 1  10 12 (d) 1  10 15
(a) Converts to 7 (b) Does not change
93. The pH value of 0.1 M NaOH solution is (when
(c) Converts to 2 (d) Changes to 10
84. In a solution of acetic acid, sodium acetate is there is a given reaction [H  ][OH  ]  10 15 )[CPMT 1997]
added, then its pH value[NCERT 1977; DPMT 1985; MP PMT 1994]
(a) 13 (b) 12
(a) Decreases (c) 11 (d) 2
(b) Increases 94. Which oxychloride has maximum pH [CPMT 1997]
(c) Remains unchanged
(a) NaClO (b) NaClO2
(d) (a) and (b) both are correct
85. If pOH of a solution is 6.0, then its pH will be (c) NaClO3 (d) NaClO4
[MP PMT 1987] 95. pH of HCl (10 12 M ) is[CPMT 1997; Pb. PET/PMT 1999]
(a) 6 (b) 10
(a) 12 (b) 12
(c) 8 (d) 14
(c)  7 (d) 14
86. In a solution of pH  5, more acid is added in
96. Which one is buffer solution [CPMT 1997]
order to reduce the pH  2 . The increase in
hydrogen ion concentration is[MP PET 1989; CPMT 1990] (a) [PO 4 – ] [[HPO 4  ] (b) [PO 33 – ] [[H 2 PO 4–  ]
(a) 100 times (b) 1000 times (c) [HPO 4–  ] [[H 2 PO 4–  ] (d) All of these
(c) 3 times (d) 5 times
 Ionic Equilibrium 371
97. When 100 ml of M / 10 NaOH solution and 50 ml 106. The pH of the aqueous solution containing
of M / 5 HCl solution are mixed, the pH of 0.49 gm of H 2 SO 4 in one litre is [EAMCET 1997]
resulting solution would be (a) 21997]
[RPMT (b) 1
(a) 0 (b) 7 (c) 1.7 (d) 0.3
(c) Less than 7 (d) More than 7 107. Which of the following solutions can act as buffer
98. How many millilitres of 6.0 M hydrochloric acid [JIPMER 1997]

should be used to prepare 150 ml of a solution (a) 0.1 molar aq. NaCl
(b) 0.1 molar aq. CH 3 COOH  0.1 molar NaOH
which is 0.30 M in hydrogen ion [Pb. PMT 1998]
(c) 0.1 molar aq. ammonium acetate
(a) 3.0 (b) 7.5
(d) None of the above
(c) 9.3 (d) 30
108. The pH of a solution obtained by mixing 50 ml of
99. The pH of 0.1 M acetic acid is 3, the dissociation
constant of acid will be 0.4 N HCl and 50 ml of 0.2 N NaOH is [KCET 1996]

(a) 1.0  10 4 (b) 1 .0  10 5 (a)  log 2 (b)  log 0.2

(c) 1 .0  10 3 (d) 1 .0  10 8 (c) 1.0 (d) 2.0

100. The pH of a buffer solution containing 25 ml of 109. Which of the following is a buffer
[MP PMT 1991; BHU 1995]
1 M CH 3 COONa and 25 ml of 1 M CH 3 COOH will
(a) NaOH  CH 3 COONa
be appreciably affected by 5 ml of [CPMT 1987]
(b) NaOH  Na2 SO 4
(a) 1 M CH 3 COOH (b) 5 M CH 3 COOH
(c) K 2 SO 4  H 2 SO 4
(c) 5 M HCl (d) 1 M NH 4 OH
(d) NH 4 OH  CH 3 COONH 4
101. The pH value of decinormal solution of NH 4 OH
110. If 4.0 gm NaOH is present in 1 litre solution, then
which is 20% ionised, is [CBSE PMT 1998] its pH will be [CPMT 1989]
(a) 13.30 (b) 14.70 (a) 6 (b) 13
(c) 12.30 (d) 12.95 (c) 18 (d) 24
102. A physician wishes to prepare a buffer solution at 111. The pOH of beer is 10.0. The hydrogen ion
pH  3 .58 that efficiently resists changes in pH
concentration will be [MP PMT 1994]
yet contains only small concentration of the
(a) 10 2 (b) 10 10
buffering agents. Which of the following weak
acids together with its sodium salt would be best (c) 10 8 (d) 10 4
to use [CBSE PMT 1997] 112. When a buffer solution of sodium acetate and
(a) m  chlorobenzoic acid (pKa  3.98 ) acetic acid is diluted with water [CPMT 1985]
(a) Acetate ion concentration increases
(b) p  chlorocinnamic acid (pKa  4.41)
(b) H  ion concentration increases
(c) 2, 5  dihydroxy benzoic acid (pKa  2.97 )
(c) OH  ion concentration increases
(d) Acetoacetic acid (pKa  3.58 )
(d) H  ion concentration remain unaltered
103. In a mixture of a weak acid and its salt, the ratio 113. What is the pH of Ba(OH )2 if normality is 10
of concentration of acid to salt is increased ten- [CPMT 1996]
fold. The pH of the solution [KCET 1996]
(a) 4 (b) 10
(a) Decreases by one (b) Increases by one- (c) 7 (d) 9
tenth 114. What will be the pH of a solution formed by
(c) Increases by one (d) Increases ten-fold mixing 40 ml of 0.10 M HCl with 10 ml of
104. When an acid or alkali is mixed with buffer 0.45 M NaOH
solution, then pH of buffer solution [CPMT 1997]
[Manipal MEE 1995]
(a) Not changes (b) Changes slightly (a) 12 (b) 10
(c) Increases (d) Decreases (c) 8 (d) 6
105. How much sodium acetate should be added to a 115. The pH of a solution having
0.1 m solution of CH 3 COOH to give a solution of  4
[H ]  10  10 moles / litre will be [BHU 1981]
pH  5.5 (pKa of CH 3 COOH  4.5) [KCET 1996]
(a) 1 (b) 2
(a) 0.1 m (b) 0.2 m
(c) 3 (d) 4
(c) 1.0 m (d) 10 .0 m
 372 Ionic Equilibrium
116. If 0.4 gm NaOH is present in 1 litre solution, then (a) Basic (b) Acid
its pH will be [CPMT 1985; BHU (c) Neutral (d) Both (a) and (b)
1980] 128. The pH of a solution is increased from 3 to 6. Its
(a) 2 (b) 10 H  ion concentration will be [EAMCET 1998]
(c) 11 (d) 12 (a) Reduced to half
117. Which of the following is not a Bronsted acid [BHU 1997] (b) Doubled
(a) CH 3 NH 4 (b) CH 3 COO  (c) Reduced by 1000 times
 (d) Increased by 1000 times
(c) H 2 O (d) HSO 4
129. Pure water is kept in a vessel and it remains
118. pH of 0.005 M H 2 SO 4 solution will be[NCERT 1980]
exposed to atmospheric CO2 which is absorbed,
(a) 0.005 (b) 2
then its pH will be
(c) 1 (d) 0.01 [MADT Bihar 1984; DPMT 2002]
119. A buffer solution is a mixture of [MP PMT 1987]
(a) Greater than 7
(a) Strong acid and strong base
(b) Less than 7
(b) Weak acid and weak base
(c) 7
(c) Weak acid and conjugate acid
(d) Depends on ionic product of water
(d) Weak acid and conjugate base
130. The pH of a solution is 2. If its pH is to be raised
120. When pH of a solution decreases, its hydrogen
ion concentration [MADT Bihar 1981]
to 4, then the [H  ] of the original solution has to
(a) Decreases (b) Increases be [MP PET 1994]
(c) Rapidly increases (d) Remains always (a) Doubled
constant (b) Halved
121. If the pH of a solution is 4.0 at 25 o C, its pOH (c) Increased hundred times
would be (K w  10 14 ) [MP PMT 1989]
(d) Decreased hundred times
131. Which of the following solutions cannot act as a
(a) 4.0 (b) 6.0 buffer
(c) 8.0 (d) 10.0 [EAMCET 1998]
122. An aqueous solution whose pH  0 is (a) NaH2 PO4  H 3 PO4
[CPMT 1976; DPMT 1982]
(b) CH 3 COOH  CH 3 COONa
(a) Alkaline (b) Acidic
(c) HCl  NH 4 Cl
(c) Neutral (d) Amphoteric
(d) H 3 PO4  Na2 HPO4
123. In a solution of acid H  concentration is 10 10 M .
The pH of this solution will be 132. Assuming complete ionisation, the pH of
(a) 8 (b) 6 0.1 M HCl is 1. The molarity of H 2 SO 4 with the
(c) Between 6 and 7 (d) Between 3 and 6 same pH is

124. The concentration of hydronium (H 3 O ) ion in [KCET 1998]
water is (a) 0.2 (b) 0.1
[CET Pune 1998] (c) 2.0 (d) 0.05
(a) Zero (b) 1  10 gm ion / litre
7 133. The pH of blood is
(a) 5.2 (b) 6.3
(c) 1  10 14 gm ion / litre (d) 1  10 7 gm ion / litre
(c) 7.4 (d) 8.5
125. A solution whose pH value is less than 7 will be
134. The pH of 10 8 molar aqueous solution of HCl is
(a) Basic (b) Acidic
[CPMT 1988; MNR 1983, 90; MP PMT 1987; IIT 1981;
(c) Neutral (d) Buffer
BHU 1995; AFMC 1998; MP PET 1989, 99; BCECE 2005]
126. When the pH of a solution is 2, the hydrogen ion
(a)  8
concentration in moles per litre is
(b) 8
[NCERT 1973; MNR 1979]
(c) 6  7 (Between 6 and 7)
(a) 1  10 14 (b) 1  10 2
(d) 7  8 (Between 7 and 8)
(c) 1  10 7 (d) 1  10 12
135. As the temperature increases, the pH of a KOH
127. A base is dissolved in water yields a solution with
solution
a hydroxide ion concentration of 0.05 mol litre 1 .
[UPSEAT 2001]
The solution is [AFMC 1997]
(a) Will decreases
 Ionic Equilibrium 373
(b) Will increases (c) Pb (OH )Cl (d) Na2 HPO4
(c) Remains constant 147. Given a 0.1M solution of each of the following.
(d) Depends upon concentration of KOH solution Which solution has the lowest pH [MNR 1987]
136. The hydrogen ion concentration in a given (a) NaHSO 4 (b) NH 4 Cl
solution is 6  10 4 . Its pH will be [EAMCET 1978] (c) HCl (d) NH 3
(a) 6 (b) 4 148. Out of the following, which pair of solutions is not
(c) 3.22 (d) 2 a buffer solution
N (a) NH 4 Cl  NH 4 OH
137. The pH of HCl would be approximately
100 (b) NaCl  NaOH
[CPMT 1971; DPMT 1982, 83; (c) Na2 HPO4  Na3 PO4
MP PMT 1991; Bihar MEE 1996] (d) CH 3 COOH  CH 3 COONa
(a) 1 (b) 1.5 149. If the dissociation constant of an acid HA is
(c) 2 (d) 2.5 1  10 5 , the pH of a 0.1 molar solution of the acid
138. A solution which is resistant to change of pH will be approximately [NCERT 1979]
upon the addition of an acid or a base is known as (a) Three (b) Five
[BHU 1979] (c) One (d) Six
(a) A colloid (b) A crystalloid 150. pH value of N / 10 NaOH solution is
(c) A buffer (d) An indicator [CBSE PMT 1996;Pb. CET 2001; Pb. PMT 2002]
139. 10 6 M HCl is diluted to 100 times. Its pH is (a) 10 (b) 11
[CPMT 1984] (c) 12 (d) 13
(a) 6.0 (b) 8.0 151. A solution of sodium borate has a pH of
(c) 6.95 (d) 9.5 approximately
140. The pH of a 10 10 molar HCl solution is [JIPMER 2001]
approximately (a) < 7 (b) > 7
[NCERT 1977] (c) = 7 (d) Between 4 to 5
(a) 10 (b) 7 152. If pH of A, B, C and D are 9.5, 2.5, 3.5 and 5.5
(c) 1 (d) 14 respectively, then strongest acid is [AFMC 1995]
141. The H  ion concentration is 1 .0  10 6 mole/litre in (a) A (b) C
a solution. Its pH value will be (c) D (d) B
[MP PMT 1985; AFMC 1982] 153. At 25 C the pH value of a solution is 6. The
(a) 12 (b) 6 solution is
(c) 18 (d) 24 [AFMC 2001]
142. The pH of a solution is the negative logarithm to (a) Basic (b) Acidic
the base 10 of its hydrogen ion concentration in (c) Neutral (d) Both (b) and (c)
[Manipal MEE 1995]
154. A certain buffer solution contains equal
(a) Moles per litre (b) Millimoles per litre
concentration of X  and HX . The K a for HX is
(c) Micromoles per litre (d) Nanomoles per litre
143. When 10 8 mole of HCl is dissolved in one litre of 10 8 . The pH of the buffer is
water, the pH of the solution will be [UPSEAT 2001]
[CPMT 1973, 94; DPMT 1982] (a) 3 (b) 8
(a) 8 (b) 7 (c) 11 (d) 14
(c) Above 8 (d) Below 7 155. The dissociation constant of HCN is 5  10 10 . The
144. The pH of the solution containing 10 ml of 0.1 N pH of the solution prepared by mixing 1.5 mole of
NaOH and 10 ml of 0.05 N H 2 SO 4 would be HCN and 0.15 moles of KCN in water and making
[CPMT 1987; Pb. PMT 2002,04] up the total volume to 0 . 5 dm 3 is
(a) 0 (b) 1 (a) 7.302 (b) 9.302
(c) > 7 (d) 7 (c) 8.302 (d) 10.302
145. The pH of 0.001 molar solution of HCl will be 156. Which buffer solution out of the following will
[MP PET 1986; MP PET/PMT 1988; CBSE PMT 1991] have pH  7
(a) 0.001 (b) 3 [MP PET 2001]
(c) 2 (d) 6 (a) CH 3 COOH  CH 3 COONa
146. Which salt can be classified as an acid salt [CPMT 1989]
(a) Na2 SO 4 (b) BiOCl (b) HCOOH  HCOOK
 374 Ionic Equilibrium
(c) CH 3 COONH 4 [AIIMS 1982; CPMT 1994; MP PET 1994]

(d) NH 4 OH  NH 4 Cl (a) HCl and NaCl (b) NaOH and NaNO3

157. The pKa of equimolecular sodium acetate and (c) KOH and KCl (d) NH 4 OH and NH 4 Cl
acetic acid mixture is 4.74. If pH is [DPMT 2001] 166. If the pH of a solution of an alkali metal
(a) 7 (b) 9.2 hydroxide is 13.6, the concentration of hydroxide
is [JIPMER 2000]
(c) 4.74 (d) 14
(a) Between 0.1 M and 1 M
158. pH of NaCl solution is [CET Pune 1998]
(b) More than 1 M
(a) 7 (b) Zero
(c) Less than 0.001 M
(c)  7 (d)  7
(d) Between 0.01 M and 1 M
159. A solution of sodium chloride in contact with
167. The pK a of acetylsalicylic acid (aspirin) is 3.5.
atmosphere has a pH of about [NCERT 1972, 77]
The pH of gastric juice in human stomach is
(a) 3.5 (b) 5
about 2-3 and the pH in the small intestine is
(c) 7 (d) 1.4
about 8. Aspirin will be
160. Which would decrease the pH of 25 cm 3 of a [IIT 1988; KCET 2003]
0.01 M solution of hydrochloric acid [MH CET 2001] (a) Unionized in the small intestine and in the
3 stomach
(a) The addition of 25 cm 0.005 M hydrochloric
(b) Completely ionized in the small intestine and
acid
in the
(b) The addition of 25 cm 3 of 0.02 M hydrochloric
stomach
acid
(c) Ionized in the stomach and almost unionized
(c) The addition of magnesium metal in the small intestine
(d) None of these (d) Ionized in the small intestine and almost
161. The condition for minimum change in pH for a unionized in the stomach
buffer solution is [RPMT 2000] 168. The concentration of hydrogen ion in water is
(a) Isoelectronic species are added [MP PET 1990]
7
(b) Conjugate acid or base is added (a) 8 (b) 1  10
(c) pH  pKa (c) 7 (d) 1 / 7
(d) None of these 169. pH of a 10 M solution of HCl is [CBSE PMT 1995]
162. A buffer solution with pH 9 is to be prepared by (a) Less than 0 (b) 2
mixing NH 4 Cl and NH 4 OH . Calculate the number (c) 0 (d) 1
of moles of NH 4 Cl that should be added to one 170. The pH of 1 N H 2 O is [CPMT 1988]
5
litre of 1.0 M NH4 OH . [K b  1 . 8  10 ] [UPSEAT 2001] (a) 7 (b) >7
(a) 3.4 (b) 2.6 (c) <7 (d) 0
(c) 1.5 (d) 1.8 171. If H  ion concentration of a solution is increased by
163. The ionization constant of a certain weak acid is 10 times its pH will be [DCE 2000]
4
10 . What should be the [salt] to [acid] ratio if (a) Increase by one (b) Remains unchanged
we have to prepare a buffer with pH = 5 using (c) Decrease by one (d) Increase by 10
172.CET
this acid and one of the salts [CPMT 2000; KCET 2000; Pb. The gastric juice in our stomach contains enough
2000]
(a) 1 : 10 (b) 10 : 1 HCl to make the hydrogen ion concentration
about 0.01 mole / litre. The pH of gastric juice is[NCERT 1974
(c) 5 : 4 (d) 4 : 5
164. Which solution has the highest pH value [JIPMER 2000] (a) 0.01 (b) 1
(a) 1 M KOH (c) 2 (d) 14
173. Addition of which chemical will decrease the
(b) 1 M H 2 SO 4 hydrogen ion concentration of an acetic acid
(c) Chlorine water solution [MP PMT 1990]
(d) Water containing carbon dioxide (a) NH 4 Cl (b) Al2 (SO 4 )3
165. One weak acid (like CH 3 COOH ) and its strong (c) AgNO3 (d) HCN
base together with salt (like CH 3 COONa ) is a 174. The one which has the highest value of pH is
buffer solution. In which pair this type of (a) Distilled water
characteristic is found
 Ionic Equilibrium 375
(b) NH 3 solution in water 186. The concentration of hydrogen ion [H  ] in 0.01 M
(c) NH 3 HCl is
[EAMCET 1979]
(d) Water saturated with Cl2 12 2
(a) 10 (b) 10
175. The solution of Na2 CO3 has pH [AMU 1988]
(c) 10 1 (d) 10 12
(a) Greater than 7 (b) Less than 7 187. A solution of weak acids is diluted by adding an
(c) Equal to 7 (d) Equal to zero equal volume of water. Which of the following
176. Which is not a buffer solution [CPMT 1990] will not change
(a) NH 4 Cl  NH 4 OH [JIPMER 1997]
(a) Strength of the acid
(b) CH 3 COOH  CH 3 COONa
(b) The value of [ H 3 O  ]
(c) CH 3 COONH 4
(c) pH of the solution
(d) Borax + Boric acid (d) The degree of dissociation of acid
177. What will be hydrogen ion concentration in moles 188. Ka of H 2O2 is of the order of [DCE 2004]
litre 1 of a solution, whose pH is 4.58 [UPSEAT 2001] 12 14
(a) 10 (b) 10
(a) 2.63  10 5 (b) 3.0  10 5 (c) 10 16 (d) 10 10
(c) 4 .68 (d) None of these 189. Equivalent weight of an acid [UPSEAT 2004]
178. Assuming complete dissociation, the pH of a 0.01 (a) Depends on the reaction involved
M NaOH solution is equal to (b) Depends upon the number of oxygen atoms
[NCERT 1975; CPMT 1977; DPMT 1982; BHU 1997] present
(a) 2.0 (b) 14.0 (c) Is always same
(c) 12.0 (d) 0.01 (d) None of the above
179. 50 ml of 2 N acetic acid mixed with 10 ml of 190. pH scale was introduced by [UPSEAT 2004]
1 N sodium acetate solution will have an (a) Arrhenius (b) Sorensen
approximate pH of (c) Lewis (d) Lowry
[MP PMT/PET 1988] 191. Buffer solution is prepared by mixing[MH CET 2003]
(a) 4 (b) 5 (a) Strong acid + its salt of strong base
(c) 6 (d) 7 (b) Weak acid + its salt of weak base
180. The hydrogen ion concentration of 0.001 (c) Strong acid + its salt of weak base
M NaOH solution is [AFMC 1983] (d) Weak acid + its salt of strong base
(a) 1  10 2 mole / litre (b) 1  10 11 mole / litre 192. The pH of millimolar HCl is [MH CET 2004]
(c) 1  10 14 mole / litre (d) 1  10 12 mole / litre (a) 1 (b) 3
181. A weak monoprotic acid of 0.1 M, ionizes to 1% in (c) 2 (d) 4
solution. What will be the pH of solution [MNR 1988] 193. Which of the following is a Lewis base[CPMT 2004]
(a) 1 (b) 2 (a) NaOH (b) NH 3
(c) 3 (d) 11 (c) BCl3 (d) All of these
182. pH of a solution is 4. The hydroxide ion
194. What will be the pH value of 0.05 M
concentration of the solution would be
[NCERT 1981; CBSE PMT 1991; MP PMT 1994] Ba(OH )2 solution
(a) 10 4 (b) 10 10 [CPMT 2004]

(c) 10 2 (d) 10 12 (a) 12 (b) 13

183. The pH of an aqueous solution containing (c) 1 (d) 12.96
195. In a mixing of acetic acid and sodium acetate the
[H  ]  3  10 3 M is [MP PET 2001,04]
ratio of concentration of the salts to the acid is
(a) 2.471 (b) 2.523 increased ten times. Then the pH of the solution [KCET 200
(c) 3.0 (d) – 3
(a) Increase by one (b) Decreases by one
184. pH of blood is maintained constant by
(c) Decrease ten fold (d) Increases ten fold
mechanism of
196. The rapid change of pH near the stoichiometric
[MH CET 2002]
point of an acid-base titration is the basis of
(a) Common ion effect (b) Buffer
indicator detection. pH of the solution is related
(c) Solubility (d) All of these to ratio of the concentrations of the conjugate
185. The pH of normal KOH is [MP PET 1990]
acid (HIn) and base (In ) forms of the indicator by
(a) 1 (b) 0
the expression [CBSE PMT 2004]
(c) 14 (d) 7
 376 Ionic Equilibrium
[HIn] [In  ] (a) The conjugate base of H 2 PO 4 is HPO 42 
(a) log  pH  pK In (b) log  pH  pK In
[In ] [HIn] (b) pH  pOH  14 for all aqueous solutions

[In ] [HIn] (c) The pH of 1  10 8 M HCl is 8
(c) log  pK In  pH (d) log  pK In  pH
[HIn] [In  ] (d) 96,500 coulombs of electricity when passed
197. Which of the following statement(s) is(are) through a CuSO4 solution deposits 1 gram
correct equivalent of copper at the cathode
[IIT 1998] 204. The pH value of 0.1 M HCl is approximately 1.
(a) The pH of 1 . 0  10 8 M solution of HCl is 8 What will be the approximate pH value of 0.05
(b) The conjugate base of H 2 PO 4 is HPO 42  M H 2 SO 4
[MP PMT 1991]
(c) Autoprotolysis constant of water increases
(a) 0.05 (b) 0.5
with temperature
(c) 1 (d) 2
(d) When a solution of a weak monoprotic acid is
titrated against a strong base, at half 205. The K sp of Mg(OH )2 is 1  10 12 , 0 . 01 M Mg (OH ) 2 will
neutralization point pH  12 pK a precipitate at the limiting pH [DPMT 2005]
(a) 3 (b) 9
198. An aqueous solution of sodium carbnate has a pH
(c) 5 (d) 8
greater than 7 becaue [DCE 2003]
206. The pH of an aqueous solution having hydroxide
(a) It contains more carbonate ions than H 2 O
ion concentration as 1  10 5 is [MP PMT 1991]
molecules
(a) 5 (b) 9
(b) Contains more hydroxide ions than carbonate
(c) 4.5 (d) 11
ions
(c) Na  ions react with water
(d) Carbonate ions react with H 2 O
199. A pH of 7 signifies [CPMT 1974; DPMT 1982]
(a) Pure water (b) Neutral solution
(c) Basic solution (d) Acidic solution
200. Assuming complete dissociation, which of the 1. The K SP of AgI is 1 . 5  10 16 . On mixing equal
following aqueous solutions will have the same volumes of the following solutions, precipitation
pH value will occur only with
[Roorkee Qualifying 1998] [AMU 2000]
(a) 100 ml of 0.01 M HCl 7  19 
(a) 10 M Ag and 10 MI
(b) 100 ml of 0.01 M H 2 SO 4 (b) 10 8 
M Ag and 10 8
M I
(c) 50 ml of 0.01 M HCl
(c) 10 16 M Ag  and 10 16 M I 
(d) Mixture of 50 ml of 0.02 M H 2 SO 4 and 50 ml
(d) 10 9 M Ag  and 10 9 M I 
of 0.02 M NaOH
2. The strongest Bronsted base in the following
201. A buffer solution can be prepared from a mixture anion is
of
[IIT 1981; MP PET 1992, 97; MP PMT 1994; RPMT 1999;
[IIT 1999; KCET 1999; MP PMT 2002]
KCET 2000; AIIMS 2001; UPSEAT 2002;
(a) Sodium acetate and acetic acid in water AFMC 2002; Pb. CET 2004]
(b) Sodium acetate and hydrochloric acid in water
(a) ClO  (b) ClO 2
(c) Ammonia and ammonium chloride in water
(d) Ammonia and sodium hydroxide in water (c) ClO 3 (d) ClO 4
202. Which of the following will not function as a 3. Which one of the following compound is not a
buffer solution protonic acid
[Roorkee 2000] [CBSE PMT 2003]
(a) NaCl and NaOH (a) SO 2 (OH )2 (b) B(OH )3
(b) NaOH and NH 4 OH
(c) PO(OH )3 (d) SO (OH )2
(c) CH 3 COONH 4 and HCl
4. Calculate the hydrolysis constant of the salt
(d) Borax and boric acid containing NO2 . Given the K a for HNO 2
203. Which one of the following statements is not true
 4 .5  10 10
[AIEEE 2003]
 Ionic Equilibrium 377
[UPSEAT 2001] (a) 1 .0  10 5 (b) 1 .0  10 9
5
(a) 2.22  10 (b) 2 .02  10 5
(c) 1 .0  10 9 (d) 1 .0  10 14
5
(c) 4 .33  10 4
(d) 3.03  10 14. The pH of 0.1 M solution of the following salts
1
5. The molar solubility (mol L ) of a sparingly increases in the order [IIT 1999]
soluble salt MX 4 is ' s' . The corresponding (a) NaCl  NH 4 Cl  NaCN  HCl
solubility product is K sp . ' s ' is given in terms of (b) HCl  NH 4 Cl  NaCl  NaCN
K sp by the relation [AIEEE 2004] (c) NaCN  NH 4 Cl  NaCl  HCl
(d) HCl  NaCl  NaCN  NH 4 Cl
(a) s  (256 K sp )1 / 5 (b) s  (128 K sp )1 / 4
15. Which of the following is the strongest acid
(c) s  (K sp / 128 )1 / 4 (d) s  (K sp / 256 )1 / 5 [AMU 1999; MH CET 1999, 2002]
6. Electrophiles are [RPET 2000] (a) SO (OH )2 (b) SO 2 (OH )2
(a) Lewis acids (b) Lewis base (c) ClO3 (OH ) (d) PO(OH )3
(c) Bronsted acid (d) Bronsted base 16. The strongest of the four acids listed below is
7. Total number of moles for the reaction 2 HI ⇄ [NCERT 1984]
H 2  I2 . if  is degree of dissociation is[CBSE PMT 1996] (a) HCOOH (b) CH 3 COOH

(a) 2 (b) 2   (c) ClCH2 COOH (d) FCH2 COOH

(c) 1 (d) 1   17. Which equilibrium can be described as an acid-

base reaction using the Lewis acid-base definition
8. Which one is a Lewis acid [RPMT 1997]
but not using the Bronsted-Lowry definition[AIIMS 1980]
(a) ClF3 (b) H 2 O
(a) 2 NH 3  H 2 SO 4 ⇄ 2 NH 4  SO 42 
(c) NH 3 (d) None of these
(b) NH 3  CH 3 COOH ⇄ NH 4  CH 3 COO 
9. Heat of neutralisation of weak acid and strong
base is less than the heat of neutralisation of (c) H 2 O  CH 3 COOH ⇄ H 3 O   CH 3 COO 
strong acid and strong base due to [KCET 2002]
(d) [Cu (H 2 O)4 ]2   4 NH 3 ⇄ [Cu ( NH 3 )4 ]2   4 H 2 O
(a) Energy has to be spent for the total
dissociation of weak acid 18. The hydride ion H  is stronger base than its
(b) Salt of weak acid and strong base is not stable hydroxide ion OH  . Which of the following
reaction will occur if sodium hydride (NaH ) is
(c) Incomplete dissociation of weak acid
dissolved in water [CBSE PMT 1997]
(d) Incomplete neutralisation of weak acid
10. pKa values of two acids A and B are 4 and 5. The (a) H  (aq )  H 2 O  H 2 O

strengths of these two acids are related as[KCET 2001] (b) H  (aq )  H 2 O (l)  OH   H 2
(a) Acid A is 10 times stronger than acids B (c) H   H 2 O  No reaction
(b) Strength of acid A : strengtha of acid B  4 : 5
(d) None of these
(c) The strengths of the two acids can not be
compared 19. Dissociation constant of a weak acid is 1  10 4 .
Equilibrium constant of its reaction with strong
(d) Acid B is 10 times stronger than acid A
base is [UPSEAT 2003]
11. The dissociation constant of two acids HA1 and
(a) 1  10 4 (b) 1  10 10
4 5
HA 2 are 3.14  10 and 1 .96  10 respectively.
(c) 1  10 10 (d) 1  10 14
The relative strength of the acids will be
20. Arrange the acids (I) H 2 SO 3 (II) H3PO3 and (III)
approximately [RPMT 2000]
HClO3 in the decreasing order of acidity [UPSEAT 2001]
(a) 1 : 4 (b) 4 : 1
(a) I > III > II (b) I > II > III
(c) 1 : 16 (d) 16 : 1
(c) II > III > I (d) III > I > II
12. An aqueous solution of ammonium acetate is
21. Self-ionisation of liquid ammonia occurs as,
[NCERT 1980, 81; RPMT 1999]
2NH 3 ⇄ NH 4  NH 2 ; K  10 10 . In this solvent, an
(a) Faintly acidic (b) Faintly basic
acid might be [JIPMER 2001]
(c) Fairly acidic (d) Almost neutral
(a) NH 4
13. The dissociation constant of a weak acid is
1.0  10 5 , the equilibrium constant for the (b) NH 3
reaction with strong base is (c) Any species that will form NH 4
[MP PMT 1990]
 378 Ionic Equilibrium
(d) All of these 31. Which is neucleophile [DPMT 2001; RPMT 2002]
22. H f (H 2O)  X ; Heat of neutralisation of (a) BF3 (b) NH 3
CH 3 COOH and NaOH will be [BHU 2003] (c) BeCl 2 (d) H 2 O
(a) Less than 2X (b) Less than X 32. The solubility of CuBr is 2  10 4 mol /l at 25 C . The
(c) X (d) Between X and 2X K sp value for CuBr is [AIIMS 2002]
23. Which of the following oxides will not give OH  in
(a) 4  10 8 mol 2 l 2 (b) 4  10 11 mol 2 L1
aqueous solution [NCERT 1980]
(a) Fe2 O3 (b) MgO (c) 4  10 4 mol 2l 2 (d) 4  10 15 mol 2 l 2
33. A 0.004 M solution of Na2 SO 4 is isotonic with a
(c) Li2 O (d) K 2 O
0.010 M solution of glucose at same temperature.
24. A precipitate of CaF2 (K sp  1.7  10 10 ) will be The apparent degree of disociation of Na2 SO 4 is
obtained when equal volume of the following are [IIT JEE Screening 2004]
mixed (a) 25% (b) 50%
[MP PMT 1990, 95; IIT 1982; MNR 1992] (c) 75% (d) 85%
(a) 10 4 M Ca 2  and 10 4 M F  34. K sp for Cr(OH )3 is 2.7  10 31 . What is its solubility
(b) 10 2 M Ca 2  and 10 3 M F  in moles / litre. [JEE Orissa 2004]

(c) 10 5
M Ca 2
and 10 3
MF  (a) 1  10 8 (b) 8  10 8
(c) 1 . 1  10 8 (d) 0.18  10 8
(d) 10 3 M Ca 2  and 10 5 M F 
35. pK a of acetic acid is 4.74 . The concentration of
25. The degree of hydrolysis of a salt of weak acid
CH 3 COONa is 0.01 M. The pH of CH 3 OONa is
and weak base in its 0.1 M solution is found to be
50%. If the molarity of the solution is 0.2 M, the [Orissa JEE 2004]
percentage hydrolysis of the salt should be[AMU 1999] (a) 3.37 (b) 4.37
(a) 50% (b) 35% (c) 4.74 (d) 0.474
(c) 75% (d) 100% 36. If the solubility product of AgBrO3 and
5 5
26. The pH of 0.1 M solution of a weak monoprotic Ag 2 SO 4 are 5.5  10 and 2  10 respectively, the
acid 1% ionized is [UPSEAT 2001; Pb. PMT 2001] relationship between the solubilities of these can
(a) 1 (b) 2 be correctly represented as [EAMCET 1985]
(c) 3 (d) 4 (a) S AgBrO 3  S Ag 2SO 4 (b) S AgBrO 3  S Ag 2SO 4
27. Which one is the strongest acid (c) S AgBrO 3  S Ag 2SO 4 (d) S AgBrO 3  S Ag 2SO 4
[MH CET 1999; AMU 1999,2000;
37. The ionisation constant of phenol is higher than
Pb.CET 2001,03; MP PET 2001]
that of ethanol because [JIPMER 2002]
(a) HClO (b) HClO2
(a) Phenoxide ion is bulkier than ethanoxide
(c) H 2 SO 4 (d) HClO4 (b) Phenoxide ion is stronger base than
28. Which of the following is Lewis acid [Pb. CET 2000] ethanoxide
(a) S (b) : CH 2 (c) Phenoxide ion is stabilised through
delocalisation
(c) (CH 3 )3 B (d) All of these (d) Phenoxide ion is less stable than ethoxide
29. The solubility product of Mg (OH )2 is 1 .2  10 11 . The 38. A weak acid HX has the dissociation constant
solubility of this compound in gram per 100 cm 3
of 1  10 5 M . It forms a salt NaX on reaction with
alkali. The degree of hydrolysis of 0.1 M solution
solution is
of NaX is
[Roorkee 2000]
[IIT JEE Screening 2004]
4
(a) 1.4  10 (b) 8.16  10 4 (a) 0.0001% (b) 0.01%
(c) 0.816 (d) 1.4 (c) 0.1% (d) 0.15%
30. What is [H  ] of a solution that is 0.01 M in 39. In the equilibrium A   H 2 O ⇌ HA  OH 
HCN and 0.02 M in NaCN (K a  1 . 0  10 5 ) . The degree of hydrolysis of 0.001
10
(Ka for HCN  6.2  10 ) [MP PMT 2000] M solution of the salt is [AMU 1999]
3 4
(a) 3 .1  10 10 (b) 6 . 2  10 5 (a) 10 (b) 10
5
(c) 6 . 2  10 10 (d) 3 . 1  10 10 (c) 10 (d) 10 6
 Ionic Equilibrium 379
40. The sulphide ion concentration [S 2  ] in saturated (c) 2.8  10 9 ML1 (d) 2.5  10 7 ML1
H 2 S solution is 1  10 22 . Which of the following 47. The solubility product of a binary weak
sulphides should be quantitatively precipitated by electrolyte is 4  10 10 at 298 K . Its solubility in
H 2 S in the presence of dil. HCl mol dm 3 at the same temperature is [KCET 2001]
Sulphide Solubility Product (a) 4  10 5 (b) 2  10 5
(I) 1 . 4  10 16 (c) 8  10 10 (d) 16  10 20
(II) 1 .2  10 22 48. Solubility of AgCl at 20 C is 1 .435  10 3 gm per litre .
o

The solubility product of AgCl is

(III) 8 . 2  10 46
[CPMT 1989; BHU 1997; AFMC 2000; CBSE PMT 2002]
(IV) 5 . 0  10 34
(a) 1  10 5 (b) 1  10 10
(a) I, II (b) III, IV 5
(c) 1 .435  10 (d) 108  10 3
(c) II, III, IV (d) Only I 49. pK a value for acetic acid at the experimental
41. When equal volumes of the following solutions temperature is 5. The percentage hydrolysis of
are mixed, precipitation of AgCl (K sp  1.8  10 10 ) 0.1 M sodium acetate solution will be
will occur only with (a) 1  10 4 (b) 1  10 2
[IIT 1988; CBSE PMT PMT 1992; DCE 2000] 3
(c) 1  10 (d) 1  10 5
4  4 
(a) 10 M Ag and 10 M Cl 50. At 30 o C, the solubility of Ag 2 CO3 (K sp  8  10 12 )
5  5 
(b) 10 M Ag and 10 M Cl would be greatest in one litre of [MP PMT 1990]
(a) 0.05 M Na2 CO3 (b) 0.05 M AgNO3
(c) 10 6 M Ag  and 10 6 M Cl 
(c) Pure water (d) 0.05 M NH 3
(d) 10 10 M Ag  and 10 10 M Cl 
51. The values of K sp for CuS, Ag2 S and HgS are
42. K sp of an electrolyte AB is 1  10 10 . [ A  ]  10 5 M , 10 31
, 10 42
and 10 54
respectively. The correct
which concentration of B will not give order of their solubility in water is [MP PMT 2003]
precipitate of AB (a) Ag 2 S  HgS  CuS (b) HgS  CuS  Ag 2 S
[BHU 2003]
(c) HgS  Ag 2 S  CuS (d) Ag 2 S  CuS  HgS
6 5
(a) 5  10 (b) 1  10 52. The pH of a soft drink is 3.82. Its hydrogen ion
(c) 2  10 5 (d) 5  10 5 concentration will be [MP PET 1990]
43. One litre of water contains 10 7 mole hydrogen (a) 1 .96  10 2 mol / l (b) 1 . 96  10 3 mol / l
ions. The degree of ionization in water will be [CPMT 1985, 88,
(c)93]
1 .5  10 4 mol / l (d) 1 . 96  10 1 mol / l
7 9
(a) 1.8  10 % (b) 0.8  10 % 53. The pH of a solution at 25 C containing 0.10 m
7
(c) 3.6  10 % (d) 3.6  10 9% sodium acetate and 0.03 m acetic acid is (pKa for
44. If the solubility products of AgCl and AgBr are CH 3 COOH  4.57 ) [AIIMS 2002; BHU 2002]
1 .2  10 10 and 3 . 5  10 13 respectively, then the (a) 4.09 (b) 5.09
relation between the solubilities (denoted by the (c) 6.10 (d) 7.09
symbol ' S ' ) of these 54. A weak acid is 0.1% ionised in 0.1 M solution. Its
salts can correctly be represented as [MP PET 1994] pH is
(a) S of AgBr is less than that of AgCl [BVP 2004]
(a) 2 (b) 3
(b) S of AgBr is greater than that of AgCl
(c) 4 (d) 1
(c) S of AgBr is equal to that of AgCl
55. The solubility product of As 2 S 3 is 2 .8  10 72 .
6
(d) S of AgBr is 10 times greater than that of What is the solubility of As 2 S 3
AgCl
(a) 1 .09  10 15 mole / litre
45. If the solubility product of lead iodide (Pbl2 ) is
(b) 1 . 72  10 15 mole / litre
3 .2  10 8 , then its solubility in moles/litre will be [MP PMT 1990]
(c) 2 .3  10 16 mole / litre
(a) 2  10 3 (b) 4  10 4
(d) 1 . 65  10 36 mole / litre
(c) 1 .6  10 5 (d) 1 .8  10 5
46. Calculate the solubility of AgCl (s) in 0.1 M NaCl at 56. For a weak acid HA with dissociation constant
10 9 , pOH of its 0.1 M solution is [CBSE PMT 1989]
25 C. K sp ( AgCl)  2.8  10 10 [UPSEAT 2001]
(a) 9 (b) 3
(a) 3.0  10 8 ML1 (b) 2.5  10 7 ML1 (c) 11 (d) 10
 380 Ionic Equilibrium
57. The dissociation of water at 25 o C is 1.9  10 7% (a) 10.56 gm (b) 15 gm
and the density of water is 1 .0 g / cm .3
The (c) 12.74 gm (d) 16.25 gm
66. pH of a solution produced when an aqueous
ionisation constant of water is [IIT 1995]
solution of pH 6 is mixed with an equal volume
(a) 3.42  10 6 (b) 3.42  10 8
of an aqueous solution of pH 3 is about [KCET 2001]
14
(c) 1 .00  10 (d) 2 .00  10 16
(a) 3.3 (b) 4.3
58. What is the pH of 0.01 M glycine solution? For
(c) 4.0 (d) 4.5
glycine, Ka 1  4 . 5  10 3 and Ka 2  1 . 7  10 10 at 298
67. Calculate the H  ion concentration in a 1.00 (M)
K
[AIIMS 2004] HCN litre solution (K a  4  10 10 ) [Bihar CEE 1995]
(a) 3.0 (b) 10.0 (a) 4  10 14 mole / litre
(c) 6.1 (d) 7.2
(b) 2  10 5 mole / litre
59. The concentration of [H  ] and concentration of
[OH  ] of a 0.1 aqueous solution of 2% ionised (c) 2 .5  10 5 mole / litre
weak acid is (d) None of these
[Ionic product of water  1  10 14 ] 68. The number of moles of hydroxide (OH  ) ion in
[DPMT 2004; CBSE PMT 1999] 0.3 litre of 0.005 M solution of Ba(OH )2 is[JIPMER 2001]
(a) 2  10 3 M and 5  10 12 M (a) 0.0050 (b) 0.0030
(b) 1  10 3 M and 3  10 11 M (c) 0.0015 (d) 0.0075
(c) 0 .02  10 3 M and 5  10 11 M 69. The pH of pure water or neutral solution at 50 C
2 13 is …. (pKw  13 .26  13 . 26 at 50 C)
(d) 3  10 M and 4  10 M
[Pb. PMT 2002; DPMT 2002]
60. If solubility product of HgSO 4 is 6 .4  10 5 , then (a) 7.0 (b) 7.13
its solubility is [BHU 2004] (c) 6.0 (d) 6.63
(a) 8  10 3 mole / litre (b) 6.4  10 5 mole / litre 70. pH of 0.1 M solution of a weak acid (HA) is 4.50.
3 6 It is neutralised with NaOH solution to decrease
(c) 6.4  10 mole / litre (d) 2.8  10 mole / litre
61. At 298K a 0.1 M CH 3 COOH solution is 1.34% the acid content to half pH of the resulting
solution [JIPMER 2002]
ionized. The ionization constant K a for acetic acid
(a) 4.50 (b) 8.00
will be (c) 7.00 (d) 10.00
[AMU 2002; AFMC 2005]
71. If 50 ml of 0.2 M KOH is added to 40 ml of
(a) 1 .82  10 5 (b) 18 .2  10 5
0.5 M HCOOH , the pH of the resulting solution is
(c) 0 .182  10 5 (d) None of these
62. Hydrogen ion concentration of an aqueous (K a  1 . 8  10 4 ) [MH CET 2000]

solution is 1  10 4 M . The solution is diluted with (a) 3.4 (b) 7.5

equal volume of water. Hydroxyl ion (c) 5.6 (d) 3.75
concentration of the resultant solution in terms of 72. The Bronsted acids in the reversible reaction are
mol dm 3 is [KCET 2001] HCO 3 (aq .)  OH  (aq .) ⇄ CO 32  (aq .)  H 2 O [DPMT 2002]
(a) 1  10 8 (b) 1  10 6 (a) OH  and CO 32 
10 10
(c) 2  10 (d) 0 . 5  10
(b) OH  and H 2 O
63. Which one of the following is not a buffer solution
[AIIMS 2003] (c) HCO 3 and H 2 O
(a) 0.8 M H 2 S  0.8 M KHS
(d) HCO 3 and CO 32 

(b) 2 M C6 H 5 NH 2  2 M C6 H 5 N H 3 Br 73. A 0.1N solution of an acid at room temperature
(c) 3 M H 2CO3  3 M KHCO3 has a degree of ionisation 0.1. The concentration
(d) 0.05 M KClO4  0.05 M HClO4 of OH  would be [MH CET 1999]

64. The hydrogen ion concentration of a 0.006 M (a) 10 12 M (b) 10 11 M
(c) 10 9 M (d) 10 2 M
benzoic acid solution is (K a  6  10 5 ) [MP PET 1994]
74. Increasing order of acidic character would be[RPMT 1999]
(a) 0.6  10 4 (b) 6  10 4 (a) CH 3 COOH  H 2 SO 4  H 2CO3
(c) 6  10 5 (d) 3.6  10 4 (b) CH 3 COOH  H 2CO3  H 2 SO 4
65. Calculate the amount of (NH 4 )2 SO 4 in grams which
(c) H 2CO3  CH 3 COOH  H 2 SO 4
must be added to 500 ml of 0.200 M NH 3 to yield a
(d) H 2 SO 4  H 2CO3  CH 3 COOH
solution with pH  9 . 35 (Kb for NH 3  1 . 78  10 5 ) [UPSEAT 2001]
 Ionic Equilibrium 381
75. The correct order of increasing [ H 3 O  ] in the
following aqueous solutions is [UPSEAT 2000]
(a) 0.01 M H2S <0.01 M H2SO4 < 0.01 M NaCl
< 0.01 M NaNO2
(b) 0.01 M NaCl <0.01 M NaNO2 < 0.01 M H2S
< 0.01 M H2SO4
(c) 0.01 M NaNO2 <0.01 M NaCl < 0.01 M H2S
< 0.01 M H2SO4
(d) 0.01 M H2S < 0.01 M NaNO2 < 0.01 M NaCl
< 0.01 M H2SO4
76. A base dissolved, in water, yields a solution with
a hydroxyl ion concentration of 0 . 05 mol litre 1 . The
solution is
[CBSE PMT 2000]
(a) Basic (b) Acid
(c) Neutral (d) Either (b) or (c)
77. In the given reaction, the oxide of sodium is
 4 Na  O2  2 Na2 O 
….   [Orissa JEE 2002]
 Na2 O  H 2 O  2 NaOH 
(a) Acidic (b) Basic
(c) Amphoteric (d) Neutral
78. What is the pH of a 1M CH 3 COOH a solution K a of
acetic acid  1 .8  10 5.
K  10 14 mol 2 litre 2 [DPMT 2002]
(a) 9.4 (b) 4.8
(c) 3.6 (d) 2.4
 Ionic Equilibrium 379
8. Assertion : Sb (III) is not precipitated as
sulphide when in its alkaline
solution H 2 S is passed.
Reason : The concentration of S 2  ion in
alkaline medium is inadequate for
precipitation.
Read the assertion and reason carefully to mark the [AIIMS 2004]
correct option out of the options given below : 9. Assertion : Ionic reactions are not
instantaneous.
(a) If both assertion and reason are true and the Reason : Oppositely charged ions exert
reason is the correct explanation of the assertion. strong forces.
(b) If both assertion and reason are true but reason is
not the correct explanation of the assertion.
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
(e) If assertion is false but reason is true.
1. Assertion : pH of hydrochloric acid solution is
less than that of acetic acid solution
of the same concentration.
Electrical conductors, Arrenius theory and
Reason : In equimolar solutions, the number Ostwald’s dilution law
of titrable protons present in
hydrochloric acid is less than that 1 c 2 b 3 b 4 b 5 b
persent in acetic acid. 6 a 7 b 8 d 9 a 10 a
[NDA 1999]
11 c 12 d 13 b 14 b 15 d
2. Assertion : A ionic product is used fro any
types of electrolytes whereas 16 d 17 b 18 b 19 c 20 c
solubility product is applicable 21 a 22 c 23 b 24 d 25 c
only to sparingly soluble salts. 26 d 27 a 28 d 29 d 30 c
Reason : Ionic product is defined at any 31 b 32 c 33 c 34 c 35 a
stage of the raction whereas 36 c
solubility product is only appicable
to the saturation stage.
[AIIMS 2001] Acids and Bases
3. Assertion : A solution of FeCl3 in water
produce brown precipitate on 1 a 2 d 3 a 4 c 5 b
standing. 6 d 7 b 8 c 9 b 10 a
Reason : Hydrolysis of FeCl3 takes place in 11 a 12 c 13 a 14 d 15 d
water 16 b 17 b 18 d 19 a 20 b
4. Assertion : BaCO3 is more soluble in 21 d 22 b 23 b 24 c 25 d
HNO3 than in plain water. 26 c 27 c 28 d 29 b 30 b
Reason : Carbonate is a weak base and reacts 31 b 32 c 33 d 34 a 35 a
with the H  from the strong acid, 36 a 37 c 38 c 39 c 40 a
casuing the barium salt to 41 c 42 d 43 c 44 a 45 a
dissociate. 46 c 47 c 48 d 49 a 50 b
5. Assertion : CHCl 3 is more acidic than CHF3 . 51 b 52 a 53 a 54 a 55 d
Reason : The conjugate base of CHCl 3 is more 56 b 57 ab 58 a 59 c 60 d
stable than CHF3 . 61 a 62 b 63 b 64 b 65 a
6. Assertion : Addition of silver ions to a mixture 66 a 67 d 68 a 69 a 70 b
of aqueous sodium chloride and 71 b 72 d 73 b 74 d 75 b
sodium bromide solution will first 76 b 77 a 78 a 79 b 80 a
precipitate AgBr rather than AgCl . 81 d 82 b 83 b 84 d 85 bd
Reason : K sp of AgCl  K sp of AgBr .[AIIMS 2004] 86 a 87 d 88 a 89 d 90 c
7. Assertion : The pKa of acetic acid is lower than 91 a 92 a 93 a 94 d 95 b
that of phenol. 96 c 97 b 98 c 99 d 100 c
Reason : Phenoxide ion is more resonance 101 a 102 a 103 c 104 c 105 a
stabilized. [AIIMS 2004] 106 a 107 d 108 b 109 c 110 d
 380 Ionic Equilibrium
111 b 112 c 113 c 114 a 115 c 41 a 42 a 43 b 44 d 45 b
116 d 117 d 118 c 119 c 120 c 46 a 47 b 48 a 49 c 50 a
121 a 122 d 123 b 124 a 125 b 51 a 52 c 53 c 54 c 55 d
126 c 127 c 128 d 129 c 130 b 56 a 57 c 58 b 59 b 60 c
131 b 132 c 133 a 134 c 135 a
61 b 62 c 63 b 64 b 65 c
136 c 137 c 138 b 139 b 140 b
66 a 67 b 68 d 69 a 70 c
141 b 142 a 143 b 144 a 145 a
71 d 72 a 73 b 74 a 75 b
146 a 147 b 148 b 149 c 150 a
76 a 77 a 78 c 79 b 80 a
151 c 152 c 153 d 154 c 155 a
81 b 82 c 83 b 84 b 85 c
156 b 157 a 158 d 159 b 160 d
161 b 162 d 163 c 164 d 165 a 86 b 87 a 88 a 89 a 90 d
91 b 92 c 93 a 94 a 95 c
Common ion effect, Isohydric solutions, Solubility 96 b 97 b 98 b 99 b 100 b
product, Ionic product of water and Salt hydrolysis 101 c 102 c 103 a 104 a 105 c
106 a 107 c 108 c 109 d 110 b
1 b 2 c 3 b 4 b 5 b 111 d 112 d 113 b 114 a 115 c
6 d 7 c 8 a 9 c 10 a 116 d 117 b 118 b 119 d 120 c
11 b 12 b 13 a 14 d 15 d 121 d 122 b 123 c 124 d 125 b
16 b 17 c 18 c 19 d 20 c 126 b 127 a 128 c 129 b 130 d
21 d 22 d 23 d 24 b 25 a 131 c 132 d 133 c 134 c 135 a
26 d 27 a 28 d 29 b 30 b 136 c 137 c 138 c 139 c 140 b
31 a 32 d 33 a 34 c 35 d 141 b 142 a 143 d 144 b 145 b
36 b 37 b 38 c 39 b 40 a 146 d 147 c 148 b 149 a 150 d
41 a 42 d 43 b 44 a 45 b 151 b 152 d 153 b 154 b 155 c
46 d 47 b 48 c 49 c 50 c 156 d 157 c 158 a 159 c 160 d
51 b 52 d 53 a 54 d 55 c 161 c 162 d 163 b 164 a 165 d
56 d 57 b 58 c 59 d 60 c 166 a 167 d 168 b 169 c 170 a
61 b 62 b 63 a 64 bc 65 d 171 c 172 c 173 d 174 b 175 a
66 a 67 d 68 a 69 d 70 c 176 c 177 a 178 c 179 a 180 b
71 c 72 d 73 d 74 d 75 a 181 c 182 b 183 b 184 b 185 c
76 c 77 b 78 d 79 b 80 d 186 b 187 b 188 a 189 a 190 b
81 c 82 c 83 d 84 c 85 d 191 d 192 b 193 b 194 b 195 a
86 d 87 b 88 c 89 b 90 a 196 b 197 b 198 b 199 a 200 ad
91 a 92 a 93 c 94 c 95 a 201 ac 202 a bc 203 c 204 c 205 b
96 d 97 d 98 b 99 b 100 ab 206 b
101 d 102 c 103 c 104 a 105 c
106 c 107 c 108 a 109 b 110 b Critical Thinking Questions
111 b 112 a 113 a 114 a 115 b
116 a
1 b 2 a 3 b 4 a 5 d
6 a 7 c 8 a 9 a 10 a
Hydrogen ion concentration - pH scale and 11 b 12 d 13 c 14 d 15 c
Buffer solution
16 d 17 d 18 b 19 b 20 d
21 a 22 b 23 a 24 b 25 a
1 a 2 c 3 d 4 b 5 b
26 c 27 d 28 d 29 b 30 d
6 d 7 a 8 c 9 b 10 d
31 b 32 a 33 c 34 a 35 a
11 a 12 d 13 c 14 a 15 b
36 b 37 c 38 b 39 a 40 b
16 d 17 b 18 c 19 c 20 d
41 a 42 a 43 a 44 a 45 a
21 b 22 c 23 a 24 d 25 b
46 c 47 b 48 b 49 b 50 c
26 a 27 a 28 d 29 b 30 b
31 d 32 b 33 a 34 a 35 c 51 d 52 c 53 b 54 c 55 a

36 c 37 c 38 a 39 a 40 d 56 d 57 d 58 c 59 a 60 a
 Ionic Equilibrium 381
61 a 62 c 63 d 64 b 65 a 17. (b) The degree of ionisation of a solute depends
66 a 67 b 68 b 69 d 70 b
upon its nature, concentration, and
temperature.
71 a 72 c 73 a 74 c 75 c
18. (b) Mathematical form of Ostwald’s dilution law.
76 a 77 b 78 a 19. (c) It is a weak electrolyte because it’s ionization
is very less.
20. (c) When we add NH4 OH in NH4 Cl solution
Assertion & Reason
ionization of NH4 OH is decreased due to
common ion effect.
1 c 2 b 3 a 4 a 5 a
21. (a) BaCl2 ⇌ Ba 2  + 2 Cl 
6 c 7 c 8 a 9 e
Initially 1 0 0
After dissociation a    2
Total = 1      2  1  2
1 .98  1 0 .98
   0 .49
 
for a mole   0.49
0 .49
For 0.01 mole    49
0 .01
Electrical conductors, Arrhenius theory and 22. (c) It is an ionic salt.
Ostwald's dilution law
23. (b) Due to common ion effect of H  .

1. (c) C12H 22O11 is a sugar and non-electrolyte. 24. (d) Current does not affect the degree of
ionization.
2. (b) It is a weak electrolyte since it is slightly
25. (c) Polar solvent facilitate ionisation of strong
ionized.
electrolytes due to dipole-ion attraction.
3. (b) It is a weak electrolyte since slightly ionized.
4. (b) Because the degree of dissociation is inversely 26. (d) HA ⇌ H   A 
proportional to the concentration of the
K  Ca 2  0.1  (10 4 )2  10 9
electrolyte.
5. (b) Electrolytes are those substances which on 28. (d) Degree of dissociation  = ?
dissolving in water give ions. 1
2 Normality of solution = 0.1 N  N
 2C 0 . 01  0 . 01  10
6. (a) K  ;   1  K   2C    1
1  100  100  Volume = 10 litre
8
 1  10 . Dissociation constant K  1  10 5
7. (b) As NaCl ionises completely to yield free ions.
2
8. (d) CH 3COONa ⇌ CH 3 COO   Na  K ;   KV  1  10 5  10 ;   1  10 2
V
H 2 O ⇌ H   OH 
29. (d) MgCl2 ⇌ Mg    2Cl  in aqueous solution it is
CH3COOH  NaOH
dissociated into ions.
9. (a) NaCl , being a salt, is a strong electrolyte.
10. (a) We can determine by measurement of very 30. (c) Ostwald’s dilution formula is  2  K(1   ) / C
dilute HF solutions. but for weak electrolyte  is very small. So
11. (c) According to the Ostwald’s dilution formula that (1   ) is neglected for weak electrolytes.
K(1   ) So for weak electrolyte the dilution formula is
2  . But for weak electrolytes  is
C K
 .
very small. So that (1   ) can be neglected. So C
Ka  32 
2
that   . 31. (b) Ka  C  2  0 .2     2 .048  10  4 .
C
 100 
12. (d) Arrhenius proposed the theory of ionisation.
13. (b) higher the dielectric constant of a solvent 32. (c) H2SO4 ⇌ H   H  SO 4 ⇌ H   SO 4 
more of its ionising power. Because of it is completely ionised.
14. (b)   dilution of solution. 33. (c) Colour of electrolyte depends on the nature of
15. (d) Generally ionic compound are conduct both ions.
electricity in fused state.
16. (d) According to Ostwald’s dilution law because e.g. CuSO4 is blue because Cu 2  ions are blue.
degree of ionization is directly proportional to
the dilution.
 382 Ionic Equilibrium
34. (c) Ionisation depends upon dilution, when 24. (c) Because it is a electron pair acceptor it’s
dilution increases then ionisation is also central atom have a vacant d-orbital.
increased. 25. (d) HClO4 is a acid and their conjugate base is
35. (a) More is K a , lesser is pKa (pKa   log Ka ) more
ClO 4 .
is acidic strength.
26. (c) It is completely ionised because their
ionization is very high.
Acids and Bases 27. (c) NaHCO3 in water is alkaline in nature due to
hydrolysis of HCO 3 ion. NaCO3 ⇌ Na   HCO 3
1. (a) CO doesn’t have a vacant d-orbital.
28. (d) In this reaction H 2 O acts as a acid.
2. (d) HClO4  H2O ⇌ H 3 O   ClO 4
29. (b) The basic character of hydride decreases
Conjugate acid and base pair
down the group.
3. (a) FeCl3  3 H 2O ⇌ Fe (OH )3  3 HCl . Strong acid 30. (b) Its ionization is very less.
and weak base. 32. (c) Hydrolysis of Cu 2  produces H ions in
4. (c) Na2CO3  2 H 2O ⇌ 2 NaOH  H2CO3 solution.
5. (b) Those substance accept the proton are called Cu 2   2 H 2 O  Cu (OH )2  2 H 
Bronsted base and which is donate the proton 33. (d) Both possess the tendancy to accept proton.
are called Bronsted acid.
34. (a) HF does not give proton easily.
HCO 3  H  ⇌ H2CO3 Bronsted base.
35. (a) In weak electrolyte the degree of dissociation
HCO 3 ⇌ H   CO 3  Bronsted acid. is very small. So it increases with increasing
dilution.
7. (b) The value of pK a for strong acid is less.
36. (a) Because it is a electron pair acceptor.
8. (c) Because it is a salt of strong base and weak I step
acid. 37. (c) H3 PO4 H   H 2 PO 4
9. (b) Because it is conjugate base of weak acid. II step
H 2 PO 4 H   HPO 4 
 
CH 3 COOH ⇌ CH 3 COO  H . III step
HPO 4  H   PO 4  

11. (a) Those compound which accept H is called
38. (c) Na2 HPO4 on hydrolysis of HPO 42  ion produces
bronstad base NO 3 accept H  and form
HNO3 . So it is a base. free OH  ion in solution.
39. (c) H2SO4 ⇌ H   HSO 4 .
13. (a) Larger the size of halogen atom less is the
back donation of electrons into empty 2p 40. (a) Fe 3   3 H 2 O  Fe (OH )3  3 H 
orbital of B. 
41. (c) H 2 PO4 ⇌ H   HPO42 action.
14. (d) H 2O  NH 3 ⇌ NH 4   OH  Conjugate acid

16. (b) NH 2 ⇌ NH 2  H  42. (d) H   OH  ⇌ H 2 O, it is a neutralization reaction.

Conjugate acid, base pair. 43. (c) It is a conjugate base of the strong acid.
17. (b) Those substances which lose proton are called 44. (a) Because those acid have higher pKa value are
acid. weak acid.
e.g. strong acid have a strong tendency to 45. (a) Conjugate acid is obtained from the base by
donate a proton. gain of H  .
18. (d) Electron donating species called nucleophile. 46. (c) CH 3 COOH is weak acid shows dissociation
NH 3 have a lone pair of electron.
equilibrium as CH 3 COOH ⇌ CH 3 COO   H 
19. (a) H 2 O acts as acid as it provides H  to NH 3 . 1
47. (c) pKa  log10
 
20. (b) CH3COOH  HF ⇌ CH 3 COOH 2  F . HF gives Ka

H 
to the CH 3 COOH . So it is a conjugate base 48. (d) A weak acid and strong base.
49. (a) In NaH2 PO2 both hydrogen are bonded with
of HF.
‘P ,’ so it is not replaceable.
22. (b) Ba(NO3 )2 does not undergo hydrolysis.
50. (b) Aqueous solution of Na2CO3 is alkaline due to
23. (b) H2SO4 is a mineral acid.
hydrolysis of CO 3  .
 Ionic Equilibrium 383
51. (b) Because they give CO 3  in solution. 73. (b) Because it is a salt of strong acid and strong
base.
2  0.2 M
52. (a) M.eq. of 0.2M H 2 SO 4   100  0 .04 H  (aq)  Cl  (aq)  Na  (aq)  OH  (aq) ⇌
1000
m/l
0.2 H 2 O(l)  Na  (aq)  Cl 
M.eq. of .2M NaOH   100  0 .02 m/l
1000 74. (d) CCl4 is not a Lewis or bronsted acid. It does

left [H ]  .04  .02  .02 . not contain H  .

Total volume  200 

.02
 .0001  10  4 M 75. (b) NH 4 Cl  H 2 O ⇌ NH 4 OH  HCl . So it is
Weak base Strong acid
200
pH  4 . acidic in nature.
76. (b) Cu(II) complexes are blue. The four water
53. (a) H 3 BO 3 is a weak monobasic acid it does not
molecules are attached with secondary
act as a H  donor but behaves as a Lewis acid. valencies of the metal atom e.g.
54. (a) Because SnCl 2 is a electron acceptor according [Cu(H 2 O)4 ] SO 4 . H 2 O .
to Lewis concept. 77. (a) The species which can accept as well as
55. (d) ROH is a Lewis base because it has an lone donate H  can act both as an acid and a base.
pair of electron. HSO 4  H  ⇌ H 2 SO 4
 
56. (b) H 2 SO 4  2 H 2 O ⇌ 2 H 3 O  SO 4
base

HSO 4 ⇌ SO 42   H 
 
NaOH ⇌ Na  OH acid

1 mole of H 2 SO 4 acid gives 2 moles of 78. (a) NH 4 is the weakest acid. So its conjugate base
H 3 O  ions. So 2 moles of OH  are required is strongest.
for complete neutralization. 79. (b) Ag  is an electron deficient compound and
57. (ab) Diprotic solvents give hence is a Lewis acid.
2 H  ions or OH  ions. 80. (a) H 3 PO 4 ⇌ H   H 2 PO 4
Conjugate acid
58. (a) N NaOH  1  1  1 N
81. (d) HS 2 O 8 ⇌ H   S 2 O 8 
N H 2SO 4  2  10  20 N Conjugate acid Conjugate base

M.eq. of NaOH  1  100  100 82. (b) PH3 donates electron pair to BCl 3 .
M.eq. of H 2 SO 4  20  10  200 83. (b) The conjugate base of weak acid is a strong
base.
Thus M.eq. of acid are left and therefore pH<
7, so the resulting mixture will be acidic. 84. (d) OH   O 2  H 
Conjugate base of OH 
60. (d) PH 3 is a Lewis base. 85. (bd) Presence of lone pair of electron and they
61. (a) Because of CH 3 COONa is a salt of weak acid donate two electron pairs.
and strong base. 86. (a) On increasing oxidation number Acidic strength
increases.
62.  H
(b) Acid 

 conjugate base. 87. (d) H 3 PO4 is shows +5 maximum oxidation state.

Base  H 
 conjugate acid. 88. (a) C 2 H 5 is a strongest base.
63. (b) HCl  Cl  89. (d) NaOCl is a mixture of strong base and weak
Acid Base
acid.
65. (a) HClO 4  H 2 SO 4  HCl  HNO 3 .
Aciedic character decreases
90. (c) NH 4 OH gives minimum OH  ion. So it is a
weak base.
66. (a) Those substances which accept the H  are
called conjugate base. 91. (a) Solution become acidic and methyl orange act
67. (d) NH 3 is a Lewis base, which donate a lone pair on acidic pH.
of electron. 92. (a) Larger is bond length, more is acidic nature
(for halogen acids). HF bond length is small.
69. (a) FeCl3  3 H 2 O ⇌ Fe(OH )3  3 HCl . Strong acid
93. (a) HCl is accepting proton in HF medium and
have less than 7 pH.
acts as weak base.
70. (b) It donates their e  pair. 95. (b) For oxoacids of the same element, the acidic
71. (b) The strength of the acid will depend upon the strength increases with increase in the
proton donation. oxidation number of that element.
 384 Ionic Equilibrium
1 3 5 7 Al (OH )3  H 2 SO 4
HClO  HClO2  HClO3  HClO4 Weak base Strong acid
Neutralization
96. (c) Because their conjugate base and conjugate 132. (c) NaOH  HCl NaCl H 2 O
Reaction Salt
acids are strong.
133. (a) Conjugate acid is obtained from the base by
97. (b) HCl is a strong acid and their conjugate base
is a very weak base. gain of H  .
134. (c) KCl is a ionic compound .
100. (c) NH 3 ⇌ NH 2  H 
135. (a) H 3 BO 3  H 2 O ⇌ [B(OH ) 4 ]   H 

101. (a) H 2 SO 4 ⇌ H   HSO 4 ⇌ H   SO 4
H 3 BO 3 is a weak monobasic acid if does not
HSO 4 is conjugate base. But it is also an acid act as a H  donor but behaves as a Lewis
 acid.
because it lose H .
102. (a) BF3 is a Lewis acid because ‘B’ has incomplete 136. (c) Because it is not accept the proton.
octet. 137. (c) NH 4 Cl is a salt of weak base ( NH 4 OH )and
strong acid (HCl).
104. (c) H 3 O  , however it exists as H 9 O 4 .
138. (b) Because it accept electron pair from the PH 3
105. (a) Al 2 (SO 4 )3 is a salt of weak base Al 2 (OH )3 and
139. (b) NH 4 ⇌ NH 3  H 
strong acid H 2 SO 4 .
141. (b) Hydrolysis of Fe 3 
106. (a) Al    of AlCl3 undergoes hydrolysis.
Fe 3   3 H 2 O  Fe (OH ) 3  3 H 
107. (d) H 2 SO 4 ⇌ H   HSO 4
142. (a) According to the Lewis concept.
109. (c) Conjugate base of H 2 SO 4 is HSO 4 . 143. (b) Conjugate base is obtained from the acid by
110. (d) Presence of lone pair. loss of H  .
111. (b) According to Bronsted principle HNO 3 is acid 144. (a) BF3 accept electron pair from NH 3 so it is
Lewis acid.
they give H  in aqueous solution and form
145. (a) CH 4 has almost no acidic nature and thus
NO 3 .
CH 3 is strongest base.
112. (c) H 2 O  H 2 O ⇌ H 3 O   OH  .
146. (a) CuSO 4 is a salt of weak base, (Cu(OH ) 2 ) and
113. (c) NH 4 is a conjugate acid;
strong acid (H 2 SO 4 ) .
NH 4 ⇌ NH 3  H  147. (b) Weak acid consists of highest pK a value and
114. (a) AlCl3  3 H 2 O ⇌ Al (OH ) 3  3 HCl strongest acid consist of less pK a value.
Stron acid

116. (d) HCl is a strong acid its conjugate base means
Cl  is a weak base.
117. (d) Hydrazoic acid (HN 3 ) is a Lewis acid.
118. (c) Smaller the pK a value than. Stronger the acid.
120. (c) BF3 is acidic because due to Lewis concept it
accept a lone pair of electron.
122. (d) Because it is a weak electrolyte.
126. (c) AlCl3 and SO 2 both are example of Lewis
theory.
127. (c) Na 2 CO3  2 H 2 O ⇌ 2 NaOH  H 2 CO 3 . It is a
strong base and weak acid so it is a basic.
129. (c) H 2 O  NH 3 ⇌ NH 4  OH  .
Acid base
In this reaction H 2 O acts as acid because it
donate a proton.
130. (b) H 2 SO 4  H 2 O ⇌ H 3 O   HSO 4
Conjugate acid and base
3 2
2 (SO 4 )3 ⇌ 2 Al
131. (b) Alpair  3 SO 4
149. (c) Because it gain and also lose the proton
H 2 O  H 2 O ⇌ H 3 O   OH 
150. (a) H 2 O  H 2 O ⇌ H 3 O   OH 
151. (c) HBr  H 2 O ⇌ H 3 O   Br 
152. (c) Because both are strong acid and strong base.
153. (d) LiAlH4 is a nucleophilic and capable of
donating electron pair, thus acts as a Lewis
base.
154. (c) The solvent which neither accept proton nor
donates.
155. (a) Because of F  is a highly electronegative. So it
is easily lose the electron and reaction occur
rapidly.
156. (b) Strong acid can be used titrate both strong
and weak base.
159. (b) For a weak acid value of pKa will be vary
high but in case of strong acid value of pKa
will be vary low.
160. (d) Boron halides behave as Lewis acid because of
their electron deficient nature eg., as
 Ionic Equilibrium 385
F 11. (b) CaF2 ⇌ Ca   2 F  ; K sp  4S 3
(S ) 2
(2 S )
(Deficiency of two electron for inert
B configuration) 12. (b) Due to common ion effect.
F F 13. (a) Ag 2 CrO4 ⇌ [2 Ag  ]  [CrO 4  ]
161. (b) Gaseous HCl does not give H  but liquid HCl
gives H  in aquous solution there for gaseous Hence K sp  [ Ag  ]2 [CrO4  ]
HCl is not a Arrhenius acid due to covalent
14. (d) K sp for CaF 2  4 s 3  4  [2  10 4 ]3  3.2  10 11 .
bonding in gaseous condition.
162. (d) H 2 O  H   OH  [Acid due to donation of 15. (d) The concentration of S 2  ions in group II is
Acid lowered by maintaining acidic medium in the
proton] presence of NH 4 Cl . The ionization of H 2 S is
H 2 O  H   H 3 O  [Basic due to gaining of supressed due to common ion effect. So the
Base ionic product is less than solubility product.
proton]
16. (b) NH 4 Cl is hydrolysed and give [H  ]
163. (c) F  strongest conjugate base due to it smallest
size in a group and gain proton due to most NH 4 Cl  H. OH ⇌ NH 4 OH  HCl
electronegative capacity. 
NH 4  H . OH ⇌ NH 4 OH  H 
 
H  F  HF
17. (c) FeCl3 is a salt of weak base (Fe(OH )3 ) and
164. (d) H 2 PO 4  H   HPO 42 
Conjugate acid Conjugate base strong acid (HCl).
18. (c) For the precipitation of an electrolyte, it is
165. (a) HSO 4 H  SO 42 
Conjugate acid Conjugate base necessary that the ionic product must exceed
its solubility product.
Common ion effect, Isohydric solutions, Solubility 19. (d) K sp  [ Ag  ]2 [Cro 4  ]  [2S ]2 [0.01]
product, Ionic product of water and Salt hydrolysis
= 4 S 2 [0.01]  4[2  10 8 ]2  0.01  16  10 18 .
20. (c) Complex salts contain two different metallic
1. (b) Solubility of Al 2 (SO 4 )3
elements but give test for only one of them.

Al 2 (SO 4 )3 ⇌ 2 Al     3 SO 4 e.g. K 4 Fe(CN )6 does not give test for Fe 3  ions.
K sp  [ Al 3  ] 2 [SO 42  ]3 21. (d) 10 3 N KOH will give [OH  ]  10 2 M
2. (c) Due to common ion effect. pOH  2
3. (b) MX 2 ⇌ M 2   2 X 
S 2S  pH  pOH  14 , pH  14  2  12
K sp  (2S )2 (S )  4 S 3 22. (d) It is FeSO 4 (NH 4 )2 SO 4 . 10 H 2 O .

K sp 4  10 12 23. (d) Salt of a strong base with a weak acid.

 S 2 3 3  1 .0  10 4 M . 24. (b) NH 4 CN is a salt of weak acid and weak base
4 4
5. (b) MX 2 ⇌ M   2 X  ; K sp  4S 3 and thus for it
2 (S ) (2 S ) 25. (a) Because it is a salt of strong base with a weak
acid.
K sp 1  10 11
S 3 3  1 .35  10  4 26. (d) Because CCl4 is a organic solvent and AgNO3 is
4 4
insoluble in organic solvent.
8. (a) Mg(OH )2 ⇌ Mg    2 OH2 
(X ) (2 X )
27. (a) SnS 2 ⇌ Sn 4   2S 2 
K sp  4 X 3
K sp  [Sn 4  ] [S 2  ] 2
 
9. (c) BaSO 4 ⇌ Ba  SO
(S ) (S )
4 28. (d) It does not dissociate much or its ionization is
0 . 01 5 very less.
Ksp  S 2  S  S  0.01  S 29. (b) NaHCO 3 has one replaceable hydrogen.

K sp 1  10 9 30. (b) CaOCl 2 has two anions Cl  and OCl  along

S (SO 2  )    10 7 mole/litre
4 S (Ba   ) 0.01 with Ca 2  ions.

(a) AB 2 ⇌ A   2 B 5 4  10 9
10. 31. (a) K sp  4 S 3 , S3   10 9
110  5 210 4
K sp  [1  10 ] [2  10 5 ]2  4  10 15
5
S  10 3 M .
 386 Ionic Equilibrium
32. (d) Be(OH )2 has lowest solubility and hence AgI ⇌ Ag   I 
lowest solubility product. Common ion
NaI ⇌ Na   I 
33. (a) Because it is a salt of strong acid and strong
base. 48. (c) K sp of BaSO 4  1 .5  10 9 ; Ba    0 .01 M
 
34. (c) NH 4 OH ⇌ NH 4  OH
1.5  10 9
 
SO 4    1.5  10 7
NH 4 Cl ⇌ NH 4  Cl
Common ion 0.01
49. (c) AgCrO4 ⇌ 2 Ag   CrO 4
( 2 S )2 S
35. (d) It is a less ionic, so that least soluble in water.
K sp  4S 3 given 2 S  1 .5  10 4
36. (b) pH of 9 means the salt solution should be
fairly basic. K sp  (2S )2  S
 
37. (b) CH 3 COOH ⇌ CH 3 COO H
 1 . 5  10 4 
  (1 . 5  10 4 )2     1.6875  10 12

On adding CH 3 COONa , [H ] decreases.  2 
38. (c) 0.01 M CaCl2 gives maximum Cl  ions to keep 50. (c) PbCl2 ⇌ Pb 2   2Cl 
S S
K sp of AgCl constant, decrease in [ Ag  ] will be
K sp of PbCl 2  [Pb 2  ]  [Cl  ] 2 ; K sp  S  (2S ) 2
maximum.
39. (b) Due to the common ion effect. K sp K sp
K sp  S  4S 2  4 S 3 ; S 3  ; S  3
40. (a) K sp  4 s 3 4 4
 
51. (b) AgCl ⇌ [ Ag ] [Cl ] ; K sp  S  S ; K sp  S 2
K sp 1 .0  10 6
S 3 3  6 .3  10 3 .
4 4 S  K sp  1.44  10 4  1 .20  10 2 M.
42. (d) K w increases with increase in temperature.
52. (d) By formula BA 2  B   2 A 
43. (b) It contains two cations and one anion.
K sp  4 x 3
44. (a) HgSO 4 of K sp  S 2

53. (a) AgCrO4  2 Ag   CrO 4
5 3
S  K sp ; S  6.4  10 ; S  8  10 m/l. S 2S S

K sp  (2S )2 S  4 S 3
45. (b) The solubility of BaSO 4 in g/litre is given
2 .33  10 3
1 1
 K sp  3  32  10 12 3
S       2  10 4 M.
W 2 .33  10 3   
 in mole/litre. n   1  10 5   4   4 
m . wt 233
54. (d) Common ion effect is noticed only for weak
Because BaSO 4 is a compound electrolyte dissociation. H 2 SO 4 is strong

K sp  S 2  [1  10 5 ]2  1  10 10 electrolyte.
55. (c) When we added barium ion in chromate ion
46. (d) AgCl ⇌ Ag   Cl  solution we obtained yellow ppt of BaCrO4 .
a a a

BaCl2  K 2 CrO4  BaCrO4   2 KCl

NaCl ⇌ Na   Cl  Yellow ppt.
0 .02 0 . 02 0 . 02

56. (d) AB is a binary electrolyte.

K sp AgCl  1.20  10 10
S  K sp  1 . 21  10 6  1 . 1  10 3 M
K sp AgCl  [ Ag  ] [Cl  ]  a  [a  0 .2]  a 2  0 .2a
57. (b) Precipitation occurs when ionic product >
a 2 is a very small so it is a neglected. solubility.
K sp AgCl  0.2a 58. (c) For a binary electrolyte, so that

1 .20  10 10  0 .2a Ksp  S  S  S 2

1.20  10 10 S  K sp .
a  6  10 10 mole
0.20
61. (b) CH 3 COONa is a salt of weak acid and strong
47. (b) Solubility is decreased due to common ion
base. Hence its aqueous solution is alkaline.
effect.
 Ionic Equilibrium 387
62. (b) BaSO 4 ⇌ Ba 2   SO 4  OH   H  ⇌ H 2 O . So that S 2  is increased.
Solubility constant  S  S 81. (c) BaSO 4 ⇌ Ba 2   SO 42 
1.5  10 19  S 2 ; S  1.5  10 19 ; S  3 .9  10 5
K sp  S 2  S  K sp ; K sp  [Ba 2  ]  [SO 42  ]
 
65. (d) Ca(OH )2 ⇌ Ca  2OH
(S ) ( 2 S )2
4  10 10  [1  10 4 ]  [SO 42  ]
K sp  4 S 3
 4  3  3  3  12 3
4  10 10
66. (a) Due to common ion effect. [SO 42  ]   4  10 6 .
1  10  4
67. (d) PbCl2 ⇌ Pb 2   2Cl 
2 (S ) (2 S ) 82. (c) AB 2 ⇌ A 2   2 B 
(S ) 2
(2 S )
K sp  4 S 3  4  (2  10 2 )3  3.2  10 5
K sp  4S 3

 
68. (a) Ag 2 S ⇌ 2 Ag  S
K sp 4  10 12
S 3 3  1  10 4 gm . mol / litre
K sp  4S 3 4 4
K sp 3 .2  10 11 K sp AB 1  10 8
S  3 3  2  10 6 83. (d) [B]    1  10 5 M
4 4 [ A] 10 3
Where ionic product > K sp , ppt formed
69. (d) CaCO3 ⇌ Ca    CO 3 
S
 8 should be more then 10 5 M .
S S

Solubility product of CaCO3

84. (c) NaCl(s) ⇌ Na(aq )  Cl(aq )
K sp  S ; S  K sp
2
HCl ⇌ H   Cl  . The increase in [Cl  ] brings in
It is a binary electrolyte. an increase in [ Na  ] [Cl  ] which will lead for
S 2  K sp ; (3.05  10 4 )2  K sp ; K sp  9.3  10 8 backward reaction because

71. (c) PbCl2  Pb   2Cl  K sp (NaCl)  [ Na  ] [Cl  ]

S 2S
means Ionic product  K sp
K sp  S  (2S )  [6.3  10 3 ]  [12 .6  10 3 ]2 .
2

85. (d) BaSO 4 ⇌ Ba    SO 4 

72. (d) A salt of strong acid and strong base cannot be (S ) (S )
hydrolysed. In this case the equilibrium
cannot shifted towards the backward. K sp  S 2 ; S  K sp  1 . 3  10 9
73. (d) If we mixed any substance into the solution.
 3 .6  10 5 mol / litre
Then the value of pH is increased these
substance is a salt of weak acid and strong 87. (b) Alkaline,
base. CH 3 COONa  H 2 O ⇌ CH 3 COOH  NaOH
Weak acid Strong base
74. (d) It is a salt of strong base and weak acid.
88. (c) Because it is a strong base.
75. (a) K sp  4 s 3  4  [2.5  10 2 ]3  62 .5  10 6 .
89. (b) For pure water [H  ]  [OH  ] ,  K w  10 12 s
Na   Cl 
76. (c) NaCl ⇌ 90. (a) MX 2 ⇌ M 2   2 X  ; 4 S 3  4  (0.5  10 4 )3
S S 2
(S ) (2 S )

13
K sp  S , S  K sp  36  6 .
2
 5  10
91. (a) Solubility coefficient  [Pb 2  ] [Cl  ]2
78. (d) PbI2 ⇌ Pb    2 I 
S 2S
K sp 92. (a) Solubility of Al(OH )3 is lesser than Zn(OH )2 .
K sp  4 S 3  4  [2  10 3 ]3  32  10 9 . 93. (c) NaCl(s) ⇌ Na  (aq )  Cl (aq )
79. (b) When ionic product is greater than K sp then
HCl ⇌ H   Cl 
precipitation occur The increase in [Cl  ] brings in an increase in
K sp  10 2 M Ca 2   10 3 M F  [ Na  ] [Cl  ] which will lead for backward
2  
80. (d) In IVth
group the S concentration increase reaction because K sp NaCl  [ Na ] [Cl ] .
when added the NH 4 OH because
94. (c) Common ion effect.
NH 4 OH ⇌ NH 4  OH  95. (a) CaF2 ⇌ Ca    2 F2
S S (2 S )
H 2 S ⇌ 2 H   S 2
 388 Ionic Equilibrium
K sp  4S 3 112. (a) AX 2  A  2 X
x 2x
K sp 3 .2  10 11 3 . 2  10 11
S 3 3  2  10 4 m/l. K sp  4 x 3 ; x 3 ;
4 4 4
96. (d) In aqueous solution following euilibrium is x  2  10 4 mole/litre.
exist. H 2 S ⇌ H   HS 
113. (c) C6 H 5 COONH 4  C6 H 5 COO   NH 4
While adding the dilute HCl solution .25 .25 .25
0 .5 
(HCl ⇌ H   Cl  ) equilibrium is shift to the left 100 100 100
side in H 2 S ⇌ H   HS  According to Ostwald dilution law.
 2C  .25 
97. (d) M 2 X 3 ⇌ 2 M    + 3 X   K    
K sp
2 3
(2 y ) (3 y ) 1   100 
d
Solubility product K sp  108 y 5 mol
K   2C  1    Very small 
m3 .25 .25
K   .5 ; K  3.125  10 6
98. (b) Solubility is directly proportional to the K sp . 100 100
99. (b) PbCl2 ⇌ Pb   2Cl  114. (a) Sb 2 S 3  2 Sb 2  3 S   ; K sp  (2 x )2 .(3 x )3
S S (2 S )2 2x 3x
K sp  S  (2S )2  4 S 3 Ksp  108 x 5 ; K sp  108  (1  10 5 )5  108  10 25 .
K sp 1 .5  10 4 115. (b) When increasing the temperature the value of
S 3 3  3 .34  10 2 .
4 4 ionic product also increases.
101. (d) AlCl3 on hydrolysis gives weak base and K
116. (a) Hydrolysis constant h  w
strong acid among all. Ka

102. (c) Fe 3  ions are hydrolysed to develop acidic

nature. Hydrogen ion concentration - pH scale and
103. (c) K h 
Kw Buffer solution
Ka  Kb
1. (a) pH of blood does not change because it is a
104. (a) KCN is salt of strong base and weak acid.
buffer solution.
105. (c) Sulphides of Group-II radicals have low
solubility product. 2. (c) 0.001 M of NaOH means [OH  ]  .001
106. (c) Because NH 3 acts as Lewis acid and they give  10 3 M  pOH  3
electron pair to H 3 O  ion. H 3 O  is a Lewis pH  pOH  14  pH  14  3  11
base. Which accept the electron pair from 3. (d) [ H 3 O  ] means [H  ]  6 .2  10 9 mol / l
NH 3 .
pH   log (6 .2  10 9 )  8 .21
107. (c) Due to common ion effect.
108. (a) For Ag 2 SO 4  2 Ag   SO 4 4. (b) CH3NH2 + HCl  CH 3 NH 3 Cl 
2x x
0.1 0.08 0
K sp  (2 x ) . x ; K sp  4 x
2 3
; K sp  4  (2.5  10 2 )3 0.02 0 0.08
K sp  62 .5  10 6 (Basic buffer solution)
0 . 08
109. (b) For AgCl  Ag   Cl  pOH = pKb + log
x 0 . 02
x
= pKb + 0.602
K sp  x 2 ; x  K sp ,
= 3.30 + 0.602= 3.902
1  10 6  1  10 3 mole / litre .  pH = 10.09
AgCl  Ag   Cl  [H+] = 7.99  1011  8  1011 M
110. (b)
x x 5. (b) pH  pOH  pKw
4
After NaCl is added x x  1  10 6. (d) pH   log [H  ]
That is why Ag  will be less. 5 . 4   log [H  ] ; [H  ]  3.98  10 6 .
111. (b) Because of ionic product of AgI  solubility
7. (a) KCN  H 2 O ⇌ KOH  HCN . KOH is a strong base
product of its.
and HCN is a weak acid.
 Ionic Equilibrium 389
8. (c) [H  ]  10 3 M , pH   log[ 10 3 ], pH  3 [H+] = 10–3 + 10–2 = 10–3 + 10  10–3 = 11  10–3.
pH = – log(11  10–3) = 3 – log 11
9. (b) [H  ]  [OH  ]
= 3 – 1.04 = 1.95
K w  [H  ] [OH  ]  1014 26. (a) CN   H 2 O  HCN  OH 
[H  ]  10 7 , pH   log [H  ]  7 . Because OH  concentration is increased.
27. (a) On dilution the pH of acid A increases while
10. (d) pH  5 means [H  ]  10 5
pH of base B decreases.
pOH  14  pH  14  5  9 28. (d) CH 3 COONa is a salt of weak acid,
  pOH 9
[OH ]  10  10 ( CH 3 COOH ) and strong base (NaOH ) .
11. (a) pH   log [H  ] ; [H  ]  0 .01 N 29. (b) The equilibrium will shift in the backward
direction.
pH   log [10 2 ] ; pH  2 30. (b) K a  10 5 ; pH  6
12. (d) BOH B+ + OH– [Salt] [Salt]
pH  log K a  log ; 6  log 10 5  log
Initial C 0 0 [Acid] [Acid]
At eq. C – C C [Salt] [Salt]
C 6  5 log 10  log ; 6  5  log
[Acid] [Acid]
C 2 2 [Salt] [Salt] 10
Kb   C  2 assuming   1 ; 1   ~– 1 log  6  5 1 ; 
C(1   ) [Acid] [Acid] 1
10 12  10 2   2 ;  2  10 10 ;   10 5 31. (d) All are true – (a) is true for acid buffer, (b) for
basic buffer, (c) is called buffer solution.
[OH  ]  C  .01  10 5  10 7
N
13. (c) pH  4 means; [H  ]  10 4 mol 32. (b)  0 .01 N HCl ; [H  ]  10 2 M ; pH  2
100
14. (a) Buffer solution is a mixture of weak acid and [OH ]  10 2 M for NaOH
its conjugate base.
pH  pOH  14 ; pH  14  2 ; pH  12
15. (b) Adding Na2CO3 to water makes the solution
34. (a) It is a buffer solution of strong acid and its
basic and hence a pH increases from 7.
weak conjugate base.
16. (d) NaClO4 is a salt of strong acid HClO4 . So it is a
strong acid salt. 35. (c) HA ⇌ H   A 
17. (b) NaOH is a base, so that its pH  7 [H  ]  0 .1 M ; [H  ]2  Ka  C
18. (c) It is a strong base.

[H  ]  Ka  C  1  10 5  0 .1  10 6
1 M NaOH has maximum [OH ] and minimum
[H  ]  10 3 M ; pH  3
[H  ] and maximum pH.
19. (c) When pH = 7 means neutral, pH < 7 means 36. (c) As the solution is acidic, pH  7 . This is

acidic, pH > 7 means basic. because [H ] from H 2O cannot be neglected in
20. (d) As the solution is acidic, pH  7 . This is comparison to 10 8 .
because [H  ] from H 2 O [10 7 M ] cannot be 37. (c) Human body contain buffer solution. Its pH=
neglected in comparison to 10 10 M 6.8
22. (c) It is a strong acid and they lose proton in a 38. (a) It is a neutral solution and its pH = 7
solution. 39. (a) pH  5, means [H  ]  10 5 M .
 2
23. (a) [OH ]  10 M ; pOH  2 After dilution [H  ]  10 5 / 100  10 7 M
pH  pOH  14 ; pH  14  pOH
[H  ] from H 2O cannot be neglected.
pH  14  2  12
Total [H  ]  10 7  10 7  2  10 7
24. (d) Order of acidic strength is
H 2 Te  H 2 Se  H 2 S  H 2 O pH  7  0 .3010  6 .6990  7 (neutral).
Na 2 O is a salt of NaOH  H 2 O and H 2 O is least 40. (d) [H  ]   .C 
2
 .02 ; [H  ]  4  10 4 M
acidic among given acids hence pH in this 100
case will be max m . pH   log [H  ]  4  log 4 ; pH  3.3979
25. (b) pH of the solution A = 3  salt 
41. (a) pH = p K a + log  
[H+]A = 10–3 M.  acid 
pH of the solution B = 2
[H+]B =10–2 M
 390 Ionic Equilibrium
 0.2  1
  [5  log(1  10 14 )  (5)]
= 9 .30 + log   = 9.30 + 0.3010 = 9.6.
 0 .1  2
[Salt] 1 1
42. (a) pH  pK a  log   [5  14  5]   (14 )  7
[Acid] 2 2
[10 ] 55. (d) BaO, CaO and Na2O are shows more than 7 pH
pH   log (1 . 8  10 5 )  log
[100 ] because of their basic nature.
1 56. (a) MgCl2  2H2O ⇌ Mg(OH )2  2 HCl
  log 1 .8  5  log 10
57. (c) H2 SO4 ionized in two step.
  0.2553  5  1  3.7447 or  4
[Salt]
0 .1 58. (b) pH  pK a  log
43. (b) 20 ml. of 0.1 NHCl =  20 g eq. = 2  10 3 g [Acid]
1000
eq. [Salt] [Salt]
5 . 8  4 . 8  log or log  1 .0
[Acid] [Acid]
0 .001
20ml. of 0.001 KOH =  20 gm eq.
1000 [Salt]
 antilog 1 . 0  10
[Acid]
= 2 × 10 5 g eq.
[Acid] 1
 HCl left unneutralised = 2(10 3  10 5 )    0 .1
[Salt] 10
 2  10 3 (1  0.01) = 2  0 .99  10 3  1 .98  10 3 g eq . 59. (b) It contains replacable H atom.
Volume of solution = 40 ml. 60. (c) (i) 20 ml of 0.5 N HCl

1 .98  10 3 0.5 N  1000 ml 0.5 mole HCl is present in 20 ml

 [HCl] =  1000 M = 4 .95  10 2
40 20  0 .5
  1 .0  10  2
 pH = 2  log 4.95 = 2 – 0.7 = 1.3. 1000
45. (b) 10 7 M NaOH means [OH  ]  10 7 ; pOH  7 (ii) 35 ml of 0.1 N NaOH
pH  14  7  7 0.1 N  1000 ml of 0.1 mole NaOH is 35 ml
30 35  0 .1
46. (a) [H  ]  c    0.1   0.03 M   0 .35  10  2
100 1000
48. (a) The pH of buffer solution never changed. Total = 20 + 35 = 55 ml.
10 14  (1.0–0.35)10–2=0.65  10–2mole HCl
49. (c) [H  ]   10 13 mol / litre pH  13 .
10 1 HCl = H++Cl–
   8
50. (a) pH   log[H ] ; 7.4   log[H ] ; [H ]  4  10 M  [HCl] = [H+]+[Cl–]
51. (a) The pH of 0.1M HCl  1 Ionization of 55 ml contains 0.65  10–2 mole of H+ ions
H2 SO4 takes place in two steps.
0.65  10 2  10 3 6.5
1000 ml  

H2 SO4 ⇌ H  HSO 
4 ; HSO ⇌ H 
4

 SO4  55 55
52. (c) 1N NaOH solution have highest pH pH   log[H  ]   log(6.5 / 55 )

[OH ]  1; pOH  0 ; pH  pOH  14
 log 55  log 6.5  0.92
pH  14  0  14
Due to acidic nature of solutions the colour of
53. (c) H 2O ⇌ [H  ] [OH  ] phenolphthalein becomes pink.

HCl ⇌ [H  ] [Cl  ] 61. (b) [H  ]  2  10 2 M

Total [H  ]  [H  ]H 2 O  [H  ]HCl  10 7  10 8  pH  log [2  10 2 ] ;

 10 7 [1  10 1 ] pH  1 .7 i.e. in between 1 and 2.

11 63. (b) pH  4 , (H  )  10  pH  10 4 M
[H  ]  10 7 
10
65. (c) NaOH ⇌ Na   OH 
 11 
pH   log [H ]   log 10 7 

 ; pH  6 .958
 10  [OH  ]  10 5 M ; [H  ] [OH  ]  10 14

54. (c) pKa = – log Ku, pKb = – log Kb 10 14

[H  ]  ; [H  ]  10 9 M ; pH  9 .
1
pH =  [log K a  log Kw  log Kb ] 10 5
2
 Ionic Equilibrium 391
[Salt] 0 .1 80. (a) Na2 CO3 is a mixture of weak acid and strong
67. (b) pH  pK a  log ; pH  4 . 75  log
[Acid] 0 .1 base, so it is a base.
pH  4.75  log 1 ; pH  4 .75 81. (b) 10 7 N HCl means (H  )  10 7 M

68. (d) A weak acid and its salt with a strong base pH   log( H  ), pH  7
maintain pH 4 – 5 82. (c) pH  2 ; pH   log [H  ] ; 2   log [H  ]
69. (a) NaOH ⇌ Na  OH   [OH  ]  10 8 M. [H  ]  10 2  0 . 01 N
70. (c) [OH  ]  0 . 0001 N , pOH  4 , pH  pOH  14 83. (b) pH does not change on addition of some
concentration of HCl.
pH  14  pOH  14  4  10
84. (b) Solution of CH 3 COONa on addition to acid
71. (d) 0.001 M KOH solution shows a decrease in dissociation of acid due to
[OH  ]  0 .001 M  1  10 3 M common ion effect. To decrease in [H  ] or
increase pH.
[H  ]  [OH  ]  1  10 14 85. (c) pH  pOH  14 ; pH  14  pOH ; pH  14  6  8 .
1  1014
86. (b) [H  ]I  10 5 [H  ]II  10 2
[H  ] 
[OH  ] 10 2
Thus increase in [H  ]   1000 times
1  1014 10  5
[H  ]   1  10 14  10 3
1  10  3 87. (a) The HCl is a strong acid and they lose easily
H  in solution.
[H  ]  10 11 M
88. (a) X   H 2 O ⇌ OH   HX
pH  11
[OH  ] [ HX ]
72. (a) An acid buffer solution consists of solution of Kb 
[X  ]
weak acid with strong base of its salt.
73. (b) An acid buffer solution consists of a weak acid HX ⇌ H   X 
and its salt with strong base. i.e. [H  ] [ X  ]
CH3COOH  CH3COONa Ka 
[HX ]
[salt ]
74. (a) pOH  pK b  log  K a  K b  [H  ] [OH  ]  K w  10 14
[base]
0 .02 1 Hence K a  10 4
 5  log  5  log  5  (1)  4
0 .2 10 Now as [ X  ]  [HX ], pH  pK a  4 .
pH  14  pOH  14  4  10
90. (d) Buffer solution is formed. So the pH will not
75. (b) [Salt]= 0.1 M, [Acid]= 0.1 M change.
[Salt]
K a  1 .8  10 5 ; pH  log K a  log 91. (b) Na2 CO3 when react with water form strong
[Acid]
base and weak acid. So its aqueous solution is
5 0 .1 basic.
 log 1 . 8  10  log  log 1 .8  10 5
0 .1
92. (c) K w  [H 3 O  ] [OH  ]
pH  4 . 7 .
76. (a) NH 4 Cl and NH 4 OH is a buffer solution (weak Concentration of H 3 O  in distilled water  1  10 6 mol/l.
base and salt of strong acid). Now [H 3 O  ]  [OH  ]
77. (a) pH  pOH  14 ; pH  14  pOH
K w  [1  10 6 ]  [1  10 6 ]  1  10 12 .
 [OH  ]  10 7
pOH  7
93. (a) [OH  ]  10 1 M ; pOH  1

pH  14  7  7 . pH  pOH  14 ; pH  14  1  13 .

78. (c) 0.01 M Ba(OH )2  0.02 N Ba(OH )2 94. (a) Maximum pH HClO is a weak acid all of these.
So that the salt of weak acid is also weak.
N1 V1  N 2 V2
95. (c) As the solution is acidic pH  7 . This is
[0.02 N ]  [50 ml ]  N 2  100 ml

because [H ] from H 2 O [10 7 ] cannot be
0 . 02  50
N2   10 2 N ; [OH  ]  10 2 N 12
100 neglected in comparison to 10 M.
pOH  2 or pH  12 96. (b) [Normal salt + acidic salt] is a buffer solution.
79. (b) pH   log [H  ] .
 392 Ionic Equilibrium

97. (b) 100 ml of

M
NaOH = 50ml of
M
NaOH. They H 3 O   2  (H 2 SO 4 )  2  0 . 005  0 . 01 M
10 5
[H  ]  10 2 M ; pH  2
N
exactly neutralise 50 ml HCl. Hence pH of
5 107. (c) CH 3 COONH 4 is a simple buffer and called salt
resulting solution = 7. of weak acid.
98. (b) M1  6.0 M of HCl ; V1  ? 0 .4
108. (c) N.eq. for HCl   50  0 .02
1000
M 2 =0.30 M is H  concentration in solution.
0 .2
V2  150 ml of solution. N.eq. for NaOH   50  0 .1
1000
M1 V1  M 2 V2 ; 6.0  V1  .30  150 Now [OH  ] left  0 . 1  0 . 02
.30  150 [OH  ]  .08  8  10 2 M
V1   7 .5 ml.
6
pOH   log 8  10 2 M ; pOH  1 .0
99. (b) pH  3 , [H  ]  10 3 M
109. (d) Buffer is mixture of weak base and its acid
 [H  ]  K  c salt.

[10 6 ] 110. (b) [NaOH]  0 .4 40 mole l.  0.1 M

[10 3 ]2  K  c ;  K  10  5
0.1 [OH  ]  10 1 M , [H  ]  10 13 M , pH  13
100. (b) When ratio of concentration of acid to salt is
increased pH decrease. 111. (d) pH  pOH  14 , pH  4 , H   10 4 mole/litre.
101. (c) For NH 4 OH . 112. (d) Buffer solution have constant pH. When we
add the water into this buffer solution. So no
1
[OH  ]  C .  ; C  M ,   0. 2 effect on it.
10
113. (b) Ba(OH )2 ⇌ Ba 2   2OH 
 1
[OH ]   0 .2  2  10  2 M
10 One molecule on dissociation furnishes 2 OH 
pOH   log [OH  ]  log [2  10 2 ] ; pOH  1 .7 ions.

pH  14  pOH So, [OH  ]  2  10 4 N

 14  1.7  12 .30 .
[Salt] N 2  10 4
102. (c) pH  pK a  log . For small concentration N  M 2 ; M    10  4
[Acid] 2 2
of buffering agent and for maximum buffer pOH   log[OH  ]   log(1  10 4 )  4
[Salt]
capacity 1. pH  pOH  14 ; pH  14  4  10 .
[Acid]
0 .10
103. (a) [H  ] = increased ten fold means pH of solution 114. (a) M.eq. of 0.10 M HCl   40  0 .004 M
1000
decreased by one.
0 .45  10
pH  log
1 M.eq. of 0.45 M NaOH   0 .0045 M
[H  ] 1000
104. (a) Because the pH of buffer are not changed. Now left [OH  ]  0.0045  0.004  5  10 4 M
[Salt] [Salt]
105. (c) pH  pK a  log ; 5 .5  4 .5  log Total volume = 50 ml.
[Acid] [0.1]
5  10 4
log
[Salt]
 5 .5  4 .5  1 [OH  ]   1000 ; [OH  ]  1  10 2
0 .1 50
[Salt ] pOH = 2 ; pH = 14 – pOH = 12.
 antilog 1 = 10 ; [Salt]  1
0 .1 115. (c) 0.001 M HCl  10 3 M [H  ], pH  3 .
0 .49
106. (a) Moles of H 2 SO 4   5  10  3 moles of 0.4
98 116. (d) [ NaOH ]   0 .01 M ; [OH  ]  10  2 M
H 2 SO 4 present per litre of solution 40

. 005 [H  ]  10 12 , pH   log[ H  ]  12

(molarity)   . 005 M.
1
117. (b) Those substance which give a proton is called
H 2 SO 4  2 H 2 O ⇌ 2 H 3 O   SO 4  Bronsted acid while CH 3 COO  doesn’t have
one mole of H 2 SO 4 give 2 moles of H 3 O  ions. proton so it is not a Bronsted acid.
 Ionic Equilibrium 393
120. (c) pH   log [H  ] 139. (c) 10 6 M HCl  10 8 M [H  ] . Also from H 2 O

121. (d) pH  pOH  14 , pH  4 .0 [H  ]  10 7 M

pOH  14  pH ; pOH  14  4 .0  10 .0 Total [H  ]  10 7  10 8  10 7 [1  0.1]  10 7 [1 .1]
122. (b) pH  0 means [H  ]  10 o  1M . Hence solution Hence pH  7  0 .0414  6 .96 .
is strongly acidic.
140. (b) 10 10 M HCl  10 10 M [H  ] . But pH  10 because
123. (c) As the solution is acidic, pH < 7. This is
because [H  ] from H 2 O (10 7 M ) cannot be solution is acidic. This is because H  from
H 2 O(10 7 M ) cannot be neglected.
neglected in comparison to 10 10 M HCl.
124. (d) H 3 O  ⇌ OH   H 2 Total [H  ]  10 7  10 10

pOH  pH  14 ; 7  7  14 ; [H  ]  [OH  ]  10 14  10 7  (1  10 3 )  10 7 (1.001 )

10 7  10 7  10 14 ; [OH  ]  10 7 gm ion/l. That is why pH  7 (slightly less than 7)

126. (b) When pH  2 , [H  ]  10 2 M 141. (b) [H  ]  1.00  10 6 mole/litre

mol mol pH   log [1 .00  10 6 ] ; pH = 6.

127. (a) [OH  ] ion conc.  0 .05  5  10  2
l l
142. (a) [H  ] is in moles per litre.
pOH   log [OH  ]   log [5  10 2 ]
143. (d) As the solution is acidic, pH  7 . This is
pOH  1 .30 ; pH  pOH  14 
because [H ] from H 2O (10 7 M ) cannot be
pH  14  pOH  14  1.30  12 .7
neglected in comparison to 10 8 .
128. (c) When pH  3 , then [H  ]  10 3 M 145. (b) pH of 0.001 M HCl  10 3 M[H  ] , pH = 3.
after that we increased the pH from 3 to 6
146. (d) Because it can furnish H  ions in solutions.
then [H  ]  10 6 M means reduced 1000 times.
147. (c) Because it is a strong acid.
129. (b) CO2 is acidic oxide which on dissolution in
H   10 1
water develops acidic nature.
pH   log [H  ]   log [10 1 ] ; pH  1 .
130. (d) If pH of any solution is 2.
Then [H  ]  10 2 M 148. (b) Buffer solution is a combination of weak acid
and conjugate base. NaCl is a salt and NaOH is
If pH of any solution is just double then the base.
pH  4 and [H  ] will be 10 4 .
149. (a) [H  ]  Kc  10 5  0.1  10 3 , pH  3 .
131. (c) A strong acid is not used to make a buffer.
N
132. (d) pH  1 means [H  ]  10 1 M 150. (d) In NaOH have [OH  ]  10 1 M means
10
10 1 1 pOH  1 and then pH  pOH  14
Hence [H 2 SO 4 ]    0.05 M
2 20 pH  14  pOH  13 .

133. (c) The pH of blood is 7.4 due to presence of 151. (b) Borate ions are hydrolyzed to develop alkaline
bicarbonates ions nature in solution.
152. (d) Less the pH, more acidic is the solution.
134. (c) As the solution is acidic, pH < 7. This is
154. (b) The equal conc. of salt and acid.
because [H  ] from H 2 O [10 7 ] cannot be
[KCN ]
neglected in comparison to 10 8 155. (c) pH   log K a  log
[HCN ]
135. (a) pH will decrease because [OH  ] increased due  0 .15 
to this pOH is decreased. pH   log [5  10 10 ]  log   8 .302
 1.5 
136. (c) [H  ]  6  10 4 M [Salt]
157. (c) pH  pK a  log equimolar means
[Acid]
pH   log [H  ]   log [6  10 4 ]  3 .22 .
[Salt]
1; pH  4.74  0  4.74
137. (c) 0 . 01 M HCl  10 2 M [H  ], pH  2 . [Acid]

138. (c) Because buffer solution have a constant pH.

 394 Ionic Equilibrium
158. (a) Because of NaCl is a salt of strong acid and 175. (a) Na2 CO3 is basic in nature. So its pH is greater
strong base. So that it is neutral. than 7.
159. (c) When strong acid and strong base are react 176. (c) It is not a mixture of weak acid or base and
neutral salt are formed. So that NaCl is a their strong salt.
neutral salt.
177. (a) [H  ]  Antilog (4 . 58 ) ;
[Salt]
162. (d) pH  log K b  log
[Acid] [H  ]  2 .63  10 5 moles / litre
[Salt] 178. (c) 10 2 M NaOH will give [OH  ]  10 2
pH  log [1 .8  10 5 ]  log
1.0
pOH  2 , Also pH  pOH  14
[Salt] [Salt]
9  4 .7  log ; log  4.7  9  4.3 pH  12 .
1.0 1 .0
[Salt] 10  1
[Salt]
 Antilog
1
; [S alt]  1 .8 179. (a) pH  pK a  log   log 2  10 5  log 4.
1.0 4.3 [Acid] 50  2

[salt ] 180. (b) 0.001 M NaOH means [OH  ]  10 3 ; pOH  3

163. (b) pH   log K b  log
[acid] pH  pOH  14 ; pH  14  3

5   log 10  4  log
[salt ] pH  11 ; [H  ]  10 11 mole-litre–1
[acid]
181. (c) [H  ]  C . 
[salt ]
log 1 1
[acid] [H  ]  0 . 1   10 3
100
[salt ]
 antilog 1  10 : 1 pH   log [H  ]   log 10 3  3
[acid]
164. (a) 1 M KOH show highest pH value because it is a 182. (b) pH  4
strong base. pH  pOH  14 ; pOH  14  pH
165. (d) NH 4 OH is a weak acid and NH 4 Cl is a strong pOH  14  4  10 ; [OH  ]  10 10 M
base salt.
1 1
166. (a) pH  13 . 6 183. (b) pH  log  log  2 .523
[H  ] [3  10 3 ]
pOH  14  13 .6  0 .4
185. (c) It is a strong base.
[OH  ]  Antilog (0 .4 )  0 .3979 . So the value of 186. (b) [H  ] Concentration in 0.01M HCl is 10 2 M

[OH ] between 0 . 1 M and 1 M because 0.01 M HCl have only H 
167. (d) Aspirin is a weak acid. Due to common ion HCl ⇌ H   Cl  .
effect it is unionised in acid medium but
completely ionised in alkaline medium. 187. (b) The value of H 3 O  ions will not changed.

168. (b) [H  ] [OH  ]  10 14 ; (10 7 )(10 7 )  10 14 CH 3 COOH  H 2 O ⇌ CH 3 COO   H 3 O  .

169. (c) HCl  10 o M has pH  0 . The value of pH 188. (a) H 2 O2 (Hydrogen peroxide) is a corrosive
decreases as concentration further increases. volatile liquid. It is slightly acidic in nature.
170. (a) Because pure water has a 7 pH. Its pKa value is approximately 10 12 .

171. (c) When concentration of [H  ] increased then the 192. (b) pH  log
1
; pH  log
1
; pH  3 .

value of pH is decreases. H 10 3
1 193. (b) NH 3 is Lewis base because of one lone pair of
pH  log 
[H ] electron.
172. (c) The concentration of [H ]  10  2
mole/litre 194. (b) Ba (OH ) 2  Ba 2  2 OH 
. 05 M 20 .5 M
pH  log [H  ]  log [10 -2 ] ; pH  2 1 1
pOH  log  log 1
173. (d) Due to common ion effect. [OH ] .1
174. (b) In water solution. pH  pOH  14 ; pH  1  14 ; pH  14  1  13
NH 3  H 2 O ⇌ NH 4  OH  195. (a) If concentration of acid is increases ten times
in a buffer then pH of the solution is increase
concentration of OH  is increased so that
by one.
solution become more basic and the pH is
increased. 198. (b) pH  7  Basic
 Ionic Equilibrium 395
It means contain more hydroxide ions than
carbonate ions.
7. (c) 2 HI ⇌ H 2  I2
Initial 2 0 0
199. (a) At 7pH the concentration of OH  and H  are
   
equal. At equilibrium 2    2     2 .
2 2 2 2
.01  100
200. (a,d) M.eq. of 0.01 M HCl   1  10 3 8. (a) Because they have vacant d-orbital in central
1000
atom.
pH  3
9. (a) Energy has to be spent for the total
.04  50
M.eq. of .02 M H 2 SO 4   2  10 3 dissociation of weak acid.
1000
10. (a) pK a of acid A  4 ; pK a of acid B  5
0 .02  50
M.eq. of .02 M NaOH   1  10 3
1000 We know that pKa   log K a
 3 3 3
Left [H ]  2  10  1  10  1  10 ; pH  3  Acid A K a  10 4
202. (a,b,c) Because buffer solution are mixture of
weak acid or weak base and their salt. Acid B K a  10 5
203. (c) Because pH  8 is basic nature but HCl is a Hence A is ten times stronger than that of B.
strong acid.
1 K a1 3 .14  10 4
204. (c) H 2 SO 4  0.05  2 11. (b)    4 :1
2 K a2 1 .6  10 5

[H ]  0 . 1 and pH  1
12. (d) It is a salt of weak acid and weak base.
205. (b) Mg(OH )2 ⇌ Mg 2   2OH 
[H  ] [ A  ]
K sp  [Mg 2  ][OH  ] 2 13. (c) HA ⇌ H   A  ; K a  ……(i)
[HA ]
1  10 12  0 . 01 [OH  ] 2 neutralization of the weak acid with strong
 2 10  5 base is
[OH ]  1  10  [OH ]  10
 14 5 HA  OH  ⇌ A   H 2 O
[H ]  10 / 10  10 9
pH   log[H  ]   log[10 9 ]  9 [A  ]
K ……(ii)
[ HA ] [OH  ]
206. (b) [OH  ]  1  10 5
pOH   log[OH  ]  5 Ka
dividing (i) by (ii)  [H  ] [OH  ]  K w  10 14
K
pH  pOH  14  pH  14  5  9 .
Ka 10 5
Critical Thinking Questions K   10 9 .
K w 10 14

1. (b) K sp of AgI  1.5  10 16 14. (d) NH 4 Cl undergoes cationic hydrolysis hence pH
is  7 because the solution due to cationic
10 8 M Ag  and 10 8 M I 
hydrolysis in acids.
Ionic product  10 16 NaCN undergoes anionic hydrolysis hence pH
K sp  Ionic product is >7.

2. (a) HClO is the weakest acid. Its conjugate base HCl is strong acid and NaCl is neutral
solution.
ClO  is the strongest base.
Hence the pH of given solutions will
3. (b) B(OH )3 not have H 
increases.
kw 1  10 14 HCl  NaCl  NaCN  NH 4 Cl
4. (a) h    2 . 22  10 5
ka 4 . 5  10 10
15. (c) It is a HClO4
5. (d) MX 4  M  4 X ; K sp  (4 s) s ; K sp  256 s 4 5
16. (d) Smaller the K a value, strong the acid.
s 4s p

1/5 17. (d) It involves gain and loss of electron pair (Lewis
 K sp 
s   
 . concept).
 256 
18. (b) H  (aq.)  H 2 O(l)  OH   H 2 .
6. (a) Lewis acid are electrophiles because they
accept election pairs. Ka 10 4 1
19. (b) K H   14  10  10 10 .
K w 10 10
 396 Ionic Equilibrium
20. (d) Acidity is directly propotional to oxidation 34. (a) Cr (OH )3  Cr 3  3 OH 
number. As the O.No. of S, P and Cl in x 3x
H 2 SO 3 , H 3 PO3 & HClO3 is +4, +3 & +5 K sp  x .(3 x )3  27 x 4
respectively so decreasing order of acidity
will be III > I > II. K sp 2 .7  10 31
x 4 ; x 4
21. (a) A substance which can donate a proton is 27 27
known as acid so NH 4 will be a acid.
x  1  10 8 mole/litre.
22. (b) Acetic acid is a weak acid.
35. (a) H   c .   K a . c
23. (a) Because it is a acidic oxide.

2  10 2  V   10 3  V 
 2 9
2 
pH   log K a . c 
1/2

1
2
[ log K a  log c]
24. (b) [Ca ] [F ]      1 .25  10 .
 2 V   2 V  1 1
 [4 . 74  log 10  2 ]  [4 . 74  2]  3 . 37 .
25. (a) The degree of hydrolysis of a salt of weak acid 2 2
and weak base is independent of 36. (b) Ag2 SO 4 ⇌ 2 Ag   SO 4 
concentration of salt. 4S 2 S

26. (c) C  0 . 1 M ;   1 %; (H )  C   Ksp  4 S 3 ; Ksp  2  10 5
1
 0.1   10  3 ; (H  )  10 3 ; pH = 3. 2  10 5
100 S 3  0 .017 m /l  1.7  10 2
4
27. (d) HClO4 is a strong acid, because its oxidation no
is + 7. Ag BrO3 ⇌ Ag   BrO 3
S S
28. (d) Acceptor of electron pair is known as lewis
acid. S, : CH 2 , (CH 3 )3 B all can accept an Ksp  S ; Ksp  5.5  10 5
2

electron pair so answer is (d).

S  5.5  10 5  7.4  10 3 m / l.
2 
29. (b) Mg(OH ) ⇌ Mg 2
 2OH2
(s ) ( 2 s) 37. (c)
OH Phenol are more acidic
K sp 1 .2  10 11
K sp  4 S 3  S  3 3 than ethanol because of
4 4 stabilization of phenoxide
as compare to ethoxide ion.
S  8 .16  10 4
[H  ] [CN  ] 38. (b) X   H 2 O ⇌ HX  OH 
30. (d) K a  
[HCN ]
10 14 10 9
 Kh  5
so h   10 4
6 .2  10 10 
[H ] [0 .02 ] 10 10 1
[0 .01 ]
100  10 4  10 2
10
6.2  10  0.01
[H  ]   3.1  10 10 So, 0.01%.
0.02
39. (a) K a  1 .0  10 5

31. (b) N H 3 presence of lone pair of electrons. K h  hydrolysis constant
 
32. (a) CuBr ⇌ Cu  Br K w 10 14
K sp (S ) (S ) Kh    10  9
Ka 10  5
mol 2
K sp  S 2  (2  10  4 )2  4  10 8 Kh
l2 degree of hydrolysis (h ) =
C
33. (c) Na2 SO 4 ⇌ 2 Na   SO 42 
(0 . 004  x ) 2x x 10 9
 = 10 6 = 10 3 ; h  10 3
Since both the solution are isotonic 0 . 001
0 . 004  2 x  0 . 01 40. (b) Basic radicals of group II & IV are precipitated
 x  3  10 3 by H 2 S in the form of their sulphides. IInd
group in acidic medium & IV group in alkaline
3  10 3 medium. They precipitate when ionic product
 Percent dissociation   100  75 % .
0.004 increases than solubility product.
 Ionic Equilibrium 397
41. (a) After mixing [ Ag  ] [Cl  ]  K sp K sp
55. (a) K sp  [ As 3  ][S 2 ] , S  5
108
42. (a) K sp  ionic product 1  10 10  5  10 11
2 .8  10 72
43. (a) 1 litre of water contains 1000/18 mole. 5  1 .09  10 15
108
So degree of ionization
10 7  18 56. (d) Dissociation constant of HA  10 9
  1.8  10 7 %.
1000 HA ⇌ H   A 
44. (a) AgCl Ksp  1.2  10 10 Ka 10 9
[H  ]   ; [H  ]  10 4
C 0 .1
S  1.2  10 10 ; S  1 .09  10 5
pH  4
AgBr K sp  3.5  10 13
 pH  pOH  14
13 6
S  3.5  10  5 .91  10 pOH  14  pH  14  4 ; pOH  10
So that S of AgBr is less than that of AgCl. 1000
57. (d)   1.9  10 9 ; C 
45. (a) K sp  4S 3
18

4 S 3  3.2  10 8 ; S  2  10 3 M . [H  ] [OH  ]
K  C 2
(H 2 O )
2.8  10 10
46. (c)  2.8  10 9 ML1 . 1000
0.1  1 .9  10  9  1 .9  10  9   2 .0  10 16 .
18
47. (b) AB ⇌ A   B  ; K sp  S 2
58. (c) K  Ka1  Ka2  4.5  10 3  1.7  10 10
S  K sp  4  10 10  2  10 5
H   Kc  4 .5  10 3  1 .7  10 10  .01
1.435  10 3  .87  10 7
48. (b) S  1 .435  10 3 g / l ,   10 5 M
143 .5 pH   log 0 .87  10 7  7  0.93  6.07 .
K sp  S  S  10 10 59. (a) Given that
5 Concentration of solution =.1
49. (b) pKa  5 , so Ka  1  10
2
Ka 1  10 5 Degree of ionisation  2 %   . 02
   1  10  2 100
C 0.1
Ionic product of water  1  10 14
50. (c) Presence of common ion decreases the
solubility of salt. Concentration of [H  ] = Concentration of
solution X degree of ionisation
51. (d) Ag2 S  CuS  HgS . 3
 .1  .02  2  10 M
Solubility of CuS  10 31  3.16  10 16 mol / lit. Ionic prod uct of water
Concentration of [OH  ] 
[H  ]
Solubility of Ag 2 S
1  10 14
K sp 10 42   0.5  10 11  5  10 12 M .
3 3  6 .3  10  5 mole / litre 2  10  3
4 4
60. (a) HgSO 4  Hg    SO 4 
x x
Solubility of HgS  K sp  10 54  10 27 mol / litre.
K sp  x 2 ; x  K sp ; x  6.4  10 5
52. (c) pH  3 . 82   log [H  ]
x  8  10 3 mole/litre.
[H  ]  1.5  10 4 mole/litre.
2
 1 .34  5
53. (b) pH  pKa  log
[salt]
 4 .57  log
0 .10
 5 .09 61. (a) K  c 2  0 .1     1 .8  10 .
acid 0 .03  100 

54. (c) For a monobasic acid 62. (c) [H  ]  1  10 4 M  [H  ] [OH  ]  1  10 14

[H  ]  C  1  10 14
 [OH  ]   2  10 10 M
1 0.5  10  4
  0 .001  10 4  pH = 4
10
 398 Ionic Equilibrium
63. (d) Because HClO4 is a strong acid. While buffer is 0 .01
pH  log (1 .8  10  4 )  log
a mixture of weak acid and their salt. 0 .02
64. (b) Initial concentration = 0.006 M  pH  4  log (1.8)  log 0.5
K a  6  10 5
pH  4  log (1.8)  0.301
equilibrium reaction.
pH  3.4
C6 H 5 COOH ⇌ C6 H 5 COO   H 
C O O initial 72. (c) HCO 3  and H 2 O
C (1  a) Ca Ca

Ka  C 2 ( 1    1) for weak electrolyte

73. (a) [H  ]  C    0.1  0.1  10 2 M
5
Ka 6  10
  ;   ;   10 1 pH = 2; pOH = 12 ; [OH  ]  10 12 M .
C 0 .006
74. (c) Decreasing order of acidic character is
 [H  ]  C   0 .006  10 1  6  10 4 M. H 2 SO 4  CH 3 COOH  H 2 CO 3
[Salt ] 75. (c) The acidic nature increases in the order.
65. (a) pOH  pKb  log
[Base ]
NaNO2  NaCl  H 2S  H 2SO4
5 [Salt]
14  9 .35   log(1 .78  10 )  log 76. (a) [OH  ]  0.05  5  10 2 M
100
pOH  2  log 5  1 .3
w
[Salt ]  79 .9   1000  79 .9  w  10 .56
132 pH  pOH  14

66. (a) pH  6 means [H  ]  10 6 M pH  14  1.3  12 .7

pH  3 means [H  ]  10 3 M 77. (b) Na 2 O form NaOH. So that it is basic oxide.

After mixing, 78. (a) CH 3 COO   H 2 O ⇌ CH 3 COOH  OH 

(10 6  10 3 ) 1 .001  10 3 10 14

Total [H  ]    [OH  ]  c  h; h 
Kw
c  1
2 2 Ka 1 .8  10 5
 5 .005  10 4
 2 . 35  10 5
pH  4  log 5.005 ; pH  3 . 301 .
 pOH  4 .62 ; pH  9 .38  9 .4

67. (b) [H ]  K  C
Assertion & Reason
[H  ]  4  10 10  1 ; [H  ]  2  10 5 mole/litre

68. (b) Moles of [OH  ]  M  V 1. (c) HCl is a strong electrolyte since it will
produce more H  , comparison than that of
Number of NaOH  0 . 3  0 . 005  2  0 . 0030
CH 3 COOH . Hence assertion is true but reason
69. (d) [H  ] [OH  ]  10 13 .26 false.
   2 13 .26
 [H ]  [OH ],  [H ]  10 2. (b) For sparingly soluble salts, reason is not a
correct explanation. Hence both assertion and
13 .26
[H  ]  10 2 reason are true but reason is not a correct
explanation of assertion.
pH = 6.63.
3. (a) Aq. solution of FeCl3 on standing produce
[Salt ]
70. (b) pH  pKa  log brown ppt. Due to hydrolysis it produce ppt.
[ Acid ]
of Fe(OH )3 which is of brown colour. Hence
pH  pKa both are correct and reason is a correct
Ka  0.1  (10 3.5 2
)  0.1  10 7
 10 8
 pH  8 explanation.
4. (a) Barium carbonate is more soluble in HNO3 than
[Salt]
71. (a) pH  log K a  log in water become carbonate is a weak base and
[Acid]
reacts with the H  ion of HNO3 causing the
0 .2  50 0 .5  40
[Salt]   0.01 ; [Acid]   0 .02 barium salt to dissociate.
1000 1000
BaCO3  HNO 3  Ba(NO3 )2  CO2  H 2 O
 Ionic Equilibrium 399
5. (a) The conjugate base of CHCl 3 is more stable
than conjugate base of CHF3 (CF3 ) .
CCl3 stabilized by –I effect of chlorine atoms
as well as by the electrons. But conjugate base
of CH 3 (CH 3 ) is stabilized only by –I effect of
flourine atoms. Here both assertion and
reason are true and reason is correct
explanation of assertion.
6. (c) Ionic product of AgBr is greater than that of
AgCl in comparison with there solubility
product AgBr will precipitate. First rather
than that of AgCl .
9. (e) It is fact that ionic reactions are
instantaneous due to the fact that oppositely
charged ions exert strong forces and combine
immediately.
 398 Ionic Equilibrium

1. The most important buffer in the blood consists of (a) 1.74  10 3 (b) 3.52  10 3
[BHU 1981]
(c) 6.75  10 4 (d) 5.38  10 2
(a) HCl and Cl  (b) H 2 CO3 and HCO 3
8. If the hydrogen ion concentration of a given
(c) H 2 CO3 and Cl  (d) HCl and HCO 3 solution is 5 . 5  10 3 mol litre 1 , the pH of the
2. The solubility product of AgI at 25 C is solution will be
1 .0  10 16 mol 2 L2 . The solubility if AgI in 10 4 N [AMU 1985]
solution of KI at 25 C is approximately (in mol (a) 2.26 (b) 3.40
l 1 ) (c) 3.75 (d) 2.76
[CBSE PMT 2003] [salt ]
9. Henderson’s equation is pH  pKa + log . If
8 16 [acid ]
(a) 1.0  10 (b) 1 . 0  10
12 the acid gets half neutralized the value of pH will
(c) 1 . 0  10 (d) 1 . 0  10 10
be : [pKa  4.30 ]
M
3. The pH of the solution: 5 mL of , HCl  10 mL of [RPMT 2000]
5
(a) 4.3 (b) 2.15
M
NaOH is [MH CET 2004] (c) 8.60 (d) 7
10
(a) 5 (b) 3 10. The pH of a 0.01 M solution of acetic acid having

(c) 7 (d) 8 degree of dissociation 12.5% is [JIPMER 2000]

4. Given that the dissociation constant for H 2 O is (a) 5.623 (b) 2.903
(c) 3.723 (d) 4.509
Kw  1  10 14 mole 2 / litre 2 . What is the pH of a 0.001
11. Which of the following solutions will have
molar KOH solution [UPSEAT 2000; MP PET 2001]
pH close to 1.0
(a) 10 11 (b) 10 3 [IIT 1992; MP PET 1993; AMU 1999]
(c) 3 (d) 11 M M
(a) 100 ml of HCl  100 ml of NaOH
5. The pH of 0.1 M solution of the following salts 10 10
increases in the order [Pb. CET 2004] M M
(b) 55 ml of HCl  45 ml of NaOH
(a) NaCl  NH4 Cl  NaCN  HCl 10 10
M M
(b) HCl  NH4 Cl  NaCl  NaCN (c) 10 ml of HCl  90 ml of NaOH
10 10
(c) NaCN  NH 4 Cl  NaCl  HCl M M
(d) 75 ml of HCl  25 ml of NaOH
(d) HCl  NaCl  NaCN  NH 4 Cl 5 5
12. In which of the following solvents will AgBr have
6. The degree of hydrolysis in hydrolytic equilibrum
the highest solubility [CBSE PMT 1992]
A   H 2O ⇌ HA  OH  at salt concentration of 3 3
(a) 10 M NaBr (b) 10 M NH 4 OH
0.001 M is
(d) 10 3 M HBr
K a  1  10 5  [UPSEAT 2004]
(c) Pure water
13. How many grams of CaC2 O4 will dissolve in
(a) 1  10 3 (b) 1  10 4
distilled water to make one litre of saturated
(c) 5  10 4 (d) 1  10 6 solution ? (Solubility product of CaC2 O4 is
7. If pK b for fluoride ion at 25 o C is 10.83, the 2 .5  10 9 mole 2 litre 2 and its molecular weight is
ionisation constant of hydrofluoric acid in water 128) [MP PET 1993; MP PMT 2000]
at this temperature is (a) 0.0064 gm (b) 0.0128 gm
[IIT 1997]
 Ionic Equilibrium 399
(c) 0.0032 gm (d) 0.0640 gm 21. According to Bronsted-Lowry concept, the correct
14. The solubility product of CuS , Ag 2 S , HgS are order of relative strength of bases follows the
order
10 31 , 10 44 , 10 54 respectively. The solubilities of
[Pb. PMT 2001]
these sulphides are in the order [CBSE PMT 1997]
  
(a) CH 3 COO  Cl  OH
(a) Ag 2 S  CuS  HgS (b) Ag 2 S  HgS  Cus

(c) HgS  Ag 2 S  Cus (d) CuS  Ag 2 S  HgS (b) CH 3 COO   OH   Cl 

15. The solubility product constant K sp of Mg(OH )2 is (c) OH   CH 3 COO   Cl 

9.0  10 12 . If a solution is 0.010 M with respect to (d) OH   Cl   CH 3 COO 

Mg 2  ion, what is the maximum hydroxide ion
22. H 2 SO 4  OH   SO 42   H 2 O Which is correct
concentration which could be present without
about conjugate acid base pair [JEE Orissa 2004]
causing the precipitation of Mg (OH )2 [Pb. PMT 1998]
2
(a) HSO 4 is conjugate acid of base SO 42 
(a) 1 . 5  10 7 M (b) 3 . 0  10 7 M
(b) HSO 4 is conjugate base of acid SO 42 
(c) 1 . 5  10 5 M (d) 3 . 0  10 5 M
(c) SO 4 is conjugate acid of base HSO 4
16. If the Kb value in the hydrolysis reaction
B   H 2 O ⇄ BOH  H  is 1.0  10 6 , then the (d) None of these
23. 1998]
hydrolysis constant of the salt would be[Roorkee Qualifying Which may be added to one litre of water to act as
a buffer
(a) 1 .0  10 6 (b) 1 .0  10 7
[JIPMER 2000]
(c) 1 .0  10 8 (d) 1 .0  10 9
(a) One mole of HC 2 H 3 O2 and 0.5 mole of NaOH
17. For a sparingly soluble salt Ap Bq , the relationship
(b) One mole of NH 4 Cl and one mole of HCl
of its solubility product (LS ) with its solubility (S )
(c) One mole of NH 4 OH and one mole of NaOH
is
[IIT Screening 2001] (d) One mole of HC 2 H 3 O2 and one mole of HCl
p q p q
(a) Ls  S p
. p .q q
(b) Ls  S q
. p .q p
24. Which of the following base is weakest [DCE 2003]

(c) Ls  S pq p
. p .q q
(d) Ls  S pq
.( p.q ) p q
(a) NH 4 OH : K b  1 . 6  10 6

18. Arrange NH 4 , H 2 O, H 3 O  , HF and OH  in (b) C 6 H 5 NH 2 : K b  3 .8  10 10

increasing order of acidic nature [BVP 2003]
(c) C 2 H 5 NH 2 : K b  5 . 6  10 4

(a) H 3 O  NH 4  HF  OH  H 2 O 

(d) C 6 H 7 N : K b  6 . 3  10 10
(b) NH 4  HF  H 3 O   H 2 O  OH 
25. HClO is a weak acid. The concentration of H 
  
(c) OH  H 2 O  NH 4  HF  H 3 O ions in 0.1 M solution of HClO (K a  5  10 8 ) will
(d) H 3 O   HF  H 2 O  NH 4  OH  be equal to
[CPMT 1993]
19. How many grams of CaC2 O4 (molecular weight =
5 9
128) on dissolving in distilled water will give a (a) 7 . 07  10 m (b) 5  10 m
9 2 2
saturated solution [K sp (CaC2 O4 )  2.5  10 (c) 5  10 7 m
mol l ] [KCET 2003] (d) 7  10 4 m
(a) 0.0064 g (b) 0.1280 g 26. Upto what pH must a solution containing a
(c) 0.0128 g (d) 1.2800 g precipitate of Cr(OH )3 be adjusted so that all of
20. If the concentration of CrO 4 ions in a saturated precipitate dissolves

solution of silver chromate is 2  10 4 . Solubility (When Cr 3   0.1 mol / l, K sp  6  10 31 ) [MP PET 2003]
product of silver chromate will be [MP PET 1992; CPMT 1993]
(a) Upto 4.4 (b) Upto 4.1
8 12
(a) 4  10 (b) 8  10 (c) Upto 4.2 (d) Upto 4.0
12 12
(c) 12  10 (d) 32  10 27. NH 4 Cl is acidic, because [JEE Orissa 2004]
 400 Ionic Equilibrium
(a) On hydrolysis NH 4 Cl gives weak base NH 4 OH 34. 40 mg of pure sodium hydroxide is dissolved in 10
and strong acid HCl litres of distilled water. The pH of the solution is
[Kerala PMT 2004]
(b) Nitrogen donates a pair of electron
(a) 9.0 (b) 10
(c) It is a salt of weak acid and strong base
(c) 11 (d) 12
(d) On hydrolysis NH 4 Cl gives strong base and
(e) 8
weak acid
35. Solubility of PbI2 is 0.005 M. Then, the solubility
28. A solution of weak acid HA containing 0.01 moles
product of PbI2 is [BVP 2004]
of acid per litre of solutions has pH  4 . The
percentage degree of ionisation of the acid and (a) 6 .8  10 6
the ionisation constant of acid are respectively [UPSEAT 2001]
(b) 6 .8  10 6
(a) 1 %, 10 6 (b) 0 . 01 %, 10 4
(c) 2 .2  10 9
(c) 1 %, 10 4 (d) 0 .01 %, 10 6
(d) None of these
29. The pH of a buffer solution containg 0.2 mole per
36. A monoprotic acid in a 0.1 M solution ionizes to
litre CH 3 COONa and 1.5 mole per litre CH 3 COOH is
0.001%. Its ionisation constant is
(Ka for acetic acid is 1 .8  10 5 ) [CPMT 2001]
[MP PET 1985,88,99; MP PMT1988; CPMT 2003]
(a) 4.87 (b) 5.8
(c) 2.4 (d) 9.2 (a) 1 .0  10 3 (b) 1 .0  10 6
30. 100 mL of 0.04 N HCl aqueous solution is mixsed (c) 1 .0  10 8 (d) 1 .0  10 11
with 100 mL of 0.02 N NaOH solution. The pH of 37. Select the pK a value of the strongest acid from the
the resulting solution is [UPSEAT 2004]
following
(a) 1.0 (b) 1.7
[KCET 2004]
(c) 2.0 (d) 2.3
31. An alcoholic drink substance pH  4 .7 then (a) 1.0 (b) 3.0
OH ion concentration of this solution is (c) 2.0 (d) 4.5
14
(K w  10 2 2
mol / l )
38. At 90°C, pure water has H 3 O  ion concentration
[RPMT 2002]
10 10
of 10 6 mol / L1 . The K w at 90°C is [DCE 2004]
(a) 3  10 (b) 5  10
(c) 1  10 10 (d) 5  10 8 (a) 10 6 (b) 10 14
32. In its 0.2 M solution, an acid ionises to an extent (c) 10 12 (d) 10 8
of 60%. Its hydrogen ion concentration is
39. By adding 20 ml 0.1 N HCl to
(a) 0.6 M (b) 0.2 M
(c) 0.12 M (d) None of these 20 ml 0.1 N KOH , the pH of the obtained solution
33. pH of 0.1 M NH 3 aqueous solution is will be [CPMT 1975, 86, 93]

(Kb  1 .8  10 5 ) [UPSEAT 2004] (a) 0 (b) 7

(a) 11.13 (b) 12.5 (c) 2 (d) 9

(c) 13.42 (d) 11.55
 Ionic Equilibrium 401

(SET -9)

1. (b) Blood consists of H 2 CO 3  HCO 3 buffer pH   log [H  ] ; pH   log [5 .5  10 3 ] ; pH  2 . 26

solution. [Salt]
9. (a) pH  pK a  log
2. (c) AgI ⇌ Ag   I  ; Ksp  S 2  10 4  S [Acid]
(s) (s)
1
1.0  10 16 mol 2
S 4
 1  10 12 2 pH  4 . 3  log 2  4 . 3  log 1 ; pH  4 .3  0  4 .3
10 l 1
1 2
3. (c) Milliequivalents of HCl  5  1
5 1 .25
10. (b) [H  ]  C   0 .01 
1 100
Milliequivalents of NaOH  10  1
10 H   1 .25  10 3 ; pH  between 2 or 3  2.90
M M 1
 5 ml HCl  10 ml HCl 11. (d) M.eq. of HCl   75  15
5 5 5
Hence the solution will be neutral i.e., pH  7 . 1
M.eq. of NaOH  25  5
4. (d) pH  14  pOH  14  3  11 5

5. (b) HCl is strong acid. In its .1M solution, Total No. of eq.  15  5  10

[H ]  0 .1M and hence, pH  1 Total volume = 100
NH 4 Cl(aq ) hydrolyses in solution and give acidic 10 1
Normality   , [H  ]  10 1 M
solution which is less acidic than .1M HCl . 100 10
NaCl is not hydrolysed in aqueous solutions. 12. (b) AgBr are not dissolved in NaBr and HBr due to
Its pH  7 NaCN undergoes hydrolysis in common ion effect. And pure water is a
solution to give alkaline solution. So that pH neutral solvent. They do not have ions.
increases in the order, 13. (a) CaC2 O 4 is a binary electrolyte. Then solubility
HCl  NH4 Cl  NaCl  NaCN is
14
Kw 10 S  K sp  2 . 5  10 9
6. (a) K h    10  9
Ka 1  10  5
 5  10 5 mole/l.  0 . 0064 gm/l.
Kh 1  10 9
Kh   2C ;     1  10  3 14. (a)
C .001
15. (d) Mg(OH ) 2 ⇌ Mg    2 OH 
7. (c) Ka  Kb  Kw K sp  S ( 2 S )2

Kw 10 14 K sp  S  4S 2
K a    6.75  10 4
Kb 1.48  10 11
K sp 9  10 12
8. (a) [H  ]  5.5  10 3 mole/litre
S2   2.25  10 10
S 4 .010  4
 402 Ionic Equilibrium
S  2.25  10 10  1.5  10 5 m/l H  10 4
   2  10  6
C 10
Kw 10 14
16. (c) For hydrolysis of B  ; K H    10 8 . [Salt]
Kb 10 6 29. (a) pH  log K a  log
[Acid]
17. (a) A p Bq ⇌ pA1  qB p 
0 .2
  log [1 .8  10 5 ]  log  4 .87
q p p q p q
Ls  [ A ] [B ]  ( p  S ) (q  S )  S p q p q
. p .q . 0.1
30. (c) N1V1  .04  100  4
18. (c) H 3 O   HF  NH 4  H 2 O  OH  .
N 2 V2  .02  100  2
Acidic nature is decreasing order.
N 1 V1  N 2 V2  N 3 V3
19. (a) Solubility of CaC 2 O4  K sp  2 .5  10 9
4  2  N 3  200 , N 3  10 2 M
5 1
 5  10 molL
1 1
pH  log 10  log 10  2.
 5  10 5  128  640  10 5  0 . 0064 g H 10  2
20. (d) K sp of Ag 2 CrO 4  [ Ag  ] 2 [Cro 4  ] 31. (b) pH  4 .7

CrO 4   2  10 4 then Ag   2  2  10 4 pH  pOH  14 ; pH  14  4 .7 ; pOH  9 .3

[OH  ]  Antilog [ pOH ]  Antilog [9 .3]

K sp  (4  10 4 )2 (2  10 4 )  32  10 12

21. (c) Relative strength of bases can be shown by [OH  ]  5  10 10

their conjugated acids.
Conjugate acid of OH  is H 2O which is a
CH 3 COO 
weak acid conjugate acid of is
***
CH 3 COOH which is stronger than H 2O . while 32. (c) [H  ]  C .  ,  0 .2  0 .60  0 .12 M
conjugate acid of Cl  is HCl which is
33. (a) NH 4 OH ⇌ NH 4  OH 
strongest out of there. so the order of relative
strength of bases is OH   CH 3 COO   Cl  . 1 .8  10 5
K b  C 2 ;   2 ;   1.34  10 3
22. (a) HSO 4  OH   SO 42   H 2 O .1
[OH  ]   . C  1 .34  10 3  .1
Conjugate acid Conjugate base

23. (a) One mole oxalic acid & 0.5 mole of NaOH will
1
make. pOH  log 10 ; pOH  2 .87
1 . 34  10  4
24. (b) Smallest value of Kb indicates that aniline
pH  pOH  14 ; pH  2.87  14
(C2 H5 NH 2 ) is the weakest base.
pH  14  2 .87 ; pH  11 . 13
25. (a) [H  ] 2  C .   0 .1  5  10 8
Solute in 1 litre solution
34. (b) M 
H   5  10 9  7.07  10 5 M. Molecular weight of solute

26. (d) K sp  [Cr 3  ][OH  ]3 40  10 3 1

   10 4 M
40 10
6  10 31
[OH ] 3  K sp / Cr 3    6  10  30 1 1
1  10 1 pOH  log 10  log 10 4
 10
[OH  ] 10  4
[OH ]  1.8  10
pH  pOH  14 ; pH  4  14  pH  10 .
pOH  (log 1.8  log 10 10 )  10  0 .25  1  11 . 25
35. (d) PbI 2  Pb  I 2
pH  14  11 .25  2.27 x 2x

27. (a) NH 3 Cl  H 2 O ⇌ NH 4 OH  HCl K sp  4 x 3  4(.005 )3  4  .005  .005  .4  10 6 .

NH 4 Cl is a salt of weak base & strong acid so 36. (d)  Monoprotic acid HA
solution will be acidic.
HA ⇌ H   A 

28. (a) H  C Ionisation constant = ?
 Ionic Equilibrium 403
0 .001
  0 .001 %   10 5
100

2 [10 5 ] 2
K   10 11 .
V 10
37. (a) pKa  then strongest acid
pKa  then weak acid
1
pKa 
Acidic strength

38. (c) H 3 O   H 2 O  H 
10  6 10  6 10  6

K w  [H 2 O][ H  ] = [10 6 ][10 6 ]  10 12

39. (b) Neutralization reaction will takes place and

form salt of strong acid and strong base.
Which does not hydrolysed and thus pH  7 .

`
Thermodynamics and Thermochemistry
Thermodynamics
Thermodynamics (Greek word thermo means heat
and dynamics means motion) is the branch of science
which deals with the study of different forms of energy
and the quantitative relationships between them.
The complete study of thermodynamics is based
upon three generalizations called first, second and third
law of thermodynamics. These laws have been arrived
purely on the basis of human experience and there is no
theoretical proof for any of these laws.
Basic concepts
(1) System, surroundings and Boundary : A
specified part of the universe which is under
observation is called the system and the remaining
portion of the universe which is not a part of the
system is called the surroundings.
The system and the surroundings are separated by
real or imaginary boundaries. The boundary also defines
the limits of the system. The system and the
surroundings can interact across the boundary.
(2) Types of systems
(i) Isolated system : This type of system has no
interaction with its surroundings. The boundary is
sealed and insulated. Neither matter nor energy can be
exchanged with surrounding. A substance contained in
an ideal thermos flask is an example of an isolated
system.
(ii) Closed system : This type of system can
exchange energy in the form of heat, work or radiations
but not matter with its surroundings. The boundary
between system and surroundings is sealed but not
insulated. For example, liquid in contact with vapour in
a sealed tube and pressure cooker.
Thermodynamics and Thermochemistry 403
Chapter
10
(iii) Open system : This type of system can
exchange matter as well as energy with its surroundings.
The boundary is neither sealed nor insulated. Sodium
reacting with water in an open beaker is an example of
open system.
(iv) Homogeneous system : A system is said to be
homogeneous when it is completely uniform
throughout. A homogeneous system is made of one
phase only. Examples: a pure single solid, liquid or gas,
mixture of gases and a true solution.
(v) Heterogeneous system : A system is said to be
heterogeneous when it is not uniform throughout, i.e.,
it consist of two or more phases. Examples : ice in
contact with water, two or more immiscible liquids,
insoluble solid in contact with a liquid, a liquid in
contact with vapour, etc.
(vi) Macroscopic system : A macroscopic system
is one in which there are a large number of particles
(may be molecules, atoms, ions etc. )
(3) Macroscopic properties of the system
Thermodynamics deals with matter in terms of
bulk (large number of chemical species) behaviour. The
properties of the system which arise from the bulk
behaviour of matter are called macroscopic properties.
The common examples of macroscopic properties are
pressure, volume, temperature, surface tension,
viscosity, density, refractive index, etc.
The macroscopic properties can be subdivided
into two types,
(i) Intensive properties : The properties which do
not depend upon the quantity of matter present in the
system or size of the system are called intensive
properties. Its examples are pressure, temperature,
density, specific heat, surface tension, refractive index,
 404 Thermodynamics and Thermochemistry
viscosity, melting point, boiling point, volume per
mole, concentration etc.
(ii) Extensive properties : The properties whose
magnitude depends upon the quantity of matter present
in the system are called extensive properties. Its
examples are total mass, volume, internal energy,
enthalpy, entropy etc. These properties are additive in
nature.
Any extensive property if expressed as per mole or
per gram becomes an intensive property.
(4) State of a system and State Variables
Macroscopic properties which determine the state
of a system are referred to as state variables or state
functions or thermodynamic parameters. The change in
the state properties depends only upon the initial and
final states of the system, but it is independent of the
manner in which the change has been brought about. In
other words, the state properties do not depend upon a
path followed.
(5) Thermodynamic equilibrium : “A system is
said to have attained a state of thermodynamic
equilibrium when it shows no further tendency to change
its property with time”.
The criterion for thermodynamic equilibrium
requires that the following three types of equilibrium
exist simultaneously in a system,
(i) Chemical Equilibrium : A system in which the
composition of the system remains fixed and definite.
(ii) Mechanical Equilibrium : No chemical work
is done between different parts of the system or
between the system and surrounding. It can be
achieved by keeping pressure constant.
(iii) Thermal Equilibrium : Temperature remains
constant i.e. no flow of heat between system and
surrounding.
(6) Thermodynamic process : When the
thermodynamic system changes from one state to
another, the operation is called a process. The various
types of the processes are
(i) Isothermal process : In this process operation
is done at constant temperature. dT = 0 thus E  0 .
(ii) Adiabatic process : In this a process there is
no exchange of heat takes place between the system
and surroundings. The system is thermally isolated,
i.e., dQ = 0 and its boundaries are insulated.
(iii) Isobaric process : In this process the
pressure remains constant throughout the change i.e.,
dP = 0.
(iv) Isochoric process : In this process volume
remains constant throughout the change, i.e., dV = 0.
(v) Cyclic process : When a system undergoes a
number of different processes and finally return to its
initial state, it is termed cyclic process. For a cyclic
process dE = 0 and dH = 0.
(vi) Reversible process : A process which occurs
infinitesimally slowly, i.e. opposing force is
infinitesimally smaller than driving force and when
infinitesimal increase in the opposing force can reverse
the process, it is said to be reversible process.
(vii) Irreversible process : When the process
occurs from initial to final state in single step in finite
time and cannot be reversed, it is termed an
irreversible process. Amount of entropy increases in
irreversible process.
Irreversible processes are spontaneous in nature.
All natural processes are irreversible in nature
Internal energy, heat and Work
(1) Internal energy (E) : “Every system having
some quantity of matter is associated with a definite
amount of energy. This energy is known as internal
energy.”
E  E translatio nal  Erotational  E vibrationa l  E bonding  Eelectronic  ......
(i) Characteristics of internal energy
(a) Internal energy of a system is an extensive
property.
(b) Internal energy is a state property.
(c) The change in the internal energy does not
depend on the path by which the final state is reached.
(d) There is no change in internal energy in a
cyclic process.
(e) The internal energy of an ideal gas is a
function of temperature only.
(f) Internal energy of a system depends upon the
quantity of substance, its chemical nature,
temperature, pressure and volume.
(g) The unit of E is ergs in CGS or joules in SI
1 Joule = 10 7 ergs.
(ii) Change in internal energy ( E ) : It is neither
possible nor necessary to calculate the absolute value
of internal energy of a system then, E  E f  Ein ; E
is positive if E f  Ein and negative if E f  Ein .
(2) Heat (q) and work (w) : The energy of a
system may increase or decrease in several ways but
two common ways are heat and work.
Heat is a form of energy. It flows from one system
to another because of the difference in temperature
between them. Heat flows from higher temperature to
lower temperature. Therefore, it is regarded as energy
on the move.

Work is said to be performed if the point of
application of force is displaced in the direction of the
force. It is equal to the force multiplied by the
displacement (distance through which the force acts).
There are three main types of work which we
generally come across. These are, Gravitational work,
electrical work and mechanical work.
Mechanical work = Force  displacement = F.d
Electrical work = potential difference  charge =
V.q
Gravitational work = mgh
(i) Units of heat and work : The heat changes are
measured in calories (cal), Kilo calories (kcal), joules
(J) or kilo joules (kJ). These are related as, 1 cal = 4.184
J; 1kcal = 4.184kJ
The S.I. unit of heat is joule (J) or kilojoule. The
Joule (J) is equal to Newton – metre (1 J= 1 Nm).
Work is measured in terms of ergs or joules. The
S.I. unit of work is Joule.
1 Joule = 10 7 ergs = 0.2390 cal.
1 cal > 1 joule > 1 erg
(ii) Sign conventions for heat and work
Heat absorbed by the system = q positive
Heat evolved by the system = q negative
Work done on the system = w positive
Work done by the system = w negative.
Zeroth law of thermodynamics
This law forms the basis of concept of temperature.
This law can be stated as follows,
“If a system A is in thermal equilibrium with a
system C and if B is also in thermal equilibrium with
system C, then A and B are in thermal equilibrium with
each other whatever the composition of the system.”
A ⇌ C B ⇌ C
A ⇌ B
First law of thermodynamics
Helmholtz and Robert Mayer proposed first law of
thermodynamics. This law is also known as law of
conservation of energy. It states that,
“Energy can neither be created nor destroyed
although it can be converted from one form into
another.”
E2  E1  E  q  w
i.e. (Change in internal energy) = (Heat added to
the system) +(Work done on the system)
Thermodynamics and Thermochemistry 405
If a system does work (w) on the surroundings, its
internal energy decreases. In this case,
E  q  (w)  q  w
i.e.(Change in internal energy)=(Heat added to
the system) – (work done by the system)
The relationship between internal energy, work
and heat is a mathematical statement of first law of
thermodynamics.
Enthalpy and Enthalpy change
Heat content of a system at constant pressure is
called enthalpy denoted by ‘H’.
From first law of thermodynamics, q  E  PV
……….(i)
Heat change at constant pressure can be given as
q  E  PV
……….(ii)
At constant pressure heat can be replaced at
enthalpy.
H  E  PV
………(iii)
H  Heat change or heat of reaction (in
chemical process) at constant pressure
E  Heat change or heat of reaction at constant
volume.
In case of solids and liquids participating in a
reaction,
H  E (PV  0)
Difference between H and E is significant
when gases are involved in chemical reaction.
H  E  PV
H  E  nRT
PV  nRT
Here, n  nP – nR
Specific and Molar heat capacity
(1) Specific heat (or specific heat capacity) of a
substance is the quantity of heat (in calories, joules,
kcal, or kilo joules) required to raise the temperature of
1g of that substance through 1 o C . It can be measured at
constant pressure (c p ) and at constant volume (cv ) .
(2) Molar heat capacity of a substance is the
quantity of heat required to raise the temperature of 1
mole of the substance by 1 o C .
 Molar heat capacity = Specific heat capacity 
Molecular weight, i.e., Cv  cv  M and C p  c p  M .
 406 Thermodynamics and Thermochemistry
(3) Since gases on heating show considerable If the external pressure is decreased by an
tendency towards expansion if heated under constant infinitesimal amount dP, the gas will expand by an
pressure conditions, an additional energy has to be infinitesimal volume, dV. As a result of expansion, the
supplied for raising its temperature by 1o C relative to pressure of the gas within the cylinder falls to Pgas  dP ,
that required under constant volume conditions, i.e., i.e., it becomes again equal to the external pressure
C p  Cv or C p  Cv  Work done in expansion, PV ( R) and, thus, the piston comes to rest. Such a process is
repeated for a numberPext Pext –step
of times, i.e., in each dP the
where, Cp  molar heat capacity at constant
gas expands by a volume dV.
pressure
Cv  molar heat capacity at constant dV
volume.
(4) Some useful relations of Cp and Cv Pgas
(i) C p  Cv  R  2 calories 8.314 J Pgas

3 3 Fig. 10.1
(ii) C v  R (for monoatomic gas) and Cv   x
2 2
(for di and polyatomic gas), where x varies from gas to Since the system is in thermal equilibrium with
gas. the surroundings, the infinitesimally small cooling
Cp produced due to expansion is balanced by the
(iii)   (Ratio of molar capacities) absorption of heat from the surroundings and the
Cv
temperature remains constant throughout the
(iv) For monoatomic gas, Cv  3 calories whereas, expansion.
C p  Cv  R  5 calories The work done by the gas in each step of
expansion can be given as,
5
R
Cp dw  (Pext  dP)dV  Pext .dV  dP . dV
(v) For monoatomic gas, ( )   2  1 . 66
Cv 3 dP .dV , the product of two infinitesimal quantities,
R
2 is negligible.
7 The total amount of work done by the isothermal
Cp R
(vi) For diatomic gas ( )   2  1 . 40 reversible expansion of the ideal gas from volume V1 to
Cv 5
R V2
2 volume V2 is, given as, w  nRT log e or
V1
Cp 8R
(vii) For triatomic gas ( )    1 . 33 V2
Cv 6R w  2.303 nRT log 10
V1
Expansion of an ideal gas At constant temperature, according to Boyle’s law,
V P P
(1) Isothermal Expansion : For an isothermal P1 V1  P2 V2 or 2  1 So, w  2.303 nRT log 10 1
V1 P2 P2
expansion, T  0 ; E  0.
Isothermal compression work of an ideal gas may
According to first law of thermodynamics,
be derived similarly and it has exactly the same value
E  q  w q  w
with positive sign.
This shows that in isothermal expansion, the V P
w compressio n  2.303 nRT log 1  2.303 nRT log 2
work is done by the system at the expense of heat V2 P1
absorbed. (ii) Work done in irreversible isothermal
Since for isothermal process, E and T are zero expansion : Two types of irreversible isothermal
respectively, hence, H  0 expansions are observed, i.e., (a) Free expansion and
(i) Work done in reversible isothermal (b) Intermediate expansion. In free expansion, the
expansion : Consider an ideal gas enclosed in a external pressure is zero, i.e., work done is zero when
cylinder fitted with a weightless and frictionless gas expands in vacuum. In intermediate expansion, the
piston. The cylinder is not insulated. The external external pressure is less than gas pressure. So, the
pressure, Pext is equal to pressure of the gas, Pgas . work done when volume changes from V1 to V2 is given
Pext  Pgas  P by


V2
w   Pext  dV   Pext (V2  V1 )
V1
 Thermodynamics and Thermochemistry 407
Since Pext is less than the pressure of the gas, the  T P  T1 P2 
or w  Cv (T2  T1 )   RPext  2 1 

work done during intermediate expansion is  P1 P2 
numerically less than the work done during reversible
isothermal expansion in which Pext is almost equal to
Spontaneous and Non-spontaneous processes
Pgas . A process which can take place by itself under the
given set of conditions once it has been initiated if
(2) Adiabatic Expansion : In adiabatic expansion, necessary, is said to be a spontaneous process. In other
no heat is allowed to enter or leave the system, hence, words, a spontaneous process is a process that can
q0. occur without work being done on it. The spontaneous
According to first law of thermodynamics, processes are also called feasible or probable processes.
E  q  w  E  w On the other hand, the processes which are
forbidden and are made to take place only by supplying
work is done by the gas during expansion at the
energy continuously from outside the system are called
expense of internal energy. In expansion, E decreases
non-spontaneous processes. In other words, non
while in compression E increases.
spontaneous processes can be brought about by doing
The molar specific heat capacity at constant
work.
volume of an ideal gas is given by
Examples of Spontaneous and Non-spontaneous
 dE  processes
Cv    or dE  Cv .dT
 dT v (1) The diffusion of the solute from a
and for finite change E  Cv T So, w  E  Cv T concentrated solution to a dilute solution occurs when
these are brought into contact is spontaneous process.
The value of T depends upon the process
whether it is reversible or irreversible. (2) Mixing of different gases is spontaneous
process.
(i) Reversible adiabatic expansion : The
following relationships are followed by an ideal gas (3) Heat flows from a hot reservoir to a cold
under reversible adiabatic expansion. reservoir is spontaneous process.
(4) Electricity flows from high potential to low
PV   constant
potential is spontaneous process.
where, P = External pressure, V = Volume
(5) Expansion of an ideal gas into vacuum through
Cp a pinhole is spontaneous process.
 
Cv All the above spontaneous processes becomes
where, Cp  molar specific heat capacity at non-spontaneous when we reverse them by doing work.
constant pressure, Cv  molar specific heat capacity at Spontaneous process and Enthalpy change : A
spontaneous process is accompanied by decrease in
constant volume.
internal energy or enthalpy, i.e., work can be obtained
  1 1 
 T1  P  P  by the spontaneous process. It indicates that only
   1    2 
T  P   exothermic reactions are spontaneous. But the melting
 2   2   P1 
of ice and evaporation of water are endothermic
knowing  , P1 , P2 and initial temperature T1 , the
processes which also proceeds spontaneously. It means,
final temperature T2 can be evaluated. there is some other factor in addition to enthalpy
(ii) Irreversible adiabatic expansion : In free change (H ) which explains the spontaneous nature of
expansion, the external pressure is zero, i.e, work done the system. This factor is entropy.
is zero. Accordingly, E which is equal to w is also Second law of thermodynamics
zero. If E is zero, T should be zero. Thus, in free
All the limitations of the first law of
expansion (adiabatically), T  0 , E  0 , w  0 and
thermodynamics can be remove by the second law of
H  0 .
thermodynamics. This law is generalisation of certain
In intermediate expansion, the volume changes experiences about heat engines and refrigerators. It has
from V1 to V2 against external pressure, Pext . been stated in a number of ways, but all the statements
 RT RT  are logically equivalent to one another.
w  Pext (V2  V1 )   Pext  2  1 
 2P P1  (1) Statements of the law
(i) Kelvin statement : “It is impossible to derive a
 T P  T1 P2 
  Pext  2 1  R
 continuous supply of work by cooling a body to a
 P1 P2 
 408 Thermodynamics and Thermochemistry
temperature lower than that of the coldest of its
surroundings.”
(ii) Clausius statement : “It is impossible for a
self acting machine, unaided by any external agency, to
transfer heat from one body to another at a higher
temperature or Heat cannot itself pass from a colder
body to a hotter body, but tends invariably towards a
lower thermal level.”
(iii) Ostwald statement : “It is impossible to
construct a machine functioning in cycle which can
convert heat completely into equivalent amount of work
without producing changes elsewhere, i.e., perpetual
motions are not allowed.”
(iv) Carnot statement : “It is impossible to take
heat from a hot reservoir and convert it completely into
work by a cyclic process without transferring a part of it
to a cold reservoir.”
(2) Proof of the law : No rigorous proof is
available for the second law. The formulation of the
second law is based upon the observations and has yet
to be disproved. No deviations of this law have so far
been reported. However, the law is applicable to cyclic
processes only.
The Carnot cycle
Carnot, a French engineer, in 1824 employed
merely theoretical and an imaginary reversible cycle
known as carnot cycle to demonstrate the maximum
convertibility of heat into work.
The system consists of one mole of an ideal gas
enclosed in a cylinder fitted with a piston, which is
subjected to a series of four successive operations.
For cyclic process, the essential condition is that
net work done is equal to heat absorbed. This condition
is satisfied in a carnot cycle.
w T  T1
 2  Thermodynamic efficiency
q2 T2
Thus, the larger the temperature difference
between high and low temperature reservoirs, the more
the heat converted into work by the heat engine.
T2  T1
Since  1 , it follows that w  q 2 . This means
T2
that only a part of heat absorbed by the system at the
higher temperature is transformed into work. The rest
of the heat is given out to surroundings. The efficiency
of the heat engine is always less then 1. This has led to
the following enunciation of the second law of
thermodynamics.
It is impossible to convert heat into work without
compensation.
Entropy and Entropy change
(1) Definition : Entropy is a thermodynamic state
quantity which is a measure of randomness or disorder
of the molecules of the system.
Entropy is represented by the symbol “S”. It is
difficult to define the actual entropy of a system. It is
more convenient to define the change of entropy during
a change of state.
The entropy change of a system may be defined as
the integral of all the terms involving heat exchanged
(q) divided by the absolute temperature (T) during each
infinitesimally small change of the process carried out
reversibly at constant temperature.
q rev
S  S final  S initial 
T
If heat is absorbed, then S  ve and if heat is
evolved, then S  ve .
(2) Units of entropy : Since entropy change is
expressed by a heat term divided by temperature, it is
expressed in terms of calorie per degree, i.e.,cal deg-1 .
In SI units, the entropy is expressed in terms of joule
per degree Kelvin, i.e., JK 1 .
(3) Characteristics of entropy : The important
characteristics of entropy are summed up below
(i) Entropy is an extensive property. Its value
depends upon the amount of the substance present in
the system.
(ii) Entropy of a system is a state function. It
depends upon the state variables (T , p, V , n) .
(iii) The change in entropy in going from one
state to another is independent of the path.
(iv) The change in entropy for a cyclic process is
always zero.
(v) The total entropy change of an isolated
system is equal to the entropy change of system and
entropy change of the surroundings. The sum is called
entropy change of universe.
S universe  S sys  S Surr
(a) In a reversible process, S universe  0 and,
therefore
S sys  S Surr
(b) In an irreversible process, S universe  0 . This
means that there is increase in entropy of universe is
spontaneous changes.
(vi) Entropy is a measure of unavailable energy
for useful work.
Unavailable energy = Entropy × Temperature
(vii) Entropy, S is related to thermodynamic
probability (W) by the relation,
S  k loge W and S  2.303 k log10W
 Thermodynamics and Thermochemistry 409
where, k is Boltzmann's constant T2 p
S  nC P ln  nR ln 2 . Assuming C p , is
(4) Entropy changes in system & surroundings T1 p1
and total entropy change for Exothermic and constant
Endothermic reactions : Heat increases the thermal (a) Thus, for an isothermal process (T constant),
motion of the atoms or molecules and increases their V p
disorder and hence their entropy. In case of an S  nR ln 2 or  nR ln 2
V1 p1
exothermic process, the heat escapes into the
(b) For isobaric process (p constant),
surroundings and therefore, entropy of the
T2
surroundings increases on the other hand in case of S  n C p ln
endothermic process, the heat enters the system from T1
the surroundings and therefore. The entropy of the (c) For isochoric process (V constant),
surroundings decreases. T2
S  n Cv ln
In general, there will be an overall increase of the T1
total entropy (or disorder) whenever the disorder of (d) Entropy change during adiabatic expansion : In
the surroundings is greater than the decrease in such process q=0 at all stages. Hence S  0 . Thus,
disorder of the system. The process will be spontaneous reversible adiabatic processes are called isoentropic
only when the total entropy increases. process.
(5) Entropy change during phase transition : Free energy and Free energy change
The change of matter from one state (solid, liquid or
gas) to another is called phase transition. Such changes Gibb's free energy (G) is a state function and is a
occur at definite temperature such as melting point measure of maximum work done or useful work done
(solid to liquid). boiling point (liquid to vapours) etc, from a reversible reaction at constant temperature and
and are accompanied by absorption or evolution of pressure.
heat.
(1) Characteristics of free energy
When a solid changes into a liquid at its fusion (i) The free energy of a system is the enthalpy of
temperature, there is absorption of heat (latent heat). the system minus the product of absolute temperature
Let H f be the molar heat of fusion. The entropy and entropy i.e., G  H  TS
change will be (ii) Like other state functions E, H and S, it is also
H f expressed as G . Also G  H  TS system where S is
S f 
Tf entropy change for system only. This is Gibb's
Helmholtz equation.
Similarly, if the latent heat of vaporisation and
sublimation are denoted by H vap and (iii) At equilibrium G  0

H sub, respectively, the entropy of vaporisation and (iv) For a spontaneous process decrease in free
energy is noticed i.e., G  ve .
sublimation are given by
(v) At absolute zero, TS is zero. Therefore if
H vap H sub
S vap  and S sub  G is – ve, H should be – ve or only exothermic
Tb Ts reactions proceed spontaneously at absolute zero.
Since H f , H vap and H Sub are all positive, these (vi) Gsystem  TS universe , where H  0
processes are accompanied by increase of entropy and (vii) The standard free energy change,
the reverse processes are accompanied by decrease in
G o  2 . 303 RT log 10 K , where K is equilibrium
entropy.
constant.
(6) Entropy change for an ideal gas : In going
from initial to final state, the entropy change, S for an (a) Thus if K  1, then G o  ve thus reactions
ideal gas is given by the following relations, with equilibrium constant K>1 are thermodynamically
(i) When T and V are two variables, spontaneous.

S  nCv ln
T2 V
 nR ln 2 . Assuming Cv is (b) If K<1, then G o  ve and thus reactions
T1 V1 with equilibrium constant K<1 are thermodynamically
constant spontaneous in reverse direction.
(ii) When T and p are two variables, (2) Criteria for spontaneity of reaction : For a
spontaneous change G  ve and therefore use of
 410 Thermodynamics and Thermochemistry
G  H  T S , provides the following conditions for a change to be spontaneous.

Table :10.1 Criteria for spontaneity of reaction

ΔH ΔS ΔG Reaction characteristics Example
– + Always negative Reaction is spontaneous at all 2 O 3 ( g )  3 O 2( g )
temperatures
+ – Always positive Reaction is non spontaneous at all 3 O 2( g )  2 O 3 ( g )
temperatures
– – Negative at low Reaction is spontaneous at low CaO(s)  CO 2(g)  CaCO3(s)
temperature but positive temperature but becomes non
at high temperature spontaneous at high temperature
+ + Positive at low Reaction is non spontaneous at low CaCO3(s)  CaO(s)  CO 2(g)
temperature but negative temperature but becomes spontaneous at
at high temperature high temperature

Third law of thermodynamics exothermic reactions may be represented as,

This law was first formulated by German chemist
Walther Nernst in 1906. According to this law,
“The entropy of all perfectly crystalline solids is
zero at the absolute zero temperature. Since entropy is a
measure of disorder, it can be interpretated that at
absolute zero, a perfectly crystalline solid has a perfect
order of its constituent particles.”
The most important application of the third law of
thermodynamics is that it helps in the calculation of
absolute entropies of the substance at any temperature
T.
S  2.303 C p log T
Where CPis the heat capacity of the substance at
constant pressure and is supposed to remain constant
in the range of 0 to T.
Limitations of the law
(1) Glassy solids even at 0oK has entropy greater
than zero.
(2) Solids having mixtures of isotopes do not have
zero entropy at 0oK. For example, entropy of solid
chlorine is not zero at 0oK.
(3) Crystals of CO, N2O, NO, H2O, etc. do not have
perfect order even at 0oK thus their entropy is not
equal to zero.
Thermochemistry
“Thermochemistry is a branch of physical chemistry
which is concerned with energy changes accompanying
chemical transformation. It is also termed as chemical
energetics. It is based on the first law of
thermodynamics.”
Exothermic and Endothermic reactions
(1) Exothermic reactions : The chemical
reactions which proceed with the evolution of heat
energy are called exothermic reactions. The heat
energy produced during the reactions is indicated by
writing +q or more precisely by giving the actual
numerical value on the products side. In general
A  B  C  D  q (heat energy)
In the exothermic reactions the enthalpy of the
products will be less than the enthalpy of the reactants,
so that the enthalpy change is negative as shown below
H  H p  H r ; H p  H r ; H   ve
Examples : (i) C(s)  O2 (g)  CO2 (g)  393 .5kJ
(at constant temperature and pressure)
or C(s)  O2 (g)  CO2 (g); H  393 . 5 kJ
1
(ii) H 2 (g)  O 2 (g)  H 2 O(l); H  285 . 8 kJ
2
(iii) Fermentation is also an example of
exothermic reaction.
(2) Endothermic reactions : The chemical
reactions which proceed with the absorption of heat
energy are called endothermic reactions. Since the heat
is added to the reactants in these reactions, the heat
absorbed is indicated by either putting (–) or by writing
the actual numerical value of heat on the reactant side
A  B  C  D  q (heat energy)
The heat absorbed at constant temperature and
constant pressure measures enthalpy change. Because
of the absorption of heat, the enthalpy of products will
be more than the enthalpy of the reactants.
Consequently, H will be positive (ve ) for the
endothermic reactions.
H  H p  H r ; H p  H r ; H  ve
Example : (i) N 2 (g)  O2 (g)  2 NO(g); H  180 .5 kJ
(ii) C(s)  2S (s)  CS 2 (l) H  92 .0kJ
(iii) Preparation of ozone by passing silent
electric discharged through oxygen is the example of
endothermic reaction.
(iv) Evaporation of water is also the example
of endothermic reaction.
For exothermic reaction : H or E  ve
For endothermic reaction : H or E  ve

Heat of reaction or Enthalpy of reaction
Heat of reaction is defined as the amount of heat
evolved or absorbed when quantities of the substances
indicated by the chemical equation have completely
reacted. The heat of reaction (or enthalpy of reaction)
is actually the difference between the enthalpies of the
products and the reactants when the quantities of the
reactants indicated by the chemical equation have
completely reacted. Mathematically,
Enthalpy of reaction (heat of reaction)
 H  H P  H R
(1) Factors which influence the heat of reaction
: There are a number of factors which affect the
magnitude of heat of reaction.
(i) Physical state of reactants and products :
Heat energy is involved for changing the physical state
of a chemical substance. For example in the conversion
of water into steam, heat is absorbed and heat is
evolved when steam is condensed. Considering the
following two reactions
1
H 2 (g)  O 2 (g)  H 2 O(g); H   57 .8 kcal
2
1
H 2 (g )  O 2 (g)  H 2 O(l); H   68 .32 kcal
2 (2) Types of heat of reaction
It is observed that there is difference in the value
of H if water is obtained in gaseous or liquid state.
H value in second case is higher because heat is
evolved when steam condenses. Hence, physical sate
always affects the heat of reaction.
(ii) Allotropic forms of the element : Heat energy
is also involved when one allotropic form of an element
is converted into another. Thus, the value of H
depends on the allotropic form used in the reaction. For
example, the value of H is different when carbon in
the form of diamond or in amorphous form is used.
C (diamond) O2 (g)  CO2 (g); H   94 .3 kcal
C (amorphous) O2 (g)  CO2 (g); H   97 .6 kcal
The difference between the two values is equal to
the heat absorbed when 12g of diamond is converted
into 12g of amorphous carbon. This is termed as heat of
transition.
(iii) Temperature : Heat of reaction has been
found to depend upon the temperature at which
reaction is occurring. The variation of the heat of
reaction with temperature can be ascertained by using
Kirchhoff's equation.
H T2  H T1
 C P
T2  T1
Thermodynamics and Thermochemistry 411
Kirchhoff's equation at constant volume may be
given as,
ET2  ET1
 C
T2  T1
(iv) Reaction carried out at constant pressure or
constant volume : When a chemical reaction occurs at
constant volume, the heat change is called the internal
energy of reaction at constant volume. However, most
of the reactions are carried out at constant pressure;
the enthalpy change is then termed as the enthalpy of
reaction at constant pressure. The difference in the
values is negligible when solids and liquids are
involved in a chemical change. But, in reactions which
involve gases, the difference in two values is
considerable.
E  nRT  H or qv  nRT  q p
E = q v  heat change at constant volume;
E H = q p  heat change at constant pressure,
n  total number of moles of gaseous product
- total number of moles of gaseous reactants.
(i) Heat of formation : It is the quantity of heat
evolved or absorbed (i.e. the change in enthalpy) when
one mole of the substance is formed from its
constituent elements under given conditions of
temperature and pressure. It is represented by H f .
When the temperature and pressure are as 25°C and 1
atmospheric pressure. The heat of formation under
these conditions is called standard heat of formation. It
is usually represented by H 0f .
The standard heat of formation of 1 mole of
NH 3 (g) and 1 mole of HCl (g) .
1 3
N 2 (g)  H 2 (g)  NH 3 (g); H (g)  11 kcal
2 2
1 1
H 2 (g)  Cl 2 (g)  HCl ; H f  22 kcal
2 2
It may be calculated by
H 0  [H 0 (products) – H 0 (Reactants) ]
(ii) Heat of combustion : It is the amount of heat
evolved or absorbed (i.e. change in enthalpy) when one
mole of the substance is completely burnt in air or
oxygen. For example
CH 4 (g)  2O2 (g)  CO2 (g)  2H 2 O(l); H   192 kcal
C2 H 6 (g)  3.5 O2 (g)  2CO2 (g)  3 H 2 O(l); H   372 .8 kcal
 412 Thermodynamics and Thermochemistry
It may be calculated by
H 0  [H 0f (P roducts)- H 0f (Reactants)]
The enthalpy or heat of combustion have a
number of applications. Some of these are described
below,
(a) Calorific value of foods and fuels : Energy is
needed for the working of all machines. Even human
body is no exception. Coal, petroleum, natural gas etc.
serve as the principal sources of energy for man-made
machines, the food which we eat serves as a source of
energy to our body.
The energy released by the combustion of foods or
fuels is usually compared in terms of their combustion
energies per gram. It is known as calorific value. The
amount of heat produced in calories or Joules when one
gram of a substance (food or fuel) is completely burnt
or oxidised.
When methane burns, 890.3 kJ mol–1 of energy is
released.
CH 4 (g)  2O 2 (g)  CO 2 (g)  2 H 2 O(l); H CH 4  890 .3 kJ
1 mole (16g)
So, the calorific value of methane =
890 .3
  55 .6 kJ / g
16
(b) Enthalpies of formation : Enthalpies of
formation of various compounds, which are not directly
obtained, can be calculated from the data of enthalpies
of combustions easily by the application of Hess's law.
Heat of reaction   Heat of combustion of reactants
–  Heat of combustion of products.
(iii) Heat of neutralisation : It is the amount of
heat evolved (i.e., change in enthalpy) when one
equivalent of an acid is neutralised by one equivalent of
a base in fairly dilute solution, e.g., Neutralisation
reactions are always exothermic reaction and the value
of H is (ve ) .
HCl(aq.)  NaOH (aq.)  NaCl(aq.)  H 2 O
H   13 .7 kcal
The heat of neutralisation of a strong acid against
a strong base is always constant (13 .7 kcal or
1
57 kJ mole ) . It is because in dilute solutions all strong
acids and bases ionise completely and thus the heat of
neutralisation in such cases is actually the heat of
 
formation of water from H and OH ions, i.e.,
 
H  OH  H 2 O; H   13 .7 kcal
In case of neutralisation of a weak acid or a weak
base against a strong base or acid respectively, since a part
of the evolved heat is used up in ionising the weak acid or
1 1
base, it is always less than 13 .7 kcal mole (57 kJ mole ).
For example,
HCN (aq.)  NaOH (aq.)  NaCN(aq.)  H 2 O
H   2.9 kcal
HCN (aq.) ⇌ H+ + CN–; H = 10.8 Kcal
10 .8 KCal of heat is absorbed for ionisation of
HCN it is heat of dissociation or ionisation
(iv) Heat of solution : It is the amount of heat
evolved or absorbed (i.e., change in enthalpy) when one
mole of the solute is dissolved completely in excess of
the solvent (usually water). For example,
NH 4 Cl(s)  H 2 O(l)  NH 4 Cl(aq.); H   3.90 kcal
BaCl2 (s)  H 2 O(l)  BaCl2 (aq.); H   2.70 kcal
(v) Heat of hydration : It is the amount of heat
evolved or absorbed (i.e change in enthalpy) when 1 mole
of an anhydrous or a partially hydrated salt combines
with the required number of moles of water to form a
specific hydrate. For example,
CuSO 4 (s)  5 H 2 O(l)  CuSO 4 . 5 H 2 O(s); H   18 .69
(vi) Heat of vapourisation : When a liquid is
allowed to evaporate, it absorbs heat from the
surroundings and evaporation is accompanied by
increase in enthalpy. For example: 10 .5 k cals is the
increase in enthalpy when one mole of water is allowed
to evaporate at 25 o C . When the vapours are allowed to
condense to liquid state, the heat is evolved and
condensation of vapour is accompanied by decrease in
enthalpy.
The evaporation and condensation can be
represented as,
H 2 O(l)  H 2 O(g); H   10 .5 kcals (43 .93 kJ)
H 2 O(g)  H 2 O(l); H   10 .5 kcals (43 .93 kJ)
Thus the change in enthalpy when a liquid
changes into vapour state or when vapour changes into
liquid state is called heat of vapourisation.
(vii) Heat of fusion : When a solid is allowed to
melt, it changes into liquid state with the absorption of
heat (increase in enthalpy) and when a liquid is
allowed to freeze, it changes into solid with the
evolution of heat (decrease in enthalpy). The change in
enthalpy of such type of transformations is called
enthalpy of fusion. For example,
H 2 O(ice)  H 2 O(liquid); H   1.44 kcals ( 6.02 kJ)
H 2 O (liquid)  H 2 O (ice); H   1.44 kcals( 6.02 kJ)

(viii) Heat of precipitation : It is defined as the
amount of heat liberated in the precipitation of one
mole of a sparingly soluble substance when solutions of
suitable electrolytes are mixed, for example
Ba 2   SO 42  (aq )  BaSO 4 (s): H   4 .66 kcal
(ix) Heat of sublimation : Sublimation is a
process in which a solid on heating changes directly
into gaseous state below its melting point.
Heat of sublimation of a substance is the amount
of heat absorbed in the conversion of 1 mole of a solid
directly into vapour phase at a given temperature
below its melting point.
I2 (s)  I2 (g) ; H   62 .39 kJ
Most solids that sublime are molecular in nature
e.g. iodine and naphthalene etc.
H sub .  H fusion  H vaporisati on
(3) Experimental determination of the heat of
reaction : The heat evolved or absorbed in a chemical
reaction is measured by carrying out the reaction in an
apparatus called calorimeter. The principle of
measurement is that heat given out is equal to heat
taken, i.e., Q  (W  m)  s  (T2  T1 ),
Where Q is the heat of the reaction (given out), W
is the water equivalent of the calorimeter and m is the
mass of liquid in the calorimeter and s its specific heat,
T2 is the final temperature and T1 the initial
temperature of the system. Different types of
calorimeters are used but two of the common types are,
(i) Water calorimeter and (ii) Bomb calorimeter
Bomb calorimeter : This is commonly used to find
the heat of combustion of organic substances.
Since the reaction in a bomb calorimeter proceeds
at constant volume, the heat of combustion measured is
E
(W  m )(t 2  t1 )  s
E   M kcal
w1
Where M is the molecular mass of the substance,
w 1 is the weight of substance taken, W is the water
equivalent of calorimeter, m is the mass of liquid in the
calorimeter and s is the specific heat of liquid.
H can be calculated from the relation,
H  E  nRT
Laws of thermochemistry
Thermodynamics and Thermochemistry 413
(1) Levoisier and Laplace law : According to this
law enthalpy of decomposition of a compound is
numerically equal to the enthalpy of formation of that
compound with opposite sign, For example,
C(s)  O2  CO2 (g); H  94 .3 kcal
CO2 (g)  C(s)  O2 (g); H  94 .3kcal
(2) Hess's law (the law of constant heat
summation) : This law was presented by Hess in 1840.
According to this law “If a chemical reaction can be
made to take place in a number of ways in one or in
several steps, the total enthalpy change (total heat
change) is always the same, i.e. the total enthalpy
change is independent of intermediate steps involved in
the change.” The enthalpy change of a chemical reaction
depends on the initial and final stages only. Let a
substance A be changed in three steps to D with
enthalpy change from A to B, H1 calorie, from B to
C, H 2 calorie and from C to D, H 3 calorie. Total
enthalpy change from A to D will be equal to the sum of
enthalpies involved in various steps, Total enthalpy
change H steps  H1  H 2  H 3
Now if D is directly converted into A, let the
enthalpy change be H direct. According to Hess's law
H steps  H direct  0, i.e. H steps must be equal to H direct
numerically but with opposite sign. In case it is not so,
say H steps (which is negative) is more that
H direct (which is positive), then in one cycle, some
energy will be created which is not possible on the
basis of first law of thermodynamics. Thus, H steps
must be equal to H direct numerically.
(i) Experimental verification of Hess's law
(a) Formation of carbon dioxide from carbon
First method : carbon is directly converted into
CO 2 (g).
C(s)  O2 (g)  CO2 (g); H  94 .0 kcal
Second method : Carbon is first converted into
CO (g) and then CO (g) into CO2 (g) , i.e. conversion has
been carried in two steps,
1
C(s)  O 2  CO (g) ; H  26 .0 kcal
2
1
CO(g)  O 2  CO 2 (g); H   68 .0 kcal
2
Total enthalpy change C (s) to CO 2 (g);
H  94 .0 kcal
 414 Thermodynamics and Thermochemistry
(b) Formation of ammonium chloride from dissociation energy depends upon the nature of bond
ammonia and hydrochloric acid: and also the molecule in which the bond is present.
First method When a molecule of a compound contains more than
NH 3 (g)  HCl  NH 4 Cl(g); H   42 .2 kcal one bond of the same kind, the average value of the
dissociation energies of a given bond is taken. This
NH4Cl(g)+aq= NH4Cl(aq); H = + 4.0 kcal
average bond dissociation energy required to break each
NH 3 (g)  HCl(g)  aq  NH 4 Cl(aq); H  38 .2 kcal bond in a compound is called bond energy.

Second method Bond energy is also called, the heat of formation

of the bond from gaseous atoms constituting the bond
NH 3 (g)  aq  NH 3 (aq); H  8.4 kcal
with reverse sign.
HCl (g)  aq  HCl (aq ); H  17 .3 kcal
H(g)  Cl(g)  H  Cl (g); H   431 kJ mol 1
NH 3 (aq)  HCl(aq)  NH 4 Cl(aq); H  12 .3 kcal
Bond energy of H  Cl   (enthalpy of formation)
NH 3 (g)  HCl(g)  aq  NH 4 Cl(aq); H  38 .0 kcal  (431 )   431 kJ mol 1
(ii) Applications of Hess's law
Consider the dissociation of water molecule which
(a) For the determination of enthalpies of consists of two O  H bonds. The dissociation occurs in
formation of those compounds which cannot be two stages.
prepared directly from the elements easily using
H 2 O(g)  H(g)  OH (g); H  497 .89 kJ mol 1
enthalpies of combustion of compounds.
(b) For the determination of enthalpies of OH (g)  H (g)  O(g); H  428 .5 kJ mol 1
extremely slow reactions.
The average of these two bond dissociation
(c) For the determination of enthalpies of energies gives the value of bond energy of O  H .
transformation of one allotropic form into another.
Bond energy of O  H bond
(d) For the determination of bond energies.
497 .8  428 .5
  463 .15 kJ mol 1
H reaction   Bond energies of reactants – 2
 Bond energies of products. Similarly, the bond energy of N  H bond in NH 3
(e) For the determination of resonance energy. is equal to one – third of the energy of dissociation of
(f) For the determination of lattice energy. NH 3 and those of C  H bond in CH 4 is equal to one –

Bond energy or Bond enthalpies fourth of the energy of dissociation of CH 4 .

When a bond is formed between atoms, energy is 1664

Bond energy of C  H   416 kJ mol 1
released. Obviously same amount of energy will be 4
required to break the bond. The energy required to
[CH 4 (g)  C(g)  4 H(g); H  1664 kJ mol 1 ]
break the bond is termed bond dissociation energy. The
more precise definition is, Applications of bond energy

“The amount of energy required to break one mole (1) Heat of a reaction   Bond energy of
of bond of a particular type between the atoms in the reactants –  Bond energy of products.
gaseous state, i.e., to separate the atoms in the gaseous (2) Determination of resonance energy : When a
state under 1 atmospheric pressure and the specified compound shows resonance, there is considerable
temperature is called bond dissociation energy.” difference between the heat of formation as calculated
For example, H  H (g)  2 H (g); H   433 kJ mol 1 from bond energies and that determined
experimentally.
Cl  Cl(g)  2Cl (g); H   242 .5 kJ mol 1
Resonance energy = Experimental or actual
1 heat of formation – Calculated heat of formation.
H  Cl(g) H(g)  Cl(g); H   431 kJ mol

The bond dissociation energy of a diatomic

molecule is also called bond energy. However, the bond
 Thermodynamics and Thermochemistry 415
(c) 0
(d) Always positive
5. A well stoppered thermos flask contains some ice
 T  cubes. This is an example of a [AIIMS 1992]
 Joule thomson coeffient    
 p  H (a) Closed system
For cooling   ve (b) Open system

For Heating   ve (c) Isolated system

Neither cooling nor heating   0 (d) Non-thermodynamic system

6. Identify the intensive quantity from the following
 The temperature at which a real gas shows neither
cooling nor heating effect on adiabatic expansion [IIT JEE 1993]
(i.e.,   0 ) is called inversion temperature. (a) Enthalpy and temperature
 Hydrogen has highest calorific value. (b) Volume and temperature
 13 .7 Kcal / mol  57 KJ / mol (be cause of 1 cal =4.2 (c) Enthalpy and volume
Joule) (d) Temperature and refractive index
 Enthalpy of fusion of ice per mole is 6 KJ . 7. Which of the following units represents the
 Order of bond energy in halogen largest amount of energy[CPMT 1989; MP PET 2000]
Cl2  Br2  F2  I2 . (a) Electron volt (b) Erg
 Heat of vapourisation of water per mole is 10.5 (c) Joule (d) Calorie
KCal.
8. Energy equivalent to one erg, one joule and one
 The heat of reaction is independent of the time calorie is in the order [NCERT 1980; CPMT 1997]
consumed in the process.
(a) 1 erg 1 joule 1 calorie (b) 1 erg 1 calorie1 joule

(c) 1 calorie1 joule 1 erg (d) 1 joule 1 calorie1 erg

Basic concepts

1. Internal energy of an ideal gas depends on

(a) Volume (b) Temperature
(c) Pressure (d) None of these
2. Any series of operations so carried out that at the
end, the system is back to its initial state is called
(a) Boyle's cycle (b) Reversible process
(c) Adiabatic process (d) Cyclic process
3. One calorie is equal to [CPMT 1988]

(a) 0.4184 Joule (b) 4.184 Joule

(c) 41.84 Joule (d) 418.4 Joule
4. The total internal energy change for a reversible
isothermal cycles is
(a) Always 100 calories per degree
(b) Always negative
 414 Thermodynamics and Thermochemistry
9. Heat produced in calories by the combustion of 18. In an isochoric process the increase in internal
one gram of carbon is called energy is
(a) Heat of combustion of carbon [MP PMT 1997]
(b) Heat of formation of carbon (a) Equal to the heat absorbed
(c) Calorific value of carbon (b) Equal to the heat evolved
(d) Heat of production of carbon (c) Equal to the work done
10. Conditions of standard state used in (d) Equal to the sum of the heat absorbed and
thermochemistry is work done
(a) 0 o C and 1 atm (b) 20 o C and 1 atm 19. It is general principle that the less energy a
system contains, it is [MH CET 1999]
(c) 25 o C and 1 atm (d) 0 K and 1 atm
(a) Less stable (b) More stable
11. The temperature of the system decreases in an [KCET 2005] (c) Unstable (d) More unstable
(a) Adiabatic compression (b)Isothermal compression 20. Internal energy is an example of [Pb. PMT 2000]
(c) Isothermal expansion (d)Adiabatic expansion (a) Path function (b) State function
12. For the isothermal expansion of an ideal gas (c) Both (a) and (b) (d) None of these
(a) E and H increases 21. The process, in which no heat enters or leaves the
system, is termed as [Pb. PMT 1999; Kerala (Med.) 2002; J &
(b) E increases but H decreases
(a) Isochoric (b) Isobaric
(c) H increases but E decreases
(c) Isothermal (d) Adiabatic
(d) E and H are unaltered
22. The intensive property among these quantities is
13. If a refrigerator's door is opened, then we get [KCET 2002]
[CPMT 1980] (a) Enthalpy (b) Mass/volume
(a) Room heated (c) Mass (d) Volume
(b) Room cooled 23. In thermodynamics which one of the following is
(c) More amount of heat is passed out not an intensive property [Kerala (Med.) 2002]

(d) No effect on room (a) Pressure (b) Density

(c) Volume (d) Temperature
14. The cooling in refrigerator is due to [KCET 2005]
24. If in a container neither mass and nor heat
(a) Reaction of the refrigerator gas
exchange occurs then it constitutes a [MP PMT 1993; AFMC
(b) Expansion of ice (a) Closed system (b) Open system
(c) The expansion of the gas in the refrigerator (c) Isolated system (d) Imaginary system
(d) The work of the compressor 25. Which of the following is not a state function [DCE 2002]
15. Point out the wrong statement in relation to (a) S (b) G
enthalpy (c) H (d) Q
(a) It is a state function 26. Which of the following is true for an adiabatic
(b) It is an intensive property process
[DCE 2002; MP PET 1995, 98, 2004;
(c) It is independent of the path followed for the CPMT 1990; MP PMT 1998, 2002]
change (a) H  0 (b) W  0
(d) Its value depends upon the amount of (c) Q  0 (d) V  0
substance in the system 27. Which of the following is not a state function
16. Which of the following is zero for an isochoric [MH CET 2004; AIIMS 2001]
process (a) Internal energy (b) Enthalpy
(a) dP (b) dV (c) Work (d) Entropy
(c) dT (d) dE 28. Among them intensive property is [AFMC 2004]
17. Mark the correct statement [MP PET 1997] (a) Mass (b) Volume
(c) Surface tension (d) Enthalpy
(a) For a chemical reaction to be feasible, G
should be zero
First law of thermodynamics and Hess law
(b) Entropy is a measure of order in a system
(c) For a chemical reaction to be feasible, G
1. The first law of thermodynamics is only
should be positive
(a) The law of conservation of energy
(d) The total energy of an isolated system is
constant (b) The law of conservation of mass
 Thermodynamics and Thermochemistry 415
(c) The law of conservation of momentum 9. For the reaction N 2  3H 2 ⇌ 2 NH 3 ; H 
(d) Both (a) and (b) [Roorkee 2000; CBSE PMT 1991, 2002]
2. A mixture of two moles of carbon monoxide and
(a) E  RT (b) E  2 RT
one mole of oxygen, in a closed vessel is ignited to
convert the carbon monoxide to carbon dioxide. If (c) E  RT (d) E  2 RT
H is the enthalpy change and E is the change 10. If H is the change in enthalpy and E the
in internal energy, then [KCET 2005] change in internal energy accompanying a
(a) H  E gaseous reaction
(b) H  E [KCET 1989; CBSE PMT 1990]

(c) H  E (a) H is always greater than E

(d) The relationship depends on the capacity of (b) H  E only if the number of moles of the
the vessel products is greater than the number of the
reactants
3. Which of the following is always negative for
exothermic reaction? [BCECE 2005] (c) H is always less than E
(a) H (b) S (d) H  E only if the number of moles of the
(c) G (d) None of these products is less than the number of moles of
4. The relation between E and H is the reactants
[MP PET 1992; MP PMT 1996; MP PET/PMT 1998] 11. “The resultant heat change in a reaction is the
(a) H  E  P V (b) H  E  P V same whether it takes place in one or several
stages.” This statement is called[MP PMT/PET 1988; MP PM
(c) E  V  H (d) E  H  P V
(a) Lavoisier and Laplace law
5. At constant T and P, which one of the following (b) Hess's law
statements is correct for the reaction,
(c) Joule's law
1
CO(g)  O2 (g)  CO2 (g) (d) Le–chatelier's principle
2
[AIIMS 1982, 83; KCET 1988; BHU 1995; MP PET 1997, 99] 12. Hess's law of constant heat summation in based
on
(a) H is independent of the physical state of the
reactants of that compound [MP PET 2001]

(b) H  E (a) E  mc 2

(b) Conservation of mass

(c) H  E
(c) First law of thermodynamics
(d) H  E
(d) None of the above
6. For the reaction of one mole of zinc dust with one
13. Consider the reaction : N 2  3 H 2  2 NH 3 carried
mole of sulphuric acid in a bomb calorimeter, U
and w correspond to [AIIMS 2005] out at constant temperature and pressure. If H
(a) U  0 , w  0 (b) U  0 , w  0 and U are the enthalpy and internal energy
changes for the reaction, which of the following
(c) U  0 , w  0 (d) U  0 , w  0
expression is true [AIEEE 2005]
7. Which is not the correct relation between (a) H  0 (b) H  U
enthalpy (H ) and intrinsic energy  E) [EAMCET 1992] (c) H  U (d) H  U
(a) H  E  P V (b) H  E  n RT 14. Which of the following is the correct equation
(c) H  E  P V (d) E  H  P V [CBSE PMT 1996]
(a) U  Q  W (b) W  U  Q
8. The law of Lavoisier and Laplace illustrates
[KCET 1989] (c) U  W  Q (d) None of these

(a) The principle of conservation of energy 15. Hess law is applicable for the determination of
heat of
(b) Equivalence of mechanical and thermal energy
[AIIMS 1998; Pb. PET/PMT 1999]
(c) The principle of conservation of matter
(a) Reaction (b) Formation
(d) Equivalence of mechanical and chemical
(c) Transition (d) All of these
energy
 416 Thermodynamics and Thermochemistry
16. Enthalpy for the reaction C  O2  CO2 is 24. A schematic plot of lnK eq versus inverse of
[DPMT 1987, 91] temperature for a reaction is shown below
(a) Positive (b) Negative 6.0

(c) Zero (d) None

ln Keq
17. During an isothermal expansion of an ideal gas its
[CBSE PMT 1991]
2.0
(a) Internal energy increases 1.5×10–3 1/T (K–1) 2.0×10–3
(b) Enthalpy decreases
The reaction must be [AIEEE 2005]
(c) Enthalpy remains unaffected
(a) Exothermic
(d) Enthalpy reduces to zero
(b) Endothermic
18. The work done in ergs for the reversible
(c) One with negligible enthalpy change
expansion of one mole of an ideal gas from a
(d) Highly spontaneous at ordinary temperature
volume of 10 litres to 20 litres at 25 o C is[CMC Vellore 1991]
25. Hess law of heat summation includes [AFMC 1992]
(a) 2.303  298  0.082 log 2
(a) Initial reactants only
(b) 298  10 7  8 . 31  2 . 303 log 2 (b) Initial reactants and final products

(c) 2.303  298  0.082 log 0.5 (c) Final products only
(d) Intermediates only
(d) 8 . 31  10 7  298  2 . 303 log 0 . 5
26. An ideal gas at constant temperature and pressure
(e) 2.303  298  2 log 2 expands, then its [BHU 1998]

19. The law of conservation of energy states that (a) Internal energy remains same
[NCERT 1984] (b) Internal energy decreases
(a) The internal energy of a system is constant (c) Internal energy increases
(b) The heat content of a system is constant (d) Entropy first increases and then decreases
(c) Energy is neither created nor destroyed 27. The internal energy of a substance
(d) There is an equivalence between energy and [KCET 1998; AFMC 2001; AIIMS 2001]
mass (a) Increases with increase in temperature
20. The enthalpies of the elements in their standard (b) Decreases with increase in temperature
states are assumed to be (c) Can be calculated by the relation E  mc 2
(a) Zero at 298 K (d) Remains unaffected with change in
(b) Unit at 298 K temperature
(c) Zero at all temperatures 28. The relation between change in internal energy
(d) Zero at 273 K (E) , change in enthalpy (H ) and work done (W)

21. The heat Q for a reaction at constant volume is is represented as [AFMC 1999]

equal to (a) H  E  W (b) W  E  H

(c) E  W  H (d) E  H  W
(a) H P  H R (b) H R  H P
29. The enthalpy of neutralization of which of the
(c) EP  ER (d) None of these following acids and bases is nearly 13 .6 Kcal [Roorkee 1999
22. Which of the following expressions represents the (a) HCN and NaOH (b) HCl and KOH
first law of thermodynamics
(c) HCl and NaOH (d) HCl and NH4OH
[MP PET 1996, 2000; AFMC 1997; BHU 1999; AMU 2000;
30. Work done during isothermal expansion of one
KCET (Med.) 2000, 01; CBSE PMT 2000; MP PMT 2002]
mole of an ideal gas from 10 atm to 1 atm at 300 K
(a) E  q  W (b) E  q  W is (Gas constant = 2) [AIIMS 2000]
(c) E  q  W (d) E  q  W (a) 938.8 cal. (b) 1138.8 cal.
23. In a reversible isothermal process, the change in (c) 1381.8 cal. (d) 1581.8 cal.
internal energy is 31. Joule-Thomson expansion is [JIPMER 2000]
(a) Zero (b) Positive (a) Isobaric (b) Isoenthalpic
(c) Negative (d) None of these (c) Isothermal (d) None of these
32. In which of the following E  H [MP PMT 2001]
 Thermodynamics and Thermochemistry 417
(a) N 2 O4 (g) ⇌ 2 NO 2 (g) 1
(d) H 2 (g)  O 2 (g) ⇌ H 2 O(l)
2
(b) 2SO 2 (g)  O2 (g) ⇌ 2SO 3 (g)
41. One mole of an ideal gas is allowed to expand
(c) H 2 (g)  I 2 (g) ⇌ 2 HI (g)
freely and adiabatically into vacuum until its
1 volume has doubled. A statement which is not
(d) H 2 (g)  O 2 (g) ⇌ H 2 O(l)
2 true concerning this expression is
33. In an adiabatic expansion of an ideal gas [Pb. PMT 1998]
[KCET (Med.) 2001; MH CET 2000] (a) H  0 (b) S  0
(a) W   E (b) W  E (c) E  0 (d) W  0
(c) E  0 (d) W  0 42. o
At 27 C, one mole of an ideal gas is compressed
34. For the reaction isothermally and reversibly from a pressure of 2
o
CH 3 COOH (l)  2O2 (g) ⇌ 2CO 2 (g)  2 H 2 O(l) at 25 C atm to 10 atm. The values of E and q are (R  2) [BHU 200
and 1 atm. pressure, H  874 kJ. Then the (a) 0, – 965.84 cal
change in internal energy (E) is ….[Orissa JEE 2002] (b) – 965.84 cal, + 965.84 cal
(a) – 874 kJ (b) – 871.53 kJ (c) + 865.58 cal, – 865.58 cal
(c) – 876.47 kJ (d) + 874 kJ (d) – 865.58 cal, – 865.58 cal
35. In a closed insulated container, a liquid is stirred 43. The work done by a system is 8 joule, when 40
with a paddle to increase its temperature. In this joule heat is supplied to it. What is the increase in
process, which of the following is true[CBSE PMT 2002] internal energy of system
(a) E  W  Q  0 (b) E  0, Q  W  0 [BHU 2001]
(a) 25 J (b) 30 J
(c) E  W  0, Q  0 (d) E  Q  0, W  0
(c) 32 J (d) 28 J
36. Hess law is based on [MH CET 2002]
44. A system absorb 600J of heat and work equivalent
(a) Law of conservation of mass to 300J on its surroundings. The change in
(b) Law of conservation of energy internal energy is
(c) Enthalpy is a state function [Pb. PMT 2004]
(d) None of these (a) 300 J (b) 400 J
37. For the reaction, (c) 500 J (d) 600 J
C3 H 8 (g)  5O2 (g)  3CO2 (g)  4 H 2 O(l) 45. Work done during isothermal expansion of one
at constant temperature, H  E is [CBSE PMT 2003] mole of an ideal gas from 10 atom. to 1 atm at
300K is [BHU 2004]
(a) – RT (b) + RT
(a) 4938.8 J (b) 4138.8 J
(c) – 3RT (d) + 3RT
(c) 5744.1 J (d) 6257.2 J
38. According to Hess’s law, the heat of reaction
46. If gas, at constant temperature and pressure
depends upon
expands then its
[MP PMT 2003]
[MH CET 2003]
(a) Initial condition of reactants
(a) Entropy increases and then decreases
(b) Initial and final conditions of reactants
(b) Internal energy increases
(c) Intermediate path of the reaction
(c) Internal energy remains the same
(d) End conditions of reactants
(d) Internal energy decreases
39. The value of H  E for the following reaction at
47. For the reaction
27 o C will be 2 NH 3 (g)  N 2 (g)  3 H 2 (g) [Kerala (Med.) 2002]
PCl5 (g)  PCl3 (g)  Cl2 (g) [MH CET 2004]
(a) 8 .314  273  (2) (b) 8 .314  300  (2)
(a) H  E (b) H  E
(c) 8 .314  27  (2) (d) 8 .314  300  (2) (c) H  E (d) None of these
40. For which of the following E  H [MP PET 2003] 48. Enthalpy (H ) is equal to [MH CET 2004]
(a) N 2 O4 (g) ⇌ 2 NO 2 (g) (a) Internal energy (E)
(b) 2SO 2 (g)  O2 (g) ⇌ 2SO 3 (g) (b) Product of pressure (P) and volume (V) of gas
(c) Internal energy (E)+PV
(c) H 2 (g)  Cl 2 (g) ⇌ 2 HCl (g)
(d) Work (W) done by a system
 418 Thermodynamics and Thermochemistry
49. E o of combustion of isobutylene is  X kJ mol 1 . (c) – 6 J (d) –608 J
58. For the reaction, A(s)  2 B(g)  4 C(s)  D(l) . H and
The value of H o is [DCE 2004]
U are related as ……… [Orissa JEE 2004]
(a)  E o (b)  E o
(a) H  U (b) H  U  3 RT
(c)  0 (d)  E o
(c) H  U  RT (d) H  U  3 RT
50. One mole of an ideal gas is allowed to expand
reversibly and adibatically from a temperature of IInd & IIIrd Law of thermodynamics and Entropy
o
27 C . If the work done during the process is 3 kJ ,
then final temperature of the gas is (CV  20 J / K) [Pb. CET For a reversible spontaneous change S is
1. 2002]
E P V
(a) 100 K (b) 150 K (a) (b)
T T
(c) 195 K (d) 255 K
q
51. Which of the following is correct regarding the (c) (d) RT log K
T
internal energy of a substance [Pb. CET 2002]
2. When disorder of a system increases, the change
(a) It is a state function is said to be
(b) It increases with increase in temperature (a) Exothermic (b) Non-spontaneous
(c) It can be calculated by experiment (c) Endothermic (d) Spontaneous
(d) It remains unaffected with change in 3. The spontaneous flow of heat is always
temperature (a) From low to high pressure
(b) From high to high pressure
52. For the gaseous reaction,
(c) Unidirectional from lower temperature to
N 2O4  2NO2 [Pb. CET 2003]
higher temperature
(a) H  E (b) H  E (d) Unidirectional from the higher to lower
(c) H  0 (d) H  E temperature
4. Mixing of non-reacting gases is generally
53. 2C  O2  2CO; H  220 kJ
accompanied by
Which of the following statement is correct for (a) Decrease in entropy
this reaction (b) Increase in entropy
[BVP 2004] (c) Change in enthalpy
(a) Heat of combustion of carbon is 110 kJ (d) Change in free energy
(b) Reaction is exothermic 5. An irreversible process occuring isothermally in
an isolated system leads to
(c) Reaction needs no initiation
(a) Zero entropy
(d) All of these are correct
(b) An increase in the total entropy of the system
54. An ideal gas expands in volume from 1  10 3 m 3 to
(c) A decrease in the total entropy of the system
1  10 2 m 3 at 300 K against a constant pressure of (d) None of these
1  10 5 Nm 2 . The work done is [AIEEE 2004] 6. The entropy values (in JK-1 mol-1) of H2(g) = 130.6,
(a) 270 kJ (b) –900 kJ Cl2(g) = 223.0 and HCl(g) = 186.7 at 298 K and 1
(c) –900 J (d) 900 kJ atm pressure. Then entropy change for the
55. Internal energy is [AFMC 2004]
reaction
H 2(g)  Cl2(g)  2 HCl(g) is [BHU 2005]
(a) Partly potential and partly kinetic
(b) Totally kinetic (a) + 540.3 (b) + 727.3
(c) Totally potential (c) – 166.9 (d) + 19.8
(d) None of these 7. Which of the following is the least random state
56. For which of the reaction H  E [MP PET 2004] of water
(a) N 2  3H 2 ⇌ 2NH 3 (b) N 2  O2  2 NO (a) Ice
(b) Liquid water
(c) 2 Na  Cl2  2 NaCl (d) PCl5  PCl3  Cl2
(c) Steam
57. The work done during the expansion of a gas from (d) All present same random state
a volume of 4dm 3 to 6dm 3 against a constant 8. Which one of the following process is non-
external pressure of 3 atm is ( 1L atm  101 .32 J )[CBSE PMT 2004]
spontaneous
(a) + 304 J (b) –304 J (a) Dissolution of CuSO4 in water
 Thermodynamics and Thermochemistry 419
(b) Reaction between H 2 and O 2 to form water 1
(a) Ca(s)  O 2 (g)  CaO(s)
(c) Water flowing down hill 2
(d) Flow of electric current from low potential to (b) CaCO3 (s)  CaO(s)  CO2 (g)
high potential (c) C(s)  O2 (g)  CO2 (g)
9. Which of the following is zero during adiabatic
(d) N 2 (g)  O2 (g)  2 NO(g)
expansion of the gas
(a) T (b) S 17. The occurrence of a reaction is impossible if
(c) E (d) None of these [AIIMS 1982, 91; MP PET 1997;
10. The entropy of crystalline substances at absolute MP PMT 1999; DPMT 2002]
zero going by the third law of thermodynamics (a) H is +ve ; S is also + ve but H  T S
should be taken as (b) H is – ve ; S is also – ve but H  TS
[J & K 2005]
(c) H is – ve ; S is + ve
(a) 100
(d) H is + ve ; S is – ve
(b) 50
18. If the enthalpy of vaporization for water is 186.5
(c) Zero
kJ mol 1 , the entropy of its vaporization will be
(d) Different for different substances
[CPMT 1988; DCE 2000]
11. In which state, the matter have highest entropy
1 1
(a) Solid (b) Liquid (a) 0 .5 JK mol (b) 1 .0 JK 1 mol 1
(c) Gas (d) Equal in all (c) 1 .5 JK 1 mol 1 (d) 2 . 0 JK 1 mol 1
12. Which of the following pairs of a chemical
19. Which of the following statement is true. The
reaction is certain to result in spontaneous
entropy of the universe [MP PMT 1993; CET Pune 1998]
reaction ? [CBSE PMT 2005]
(a) Increases and tends towards maximum value
(a) Exothermic and decreasing disorder
(b) Decreases and tends to be zero
(b) Endothermic and increasing disorder
(c) Remains constant
(c) Exothermic and increasing disorder
(d) Endothermic and decreasing disorder (d) Decreases and increases with a periodic rate
13. When one mole of monoatomic ideal gas at T K 20. When enthalpy and entropy change for a chemical
undergoes adiabatic change under a constant reaction are  2 . 5  10 3 cal and 7.4 cal deg 1
external pressure of 1 atm changes volume from 1 respectively. Predict the reaction at 298 K is
litre to 2 litre.
[AFMC 1998; MH CET 1999; CBSE PMT 2000]
The final temperature in Kelvin would be[IIT 2005]
(a) Spontaneous (b) Reversible
T 2
(a) (2 / 3 ) (b) T + (c) Irreversible (d) Non-spontaneous
2 3  0 . 0821
21. The total entropy change for a system and its
2
(c) T (d) T  surroundings increases, if the process is
3  0 . 0821
(a) Reversible (b) Irreversible
14. 9.0 gm of H 2 O is vaporised at 100 o C and 1 atm
(c) Exothermic (d) Endothermic
pressure. If the latent heat of vaporisation of
22. For chemical reactions, the calculation of change
water is x J / gm , then S is given by
in entropy is normally done
x 18 x (a) At constant pressure
(a) (b)
373 100 (b) At constant temperature
18 x 1 18 x (c) At constant temperature and pressure both
(c) (d) 
373 2 373 (d) At constant volume
15. The S for the vaporisation of 1 mol of water is 23. When the value of entropy is greater, then the
88.3 J/mole K. The value of S for the ability of work
condensation of 1 mol of vapour will be (a) Is maximum (b) Is minimum
(a) 88.3 J/mol K (b) (88 .3)2 J/mol K (c) Is medium (d) None of these
24. Which of the following is true for the reaction
1
(c) – 88.3 J/mol K (d)
88 .3
J/mol K H 2 O(l) ⇌ H 2 O(g) at 100 o C and 1 atmosphere
[KCET 1991; AIIMS 1996]
16. For which reaction from the following, S will be
maximum (a) E  0 (b) H  0
[AlIMS 1982, 83, 94; AMU 2000] (c) H  E (d) H  T S
 420 Thermodynamics and Thermochemistry
25. The enthalpy change for the transition of liquid 34. If 900 J / g of heat is exchanged at boiling point of
water to steam, H vap  37 .3 kJ mol 1 at 373 K . The water, then what is increase in entropy [BHU 1998]
entropy change for the process is [MP PET 1994] (a) 43.4 J/mole (b) 87.2 J/mole
1 1 1 1 (c) 900 J/mole (d) Zero
(a) 111 . 9 J mol K (b) 37 . 3 J mol K
1 1 1
35. A container has hydrogen and oxygen mixture in
(c) 100 J mol K (d) 74 . 6 J mol K 1 ratio of 4 : 1 by weight, then [BHU 1998]
26. When a solid is converted into liquid, entropy (a) Internal energy of the mixture decreases
[MP PET 1993, 95; MP PMT 1996] (b) Internal energy of the mixture increases
(a) Becomes zero (b) Remains the same (c) Entropy of the mixture increases
(c) Decreases (d) Increases (d) Entropy of the mixture decreases
27. In a spontaneous process, the entropy of the 36. If 0.75 mole of an ideal gas expands isothermally
system and its surroundings[MP PET 1996; NCERT 1975] at 27 o C from 15 litres to 25 litres, the maximum
(a) Equals zero (b) Decreases work obtained is
(c) Increases (d) Remains constant [AFMC 1999]
28. The positive value of S indicates that [MP PMT 1997] (a) 8.40 J (b) 9.34 J
(a) The system becomes less disordered (c) 10.86 J (d) 10.43 J
(b) The system becomes more disordered 37. In which of the following conditions a chemical
reaction can not occur [AMU 1999]
(c) The system is in equilibrium position
(a) H and S increase and T S  H
(d) The system tends to reach at equilibrium
position (b) H and S decrease and H  T S
29. For reaction 2Cl(s)  Cl2 (s) , the signs of H and (c) H increases and S decreases
(d) H decreases and S increases
S respectively are [KCET 1996]
(a) +, – (b) +, + 38. An engine operating between 150 o C and 25 o C
takes 500 J heat from a higher temperature
(c) –, – (d) –, +
reservoir if there are no frictional losses, then
30. The enthalpy of water is 386 kJ . What is entropy work done by engine is
of water [MH CET 1999]
[BHU 1997] (a) 147.7 J (b) 157.75 J
(a) 0.5 kJ (b) 1.03 kJ (c) 165.85 J (d) 169.95 J
(c) 1.5 kJ (d) 22.05 kJ 39. The entropy of a perfectly crystalline solid at
31. For which of the processes is S negative[Pb. PMT 1998] absolute zero is
(a) H 2 (g)  2 H(g) [AMU 2000]
(a) Positive (b) Negative
(b) N 2 (g)1atm  N 2 (g) 8 atm
(c) Zero (d) Not definite
(c) 2SO 3 (g)  2SO 2 (g)  O2 (g) 40. Which of the following conditions will always
(d) C(diamond )  C(graphite ) lead to a non-spontaneous change [AMU 2000; KCET (Med.)
(a) Positive H and positive S
32. Identify the correct statement regarding entropy
(b) Negative H and negative S
[CBSE PMT 1998; BHU 2001]
o
(c) Positive H and negative S
(a) At 0 C , the entropy of a perfectly crystalline
(d) Negative H and positive S
substance is taken to be zero
41. Following data is known about melting of a
(b) At absolute zero of temperature, the entropy
compound AB. H  9 .2 kJ mol 1 ,
of a perfectly crystalline substance is ve
(c) At absolute zero of temperature, the entropy S  0 .008 kJ K 1 mol 1
. Its melting point is[Pb. PMT 2000; AI
of all crystalline substances is taken to be zero (a) 736 K (b) 1050 K
(d) At absolute zero of temperature, the entropy (c) 1150 K (d) 1150 o C
of a perfectly crystalline substance is taken to
be zero 42. The volume of a gas decreases from 500 cc to
33. One mole of an ideal gas at 300 K is expanded 300 cc when a sample of gas is compressed by an
isothermally from an initial volume of 1 litre to 10 average pressure of 0.6 atm. During this process
litres. The change in energy for this process is 10 J of heat is liberated. The change in internal
(R  2 cal mol 1 K 1 ) energy is [Pb. PMT 2000]

[CBSE PMT 1998] (a) – 2.16 J (b) 12.156 J

(a) 163.7 cal (b) 850.2 cal (c) 2.16 J (d) 101.3 J
(c) 1381.1 cal (d) Zero
 Thermodynamics and Thermochemistry 421
43. The standard entropies of CO2 (g), C(s) and O2 (g) (a) J mol 1 (b) JK mol 1
are 213.5, 5.690 and 205 JK 1 respectively. The
(c) J mol 1 K 1 (d) J 1 K 1 mol 1
standard entropy of formation of CO 2 (g) is[CPMT 2001]
52. The entropy changed involved in the conversion
(a) 1 .86 JK 1 (b) 1 .96 JK 1 of 1 mole of liquid water at 373 K to vapour at the
same temperature will be
(c) 2 . 81 JK 1 (d) 2 . 86 JK 1
[H vap  2.257 kJ / gm] [MP PET 2002]
44. Which of the following endothermic processes are
spontaneous [CBSE PMT 2001] (a) 0.119 kJ (b) 0.109 kJ
(a) Melting of ice (b) Evaporation of water (c) 0.129 kJ (d) 0.120 kJ
(c) Heat of combustion (d) Both (a) and (b) 53. When a liquid boils, there is [JIPMER 2002]

45. For the reaction H 2O(s) ⇌ H 2O(l) at 0 o C and (a) An increase in entropy
normal pressure [KCET 2001] (b) A decrease in entropy
(a) H  T S (b) H  T S (c) An increase in heat of vaporization
(c) H  G (d) H  T S (d) An increase in free energy
46. One mole of an ideal gas is allowed to expand 54. Which one of the following has S o greater than
reversibly and adiabatically from a temperature of zero
27 o C . If the work done during the process is 3 kJ, [AIIMS 2003]
the final temperature will be equal to (a) CaO  CO2 (g) ⇌ CaCO3 (s)
(C v  20 JK 1 )
(b) NaCl (aq) ⇌ NaCl (s)
[KCET 2000; AFMC 2000; AIIMS 2001]
(c) NaNO3 (s) ⇌ Na  (aq )  NO 3 (aq )
(a) 150 K (b) 100 K
(c) 26 .85 o C (d) 295 K (d) N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g)
47. The entropy change, in the conversion of one mole 55. The molar heat capacity of water at constant
of liquid water at 373 K to vapour at the same pressure is 75 JK 1 mol 1 . When 1.0 kJ of heat is
temperature is (Latent heat of vaporization of
supplied to 100 g of water which is free to expand
water, H vap  2.257 kJ / g)
the increase in temperature of water is[CBSE PMT 2003]
[AFMC 2002; KCET 2002] (a) 6.6 K (b) 1.2 K
1
(a) 105.9 Jk (b) 107 .9 Jk 1 (c) 2.4 K (d) 4.8 K
56. The work done to contract a gas in a cylinder, is
(c) 108 .9 Jk 1 (d) 109 .9 Jk 1
462 joules. 128 joule energy is evolved in the
48. A heat engine absorbs heat Q 1 at temperature T1 process. What will be the internal energy change
and heat Q 2 at temperature T 2 . Work done by the in the process [MP PMT 2003]
engine is (Q1  Q 2 ) . This data [AIEEE 2002] (a) + 590 joules (b) – 334 joules
(c) + 334 joules (d) – 590 joules
(a) Violates Ist law of thermodynamics
57. Highest entropy is in [BVP 2003]
(b) Violates Ist law of thermodynamics if Q 1 is –ve
(a) Hydrogen (b) Water
(c) Violates Ist law of thermodynamics if Q 2 is –
(c) Graphite (d) Mercury
ve
58. H  (aq )  OH  (aq )  H 2 O(l)
(d) Does not violate Ist law of thermodynamics S o ( 298 K ) K 1 mol 1 10 . 7  70
49. Equal volumes of monoatomic and diatomic gases Standard entropy change for the above reaction is
at same initial temperature and pressure are
[DPMT 2004]
mixed. The ratio of specific heats of the mixture
1 1
(C p / C v ) will be (a) 60 . 3 JK mol (b) 80 . 7 JK mol 1
1

[AFMC 2002] (c)  70 JK 1mol 1 (d)  10 . 7 JK 1mol 1

(a) 1 (b) 2
59. One mole of water at 100 o C is converted into
(c) 1.67 (d) 1.5
steam at 100 o C at a constant pressure of 1 atm.
50. The law formulated by Dr. Nernst is [Kerala (Med.) 2002] The change in entropy is [heat of vaporisation of
(a) First law of thermodynamics water at 100 o C  540 cal / gm ] [Pb. PMT 2004]
(b) Second law of thermodynamics (a) 8.74 (b) 18.76
(c) Third law of thermodynamics (c) 24.06 (d) 26.06
(d) Both (a) and (b) 60. For a carnot engine, the source is at 500 K and the
51. The unit of entropy is [CBSE PMT 2002] sink at 300 K . What is efficiency of this engine[BHU 2004]
 422 Thermodynamics and Thermochemistry
(a) 0.2 (b) 0.4 then the possible heat of methane will be [MP PET 1990]
(c) 0.6 (d) 0.3 (a) 47.3 kcal (b) 20.0 kcal
61. Heat require to raise the temperature of 1 mol of (c) 45.9 kcal (d) – 47.3 kcal
a substance by 1o C is called [DCE 2002] 2. Molar heat of vaporisation of a liquid is 6 kJ mol 1 .
(a) Specific heat (b) Molar heat capacity
If the entropy change is 16 J mol 1 K 1 , the boiling
(c) Water equivalent (d) Specific gravity
point of the liquid is [KCET 2005]
62. Maximum entropy will be in which of the o
following (a) 375 C (b) 375 K
[DCE 2004] (c) 273 K (d) 102 o C
(a) Ice (b) Liquid water 3. The enthalpy of fusion of ice per mole
(c) Snow (d) Water vapours (a) 18 kJ (b) 8 kJ
63. The standard entropies of CO2 (g), C(s) and O2 (g) (c) 80 kJ (d) 6 kJ
1 4. In which of the following neutralisation reactions,
are 213.5, 5.740 and 205 JK respectively. The
standard entropy of formation of CO2 is [Pb. CET 2001] the heat of neutralisation will be highest
[MP PMT 1989, 91; AIIMS 1999]
(a) 2 . 76 JK 1 (b) 2 . 12 JK 1
(a) NH4 OH and CH 3 COOH
(c) 1 . 12 JK 1 (d) 1 . 40 JK 1 (b) NH4 OH and HCl
64. Which law of thermodyanamics help in (c) NaOH and CH 3 COOH
calculating entropy at different temperatures [Pb. CET 2003]
(a) First law (b) Second law (d) NaOH and HCl
(c) Third law (d) Zeroth law 5. If S  O2  SO 2 ; (H  298 .2)
65. Entropy is maximum in case of [BVP 2004] 1
SO 2  O2  SO 3 ; (H  98 .2)
(a) Steam o
(b) Water at 0 C 2
SO 3  H 2O  H 2 SO 4 ; (H  130 .2)
(c) Water at 4 o C (d) Ice
1
66. Considering entropy (S) as a thermodynamic H 2  O2  H 2 O; (H  287 .3)
parameter, the criterion for the spontaneity of 2
any process is then the enthalpy of formation of H2 SO4 at 298K
[CBSE PMT 2004] will be
(a) S system  0 only [DPMT 1983; Orissa JEE 2005]
(a) 433 .7 kJ (b) 650 .3 kJ
(b) S surroundin gs  0 only
(c) 320 .5 kJ (d) 813 .9 kJ
(c) S system  S surroundin gs  0
6. From Kirchhoff's equation which factor affects
(d) S system  S surroundin gs  0 the heat of reaction [MP PMT 1990]

67. A process is taking place at constant temperature (a) Pressure (b) Temperature
and pressure. Then [KCET 2004] (c) Volume (d) Molecularity
(a) H  E (b) H  T S 7. The molar neutralization heat for KOH and
HNO 3 as compared to molar neutralization heat
(c) H  0 (d) S  0
of NaOH and HCl
68. The enthalpy of vapourization of a liquid is
[MP PMT 1989]
30 kJ mol 1 and entropy of vapourization is
(a) Less (b) More
75 J mol 1 K . The boiling point of the liquid at 1 (c) Equal (d) Depends on pressure
atm is [IIT JEE (Screening) 2004] 8. An exothermic reaction is one in which the
(a) 250K (b) 400K reacting substances[CPMT 1974, 79; Bihar MEE 1982;
KCET 1992; JIPMER 2001]
(c) 450K (d) 600K
(a) Have more energy than the products
(b) Have less energy than the products
Heat of reaction
(c) Are at a higher temperature than the product
(d) None of the above
1. If C  O2  CO2  94 .2 kcal 9. The heat evolved in the combustion of benzene is
given by
1
H2  O2  H 2 O  68 .3 kcal 1
2 C 6 H 6  7 O 2  6 CO 2 (g)  3 H 2 O(l); H  3264 .6 k J
2
CH4  2O2  CO2  2 H2O  210 .8 kcal
 Thermodynamics and Thermochemistry 423
Which of the following quantities of heat energy 17. H  f (298 K) of methanol is given by the
will be evolved when 39 g C6 H 6 are burnt chemical equation [AIIMS 2005]
[NCERT 1978; MP PET 1990; JIPMER 2001] (a) CH 4 (g)  1 / 2O2 (g)  CH 3 OH (g)
(a) 816.15 kJ (b) 1632.3 kJ
(b) C (graphite) 1 / 2O2 (g)  2 H 2 (g)  CH 3 OH (l)
(c) 6528.2 kJ (d) 2448.45 kJ
10. Thermochemical reactions (c) C (diamond) 1 / 2O2 (g)  2 H 2 (g)  CH 3 OH (l)
1 (d) CO(g)  2H 2 (g)  CH 3 OH (l)
C(graphite)  O 2 (g)  CO(g); H  110 .5 kJ
2 18. If H of for H 2 O2 and H 2 O are 188 kJ / mole and
1 286 kJ / mole . What will be the enthalpy change of
CO(g)  O 2 (g)  CO 2 (g); H  283 .2 kJ
2
the reaction 2H 2 O2 (l)  2H 2 O(l)  O2 (g) [MP PMT 1992]
From the above reaction, the heat of reaction for
C(graphite)  O2 (g)  CO2 (g) will be (a) 196 kJ / mole (b) 146 kJ / mole
[CPMT 1988; MP PMT 1989] (c) 494 kJ / mole (d) 98 kJ / mole
(a) – 393.7 kJ (b) + 393.7 kJ 19. The heat of transition (H t ) of graphite into
(c) – 172.7 kJ (d) + 172.7 kJ diamond would be, where
11. The following is (are) endothermic reaction [IIT JEE 1999] C(graphite)  O2 (g)  CO2 (g); H  x kJ
(a) Combustion of methane
C(diamond )  C2 (g)  CO2 (g); H  y kJ [Pb. PET 1985]
(b) Decomposition of water
(c) Dehydrogenation of ethane to ethylene (a) (x  y ) kJ mol 1 (b) (x  y ) kJ mol 1
(d) Conversion of graphite to diamond
(c) (y  x ) kJ mol 1 (d) None of these
12. Evaporation of water is
[CPMT 1973; DPMT 1982; MP PMT 1989; MP PET 1999] 20. Correct relationship between heat of fusion
(a) An endothermic change (H fus ) , heat of vaporization (H vap ) and heat of
(b) An exothermic change sublimation (H sub ) is
(c) A process where no heat change occurs (a) H fus  H vap  H sub
(d) A process accompanied by chemical reaction
(b) H vap  H fus  H sub
13. An exothermic reaction is one which
[NCERT 1977; MP PMT 1990] (c) H sub  H vap  H fus
(a) Takes place only on heating (d) H sub  H vap  H fus
(b) Is accompanied by a flame
(c) Is accompanied by a absorption of heat 21. Which of the following is an example of
endothermic reaction [MP PMT 1980]
(d) Is accompanied by evolution of heat
14. An endothermic reaction is one in which (a) C2 H 2  2 H 2  C2 H 6 ; E  314 .0 kJ
[MNR 1980; NCERT 1976] (b) C  O2  CO2 ; E  393 .5 kJ
(a) Heat is converted into electricity
(c) N 2  O2  2 NO; E  180 .5 kJ
(b) Heat is absorbed
(c) Heat is evolved (d) 2H 2  O2  2H 2 O; E  571 .8 kJ
(d) Heat is converted into mechanical work 22. If the enthalpy of B is greater than of A, the
15. Which of the following statement is correct reaction A  B is [MP PMT 1997]
[NCERT 1978] (a) Endothermic (b) Exothermic
(a) H is positive for exothermic reaction (c) Instantaneous (d) Spontaneous
(b) H is negative for endothermic reaction 23. Given that
(c) The heat of neutralization of strong acid and
2C(s)  2O2 (g)  2CO2 (g); H  787 kJ
strong base is always the same
(d) The enthalpy of fusion is negative 1
H 2 (g)  O 2 (g)  H 2 O(l); H  286 kJ
16. The absolute enthalphy of neutralisation of the 2
reaction MgO(s)  2HCl(aq)  MgCl2 (aq)  H 2 O(l) will 1
C 2 H 2 (g )  2 O 2 (g)  2CO 2 (g)  H 2 O(l); H  1301 kJ
be 2
[CBSE PMT 2005] Heat of formation of acetylene is
1
(a) Less than  57 . 33 kJ mol [KCET 1989; Orissa JEE 2005]
(b)  57 . 33 kJ mol 1 (a) 1802 kJ (b)  1802 kJ

(c) Greater than  57 .33 kJ mol 1 (c) 800 kJ (d) 228 kJ

24. Enthalpy change for reaction,
(d) 57 . 33 kJ mol 1
1 1
H 2  Cl 2  HCl , is called
2 2
 424 Thermodynamics and Thermochemistry
(a) Enthalpy of combination (b)Enthalpy of reaction (d) The method by which the final products are
(c) Enthalpy of formation (d) Enthalpy of fusion obtained from the reactants
25. The enthalpy of neutralization is about 57.3 kJ for 34. Heat of neutralisation of a strong acid by a strong
the pair base is a constant value because [KCET 1984]
(a) HCl and NH 4 OH (a) Salt formed does not hydrolyse
(b) NH 4 OH and HNO 3 (b) Only H  and OH  ions react in every case
(c) The strong base and strong acid react
(c) HCl and NaOH
completely
(d) CH 3 COOH and NaOH
(d) The strong base and strong acid react in
26. Conversion of oxygen to ozone represented by the aqueous solution
equation 3O2  2O3 is an endothermic reaction. 35. Heat of neutralisation of an acid by a base is
Enthalpy change H accompanying the reaction[KCET 1988, highest
92] when
(a) Is negative (b) Is positive [KCET 1985]
(c) Is zero (d) Depends on (a) Both the acid and base are weak
temperature (b) Both the acid and base are strong
27. The mutual heat of neutralisation of 40 gm of (c) The acid is strong and the base is weak
NaOH and 60 gm CH 3 COOH will be[MP PET/PMT 1988] (d) The acid is weak and the base is strong
(a) 56.1 kcal (b) Less than 56.1 kcal 36. The standard molar heat of formation of ethane,
(c) More than 56.1 kcal (d) 13.7 kcal CO 2 and water (l) are respectively – 21.1, – 94.1
28. The heat of formations of CO (g) and CO 2 (g) are and – 68.3 kcal. The standard molar heat of
26 . 4 kcal and 94 .0 kcal respectively. The heat combustion of ethane will be
of combustion of carbon monoxide will be [IIT JEE 1986; DPMT 2005]
[MP PET/PMT 1988; EAMCET 1993] (a) – 372 kcal (b) 162 kcal
(a) 26 .4 kcal (b) 67 .6 kcal (c) –240 kcal (d) 183.5 kcal
(c) 120 .6 kcal (d) 52 .8 kcal 37. Which of the following reaction is endothermic
[AFMC 1988]
29. The enthalpy of combustion at 25°C of H2, (a) CaCO3  CaO  CO2
cyclohexane (C6H12) and cyclohexene (C6H10) are –
241, –3920 and –800 KJ / mole respectively. The (b) Fe  S  FeS
heat of hydrogenation of cyclohexene is[BHU 2005] (c) NaOH  HCl  NaCl  H 2 O
(a) – 121 KJ / mole (b) + 121 KJ / mole (d) CH 4  2O2  CO2  2H 2 O
(c) – 242 KJ / mole (d) + 242 KJ / mole 38. In the reaction
30. Heat of neutralisation of NH 4 OH and HCl is CO2 (g)  H 2 (g)  CO(g)  H 2 O(g); H  80 kJ
[EAMCET 1980; Roorkee 1990; MP PMT 1994] H is known as
(a) 13 .7 kcal (b) 13 .7 kcal [CPMT 1987; KCET 1993; Bihar CEE 1995]
(c) 13 .7 kcal (d) None of the above (a) Heat of formation (b) Heat of combustion
31. Heat of combustion H of CH 4 , C 2 H 6 , C 2 H 4 and (c) Heat of neutralization (d) Heat of reaction
C2 H 2 gases are – 212.8, – 373.0, – 337.0 and – 39. Heat of combustion of a substance
310.5 kcal respectively at the same temperature. [CPMT 1987, 96; AFMC 1992]
The best fuel among these gases is (a) Is always positive
(a) CH 4 (b) C2 H 6 (b) Is always negative
(c) C2 H 4 (d) C2 H 2 (c) Is equal to heat of formation
(d) Nothing can be said without reaction
32. Heat of formation of CO2 (g), H 2 O(l) and CH 4 (g)
1
are – 94.0, – 68.4 and – 17.9 kcal 40. The heat change for the reaction H 2  O 2  H 2 O
2
respectively. The heat of combustion of methane
is called
is
(a) – 212.9 kcal (b) – 136.8 kcal (a) Heat of reaction (b) Heat of formation
(c) – 304.3 kcal (d) – 105.2 kcal (c) Heat of vaporisation (d) None of the above
33. The heat of reaction does not depend upon 41. The heat change H for the reaction
(a) Temperature of the reaction 2CO  O2  2CO2 ; H  135 kcal is called
(b) Physical state of reactants and products (a) Heat of formation (b) Heat of reaction
(c) Whether the reaction is carried out at (c) Heat of combustion (d) Heat of solution
constant pressure or at constant volume
 Thermodynamics and Thermochemistry 425
42. The heats of combustion of rhombic and (c) The heat set free or absorbed when one gram
monoclinic sulphur are respectively 70960 and atom of an acid is neutralized by one gram
71030 calories. What will be the heat of atom of a base at a stated temperature
conversion of rhombic sulphur to monoclinic (d) The heat set free or absorbed when a normal
[MP PMT/PET 1988] solution containing one gram equivalent of an
(a) 70960 calories (b) 71030 calories acid is neutralized by a normal solution
(c) – 70 calories (d) + 70 calories containing one gram equivalent of a base at a
43. The heat of formation of H 2 O(l) is – 68.0 kcal, the stated temperature
(e) The heat set free when one gram equivalent of
heat of formation of H 2 O(g) is likely to be
an acid is neutralized by one gram equivalent
(a) – 68.0 kcal (b) – 67.4 kcal of a base in dilute solution at a stated
(c) 80.0 kcal (d) – 58.3 kcal temperature
44. Which of the following fuels will have the highest 50. The compound with negative heat of formation
calorific value (kJ/kg) [MP PMT 1990] are known as [DPMT 1981]
(a) Charcoal (b) Kerosene (a) Endothermic compound
(c) Wood (d) Dung (b) Exothermic compound
45. The heat of combustion of carbon is –94 kcal at 1 (c) Heat of formation compound
atm pressure. The intrinsic energy of CO2 is (d) None of the above
(a) 94 kcal (b)  94 kcal 51. If H   OH   H 2 O  13 . 7 kcal , then the heat of
(c) 47 kcal (d) 47 kcal neutralization for complete neutralization of one
46. The heat of neutralisation of a strong acid and a mole of H 2 SO 4 by base will be [MP PMT 1990]
strong alkali is 57 . 0 kJ mol 1 . The heat released (a) 13.7 kcal (b) 27.4 kcal
when 0.5 mole of HNO 3 solution is mixed with (c) 6.85 kcal (d) 3.425 kcal
0.2 mole of KOH is 52. The lowest value of heat of neutralization is
[KCET 1991; AIIMS 2002; AMU (Engg.) 2002] obtained for
(a) 57 .0 kJ (b) 11 .4 kJ [KCET 1988; MP PMT 1990]
(a) HCl  NaOH
(c) 28 .5 kJ (d) 34 .9 kJ
(b) CH 3 COOH  NH 4 OH
47. A solution of 500 ml of 0.2 M KOH and 500 ml of
(c) NH 4 OH  HCl
0.2 M HCl is mixed and stirred; the rise in
temperature is T1 . The experiment is repeated (d) NaOH  CH 3 COOH

using 250 ml each of solution, the temperature 53.

Heat of neutralisation for the given reaction
raised is T2 . Which of the following is true[EAMCET 1987; MPNaOH  HCl  NaCl  H 2 O is 57 . 1 kJ mol 1 . What
PET 1994]
(a) T1  T2 (b) T1  2T2 will be the heat released when 0.25 mole of NaOH
is titrated against 0.25 mole of HCl [CPMT 1990]
(c) T1  4T2 (d) T2  9T1
1
48. Enthalpy of a compound is equal to its (a) 22 . 5 kJ mol (b) 57 . 1 kJ mol 1
[CMC Vellore 1991] (c) 14 . 3 kJ mol 1 (d) 28 . 6 kJ mol 1
(a) Heat of combustion (b) Heat of formation
54. Reaction, H2 (g)  I2 (g)  2 HI(g) H  12 .40 kcal .
(c) Heat of reaction (d) Heat of solution
According to this, the heat of formation of HI will
(e) Heat of dilution
be
49. Which is the best definition of “heat of
[MP PET 1990]
neutralization”
[CMC Vellore 1991]
(a) 12.4 kcal (b) – 12.4 kcal
(a) The heat set free when one gram molecule of (c) – 6.20 kcal (d) 6.20 kcal
a base is neutralized by one gram molecule of 55. All reactions with chemical dissociation are[MP PMT 1990]
an acid in dilute solution at a stated (a) Reversible
temperature
(b) Reversible and endothermic
(b) The heat absorbed when one gram molecule of
(c) Exothermic
an acid is neutralized by one gram molecule
of a base in dilute solution at a stated (d) Reversible or irriversible and endothermic or
temperature exothermic
56. The heat of formation is the change in enthalpy
accompanying the formation of a substance from
 426 Thermodynamics and Thermochemistry
its elements at 298 K and 1 atm pressure. Since 64. Which of the following reaction can be used to
the enthalpies of elements are taken to be zero, define the heat of formation of CO 2 (g)
the heat of formation (H ) of compounds[NCERT 1978; KCET 1993] [MP PMT 1989; MH CET 2001]
(a) Is always negative (a) C(graphite)  O2 (g)  CO2 (g)
(b) Is always positive (b) CH 4 (g)  2O2 (g)  CO2 (g)  2 H 2 O(l)
(c) May be negative or positive
1
(d) Is zero (c) CO(g)  O 2 (g)  CO 2 (g)
2
57. The heat of combustion of CH 4 (g) , C(graphite ) and H 2(g)
1
are 20 kcal,  40 kcal and 10 kcal respectively. The (d) C 6 H 6 (l)  7 O 2 (g)  6 CO 2  3 H 2 O(l)
2
heat of formation of methane is [EAMCET 1998] 65. The enthalpy of formation of ammonia is
(a) 4.0 kcal (b) 40 kcal  46 .0 kJ mol 1 . The enthalpy change for the
(c) 80 kcal (d) 80 kcal reaction 2 NH 3 (g)  2 N 2 (g)  3 H 2 (g) is
58. If a chemical reaction is accompanied by the (a) 46.0 kJ mol 1 (b) 92.0 kJ mol 1
evolution of heat, it is [BHU 1979]
(c) – 23.0 kJ mol 1 (d) – 92.0 kJ mol 1
(a) Catalytic (b) Photochemical
66. The heat of combustion of benzene determined in
(c) Endothermic (d) Exothermic a bomb calorimeter is  870 kcal mol 1 at 25 o C . The
59. A reaction that takes place with the absorption of
value of E for the reaction is
energy is
(a) 1740 kcal (b) 870 kcal
[EAMCET 1977]
(a) Burning of a candle (b) Rusting of iron (c) 872 kcal (d) 874 kcal
(c) Electrolysis of water (d) Digestion of food 67. The formation of water from H 2 (g) and O2 (g) is
60. Which of the following is an endothermic reaction an exothermic reaction because[MP PMT/PET 1988]
[EAMCET 1980; MP PMT 1980; (a) The chemical energy of H 2 (g) and O2 (g) is
IIT JEE 1989; JIPMER 2002] more than that of water
(a) 2H 2  O2  2 H 2 O (b) The chemical energy of H 2 (g) and O2 (g) is less
(b) N 2  O2  2 NO than that of water
(c) Not dependent on energy
(c) 2 NaOH  H 2 SO 4  Na2 SO 4  2 H 2 O
(d) The temperature of H 2 (g) and O2 (g) is more
(d) 3O2  C2 H 5 OH  2CO2  3 H 2 O than that of water
61. One of the phenomena which cannot be described 68. In the reaction for the transition of carbon in the
as combustion is [EAMCET 1979] diamond form to carbon in the graphite form, H
(a) Oxidation of coal in air is 453 .5 cal . This points out that [BHU 1981; KCET 1986, 89
(b) Burning of magnesium in nitrogen (a) Graphite is chemically different from diamond
(c) Reaction of antimony in chlorine (b) Graphite is as stable as diamond
(d) Lighting of an electric lamp (c) Graphite is more stable than diamond
62. Which of the following statements is correct (d) Diamond is more stable than graphite
about heat of combustion [MADT Bihar 1982] 69. In the combustion of hydrocarbons, H is [BHU 1981]
(a) It may be exothermic in some cases and (a) Negative (b) Zero
endothermic in other cases (c) Positive (d) Undeterminate
(b) It is applicable to gaseous substances only 70. The standard heats of formation in kcal mol 1 of
(c) It is always an exothermic reaction NO2 (g) and N 2 O4 (g) are 8.0 and 2.0 respectively.
(d) Its value does not change with temperature The heat of dimerization of NO2 in kcal is
1 2 NO2 (g)  N 2 O4 (g)
63. H 2  O 2  H 2 O; H  68 .39 kcal [NCERT 1983]
2
(a) 10.0 (b) – 6.0
1
K  H 2 O  Water  KOH (aq)  H 2 ; H  48 kcal (c) – 12.0 (d) – 14.0
2
71. The difference between heats of reaction at
KOH  Water  KOH (aq); H  14 kcal constant pressure and at constant volume for the
reaction 2C6 H 6 (l)  15 O2 (g)  12 CO2 (g)  6 H 2 O(l) at
The heat of formation of KOH is (in kcal)[CPMT 1988]
25 o C in kJ is
(a) 68 .39  48  14 (b) 68 .39  48  14
[IIT JEE 1991; Kerala PMT 2004]
(c) 68 . 39  48  14 (d) 68.39 + 48 + 14
 Thermodynamics and Thermochemistry 427
(a) –7.43 (b) + 3.72 (b) Solid to vapour
(c) –3.72 (d) + 7.43 (c) Liquid to vapour
72. C (diamond) C2 (g)  CO2 (g); H  395 kJ (d) One allotropic form to another allotropic form
C (graphite) O2 (g)  CO2 (g); H  393 .5 kJ 79. For the allotropic change represented by equation
C(diamond )  C(graphite ) ; the enthalpy change is
From the data, the H when diamond is formed
from graphite, is [CBSE PMT 1989; BHU 1987]
H  1.89 kJ . If 6 g of diamond and 6 g of
(a) 1.5 kJ (b)  1.5 kJ graphite are separately burnt to yield carbon
dioxide, the heat liberated in the first case is[KCET 1988; D
(c)  3.0 kJ (d) 3.0 kJ
(a) Less than in the second case by 1.89 kJ
73. Which of the following values of heat of formation
(b) More than in the second case by 1.89 kJ
indicates that the product is least stable[MP PMT 1991]
(a) 94 kcal (b)  231 .6 kcal (c) Less than in the second case by 11 .34 kJ

(c) 21 .4 kcal (d)  64 .8 kcal (d) More than in the second case by 0.945 kJ
74. Which of the following equations correctly 80. For an exothermic reaction
represents the standard heat of formation (H of ) [MP PET 1994; Manipal MEE 1995]

of methane (a) H of the products is less than H of the

[IIT JEE (Screening) 1992]
reactants
(a) C(diamond)  2 H 2 (g)  CH 4 (g) (b) H of the products is more than H of the
reactants
(b) C(graphite)  2H 2 (g)  CH 4 (l)
(c) H of the products is equal to H of the
(c) C(graphite)  2H 2 (g)  CH 4 (g) reactants
(d) C(graphite)  4 H  CH 4 (g) (d) H is always positive
75. In which of the following reactions does the heat 81.
The energy evolved is highest for which of the
following reactions
change represent the heat of formation of water[EAMCET 1991] [MP PET 1994]
 1
(a) 2 H 2 (g)  O2 (g)  2H 2 O(l); H  116 kcal (a) F  e  F (b) Cl  e  Cl 


1 (c) S  2e   S 2 (d) O  2e   O 2
(b) H 2 (g)  O 2 (g)  H 2 O(l); H  58 kcal
2 82. In the combustion of 2.0 gm of methane 25 kcal
 
(c) H (aq .)  OH (aq .)  2 H 2 O(l); H  13 . 7 kcal heat is liberated, heat of combustion of methane
would be
1
(d) C 2 H 2 (g)  2 O 2 (g)  2CO 2 (g)  H 2 O(l) ; [MP PMT 1994]
2
(a) 100 kcal (b) 200 kcal
H  310 kcal
(c) 300 kcal (d) 400 kcal
76. Values of heats of formation for SiO2 and MgO are
48 . 4 and 34 .7 kJ respectively. The heat of the 83. Complete combustion of CH 4 gives [BHU 1995]

reaction 2 Mg  SiO2  2 MgO  Si is [KCET 1990] (a) CO2  H 2 O (b) CO2  H 2

(a) 21 .16 kJ (b) 21 .10 kJ (c) COCl 2 (d) CO  CO2  H 2 O
(c) 13 .62 kJ (d) 13 .6 kJ 84. If enthalpies of formation of C 2 H 4 (g), CO2 (g) and
77. Based on the following thermochemical equations H 2 O(l) at 25 o C and 1 atm pressure be 52, – 394
H 2 O(g)  C(s)  CO(g)  H 2 (g); H  131 kJ and  286 kJ mol 1 respectively, the enthalpy of
1 combustion of C 2 H 4 (g) will be
CO(g)  O 2 (g)  CO 2 (g); H  282 kJ
2 [CBSE PMT 1995; AIIMS 1998; Pb. PMT 1999]
1
H 2 (g)  O 2 (g)  H 2 O(g); H  242 kJ (a)  1412 kJ mol 1 (b)  1412 kJ mol 1
2
(c)  141 . 2 kJ mol 1 (d)  141 . 2 kJ mol 1
C(s)  O2 (g)  CO2 (g); H  X kJ
85. Carbon and carbon monoxide burn in oxygen to
The value of X is [CBSE PMT 1992]
form carbon dioxide according to the following
(a) 393 kJ (b)  655 kJ reactions
(c)  393 kJ (d) 655 kJ C  O 2  CO 2 ; H  394 kJ mol 1
78. Heat of transition is the heat evolved or absorbed 2CO  O 2  2CO 2 ; H  569 kJ mol 1
when a substance is converted from [KCET 1984]
(a) Solid to liquid
 428 Thermodynamics and Thermochemistry
The heat of formation of 1 mol of carbon monoxide 94. 2.2016 gm of acetaldehyde produced 13 .95 kcal of
is thus heat on combustion in O 2 . Calculate the heat of
[MP PET 1995] combustion of CH 3 CHO [Bihar CEE 1995]
1 1
(a)  219 .0 kJ mol (b)  109 . 5 kJ mol (a) 279 kcal (b) 972 kcal
1
(c)  175 . 0 kJ mol (d)  87 .5 kJ mol 1 (c) 27.9 kcal (d) 2.79 kcal
86. Heat of formation in the reaction 1
95. C O 2  CO; H  42 kJ
H 2  Cl2  2HCl  44 kcal is [MP PMT 1995] 2
(a) 44 kcal (b) 44000 kcal 1
CO  O 2  CO 2 ; H  24 k J
(c) 22 kcal (d) 11 kcal 2
87. When water is added to quick lime, the reaction is The heat of formation of CO2 is [
[MP PMT 1995] (a) – 16 kJ (b) + 66 kJ
(a) Exothermic (b) Endothermic
(c) + 16 kJ (d) – 66 kJ
(c) Explosive (d) None of these 96. Standard molar enthalpy of formation of CO2 is
88. In an exothermic reaction H is equal to
[MP PMT 1995; CPMT 1999] [IIT JEE 1997; BHU 2001]
(a) Positive (b) Negative (a) Zero
(c) Zero (d) Both positive or (b) The standard molar enthalpy of combustion of
negative gaseous carbon
89. The heat change for the following reaction (c) The sum of standard molar enthalpies of
C(s)  2S (s)  CS 2 (l) is known as [MP PMT 1996] formation of CO and O 2
(a) Heat of vaporization (b) Heat of solution (d) The standard molar enthalpy of combustion of
(c) Heat of fusion (d) Heat of formation carbon (graphite)
97. In the complete combustion of butanol C4 H 9 OH (l) ,
90. The enthalpy of combustion of benzene from the
following data will be if H is enthalpy of combustion and E is the
heat of combustion at constant volume, then[EAMCET 1997
(i) 6C(s)  3 H 2 (g)  C6 H 6 (l); H  45 .9 kJ
(a) H  E
1 (b) H  E
(ii) H 2 (g)  O 2 (g)  H 2 O(l); H  285 .9 kJ
2
(c) H  E
(iii) C(s)  O2 (g)  CO2 (g); H  393 .5 kJ (d) H , E relation cannot be predicted
(a) + 3172.8 kJ (b) – 1549.2 kJ 98. C  O2  CO2 ; H  X
(c) – 3172.8 kJ (d) – 3264.6 kJ 1
CO  O 2  CO 2 ; H  Y
91. Enthalpy of formation of HF and HCl are  161 kJ 2
and  92 kJ respectively. Which of the following Then the heat of formation of CO is
statements is incorrect [KCET 2003] [BHU 1997; DPMT 2002]
(a) HCl is more stable than HF (a) X  Y (b) Y  2 X
(b) HF and HCl are exothermic compounds (c) X  Y (d) 2 X  Y
(c) The affinity of fluorine to hydrogen is greater 99. The values of heat of formation of SO 2 and SO 3
than the affinity of chlorine to hydrogen are 298 .2 kJ and 98 .2 kJ . The heat of reaction of
(d) HF is more stable than HCl the following reaction will be
92. The heat of reaction at constant pressure is given 1
SO 2  O 2  SO 3 [BHU 1997; CBSE PMT 2000]
by 2
[MP PMT 1997] (a) 200 kJ (b) 356 .2 kJ
(a) E P  E R (b) E R  E P (c) 200 kJ (d) 396 .2 kJ
(c) H P  H R (d) H R  H P 100. Calculate the standard heat of formation of
93. In an endothermic reaction, the value of H is carbon disulphide (l) , given that the standard heat
[CBSE PMT 1999; AIIMS 1998; BHU 2000; MP PMT 2000] of combustion of carbon (s) , sulphur (s) and
(a) Zero (b) Positive carbon disulphide (l) are 393 .3,  293 .72 and

(c) Negative (d) Constant  1108 .76 kJ mol 1 respectively

[Roorkee 1989; BHU 1997]
 Thermodynamics and Thermochemistry 429
(a)  128 . 02 kJ mol 1 (b)  12 . 802 kJ mol 1 (c) Twice of x (d) Less than x
109. The neutralisation of a strong acid by a strong
(c)  128 . 02 kJ mol 1 (d)  12 .802 kJ mol 1
base liberates an amount of energy per mole of
101. Fermentation is a reaction called [RPMT 1997] H  that [BHU 1998]
(a) Endothermic (b) Exothermic (a) Depends upon which acid and base are
(c) Isotemperature (d) Reversible involved
102. 8 gm of CH4 is completely burnt in air. The (b) Depends upon the temperature at which the
number of moles of water produced are[Orissa JEE 1997] reaction takes place
(a) 0.5 (b) 1 (c) Depends upon which catalyst is used
(c) 2 (d) 18 (d) Is always the same
103. For the reaction A(g)  2 B(g)  2C(g)  3 D(g) , the 110. When 0 . 5 g of sulphur is burnt to SO 2 , 4.6 kJ of
value of E at 27 o C is 19.0 kcal. The value of H heat is liberated. What is the enthalpy of
for the reaction would be (R  2 . 0 cal K 1mol 1 ) formation of sulphur dioxide[KCET 1998; AFMC 2001]
(a) + 147.2 kJ (b) – 147.2 kJ
[Roorkee Qualifying 1998]
(c) – 294.4 kJ (d) + 294.4 kJ
(a) 20.8 kcal (b) 19.8 kcal
111. Ozone is prepared by passing silent electric
(c) 18.8 kcal (d) 20.2 kcal
discharge through oxygen. In this reaction[AFMC 1998]
104. The enthalpy of solution of BaCl2 (s) and
(a) Energy is given out
BaCl2 .2 H 2 O(s) are 20 .6 and 8 . 8 kJ mol 1 (b) Energy is absorbed
respectively. The enthalpy change for the reaction (c) Oxygen is loaded with energy
BaCl2 (s)  2 H 2O  is
(d) Oxygen is dissociated into atoms
[Roorkee Qualifying 1998] 112. Combustion of glucose takes place according to
(a) 29.4 kJ (b) – 11.8 kJ the equation,
(c) – 20.6 kJ (d) – 29.4 kJ C6 H 12 O6  6O 2  6CO 2  6 H 2 O , H  72 kcal . How
105. The enthalpy change of a reaction does not much energy will be required for the production
depend on of 1.6 g of glucose (Molecular mass of glucose =
[AIIMS 1997] 180 g) [AFMC 1999]
(a) The state of reactants and products (a) 0.064 kcal (b) 0.64 kcal
(b) Nature of reactants and products (c) 6.4 kcal (d) 64 kcal
113. Given that
(c) Different intermediate reaction
C(s)  O2 (g)  CO2 (g), H  394 kJ
(d) Initial and final enthalpy change of a reaction
3 2H 2 (g)  O2 (g)  2 H 2 O(l), H  568 kJ
106. S  O2  SO 3  2 x kcal
2 CH 4 (g)  2O2 (g)  CO2 (g)  2 H 2 O(l) H  892 kJ
1 Heat of formation of CH 4 is [
SO 2  O 2  SO 3  y k cal
2 (a) – 70 kJ (b) 71.8 kJ
Find out the heat of formation of SO 2 (c) – 244 kJ (d) + 782 kJ
[AIIMS 1997; CBSE PMT 1999; KCET 1999] 114. Calculate the heat of formation of PCl5 (s) from
(a) 2 x  y (b) 2 x  y the following data
2 P(s)  3Cl2 (g)  2PCl3 (l); H  151 .8 kcal
(c) x  y (d) 2 x / y
PCl3 (l)  Cl2 (g)  PCl5 (s); H  32 .8 kcal
107. The combustion enthalpies of carbon, hydrogen
and methane are  395 .5 kJ mol 1 ,  285 . 8 kJ mol 1 [JIPMER 1999]
(a) – 108.7 kcal (b) + 108.7 kcal
and  890 . 4 kJ mol 1 respectively at 25 o C . The
(c) – 184.6 kcal (d) + 184.6 kcal
value of standard formation enthalpies of
115. When 50 cm 3 of a strong acid is added to 50 cm 3 of
methane at that temperature is [Pb. PMT 1998]
an alkali, the temperature rises by 5 o C . If
(a) 890 . 4 kJ mol 1 (b)  298 . 8 kJ mol 1
250 cm 3 of each liquid are mixed, the temperature
(c)  74 .7 kJ mol 1 (d)  107 .7 kJ mol 1 rise would be
108. Equal volumes of methanoic acid and sodium [KCET 1999]
hydroxide are mixed. If x is the heat of formation (a) 5 o C (b) 10 Co

of water, then heat evolved on neutralisation is[BHU 1998]

(c) 25 o C (d) 20 o C
(a) More than x (b) Equal to x
 430 Thermodynamics and Thermochemistry
1 [DCE 2000]
116. H 2 (g ) 
O2 (g)  H 2 O(l) ;
2 (a) 7.3 kcal (b) More than 7.3
H at 298 K = – 285.8 kJ (c) Zero (d) None of these
The molar enthalpy of vaporisation of water at 1 124. The heat evolved in the combustion of benzene is
atm and 25 o C is 44 kJ. The standard enthalpy of given by the equation
o
formation of 1 mole of water vapour at 25 C is [KCET 1999] 1
C6 H 6 (l)  7 O2 (g)  3 H 2 O(l)  6 CO2 (g)
(a) – 241.8 kJ (b) 241.8 kJ 2
(c) 329.8 kJ (d) –329.8 kJ
H  781 .0 kcal mol 1
117. When 4 g of iron is burnt to ferric oxide at
constant pressure, 29.28 kJ of heat is evolved. Which of the following quantities of heat energy
What is the enthalpy of formation of ferric oxide will be evolved when 39 g of benzene is burnt in
(At. Wt. of Fe = 56) an open container
[AIIMS 1999] [MP PET 2000]
(a) – 81.98 kJ (b) – 819.8 kJ (a) 122.25 kcal mol 1 (b) 390.5 kcal mol 1
(c) – 40.99 kJ (d) + 819.8 kJ
(c) 1562.0 kcal mol 1 (d) 586.75 kcal mol 1
118. When a strong acid, strong base or their salt are
dissolved in water, they are completely ionised. If 125. H 2 (g)  Cl 2 (g)  2 HCl(g). H  44 kcal
a strong acid is added to a strong base, H  ions 2 Na(s)  2HCl(g)  2 NaCl(s)  H 2 (g), H  152 kcal
from the former combine with OH  ions of the 1
latter forming water. The formation of each water For the reaction Na(s)  Cl 2 (g)  NaCl(s), H 
2
molecule liberates a certain quantity of energy
and the reaction is exothermic. The heat liberated [KCET 2000]
when one mole of water is formed by combining (a) – 108 kcal (b) – 196 kcal
hydrochloric acid and sodium hydroxide is 13.7 (c) – 98 kcal (d) 54 kcal
kcal. The heat liberated when one mole of water is
formed by combining sulphuric acid and sodium 126. The H of for CO 2 (g), CO(g) and H 2 O(g) are – 393.5,
hydroxide is [AMU (Engg.) 1999] –110.5 and – 241.8kJmol–1 respectively. The standard
(a) 25.5 kcal (b) 8.5 kcal enthalpy change (in kJ) for the reaction
CO2 (g)  H 2 (g)  CO(g)  H 2O(g) is[IIT JEE (Screening) 2000]
(c) 13.7 kcal (d) 34 kcal
119. 2.1 g of Fe combines with S evolving 3.77 kJ. The (a) 524.1 (b) 41.2
heat of formation of FeS in kJ/mol is [AMU (Engg.) 1999] (c) – 262.5 (d) – 41.2
(a) – 1.79 (b) – 100.5 127. Which of the following compounds will absorb the
(c) – 3.77 (d) None of these maximum quantity of heat when dissolved in the
same amount of water ? The heats of solution of
120. In the reaction: H 2  Cl 2  2HCl, H  194 kJ . Heat
these compounds at 25 o C in kJ/mole of each
of formation of HCl is [KCET 2000; AFMC 2000; CPMT 2000] solute is given in brackets [AMU (Engg.) 2000]
(a) + 97 kJ (b) + 194 kJ (a) HNO (H  33 ) (b) KCl (H  17 .64 )
3
(c) – 194 kJ (d) – 97 kJ
(c) NH 4 NO3 (H  25 .5) (d) HCl (H  74 .1)
121. Enthalpy of neutralisation of acetic acid by NaOH
is 50 .6 kJ / mol . and the heat of neutralisation of a 128. In the reaction C  2S  CS 2  H, H is the
strong acid with a strong base is – 55.9 kJ/mol. [AMU (Engg.) 2000]
What is the value of H for the ionisation of (a) Heat of combustion (b) Heat of
CH 3 COOH [AIIMS 2000] neutralisation
(a) + 5.3 kJ/mol (b) + 6.2 kJ/mol (c) Heat of solution (d) None of these
129. The heat of formation of methane
(c) + 8.2 kJ/mol (d) + 9.3 kJ/mol
C(s)  2 H 2 (g)  CH 4 (g) at constant pressure is
122. Heat of neutralization of the acid-base reaction is
57.32 kJ for [JIPMER 2000] 18500 cal at 25 o C . The heat of reaction at
constant volume would be [MH CET 2000]
(a) HNO 3  LiOH (b) HCOOH  KOH
(a) 17904 cal (b) 18202 cal
(c) HCl  NH 4 OH (d) CH 3 COOH  NaOH (c) 18798 cal (d) 19096 cal
123. The heat change for the following reaction at 130. The enthalpy of combustion of C 6 H 6 (l) is –
298 o K and at constant pressure is 7.3 kcal 3250 kJ. When 0.39 g of benzene is burnt excess
of oxygen in an open vessel, the amount of heat
A2 B(s)  2 A(s)  1 / 2 B2 (g) , H  7.3 kcal
evolved is
The heat change at constant volume would be
 Thermodynamics and Thermochemistry 431
[KCET 2000; AFMC 2000; DCE 2000] 139. What is n for combustion of 1 mole of benzene,
(a) 16.25 J (b) 16.25 kJ when both the reactants and the products are gas
(c) 32.5 J (d) 32.5 kJ at 298 K
131. C(s)  O2 (g)  CO 2 ; H  94 kcal [Pb. PMT 2001]
(a) 0 (b) 3/2
1
CO(g)  O 2 (g)  CO 2 ; H  135 .2 kcal (c) – 3/2 (d) 1/2
2
140. If C  O2  CO2  94 .2 kcal
Then heat of formation of CO (g) is [DCE 2001]
1
(a) – 26.4 kcal (b) 41.2 kcal H2  O 2  H 2 O  68 .3 kcal
2
(c) 26.4 kcal (d) – 229.2 kcal
CH 4  2O2  CO2  2 H 2 O  210 .8 kcal
132. The heat of neutralization of HCl and NaOH is
[MP PET 2001] Then the possible heat of methane will be [UPSEAT 2001]
(a) Zero (b) – 57.3 kJ (a) 47.3 kcal (b) 20.0 kcal
(c) + 57.3 kJ (d) None of these (c) 45.9 kcal (d) – 47.3 kcal
133. The following thermochemical reactions are given 141. Heat of neutralization of strong acid and weak
1 base is
M  O 2  MO  351 .4 kJ [UPSEAT 2001]
2
1
1 (a) 57 . 1 kJ mol
X O 2  XO  90 .8 k J
2 (b) 13 . 7 kJ mol 1
It follows that the heat of reaction for the (c) Less than 13 . 7 kcal mol 1
following process M  XO ⇌ MO  X is given by [AMU 2001]
(d) More than 13 . 7 kcal mol 1
(a) 422.2 kJ (b) 268.7 kJ
(c) – 442.2 kJ (d) 260.6 kJ 142. A system is changed from state A to state B by one
path and from B to A another path. If E1 and E 2
134. If the heat of combustion of carbon monoxide at
are the corresponding changes in internal energy,
constant volume and at 17 o C is – 283.3 kJ, then its
then
heat of combustion at constant pressure
[Pb. PMT 2001]
(R  8 .314 J degree -1 mol 1 ) [CPMT 2001]
(a) E1  E2  ve (b) E1  E2  ve
(a) – 284.5 kJ (b) 284.5 kJ
(c) E1  E2  0 (d) None of these
(c) 384.5 kJ (d) – 384.5 kJ
135. Heat of formation of H 2 O is 188 kJ / mole and 143. The heat evolved during the combination of 24 g C
and 128 g S following the change is
H 2 O2 is 286 kJ / mole. The enthalpy change for the
C  S 2  CS 2 ; H  22 .0 kcal [MH CET 2001]
reaction 2 H 2 O 2  2 H 2 O  O 2 is [BHU 2001]
(a) 11 kcal (b) 32 kcal
(a) 196 kJ (b) – 196 kJ
(c) 44 kcal (d) 22 kcal
(c) 984 kJ (d) – 984 kJ
144. When the aqueous solution of 0.5 mole HNO3 is
136. The values of H for the combustion of ethene
and ethyne are – 341.1 and – 310.0kcal mixed with the 0.3 mole of OH  solution, then
respectively. Which of the following is a better what will be the liberated heat (Enthalpy of
fuel [BHU 2001] neutralization is = 57.1 kJ)
(a) C 2 H 2 (b) C 2 H 4 [Kerala CET 2005]
(a) 28.5 kJ (b) 17.1 kJ
(c) Both of these (d) None of these
(c) 45.7 kJ (d) 1.7 kJ
137. For exothermic reaction, the equilibrium constant
(e) 2.85 kJ
[JIPMER 2001]
145. A cylinder of gas is assumed to contain 11.2 kg of
(a) Increases with increase of P
butane (C 4 H 10 ) . If a normal family needs 20000
(b) Decreases with increase of P
kJ of energy per day. The cylinder will last: (Given
(c) Increases with increase of temperature
that H for combustion of butane is – 2658 kJ)[AMU (Eng
(d) Decreases with increase of temperature
(a) 20 days (b) 25 days
138. In order to decompose 9 g water 142.5 kJ heat is (c) 26 days (d) 24 days
required. Hence the enthalpy of formation of
146. Compounds with high heat of formation are less
water is [KCET 2001]
stable because [KCET 2002]
(a) – 142.5 kJ (b) + 142.5 kJ
(a) High temperature is required to synthesise
(c) – 285 kJ (d) + 285 kJ them
(b) Molecules of such compounds are distorted
 432 Thermodynamics and Thermochemistry
(c) It is difficult to synthesis them 155. 1 mole of conc. HCl requires X moles of dilute
(d) Energy rich state leads to instability NaOH for neutralisation and 1 mole of concentrate
147. The heat evolved in the combustion of methane is H 2 SO 4 requires Y moles of small dilute NaOH
given by the following equations: then which of the following reaction is true [MH CET 2002
CH 4 (g)  2O 2 (g)  CO 2 (g)  H 2 O(l); H  890 .3 kJ 1 1
(a) Y  X (b) X  Y
How many grams of methane would be required 2 2
to produce 445.15 kJ of heat of combustion [AMU
(c) 2002]
X  2Y (d) None of these
(a) 4 g (b) 8 g
156. Which of the reaction defines H of
(c) 12 g (d) 16 g
148. Heats of combustion (H o ) for C(s), H 2 (g) and [IIT -JEE (Screening) 2003]
CH 4 (g) are 94 ,  68 and 213 kcal/ mol . (a) C(diamond )  O 2 (g)  CO 2 (g)
respectively. The value of H o
for the reaction, 1 1
(b) H 2 (g)  F2 (g)  HF (g)
C(s)  2 H 2 (g)  CH 4 (g) is [CBSE PMT 2002] 2 2
(a) – 85 kcal (b) – 111 kcal (c) N 2 (g)  3 H 2 (g)  2 NH 3 (g)
(c) – 17 kcal (d) – 170 kcal
1
149. If the value of H in a reaction is positive, then (d) CO(g)  O 2 (g)  CO 2 (g)
the reaction is called [BHU 2002] 2
(a) Exothermic (b) Endothermic 157. One gram sample of NH 4 NO3 is decomposed in a
(c) Polymorphic (d) Polytropic bomb calorimeter. The temperature of the
150. Enthalpy of neutralisation of NH 4 OH and HCl , is calorimeter increases by 6.12 K the heat capacity
numerically of the system is 1.23 kJ/g/deg. What is the molar
heat of decomposition for NH 4 NO3
[JIPMER 2002; Kurukshetra CEE 2002]
(a) 57 .1 kJ mol 1 (b)  57 . 1 kJ mol 1 [AIIMS 2003]
(a) – 7.53 kJ/mol (b) – 398.1 kJ/mol
(c)  57 . 1 kJ mol 1 (d) Zero
(c) – 16.1 kJ/mol (d) – 602 kJ/mol
151. The heat of neutralisation will be highest in[MP PMT 2002]
(a) NH 4 OH and CH 3 COOH 158. For which one of the following equations is H react
o

(b) NH 4 OH and HCl equal to H of for the product [CBSE PMT 2003]

(c) KOH and CH 3 COOH (a) 2CO(g)  O2 (g)  2CO2 (g)

(d) KOH and HCl (b) N 2 (g)  O3 (g)  N 2 O3 (g)
152. If a mole of H 2 molecule is heated to high
(c) CH (g)  2Cl 2 (g)  CH 2 Cl 2 (l)  2HCl(g)
temperature the following reaction takes place[Kerala (Med.) 2002] 4
(a) H 2 (g)  436 kJ  H(g)  H(g) (d) Xe(g)  2 F2 (g)  XeF4 (g)
(b) H 2 (g)  820 kJ  2 H 2 (g) 159. Enthalpy change for a reaction does not depend
(c) 2 H 2 (g)  436 J  2 H 2 upon
[AIEEE 2003]
(d) H 2  H 2  H   H 
153. Which of the following reactions is not (a) The physical states of reactants and products
exothermic (b) Use of different reactants for the same
[MP PET 2002] product
(a) C(s)  O 2 (g)  CO 2 (g) (c) The nature of intermediate reaction steps
(b) C(s)  2S (s)  CS 2 (g) (d) The differences in initial or final
(c) CH 4 (g)  2O2 (g)  CO 2 (g)  2 H 2 O(l) temperatures of involved substances

1 160. C dia + O 2  CO 2 ; H  395 .3 kJ / mole

(d) CO(g)  O 2 (g)  CO 2 (g)
2 C gr  O 2  CO 2 ; H  393 .4 kJ / mole
154. On combustion, carbon forms two oxides CO and
C gr  C dia ; H  [BHU 2003]
CO2 , Heat of formation of CO2 gas is 94.3 kcal
and that of CO is 26.0 kcal. Heat of combustion of (a) – 3.8 (b) – 1.9
carbon is [JIPMER 2002] (c) + 3.8 (d) + 1.9
(a) 26.0 kcal (b) – 94.3 kcal 161. What is the weight of oxygen that is required for
(c) 68.3 kcal (d) – 120.3 kcal the complete combustion of 2.8 kg of ethylene?[BVP 2003]
(a) 9.6 kg (b) 96.0 kg
 Thermodynamics and Thermochemistry 433
(c) 6.4 kg (d) 2.8 kg 170. How much energy is released when 6 mole of
162. For complete neutralization of HCl with NaOH , octane is burnt in air ? Given H of for
the heat of neutralization is [MP PET 2003] CO2 (g), H2O(g) and C8 H18 (l) respectively are –
1 1
(a)  13 .70 kJ mol (b)  13 .70 kJ mol 490,– 240 and + 160 kJ/mol
1
[AIIMS 2004]
(c)  57 .32 kJ mol (d)  57 . 32 kJ mol 1
(a) – 6.2 kJ (b) – 37.4 kJ
163. The heat of combustion of carbon to CO2 is (c) – 35.5 kJ (d) – 20.0 kJ
393 .5 kJ / mol . The heat released upon formation 3
171. Given : 2 Fe  O2  Fe2 O3 , H  193 .4 kJ ;
of 35.2 g of CO2 from carbon and oxygen gas is [UPSEAT 2004] 2
(a)  315 kJ (b)  31 .5 kJ 1
Mg  O2  MgO, H  140 .2 k J
(c) 315 kJ (d) 31 .5 kJ 2
What is the H of the reaction
164. Which of the following equations correctly
Mg  Fe2O3  3 MgO  2 Fe [Orissa JEE 2005]
represents the standard heat of formation (H of )
of methane (a) – 1802 kJ (b) +1802 kJ
[UPSEAT 2004] (c) – 800 kJ (d) + 228 kJ
(a) C (diamond) 4 H(g)  CH 4 (g) 172. The enthalpy change (H ) for the neutralisation
of 1M HCl by caustic potash in dilute solution at
(b) C (diamond) 2 H 2 (g)  CH 4 (g)
298 K is
(c) C (graphite) 2 H 2 (g)  CH 4 (g) [DPMT 2005]
(d) C (graphite) 4 H(g)  CH 4 (g) (a) 68 kJ (b) 65 kJ
(c) 57.3 kJ (d) 50 kJ
165. If the heat of formation of CO2 is 393 kJ . The
amount of heat evolved in the formation of 0.156
kg of CO2 is Bond energy
[MH CET 2004]
(a) 1357 .9 kJ (b) 1275 .9 kJ 1. If the bond dissociation energies of XY , X 2 and Y2
(c) 1572 .0 kJ (d) 1165 .5 kJ (all diatomic molecules) are in the ratio of 1 : 1 :
0.5 and  f H for the formation of XY is
166. Which of the following pairs has heat of 1
neutralisation equal to 13.7 Kcals [DCE 2003]  200 kJ mole . The bond dissociation energy of
(a) HCl, NH4 OH (b) HNO3 , KOH X 2 will be [AIEEE 2005]

(c) NaOH, CH3COOH (d) H2SO4 , NH4 OH (a) 100 kJ mol 1 (b) 800 kJ mol 1

167. The enthalpies of combustion of carbon and (c) 300 kJ mol 1 (d) 400 kJ mol 1
carbon monodie are –393.5 and –283 kJ mol–1 2. Energy required to dissociate 4 gm of gaseous
respectivley. The enthalpy of formation of carbon hydrogen into free gaseous atoms is 208 kcal at
monoxide per mole is
25 o C . The bond energy of H  H bond will be
[AIEEE 2004] [CPMT 1989; MP PET 2000; J & K 2005]
(a) 676 .5 kJ (b) 676 .5 kJ (a) 104 kcal (b) 10.4 kcal
(c) 110 .5 kJ (d) 110 .5 kJ (c) 1040 kcal (d) 104 cal
3. The bond dissociation energy needed to form
168. The enthalpy of combustion of methane at 25 o C
benzyl radical from toluene is ..... than the
is 890 kJ . The heat liberated when 3.2 g of
formation of the methyl radical from methane[IIT 1994]
methane is burnt in air is [KCET 2004] (a) Less (b) Much
(a) 445 kJ (b) 278 kJ (c) Equal (d) None of the above
(c) 890 kJ (d) 178 kJ 4. Which one of the following bonds has the highest
average bond energy (kcal/mol) [CPMT 1994]
169. If (i) C  O2  CO2 , (ii) C  1 / 2O2  CO , (iii)
(a) S  O (b) C  C
CO  1 / 2O2  CO2 , the heats of reaction are
(c) C  N (d) N  N
Q,  12,  10 respectively. Then Q  [Orissa JEE 2004] 5. The bond dissociation energies of gaseous H 2 ,Cl2
(a) – 2 (b) 2 and HCl are 104, 58 and 103 kcal respectively.
(c) – 22 (d) – 16 The enthalpy of formation of HCl gas would be
 434 Thermodynamics and Thermochemistry
[MP PET 1997; MP PMT 1999, 2001] (b) The reaction is non-spontaneous
(a) – 44 kcal (b) 44 kcal (c) The system is in equilibrium
(c) – 22 kcal (d) 22 kcal (d) The reaction is very much unlikely
6. The first ionization energy for Li is 5.4 eV and 4. The relation between G and H is
electron affinity of Cl is 3.61eV. The H (in [MP PMT 1994, 95, 97; AFMC 1997;
Kurukshetra CEE 1998]
kJ/mol) for the reaction Li(g)  Cl(g)  Li   Cl  is (if
(a) H  G  T S (b) G  H  T S
resulting ions do not combine with each other)
(1 eV  1 .6  10 19 J ) [MP PMT 2000, 03] (c) T S  G  H (d) H  T G  S

(a) 70 (b) 100 5. At 300 K, the reactions which have following

values of thermodynamic parameters occur
(c) 170 (d) 270
spontaneously
7. Given that C(g)  4 H(g)  CH 4 (g); H  166 kJ
[Roorkee 1999]
The bond energy C  H will be [AMU 2002] 1
(a) G  400 kJ mol
o
(a) 208 kJ/mole
(b) – 41.6 kJ/mole (b) H o  200 kJ mol 1 , S o  4 JK 1 mol 1
(c) 832 kJ/mole
(c) H o  200 kJ mol 1 , S o  4 JK 1 mol 1
(d) None of these
8. The H  H bond energy is 430 kJ mol and Cl  Cl (d) H o  200 J mol 1 , S o  40 JK 1 mol 1
bond energy is 240 kJ mol 1 . H for HCl is 90 kJ . 6. The relation G  H  T S was given by
The H  Cl bond energy is about [BVP 2003] [MP PMT 2000; KCET 2002]

(a) 180 kJ mol 1 (b) 360 kJ mol 1 (a) Boltzmann (b) Faraday
(c) Gibbs–Helmholtz (d) Thomson
(c) 213 kJ mol 1 (d) 425 kJ mol 1
7. For precipitation reaction of Ag  ions with NaCl ,
9. If enthalpies of methane and ethane are
respectively 320 and 360 calories then the bond which of the following statements is correct [CPMT 1988]
energy of C  C bond is (a) H for the reaction is zero
[UPSEAT 2003] (b) G for the reaction is zero
(a) 80 calories (b) 40 calories (c) G for the reaction is negative
(c) 60 calories (d) 120 calories (d) [G]  [H ]
10. If the bond energies of H  H , Br  Br and HBr 8. At constant pressure and temperature, the
are 433, 192 and 364 kJ mol 1 respectively, the direction to the result of any chemical reaction is
where, there is less amount of
H o for the reaction, H 2 (g)  Br2 (g)  2 HBr(g) is [CBSE PMT 2004]
(a) Entropy (b) Enthalpy
(a) + 261 kJ (b) – 103 kJ
(c) – 261 kJ (d) + 103 kJ (c) Gibb's free energy (d) None of the above
9. The dependence of Gibbs free energy on pressure
for an isothermal process of an ideal gas is given
Free energy and Work function by
[MP PET 1996]
1. The free energy change for a reversible reaction
at equilibrium is P2 V2
(a) GT  nRT ln (b) GT  nRT ln
[NCERT 1984; Kurukshetra CEE 1998; AMU 1999] P1 V1
(a) Large positive (b) Small negative
P1 V2
(c) Small positive (d) 0 (c) GT  nRT log (d) GT  nRT log
P2 V1
2. For a spontaneous change, free energy change G
is 10. For the change H 2 O(l)  H 2 O(g); P  1 atm ,
[MNR 1983; BHU 1981, 95; AMU 1999; T  373 K , the free energy change G  0 . This
DCE 2000, 01; BHU 2000; MP PMT 2003]
indicates that
(a) Positive
(a) H 2 O(l) is in equilibrium with H 2 O(g)
(b) Negative
(c) Zero (b) Water boils spontaneously at 373 K
(d) Can be positive or negative (c) Water does not boil spontaneously at 373 K
3. A minus sign of the free energy change denotes
that (d) Condensation of water vapour occurs
spontaneously at 373 K
(a) The reaction tends to proceed spontaneously
 Thermodynamics and Thermochemistry 435
11. What is the free energy change G when 1.0 mole 20.
In an irreversible process taking place at constant
o T and P and in which only pressure-volume work
of water at 100 C and 1 atm pressure is converted
is being done, the change in Gibbs free energy
into steam at 100 o C and 1 atm pressure [MP PET/PMT 1998] (dG ) and change in entropy (dS ) , satisfy the
(a) 540 cal (b) 9800 cal criteria [AIEEE 2003]
(a) (dS )V , E  0, (dG)T , P  0
(c) 9800 cal (d) 0 cal
(b) (dS )V , E  0, (dG)T , P  0
12. G o for the reaction X  Y ⇌ Z is – 4.606 kcal .
The value of equilibrium constant of the reaction (c) (dS )V , E  0, (dG)T , P  0
at 227 o C is (R  2 . 0 cal . mol 1 K 1 ) [Roorkee 1999] (d) (dS )V , E  0, (dG)T , P  0
(a) 100 (b) 10 21. The densities of graphite and diamond at 298 K are
(c) 2 (d) 0.01 2.25 and 3.31 g cm–3, respectively. If the standard
13. The standard enthalpy of the decomposition of free energy difference (G o ) is equal to 1895 J
N 2 O 4 to NO 2 is 58.04 kJ and standard entropy of mol 1 , the pressure at which graphite will be
this reaction is 176.7 J/K. The standard free transformed diamond at 298 K is
energy change for this reaction at 25 o C is [AIIMS 1999] [CBSE PMT 2003]
(a) 539 kJ (b) – 539 kJ (a) 9 . 92  10 Pa 5
(b) 9 . 92  10 8 Pa
(c) – 5.39 kJ (d) 5.39 kJ (c) 9 . 92  10 7 Pa (d) 9 . 92  10 6 Pa
14. Spontaneity of a chemical reaction is decided by 22. The free energy change for the following
the negative change in [MP PET 2001]
reactions are given below,
(a) Internal energy (b) Enthalpy
5
O2 (g)  2CO 2 (g)  H 2 O(l); G  1234 kJ
o
(c) Entropy (d) Free energy C 2 H 2 (g ) 
2
15. For a reaction at 25 o C enthalpy change and
C(s)  O 2 (g)  CO 2 (g) G o  394 kJ
entropy changes are  11 . 7  10 3 J mol 1 and
1
 105 J mol 1 K 1 respectively. What is the Gibbs H 2 (g )  O 2 (g)  H 2 O(l) G o  237 kJ
2
free energy [BHU 2001]
What is the standard free energy change for the
(a) 15.05 kJ (b) 19.59 kJ
reaction H 2 (g)  2 C (s)  C2 H 2 (g)
(c) 2.55 kJ (d) 22.55 kJ
(a) – 209 kJ (b) – 2259 kJ
16. Born-Haber cycle is used to determine[UPSEAT 2001]
(a) Crystal energy (b) Electron affinity (c) + 2259 kJ (d) 209 kJ
(c) Lattice energy (d) All of these 23. The equilibrium concentration of the species in
the reaction A  B  C  D are 3, 5, 10 and 15
17. Gibbs free energy G, enthalpy H and entropy S are
interrelated as in [MP PMT 2002] mole L1 respectively at 300 K the G for the
(a) G  H  TS (b) G  H  TS reaction is [Pb. PMT 2004]

(c) G  TS  H (d) G  S  H (a) 13.81 (b) – 1381.8

18. The essential condition for the feasibility of a (c) – 138.18 (d) 1391.6
reaction is that 24. Gibb’s free enrgy (G) is defined as [Pb. CET 2001]
[JIPMER 2002]
T
(a) The reaction should be exothermic (a) G  H  T S (b) G  H 
S
(b) The entropy of products must be larger than
(c) H  G  T S (d) G  H  T .C p
that of reactants
(c) The reaction is to be accompanied with free 25. Standard enthalpy and standard entropy changes
energy decrease for the oxidation of ammonia at 298 K are
(d) The reaction has to possess high activation  382 . 64 kJ mol 1 and  145 . 6 JK 1mol 1 ,
energy respectively. Standard Gibbs energy change for
19. The correct relationship between free energy the same reaction at 298 K is
change in a reaction and the corresponding
[CBSE PMT 2004]
equilibrium constant K c is
1
(a) – 439.3 kJ mol (b) – 523.2 kJ mol 1
[AIEEE 2003]
(a) G  RT ln Kc (b) G  RT ln Kc (c) – 221.1 kJ mol 1 (d) – 339.3 kJ mol 1
(c) G o  RT ln K c (d)  G o  RT ln K c 26. For spontaneity of a cell, which is correct
 436 Thermodynamics and Thermochemistry
[Orissa JEE 2004] (b) Fall in temperature
(a) G  0, E  0 (c) Decrease in velocity
(b) G  ve, E  0 (d) Energy used in doing work
(c) G  ve, E  ve 6. The heat content of a system is called
(a) Internal energy (b) Entropy
(d) G  ve , E  ve
(c) Free energy (d) Enthalpy
27. The free energy for a reaction having
7. To calculate the amount of work done in joules
H  31400 ca; . S  32 cal K 1 mol 1 at 1000 o C is[Orissa JEE 2005]
during reversible isothermal expansion of an
(a) – 9336 cal (b) – 7386 cal ideal gas, the volume must be expressed in [KCET (Med.) 2
(c) –1936 cal (d) + 9336 cal (a) m 3 only (b) dm 3 only
28. The H and S for a reaction at one atmospheric (c) cm 3 only (d) Any one of them
pressure are +30.558 kJ and 0 . 066 kJk 1
8. In an isobaric process, the ratio of heat supplied
respectively. The temperature at which the free to the system (dQ ) and work done by the system
energy change will be zero and below of this (dW ) for diatomic gas is [AFMC 2002]
temperature the nature of reaction would be [Kerala CET 2005]
(a) 1 : 1 (b) 7 : 2
(a) 483 K, spontaneous
(b) 443 K, non-spontaneous (c) 7 : 5 (d) 5 : 7
(c) 443 K, spontaneous 9. The enthalpy change for the reaction of 50.00 ml
of ethylene with 50.00 ml of H 2 at 1.5 atm
(d) 463 K, non-spontaneous
pressure is H  0.31 kJ . The value of E will be
(e) 463 K, spontaneous
[DPMT 2004]
(a) –0.3024 kJ (b) 0.3024 kJ
(c) 2.567 kJ (d) –0.0076 kJ
10. Enthalpy of solution of NaOH (solid) in water is
 41 . 6 kJ mol 1 . When NaOH is dissolved in water,
the temperature of water [UPSEAT 2004]

1. Adsorption of gases on solid surface is generally (a) Increase (b) Decreases

exothermic because [IIT JEE (Screening) 2004] (c) Does not change (d) Fluctuates
(a) Enthalpy is positive (b) Entropy decreases indefinitely
(c) Entropy increases (d) Free energy increase 11. In which of the following entropy decreases ?
[CPMT 1988, 94; MP PMT 2000]
2. Two mole of an ideal gas is expanded isothermally
and reversibly from 1 litre ot 10 litre at 300 K . (a) Crystallization of sucrose from solution
The enthalpy change (in kJ ) for the process is (b) Rusting of iron
[IIT JEE (Screening) 2004] (c) Melting of ice
(a) 11.4 kJ (b) –11.4 kJ (d) Vaporization of camphor
(c) 0 kJ (d) 4.8 kJ 12. For conversion C (graphite)  C (diamond) the
3. Heat of neutralization of strong acid against S is
strong base is constant and is equal to [MP PMT 2001; MP PET 2003]
[EAMCET 1980; AFMC 1989; DPMT 1991; (a) Zero (b) Positive
MP PET 1999; BHU 1999; MP PMT 1995] (c) Negative (d) Unknown
(a) 13.7 kcal (b) 57 kJ 13. For a reaction H  9 .08 kJ mol 1 and
(c) 5.7  10 4
J (d) All of the above
S  35 . 7 JK 1 mol 1
4. The value of heat generated when 36.5 gm HCl
and 40 gm of NaOH reacts during neutralization Which of the following statements is correct for
the reaction
[NCERT 1984; CPMT 1993]
[AMU (Engg.) 2000]
(a) 76.5 kcal (b) 13.7 kcal
(a) Reversible and Isothermal
(c) More than 13.7 kcal (d) 108 kcal
(b) Reversible and Exothermic
5. When a gas undergoes adiabatic expansion, it gets
cooled due to [DCE 2002]
(c) Spontaneous and Endothermic
(d) Spontaneous and Exothermic
(a) Loos of kinetic energy
14. For a reaction to occur spontaneously[CBSE PMT 1995]
 Thermodynamics and Thermochemistry 437
(a) (H  T S ) must be negative 23. For an endothermic reaction where H
represents the enthalpy of the reaction in kJ/mole,
(b) (H  T S ) must be negative
the minimum value for the energy of activation
(c) H must be negative will be
(d) S must be negative [IIT JEE 1992; MP PET 1993]
15. The total amount of energy in the universe is (a) Less than H (b) Zero
fixed, but (c) More than H (d) Equal to H
[AMU (Engg.) 1999] 24. The heat of neutralization of a strong acid by a
(a) Disorder is increasing (b)Lightning is increasing strong base is nearly equal to [MP PET 1993; BCECE 2005]
(c) Matter is increasing (d) Gravitation is (a) + 57.32 J (b) – 57.32 kJ
decreasing (c) + 13.7 J (d) – 13.7 kJ
16. If for a given substance melting point is TB and 25. A Beckmann thermometer is used to measure
freezing point is T A , then correct variation shown [Kurukshetra CEE 2002]
by graph between entropy change and (a) High temperature (b) Low temperature
temperature is [DCE 2001] (c) Normal temperature (d) All temperature
TB 26. The heat required to raise the temperature of a
TB S body by 1 K is called [AIEEE 2002]
S
(a) (b) (a) Specific heat (b) Thermal capacity
TA TA
(c) Water equivalent (d) None of these
T T 27. Mechanical work is specially important in system
that contain [Kerala (Med.) 2002]

TA TB (a) Solid-liquid (b) Liquid-liquid

(c) S TB (d) S
TA (c) Solid-solid (d) Amalgam
(e) Gases
T T 28. “The quantity of heat which must be supplied to
decompose a compound into its element is equal
17. In endothermic reaction, the value of change in
to the heat evolved during the formation of that
enthalpy (H ) is [Pb. CET 2001]
compound from the elements.” This statement is
(a) Positive (b) Negative known as
(c) Zero (d) None of these (a) Hess's law
18. Which of the following would be expected to have (b) Joule's law
the largest antropy per mole [MP PMT 2004] (c) Le–chatelier's principle
(a) SO 2Cl2 (s) (b) SO 2Cl2 (g) (d) Lavoiser and Laplace law
(c) SO 2Cl2 (l) (d) SO 2 (g) 29. Hess law deals with [BHU 1979]

19. The enthalpies of formation of Al2 O3 and Cr2 O3 (a) Changes in heat of reaction
are 1596 kJ and 1134 kJ respectively. H for (b) Rate of reaction
the reaction 2 Al  Cr2 O3  2Cr  Al2 O3 is[KCET 2003] (c) Equilibrium constant
(a) 2730 kJ (b) 462 kJ (d) Influence of pressure on volume of a gas

(c) 1365 kJ (d)  2730 kJ 30. For which one of the following reactions, H is
not equal to E [IIT JEE 1995]
20. Heat of reaction at constant volume is measured
in the apparatus (a) H 2(g)  I2(g) ⇌ 2 HI(g)

(a) Bomb calorimeter (b) Calorimeter (b) C(s)  O 2( g) ⇌ CO 2(g)

(c) Pyknometer (d) Pyrometer
(c) N 2(g)  3 H 2(g) ⇌ 2 NH 3( g )
21. Which of the following gas has the highest heat of
combustion (d) HCl(aq )  NaOH (aq ) ⇌ NaCl(aq )  H 2 O
(a) Methane (b) Ethane
31. The heat liberated when 1.89 g of benzoic acid is
(c) Ethylene (d) Acetylene
burnt in a bomb calorimeter at 25 o C increases
22. The amount of heat measured for a reaction in a
the temperature of 18.94 kg of water by
bomb calorimeter is [AIIMS 1991]
0 .632 o C .If the specific heat of water at 25 o C is
(a) G (b) H
0.998 cal/g-deg, the value of the heat combustion
(c) E (d) PV of benzoic acid is [CPMT 1999; BHU 2000]
 438 Thermodynamics and Thermochemistry
(a) 771.1 kcal (b) 871.2 kcal (c) Both x and y are unstable
(c) 881.1 kcal (d) 981.1 kcal (d) x and y are endothermic compounds
32. For a hypothetic reaction A  B , the activation 39. For the process dry ice  CO 2 (g) [KCET 2000]
energies for forward and backward reactions are (a) H is positive while  is negative
19 kJ/mole and 9 kJ/mole respectively. The heat of
(b) Both H and  are negative
reaction is
(c) Both H and  are positive
[CBSE PMT 2000]
(d) H is negative while  is positive
(a) 28 kJ (b) 19 kJ
(c) 10 kJ (d) 9 kJ 40. For melting of 3 moles of water at 0 o C the G o
is
33. The enthalpy of neutralization of HCN by NaOH
[MP PMT 2001]
is  12 .13 kJ mol 1 . The enthalpy of ionisation of
(a) Zero (b) + ve
HCN will be
(c) – ve (d) Unpredictable
[BHU 1997] 41. The equilibrium constant of a reaction at 298 K is
(a) 4.519 kJ (b) 45.10 kJ 5  10 3 and at 1000 K is 2  10 5 . What is the sign
(c) 451.9 kJ (d) 45.19 kJ of H for the reaction [Pb. CET 1998]
34. In thermodynamics, a process is called reversible (a) H  0 (b) H is negative
when (c) H is positive (d) None of these
[AIIMS 2001] 42. Which of the following has lowest fusion
(a) Surroundings and system change into each temperature
other [MP PET 2003]
(b) There is no boundary between system and (a) Naphthalene (b) Diamond
surroundings (c) NaCl (d) Mn
(c) The surroundings are always in equilibrium 43. Consider the reactions
with the system C(s)  2 H 2 (g)  CH 4 (g), H  x kcal
(d) The system changes into the surroundings C(g)  4 H(g)  CH 4 (g), H  x1 kcal
spontaneously
CH 4 (g)  CH 3 (g)  H(g), H  y kcal
35. Which of the following unit represents largest
amount of energy [AMU 2001] The bond energy of C  H bond is [JIPMER 1997]
1
(a) Calorie (b) Joule (a) y kcal mol (b) x 1 kcal mol 1
(c) Erg (d) Electron volt (c) x / 4 kcal mol 1 (d) x 1 / 4 kcal mol 1
36. Which of the following will have the highest bond
44. Given the bond energies N  N, H  H and N  H
energy
1
[MP PMT 1990] bonds are 945 , 436 and 391 kJ mole respectively,
(a) F2 (b) Cl2 the enthalpy of the following reaction
N 2 (g)  3 H 2 (g)  2 NH 3 (g) is
(c) Br2 (d) I2
[EAMCET 1992; JIPMER 1997]
37. C(graphite)  O2 (g)  CO2 (g) (a) 93 kJ (b) 102 kJ
1
H  94 . 05 kcal mol (c) 90 kJ (d) 105 kJ
C (diamond)  O 2 (g)  CO 2 (g); H  94 . 50 kcal mol 1 45. The relation between G and E for a cell is
G  nFE ; the cell reaction will be spontaneous if[MP PET
therefore [DPMT 2001]
(a) G is negative (b) G is positive
(a) C(graphite)  C(diamond) ; H 298
o
K  450 cal mol 1 (c) E is negative (d) E is positive
1
46. Which of the following is not a correct statement?
(b) C(diamond)  C(graphite) ; H 298
o
K  450 cal mol [AMU (Engg.) 2002]
(c) Graphite is the stabler allotrope (a) When G is negative, the process is
spontaneous
(d) Diamond is harder than graphite
(b) When G is zero, the process is in a state of
38. Enthalpy of formation of two compounds x and y equilibrium
are – 84 kJ and – 156 kJ respectively. Which of the (c) When G is positive, the process is non-
following statements is correct [CBSE PMT 2001] spontaneous
(a) x is more stable than y (d) None of these
(b) x is less stable than y
 Thermodynamics and Thermochemistry 439
47. If at 298 K the bond energies of C  H, C  C, C  C
and H  H bonds are respectively 414, 347, 615
and 435 kJ mol 1 , the value of enthalpy change for
Read the assertion and reason carefully to mark the
the reaction H 2 C  CH 2 (g)  H 2 (g)  H 3 C  CH 3 (g)
correct option out of the options given below :
at 298 K will be
[AIEEE 2003] (a) If both assertion and reason are true and the
(a) + 250 kJ (b) – 250 kJ reason is the correct explanation of the assertion.
(c) + 125 kJ (d) – 125 kJ (b) If both assertion and reason are true but reason is
48. The equation not the correct explanation of the assertion.
1 1 (c) If assertion is true but reason is false.
H 2  Cl 2  HCl ( H 298  22060 kcal ) means (d) If the assertion and reason both are false.
2 2
[CMC Vellore 1991]
(e) If assertion is false but reason is true.
(a) The heat absorbed when one gram molecule of
HCl is formed from its elements at 25 o C is 1. Assertion : The enthalpy of formation of
22.060 kcal gaseous oxygen molecules at 298 K
(b) The heat given out when one gram molecule of and under pressure of 1 atm is zero.
HCl is formed from its elements at 298 K is Reason : The entropy of formation of gaseous
22.060 kcal oxygen molecules under the same
(c) The heat absorbed when one atom of condition is zero. [AIIMS 1996]
hydrogen reacts with one atom of chlorine to 2. Assertion : We feel cold on touching the ice.
form one molecule of HCl at 25 o C and one
Reason : Ice is a solid form of water. [AIIMS 1999]
atmospheric pressure is 22.060 kcal
(d) The heat absorbed when one gram equivalent 3. Assertion : Entropy of ice is less than water.
of HCl is formed from its elements at 298 K is Reason : Ice have cage like structure. [AIIMS 2000]
22.060 kcal 4. Assertion : The heat absored during the
(e) The intrinsic heat of one molecule of HCl is isothermal expansion of an ideal
22.060 kcal more than the intrinsic heats of gas against vacuum is zero.
one atom of hydrogen and one atom of Reason : The volume occupied by the
chlorine molecules of an ideal gas is zero. [AIIMS 200
49. The H 2 O(g) molecule dissociates as
5. Assertion : Absolute values of internal energy
(i) H 2 O(g)  H(g)  OH (g); H  490 kJ of substance can not be determined.
(ii) OH (g)  H(g)  O(g); H  424 kJ Reason : It is impossible to determine exact
The average bond energy (in kJ) for water is values of constituent energies of the
(a) 490 (b) 424 substances.
(c) 914 (d) 914/2 [AIIMS 2002]
50. When 50 cm of 0.2 N H 2 SO 4 is mixed with 50 cm 3
3
6. Assertion : Mass and volume are extensive
of 1 N KOH , the heat liberated is [KCET 2004] properties.
(a) 11.46 kJ (b) 57.3 kJ Reason : Mass / volume is also an extensive
(c) 573 kJ (d) 573 J parameter. [AIIMS 2002]
51. Following reaction occurring in an automobile 7. Assertion : Molar entropy of vaporization of
2C8 H18 (g)  25 O2 (g)  16 CO2 (g)  18 H 2 O(g). The sign water is different from ethanol.
of H, S and G would be[CBSE PMT 1994; KCET 1999] Reason : Water is more polar than ethanol.
(a) +, –, + (b) –, +, – 8. Assertion : The increase in internal energy (E)
(c) –, +, + (d) +, +, – for the vaporiation of one mole of
52. For the reaction water at 1 atm and 373K is zero.
1
H 2 (g)  O 2 (g)  H 2 O(l), H  285 .8 kJ mol 1 Reason : For all isothermal processes E  0 .
2
[AIIMS 2003]
S  0 . 163 kJ mol 1 K 1 . What is the value of free
9. Assertion : H and E are almost the same for
energy change at 27 o C for the reaction [KCET 1999] the reaction. N 2 (g)  O2 (g) ⇌ 2 NO (g) .
1 1
(a)  236 . 9 kJ mol (b)  281 . 4 kJ mol Reason : All reactants and products are
1
(c)  334 .7 kJ mol (d)  334 . 7 kJ mol 1 gases.
[AIIMS 2003]
10. Assertion : The enthalpies of neutralisation of
strong acids and strong bases are
always same.
 440 Thermodynamics and Thermochemistry
Reason : Neutralisation is heat of formation Reason : At zero degree absolute, the
of water. constituent particles become
[AIIMS 1996] completely motionless.
11. Assertion : Zeroth law can also be termed as 22. Assertion : A process is called adiabatic if the
law of thermal equilibirum. system does not exchange heat with
Reason : Two objects in thermal equilibrium the surroundings.
with the third one, are in thermal Reason : It does not involve increase or
equilibrium with each other. decreae in temperature of the
12. Assertion : There is no reaction known for system.
which G is positive, yet it is
spontaneous.
Reason : For photochemical reactions G is
negative.
13. Assertion : Heat of neutralisation of perchloric
acid, HClO4 with NaOH is same as
is that of HCl with NaOH .
Reason : Both HCl and HClO4 are strong Basic concepts
acids.
1 b 2 d 3 b 4 c 5 c
14. Assertion : Heat absorbed in a reaction at
constant temperature and constant 6 d 7 d 8 c 9 c 10 c
volume is G . 11 d 12 d 13 a 14 c 15 b
Reason : G should be negative for the 16 b 17 d 18 a 19 b 20 b
reaction to be spontaneous.
21 d 22 b 23 c 24 c 25 d
15. Assertion : T, P and V are state variables or
state functions. 26 c 27 c 28 c

Reason : Their values depends on the state of

the system and how it is reached. First law of thermodynamics and Hess law
16. Assertion : Internal energy is an extensive
property. 1 d 2 b 3 a 4 b 5 c

Reason : Internal energy depends upon the 6 a 7 c 8 a 9 b 10 d

amount of the system. 11 b 12 c 13 c 14 c 15 b
17. Assertion : For the combustion reactions, the 16 b 17 c 18 b 19 c 20 a
value of H is always negative.
21 c 22 c 23 a 24 a 25 b
Reason : The combustions reactions are
always endothermic. 26 a 27 a 28 a 29 bc 30 c

18. Assertion : For an isothermal reversible 31 b 32 c 33 b 34 a 35 c

process Q  w i.e. work done by 36 b 37 c 38 b 39 d 40 c
the system equals the heat absorbed 41 d 42 a 43 c 44 a 45 c
by the system.
46 c 47 b 48 c 49 d 50 b
Reason : Enthalpy change (H ) is zero for
51 a 52 d 53 b 54 c 55 a
isothermal process.
56 b 57 d 58 d
19. Assertion : Enthalpy of formation of graphite is
zero but of diamond is not zero.
Reason : Enthalpy of formation of most IInd & IIIrd Law of thermodynamics and Entropy
stable allotrope is taken as zero.
20. Assertion : If a refrigerator’s door is kept open 1 c 2 d 3 d 4 b 5 b
room gets cooled. 6 d 7 a 8 d 9 b 10 c
Reason : Material kept inside the 11 c 12 c 13 d 14 d 15 c
refrigerator reamins cool.
16 b 17 d 18 a 19 a 20 a
21. Assertion : Enthalpy and entropy of any
21 d 22 c 23 a 24 d 25 c
elementary substance in the
standard state are taken as zero.
 Thermodynamics and Thermochemistry 441
26 d 27 c 28 b 29 c 30 b
31 b 32 d 33 d 34 a 35 c
36 b 37 c 38 a 39 c 40 c
41 c 42 c 43 c 44 d 45 b
46 a 47 c 48 d 49 d 50 c
51 c 52 b 53 a 54 c 55 c
56 c 57 a 58 b 59 d 60 b
61 b 62 d 63 a 64 c 65 a
66 c 67 b 68 b
 Thermodynamics and Thermochemistry 439

Heat of reaction Free energy and Work function

1 b 2 b 3 d 4 d 5 d 1 d 2 b 3 a 4 b 5 acd

6 b 7 c 8 a 9 b 10 a 6 c 7 c 8 c 9 a 10 a

11 bcd 12 a 13 d 14 b 15 c 11 d 12 a 13 d 14 d 15 b

16 a 17 b 18 a 19 b 20 c 16 d 17 b 18 c 19 d 20 b

21 c 22 a 23 d 24 c 25 c 21 b 22 d 23 b 24 a 25 d
26 d 27 a 28 d
26 b 27 b 28 b 29 a 30 c

31 a 32 a 33 d 34 b 35 b
Critical Thinking Questions
36 a 37 a 38 d 39 b 40 b

41 c 42 c 43 b 44 b 45 b 1 b 2 c 3 d 4 b 5 b
6 d 7 d 8 b 9 a 10 a
46 b 47 a 48 c 49 e 50 b
11 a 12 c 13 c 14 a 15 a
51 a 52 b 53 c 54 c 55 b
16 a 17 a 18 d 19 b 20 a
56 c 57 c 58 d 59 c 60 b
21 b 22 c 23 c 24 b 25 b
61 d 62 c 63 b 64 a 65 b
26 b 27 e 28 d 29 a 30 c
66 b 67 a 68 c 69 a 70 d
31 a 32 c 33 d 34 ac 35 a
71 a 72 b 73 d 74 c 75 b
36 b 37 c 38 b 39 c 40 a
76 b 77 a 78 d 79 d 80 a
41 b 42 a 43 a 44 a 45 d
81 b 82 b 83 a 84 b 85 b
46 d 47 d 48 b 49 d 50 d
86 c 87 a 88 b 89 d 90 d 51 b 52 a
91 a 92 c 93 b 94 a 95 d

96 d 97 c 98 a 99 c 100 c Assertion & Reason

101 b 102 c 103 d 104 d 105 c
1 b 2 b 3 b 4 c 5 a
106 a 107 c 108 d 109 d 110 c
6 b 7 b 8 a 9 b 10 a
111 a 112 b 113 a 114 a 115 a
11 a 12 d 13 a 14 e 15 c
116 a 117 b 118 c 119 b 120 a 16 a 17 c 18 b 19 a 20 e
121 a 122 a 123 d 124 b 125 b 21 c 22 c
126 b 127 c 128 d 129 d 130 b

131 d 132 b 133 d 134 a 135 a

136 a 137 d 138 c 139 d 140 b

141 c 142 d 143 c 144 b 145 c

146 d 147 b 148 c 149 b 150 b

151 d 152 a 153 b 154 b 155 b

Basic concepts
156 b 157 a 158 d 159 c 160 d

161 a 162 c 163 c 164 c 165 c 1. (b) Internal energy of an ideal gas is a function of
temperature only.
166 b 167 d 168 d 169 c 170 b
2. (d) In cyclic process, a system in a given state
171 a 172 c
goes through a series of different processes,
but in the end returns to its initial state.
Bond energy
4. (c) E  0 for isothermal reversible cycle.
5. (c) In isolated system neither exchange of matter
1 b 2 a 3 a 4 d 5 c
nor exchange of energy is possible with
6 c 7 b 8 d 9 b 10 b surroundings.
 440 Thermodynamics and Thermochemistry
9. (c) It is the definition of calorific value. 3 1
5. (c) n  1   , As n is negative, thus
11. (d) When a real gas is forced through a porous g 2 2 g
plug into a region of low pressure, it is found H  E .
that due to expansion, the gas on the side of 6. (a) Bomb calorimeter is commonly used to find
low pressure gets cooled. the heat of combustion of organic substances
The phenomenon of producing lowering of which consists of a sealed combustion
temperature when a gas is made to expand chamber, called a bomb. If a process is run in
adiabatically from a region of high pressure a sealed container then no expansion or
into a region of low pressure is known as compression is allowed, so w = 0 and ∆U = q.
Joule-Thomson effect. ∆U < 0, w = 0
12. (d) In isothermal reversible process ideal gas has 9. (b) H  E  nRT
constant volume and so E  0 and H  E  0 .
Since n  2
13. (a) The compressor has to run for longer time
Than H  E  2 RT .
releasing more heat to the surroundings.
14. (c) This is based on Joule-Thomson effect. 10. (d) If n  ve than H  E .
15. (b) Enthalpy is an extensive property. 12. (c) Hess’s law is an application of first law of
thermodynamics .
16. (b) dV  0 for an isochoric process.
13. (c) At constant P or T
17. (d) Total energy of an isolated system is constant.
18. (a) For isochoric process V  0 so qv  E i.e. H  U  nRT  n  n p  n R  2  4  2

heat given to a system under constant volume  H  U .

is used up in increasing E . 16. (b) It is a combustion reaction, H   ve .
19. (b) The less energy of a system and more is its 17. (c) During isothermal expansion of ideal gas,
stability. T  0
20. (b) The functions whose value depends only on
H  E  PV  E  nR T  0  0  0 .
the state of a system are known as state
functions. V2
18. (b) W  2 .303 nRT log
21. (d) For adiabatic process q  0 . V1

22. (b) The intensive property is mass/volume. 20

 2 .303  1  8 .314  10 7  298 log
23. (c) Volume is not an intensive property. 10
24. (c) An isolated system neither shows exchange of  298  10 7  8 . 314  2 .303 log 2 .
heat nor matter with surroundings.
20. (a) The enthalpies of all elements in their
25. (d) Q is not a state function. o
standard state at 25 C or 298K are zero.
26. (c) For adiabatic process Q  0 .
21. (c) Ev  E P  E R .
27. (c) Work is not a state function as during a
process its value depends on the path 22. (c) E  q  w .
followed. The value of enthalpy, internal 23. (a) E = 0 for reversible isothermal process.
energy and entropy depends on the state and
25. (b) Hess law includes initial reactants and final
not on the path followed to get that state,
products.
hence these are state functions.
26. (a) At constant T and P internal energy of ideal
28. (c) Surface tension is an intensive property which
gas remains unaffected.
do not depend upon the quantity of matter
present in the system. 27. (a) E increases with temperature.
28. (a) H  E  W or H  E  PV .
First law of thermodynamics and Hess law 29. (bc) Heat of neutralisation of
a strong acid and strong base is equal to
1. (d) First low of thermodynamics is also known as 13 .7 kcal .
Law of conservation of mass and energy.
p1
2. (b) Formation of CO2 from CO is an exothermic 30. (c)  W   2.303 nRT log
p2
reaction; heat is evolved from the system, i.e.,
energy is lowered. Thus, exothermic reactions 10
W  2.303  1  2  300 log  1381 .8 cal.
occur spontaneously on account of decrease in 1
enthapy of system. Thus, E  H . 31. (b) Joule-Thomson expansion is isoenthalpic.
4. (b) H  E  PV . 32. (c) Here n  0 so, E  H .
 Thermodynamics and Thermochemistry 441
33. (b) q  E  W if q  0 for adiabatic process, than 50. (b) Given number of moles =1
E  W . Initial temperature  27 o C  300 K
34. (a) For this reaction n  0 than E  H . Work done by the system  3 KJ  3000 K
35. (c) As the system is closed and insulated no heat It will be () because work is done by the
enter or leave the system, i.e. q  0 ;  E  Q  W  W . system.
37. (c) H  E  nRT ; n  3 Heat capacity at constant volume (Cv)  20 J / k
so, H  E  3 RT . We know that work done
38. (b) According to Hess’s law. The heat of reaction W  nCV (T2  T1 ) ; 3000  1  20 (T2  300 )
depends upon initial and final conditions of
3000  20 T2  6000
reactants.
(d) H  E  nRT 3000
39. 20 T2  3000 ; T2   150 K
20
also, 2 NH 3(g)  N 2(g)  3 H 2(g)
51. (a) Internal energy of a system is a state function
n  2 . and extensive property and is independent of
40. (c) n  0 for this reaction so, E  H . the path by which it is obtained.
41. (d) W = 0 is not true. 52. (d) N 2 O4 (g)  2 NO2 (g)
P For this reaction ng  2  1  1
42. (a) W  2.303 nRT log 2
P1 ng is positive i.e., there is an increase in the
10 number of gaseous moles then H  E
 2 .303  1  2  300 log  965 .84
2 53. (b) 2C  O2  2CO ; H  220 KJ
at constant temperature, E  0 . This reaction does not represent complete
E  q  w ; q  w  965 .84 cal . combustion of carbon, hence heat of
43. (c) q  40 J combustion of carbon will not be equal to
110 kJ . The negative sign of H indicates that
w  8 J (work done by the system)
this reaction is exothermic. Also, despite
E  q  w  40  8  32 J .
being spontaneous reaction, it requires
44. (a) We know that E  Q  W  600  (300 )  300 J initiation.
W  300 , because the work done by the 54. (c) W   PV  1  10 5 (1  10 2  1  10 3 )
system.
45. (c) Given that  1  10 5  9  10 3  900 J
P1  10 atm , P2  1 atm , T  300 K , n  1 55. (a) The exact value of internal energy is not
R  8.314 J / K / mol known as it includes all type of energies of
Now, by using molecules constituting the given mass of
P2 matter such as translational, vibrational,
W  2 .303 nRT log 10 rotational. The kinetic & potential energy of
P1
the nuclei & electron with in the individual
1
 2 .303  1  8 .314  300 log10 molecules and the manner in which the
10 molecule are linked together etc.
W  5744 .1 Joule
E  Etranslatio
nal  Erotational Evibrationa
l
46. (c) We know that internal energy of a gas
depends upon its pressure and temperature. Thus, we can say that internal energy is partly
Thus if a gas expands at constant temperature potential and partly kinetic.
and pressure, then its internal energy remains 56. (b) N 2 (g)  O2 (g)  2 NO(g) ; ng  2  2  0
same. H  E  ng RT ; H  E  0 ; H  E
47. (b) PCl5 (g)  PCl3 (g)  Cl2 (g)
57. (d) W   p V ; W  3  (6  4 )
For this reaction ng  2  1  1
ng is positive, i.e., there is an increase in the W  6  101 .32 ( 1 L atm  101 .32 J )
number of gaseous moles then H  E W  608 J
48. (c) Enthalpy (H ) is defined as the sum of internal
58. (d) A(s)  3 B(g)  4 C(s)  D(l)
energy E  PV , H  E  PV .
ng  0  3  3 ; H  E  ngRT [ E  U]
49. (d) (CH 3 )2 C  CH 2 (g)  6O2 (g)  4 CO2 (g)  4 H 2 O(l)
ng  4  6  2 (i.e., negative)  H  U  (3)(RT )
we know that H  E  ngRT H  U  3 (RT ) ; H  U  3 RT
 E  (ng )RT (  ng  ve )
 H  E IInd & IIIrd Law of thermodynamics and Entropy
 442 Thermodynamics and Thermochemistry
2. (d) When S  ve the change is spontaneous. (900  18 )
34. (a) S   43 .4 JK 1 mol 1 .
3. (d) Heat is always flow from the higher to lower vap 373
temperature. 35. (c) Entropy of the mixture increases due to
4. (b) Mixing of non-reacting gases increases increase in impurity.
randomness and so increase entropy . 37. (c) If H   ve and S   ve than the reaction is
5. (b) Entropy of the system increases as the process non-spontaneous i.e. can not occur.
occur irreversibly and isothermally in an 38. (a) T2  150  273  423 K
isolated system.
T1  25  273  298 K
6. (d) S o  2S HCl
o
 (S Ho 2  S Cl
o
)
2 Q  500 K
 2  186 .7  (130 .6  223 .0)  19 .8 JK 1mol 1 W T2  T1  423  298 
 ; W  500    147 .7 J .
9. (b) For adiabatic expansion q  0 than according Q T2  423 
q 39. (c) According to III law of thermodynamics.
to following relation S  , S  0 .
T 40. (c) When H  ve and S  ve reaction is non-
10. (c) It is the third law of thermodynamics. spontaneous.
11. (c) Entropy of gases is highest. H fusion 9.2
41. (c) Tm    1150 K .
12. (c) G  H  T S S fusion 0.008
for spontaneous process G should be negative 42. (c) Here: Change in
in option (3) H  ve and ΔS  ve than Volume (V)  500  300  200 cc  0.2 litre,
G  (ve )  T (ve )   ve
Pressure (P)  0.6 atm and heat liberated (q) =
15. (c) For reverse reaction sign will be change. 10J
16. (b) Solid  Gas, S is maximum. Work done (W)  PV  (0.2  0.6)  0.12 litre atm
17. (d)  ve H and  ve S both oppose the reaction. But 1 litre atm  101 .3 J .
18. (a) S  186 .5 / 373  0.5 JK 1 mol 1 . hence W  0.12  101 .3  12 .156 J . We also know
vap
20. (a) When H = –ve, S = +ve and G = –ve than that heat is liberated, therefore it would be
reaction is spontaneous . negative. Thus change in
21. (d) For endothermic process S increases. E  q  W  10  12 .16  2.16 J .
22. (c) Calculation of change in entropy is done at 43. (c) Formation of CO2 is,
constant temperature and pressure both.
C(s)  O 2(g)  CO 2(g)
23. (a) When the value of entropy is greater, then
ability of work is maximum. S o  213 .5  5 . 690  205  2 . 81 JK 1 .
24. (d) At equilibrium, G = 0
45. (b) H 2 O( g ) ⇌ H 2 O(l)
Hence 0 = H  T S or H  T S .
H we know G  H  T S
vap 37 . 3 KJ mol 1
25. (c) S vap   at equilibrium G  0
T 373 K
Therefore H  T S .
 0 .1 kJ mol 1 K 1  100 J mol 1 K 1 . 46. (a) We know that work done, W  Cv (T1  T2 )
26. (d) Solid  Liquid, S increases .
3  1000  20 (300  T2 ) ;  3000  6000  20 T2
27. (c) S  ve than process is spontaneous.
S  ve than the system is more disordered. 3000
28. (b)  T2   150 K .
29. (c) Because solid  solid, S is same and H is – 20
ve. 48. (d) It does not violates the first law of
H thermodynamics but violates the II law of
vap 386
30. (b) S vap    1 . 2 kJ . thermodynamics.
T 298
3 5
31. (b) Processes (a) and (c) take place with the 49. (d) C v  RT ; C p  RT for monoatomic gas
2 2
increase of no. of moles of gaseous species
5 7
and hence the disorder or entropy increases. Cv  RT; C p  RT for diatomic gas
(b) on increasing pressure, disorder or 2 2
randomness decreases and so also the entropy Thus for mixture of 1 mole each,
(d) is endothermic process and S is positive. 3 5
RT  RT
5 7
RT  RT
32. (d) This is the statement of third law of Cv  2 2 and C p  2 2
thermodynamics. 2 2
33. (d) For isothermal expansion of ideal gas, E  0 .
 Thermodynamics and Thermochemistry 443
3 RT 65. (a) In case of gas randomness is maximum
Therefore, C p / C v   1 .5 .
2 RT therefore entropy is maximum in case of
q rev steam.
51. (c) S   unit of S is JK 1 mol 1 . 66. (c) S system  S surroundin gs  O (for spontaneity)
T
H vap Because of S  R ln
V2
52. (b) H 2 O(l) ⇌ H 2 O( g ) , S  , V1
T
H vap .  2.257 KJ / g Here the volume of gas increase from V1 to V2
at constant temperature T.
or H vap  2.257  18 kJ / mol .  40 .7 KJ / mol
The total increase in entropy of the system
40 .7 and its surrounding during the spontaneous
hence, S   0 .109 kJ/mol /K.
373 process of expansion considered above is,
53. (a) Liquid  Vapour, entropy increases. V 
thus R ln  2  since V2  V1 it is obvious that
54. (c) NaNO3 is a solid, which is converted to liquid  V1 
ions. the spontaneous (irreversible) isothermal
expansion of a gas is accompanied by an
75
55. (c) Heat capacity of water per gram   4 . 17 J increase in the entropy of the system and its
18
surrounding considered together.
Q  mst ; 1000  100  4.17  t S system  S surroundin gs  0 .
1000 67. (b) G  H  T S
t  2 .4 K .
100  4 .17 at constant temperature and pressure G  0
56. (c) As the work is done on system, it will be 0  T  T S so H  T S
positive i.e. W  462 joule, E  128 joule (heat is evolving) dQrev. 30  10 3
68. (b) dS  ; T  ; T  400 K
From the Ist law of thermodynamics T 75
E  q  w  (128 )  (462 )  334 Joules.
Heat of reaction
57. (a) Gases show highest entropy.
58. (b) H  (aq )  OH  (aq )  H 2 O (l) 1. (b) C  O2  CO2  94 .2 Kcal. …..(i)
S ( 298 K ) K  mol 1
o 10 . 7  70
1
S o (298 K )  S P  S R  70  (10 .7  0) H2  O 2  H 2 O  68 . 3 Kcal . ….(ii)
2
80 . 7 JK 1 mol 1 On multiplication of eq. (ii) by 2 and than adding
heat of vaporis ation in eq. (i)
59. (d) The entropy change 
temperatur e C  2 H 2  2O2  CO2  2H 2 O  230 .8 Kcal …(iii)
Here, heat of vaporisation  540 cal/ gm On subtracting eq. (iii) by following eq.
 540  18 cal mol 1 CH 4  2O2  CO2  2 H 2 O  210 .8 Kcal. we get,
Temperature of water  100  273  373 K C  2H 2  CH 4 H  20 Kcal.
 entropy change 1
2. (b) S  16 J mole K 1
540  18
  26 .06 calmol 1 K 1
373 H vapour 6  1000
Tb . p.    375 K
60. (b) Given that, T1  500 K, T2  300 K S vapour 16
T  T2 500  300 200 4. (d) Heat of neutralisation between strong acid
By using,   1    0 .4 .
T1 500 500 and a strong base is about 13 .7 Kcal.
61. (b) It is molar heat capacity. 6. (b) Effect of temperature in heat of reaction is
62. (d) Entropy is the measure of randomness in the given by Kirchoff’s equation.
molecules. Randomness is maximum in case of 7. (c) Heat of neutralisation between strong acid
gases. Hence, entropy is maximum for water and a strong base is about 13 .7 Kcal.
vapours.
63. (a) Standard entropy of formation of CO2 (g) = 8. (a) For exothermic reactions H p  H R .
standard entropy of CO2 (g)  [Standard For endothermic reactions H p  H R .
entropy of C(s)  standard entropy of O2 (g) ] 9. (b) 78g of benzene on combustion produces
 213 .5  [5.740  205 ]  2.76 J / K . heat = – 3264.6 kJ
64. (c) Third law of thermodynamics help in 3264 . 6
 39 g will produce   1632 . 3 kJ .
calculating entropy of different temperatures. 2
10. (a) eq. (i ) + eq. (ii ) gives the required result.
 444 Thermodynamics and Thermochemistry
11. (bcd) (b,c,d) are endothermic reactions because 30. (c) NH 4 OH is a weak base. Heat of neutralisation
they proceeds by the absorption of heat. < 13.7kcal.
12. (a) Change of liquid to vapour takes energy in the 31. (a) CH 4 is the best fuel because its calorific value
form of heat so it is endothermic reaction.
212 .8
13. (d) In exothermic reactions heat is evolute.   13 .3 k cal/ g is higher among the
16
15. (c) H  ve for exothermic reaction. other gases.
H  ve for endothermic reaction 32. (a) Find H for CH 4  2O 2  CO 2  2 H 2 O .
(g)
Enthalpy of fusion is + ve.
16. (a) Heat of neutralisation will be less than 34. (b) In neutralisation of a strong acid and base
57 .33 kJ / mole because some amount of this only H  and OH  ions react.
energy will be required for the dissociation of 35. (b) When both acid and base are strong than heat
weak base (MgO ) of neutralisation is 57 . 1 kJ mol 1 .
18. (a) H 2  O2  H 2 O2 H of  188 kJ / mole ….(i) 7
36. (a) C 2 H 6  O 2  2 CO 2  3 H 2 O substitute the
2
1
H 2  O 2  H 2 O H of  286 kJ / mole ….(ii) values.
2
37. (a) Decomposition is an endothermic process.
eq. (i) – eq. (ii) × 2 gives the required result.
38. (d) H for this reaction is Heat of reaction.
19. (b) Graphite  diamond H t  (x  y) k J mol 1 . 40. (b) One mole of H 2 O is formed from its initial
21. (c) Heats of combustions are always exothermic components.
except oxidation of N as, 41. (c) One mole of a substance is completely
1 oxidized in air.
N 2  O 2  N 2 O H   ve
2 42. (c) S (rhombic)  O2  SO 2 , H  70960 cal. …(i)
N 2  O2  2 NO H   ve S (monoclinic)  O2  SO 2 H  71030 cal …(ii)
22. (a) For exothermic reactions H p  H R . Aim: S (rhombic)  S (monoclinic)
For endothermic reactions H p  H R . eq. (i) – eq. (ii) gives the required result.
23. (d) Aim: 2C  H 2(g)  C 2 H 2(g) . 43. (b) When H 2 O(l) is convert to form H 2 O , heat is
(g )
eq. (ii) + eq. (iii)  eq. (iv) – eq. (i) absorbed hence H1  H 2 .
find the required result. 44. (b) Out of given substances, kerosene oil has
24. (c) Enthalpy of formation of HCl. maximum calorific value.
25. (c) Heat of neutralisation between strong acid 45. (b) C(S )  O2(g)  CO 2 (g) , n g  1  1  0
and a strong base is about 13 .7 Kcal.
 E  H  94 kcal
26. (b) For endothermic reaction, H  ve .
E  ECO  (EC  EO )  E CO  (0  0 )
2 2 2
27. (b) Heat of neutralisation is less than 56.1 Kcal
when a strong base and a weak acid reacts. or ECO 2  E  94 kcal .
1 46. (b) 0.2 mole will neutralize 0.2 mole of HNO 3 ,
28. (b) Aim: CO  O 2  CO 2
2
heat evolved  57  0.2  11 .4 kJ.
 1 
H  H 0f (CO 2 )  H 0f (CO)  H 0f (O 2 ) 47. (a) Suppose heat evolved in Ist case is Q1 and that
 2 
1
  94 .0  (26 .4)  67 .6 kcal. in the IInd case it is Q 2 . Then Q 2  Q1 .
2
29. (a) But Q1  1000 T1 and Q2  500 T2
1 1
(i) H 2  O2  H 2 O, H  241 k J  500 T2   1000 T1 i.e . T2  T1 .
2 2
17 48. (c) Enthalpy of a compound = Heat of reaction of
(ii) C6 H10  O2  6 CO 2  5 H 2 O, H  3800 k J
2 that compound.
(iii) C6 H12  9O2  6CO2  6 H 2O, H  3920 kJ 49. (e) It is the definition of heat of neutralization.
50. (b) H   ve for exothermic compound.
C6 H10  H 2  C6 H12
51. (a) If acid or base or both are strong, heat of
Eq. (i) + Eq. (ii) – Eq. (iii) neutralization  13 .7 kcal.
H  241  3800  (3920 ) 52. (b) Both NH 4 OH and CH 3 COOH are weak.
 4041  3920  121 kJ 53. (c) 57 .1  0.25  14 .3 kJ mol 1 .
 Thermodynamics and Thermochemistry 445
54. (c) Heat of formation is for 1 mole. 82. (b) CH 4  2O2  CO2  2H 2 O
Hence H 0f (HI)  12 .40 / 2  6.20 kcal. Molecular weight of CH 4  12  4  16
55. (b) Chemical dissociations are reversible and
 On the combustion of 2.0gm of methane= 25.0 kcal
endothermic.
57. (c) Given,  On the combustion of 16 .0 gm  25  16  200 kcal.
2
(i) CH 4  2O2  CO2  2H 2 O , H  20 kcal
(ii) C  O2  CO2 , H  40 kcal. 83. (a) CH 4  2O2  CO2  2H 2 O .

1 84. (b) C2 H 4  3O2  2CO2  2H 2 O

(iii) H 2  O 2  H 2 O , H  10 kcal.
2 H reaction  [2  H of (CO2 )  2  H of (H 2 O)]
Aim: C  2 H 2  CH 4
(ii) + 2 × (iii) – (i) gives.  [H of (C2 H 4 )  3  H of (O2 )]
H  40  2 (10 )  ( 20 )  80 kcal.
 [ 2 (  394 )  2 (  286 )]  [52  0]  1412 kJ .
58. (d) For exothermic reaction heat is evolved.
1 85. (b) C  O2  CO2  394 kJ .
electrolys is
59. (c) H 2 O(l)      H 2(g)  O 2(g) .
2 2C  2O2  2CO2  788 kJ ….(i)
61. (d) All other are combustion phenomena.
2CO  O2  2CO2  569 kJ ….(ii)
62. (c) H combusion = –ve, so exothermic process.
2CO2  2CO  O2  569 kJ …..(iii)
1 1
63. (b) Aim: K (S )  O 2(g)  H 2(g)  KOH (S )
2 2 eq. (i) + eq. (iii) = –109.5 kJ mol–1.
eq. (ii) + eq. (i) – eq. (iii) gives 44
86. (c) H f  kcal  22 kcal .
H  48  (68 .39 )  (14 )  68 .39  48  14 . 2
64. (a) By definition of heat of formation. 87. (a) CaO(s)  H 2 O(l)  Ca (OH )2 is exothermic.
68. (c) CD  CG , H  453 .5 cal.
i.e. energy of CG is less and thus more stable. 88. (b) H  ve in exothermic reaction.
69. (a) H combustion is always negative . 89. (d) According to the definition of heat of
formation.
70. (d) H reaction  H 0f (N 2 O4 )  2H 0f (NO2 )
90. (d) Multiplying eq. (ii) by (iii) and eq. (iii) by (vi),
 2  2 (8)  14 kcal. and then add
71. (a) H  E  nRT  3  8.314  298 15
6 C  3H 2  O 2  6 CO2  6 H 2 O; H  3218 .7
 7432 J  7.43 kJ. 2
72. (b) Aim: C  C(diamond) ; eq. (i) – (ii) gives the Subtract eq. (i) from the above equation and
(graphite)
find the required result.
result.
73. (d) In the formation of a compound, more the 91. (a) HF is more stable than HCl .
heat absorbed, less stable is the compound. 92. (c) H ( H P  H R )  q p .
74. (c) C(graphite )  2 H 2(g)  CH 4 (g) .
93. (b) H  ve for endothermic reaction.
75. (b) Heat of formation is the formation of one 13 .95  44
mole of the substance from its elements. 94. (a) H   278 .7 kcal .
2 .2016
76. (b) H (reaction )  2H 0f (MgO)  H 0f (SiO2 )
95. (d) eq. (i) + eq. (ii) gives the required result.
 2 ( 34 .7)  ( 48 .4)  21 kJ.
96. (d) Standard molar heat enthalpy (H o ) of a
77. (a) eq. (i) + eq. (ii) + eq. (iii) gives
compound is equal to its standard heat of
X  131  282  242   393 kJ . formation from most stable states of initial
78. (d) It is the definition of heat of transition. components.
79. (d) C(graphite )  C(diamond ), H  1.9 kJ 97. (c) In the complete combustion of butanol
H  E .
C(graphite )  O2  CO 2 , H  H 1
98. (a) X – Y and find the required result.
C(diamond )  O2  CO2 , H  H 2 99. (c) S  O2  SO 2 H  298 .2 kJ ….(i)
(  H1 )  (  H 2 )  1.9 kJ or H 2  H1  1.9 1
SO 2  O 2  SO 3 H  98 . 2 kJ ….(ii)
For combustion of 6 g, H 2  H1 by 2
1.9 / 2  0.95 kJ. eq. (i) – (ii) and find the required result.
100. (c) C  2S  CS 2 H  ?
80. (a) H product  H reactant for exothermic reaction.
C  O2  CO2 H  393 .3 kJ ….(i)
81. (b) Due to high electron affinity of Cl the highest
energy is evolved. S  O2  SO 2 H  293 .72 kJ …..(ii)
 446 Thermodynamics and Thermochemistry
CS 2  3O2  CO2  2SO 2 H  1108 .76 kJ …..(iii) 117. (b) Given: Weight of iron burnt  4 g; Heat
eq. (ii) × 2 + eq. (i) – (iv) eq. (iii) – eq. (iv) liberated  29 .28 KJ and atomic weight of iron
and find required result . (Fe )  56 . We know that in ferric oxide
101. (b) Fermentation is exothermic reaction. (Fe2 O3 ), 2 moles of iron or 2  56  112 gram of
102. (c) CH 4  2O2  CO2  2H 2 O . iron are burnt. We also know that when
103. (d) Use H  E  n RT 4grams of iron are burnt, then heat liberated
= 29.28 kJ, therefore when 112 grams of the
H  19  2  2  10 3  300  20 .2 kcal ; n  2 .
iron are burnt, then heat liberated
104. (d)  20 . 6  8 . 8 KJ mol 1  29 . 4 kJ . 29 . 28  112
  819 . 8 kJ (Minus sign due to
106. (a) Subtract equation (ii) from (i). 4
liberation of heat).
107. (c) CH 4  2O2  CO2  2H 2 O, H   890 .4 kJ ….(i)
118. (c) H   OH   H 2 O, H neutraliza tion  13 .7 kcal .
C  O2  CO2 , H   395 .5 kJ …..(ii)
C  O2  CO2 , H   395 .5 kJ 3 . 77  56
.….(ii) 119. (b) H / mole of FeS   100 . 5 .
2 .1
1
H2  O 2  H 2 O, H   285 . 8 kJ …..(iii) 194
2 120. (a) Heat of formation   97 kJ .
2
from (i), (ii), (iii).
H (CH 4 ) 121. (a) H  Hioniz  Hneu =  50 .6  H ioniz  (55 .9)
comb .

 H f (CO 2 )  2H f (H 2 O)  H f (CH 4 )  2H f (O 2 ) H ioniz   5.3 kJ / mol .

 890 .4  395 .5  2 (285 .5)  H f (CH 4 )  2  0 122. (a) Strong acid (HNO 3 ) and strong base (LiOH ) .
123. (d) H  E  nRT or E  H  nRT
H f (CH 4 )  76 .7 kJ mol 1 .
1
108. (d) As methanoic acid is weak acid, heat of  E  7 .3   0 .002  298  7.3  0.298 = 7 kcal.
2
neutralization < x.
124. (b) Heat evolved during burning of 39 g
109. (d) Neutralization of a strong acid by a strong
base is always same. 781 .0  39
C6 H 6   390 .5 kcalmol 1
110. (c) S  O 2  SO 2 , H f   4.6 kJ 78

 0.5 gm. of sulphur on burning produce 1gm of 1

125. (b) By (i) + (ii) ; Na  Cl 2  NaCl , H  196 kcal .
SO 2 2

 32 gm of sulphur on burning produce 64 gm.. 126. (b) C  O2  CO2(g) , H of  393 .5 kJ mol 1 ….(i)
of SO 2 1
C O 2  CO ( g ) , H of  110 . 5 kJ mol 1 ….(ii)
 H  (  4.6 kJ )  64   294 .4 kJ . 2
111. (a) 3O 2 ⇌ 2O3 – energy is given out. H2 
1
O 2  H 2 O( g ) , H of  241 .8 kJmol 1
...(iii)
2
72  1 . 6
112. (b) H per 1 . 6 g   0 . 64 kcal . By (ii) + (iii) – (i)
180
113. (a) C  O2  CO2 , H  394 kJ …..(i) CO2(g)  H 2(g)  CO(g)  H 2 O(g) , H  41 .2 .

2 H 2  O2  2 H 2 O, H  568 kJ ….(ii) 127. (c) More +ve is H s more is heat of solution.

CH 4  2O2  CO2  2 H 2 O, H  892 kJ …..(iii) 128. (d) CS 2 is formed from its initial components
(i) + (ii) – (iii) and find the required result. carbon and sulphur so, H is heat of
115. (a) No doubt heat evolved during neutralisation formation of CS 2 .
of 250 cm 3 of each acid and base is five time 129. (d) H  18500  E  nRT
the heat evolved during neutralisation of or 18500  E  (1)  2  298  19096 cal .
50 cm 3 of each acid and base but the quantity if 130. (b) Heat evolved during combustion of 0.39g
solution taking heat is also five time thus 3250  0 .39
C6 H 6   16 .25 k J.
same temperature rise is noticed. 78
1 1
116. (a) H 2  O 2  H 2 O(l) ; H  285 . 8 KJ 131. (d) By (i) – (ii) : C  O 2  CO ; H  229 . 2 .
2 2
H 2 O(l)  H 2 O(g) ; H  44 KJ 132. (b) Strong acid (HCl ) and strong base (NaOH )
1 shows Hneutralization = –57.3 kJ.
 H2  O 2  H 2 O( g ) ; H o  241 . 8 KJ
2 133. (d) By (i) – (ii) and find required result.
 Thermodynamics and Thermochemistry 447

134. (a) CO ( g ) 
1 1
O 2  CO ( g ) , n  1  1   
1 C(s)  O2(g)  CO2(g) H  94 kcalmol 1 …..(ii)
2 (g) 2 2
1
H  E  nRT H 2( g )  O 2( g )  H 2 O(l) H  68 kcal mol  1 … (iii)
2
1 8 . 314
H  283 . 3    290  284 . 5 kJ . CH 4  3 / O 2  CO 2  2 H 2 O
2 1000 2
1 H  213 kcal mol 1 … (iv)
135. (a) H 2  O 2  H 2 O H  188 kJ /mole ..…..(i)
2
to obtain equation (i) operate-(ii) + 2 × (iii) –
H 2  O2  H 2 O2 ; H  286 kJ/mole ..….(ii) (iv).
By 2 × (i) and (ii) 149. (b) H  ve for endothermic reactions.
2 H 2  O2  2 H 2 O ; H  376 kJ/mole …..(iii) 150. (b) It pertains to neutralization of strong acid
weak base.
2 H 2  2O2  2H 2 O2 H  572 kJ/mole …..(iv)
151. (d) Strong base (KOH) and strong acid (HCl)
By (iii) – (iv)
153. (b) This reaction absorbed heat, so it is
2H 2 O2  2 H 2 O  O2 H  196 kJ . endothermic reaction.
136. (a) H for C2 H 6  341 .1 K cal 154. (b) C  O2  CO2 , H   94 .3
341 . 1 This is also heat of formation of CO2
its calorific value   11 . 37 kcal / g .
30
1
H for C2 H 2  310 .0 kcal C O 2  CO , H  26 . 0 .
2
310 . 0 1
its Calorific value   11 . 92 , 155. (b) X  Y .
26 2
hence C2 H 2 is a better fuel. 157. (a) Molecular weight of NH 4 NO3  80
138. (c) For the decomposition of 9gm of water heat Heat evolved  1 .23  6 .12
required  142 .5 kJ
 Molar heat capacity  1 .23  6 .12  C .
we know H 2 O  2  16  18
158. (d) Both X e and F2 are gaseous elements at 25 o C
Therefore heat required for decomposition of and in their standard states and form XeF4 (g)
18
18gm water   142 . 5  285 KJ hence H(f )  H react

.
9
Than, enthalpy of formation of water is 159. (c) According to Hess low, enthalpy change for a
reverse of heat required = – 285 kJ. reaction does not depend on the nature of
15 inter mediate reaction steps.
139. (d) C 6 H 6 ( g )  O 2( g )  6 CO 2( g )  3 H 2 O( g )
2 160. (d) By (ii) – (i), C gr  Cdia , H  1.9 .
15 1
n  6  3  1   . 162. (c) Heat of neutralization of strong acid and
2 2
strong base is equal to the  57 . 32 KJ mol 1
140. (b) By 2 × (i) + (ii) – (iii)
163. (c) C  O2  CO2 H  393 .5 KJ / mol
H of methane  20 .0 kcal .
 44 gm of CO2 form by which heat released
141. (c) Heat of neutralization of strong acid and weak
base is less than 13 . 7 kcal mol 1 .  393 . 5 kJ
142. (d) E  0 for a cyclic process.  1 gm of CO2 form by which heat released
143. (c) 22 .0  2  44 kcal . 393 .5

44
144. (b) 0.3 mole OH  , neutralize 0.3 mole of HNO 3
 35 .2 gm (given) of CO2 form by which heat
Evolved heat,  57 .1  0.3  17 .13 kJ
released
146. (d) Compounds with high heat of formation are
393 .5
less stable because energy rich state leads to   35 .2  315 kJ
instability. 44
445 .15  16 164. (c) C(graphite )  2 H 2 (g)  CH 4 (g)
147. (b) CH 4 required   8 gm .
890 .3
165. (c) Heat of formation of a substance is the heat
148. (c) C(s)  2 H 2 (g)  CH 4 (g) …..(i) exchanged when one mole of that substance is
formed by its constituent elements.
 448 Thermodynamics and Thermochemistry
 Heat evolved when 1 mole (44 g) CO2 is On multiplying eq. (ii) by 3
formed  393 kJ 3
3 Mg  O 2  3 MgO; H  420 .6 kJ ......(iiii)
 Heat evolved when 0.156 Kg (156 g) is 2
393  156 Resulting equation can be obtained by
formed  subtracting eq. (i) from (iii)
44
 H for the process  1572 kJ  1572 .0 kJ 3
3 Mg  O 2  3 MgO; H  420 .6 kJ
2
166. (b) It is heat of neutralisation (13 .7 Kcal) for
3
strong acid and strong base. 2 Fe  O 2  Fe 2 O 3 ; H  193 .4 k J
2
167. (d) C(s)  O2 (g)  CO2 (g) Subtraction :
H  393 . 5 KJ mol 1
…..(i) 3 Mg  Fe 2 O3  2Fe  3 MgO; H  227 .2 kJ

CO(g)  1 / 2O2 (g)  CO2 (g) 172. (c) HCl and KOH both are strong

H  283 KJ mol 1 …..(ii) Bond energy

On substracting equation (ii) from equation
(i) 1. (b) XY  X (g)  Y(g) ; H  a kJ / mole ……….(i)
We get X 2  2 X ; H  a kJ / mole ……….
1
C(s)  O2 (g)  CO(g) ; H  110 . 5 KJ mol (ii)

The enthalpy of formation of carbon Y 2  2Y ; H  0.5 a kJ / mole

monooxide per mole  110 . 5 KJ mol 1 ……….(iii)

168. (d) 1 mole (i.e.,) 16 gm of methane on combustion 1 1

 (ii)   (iii) - (i), gives
liberate 890 kJ 2 2
1 1
890  3 .2 X 2  Y 2  XY ;
 3.2 gm will liberate   178 KJ 2 2
16
 a 0.5 
169. (c) C  O2  CO2 ; H  q H     a  a  kJ / mole
 2 2 
C  1 / 2O2  CO ; H  12 …..(i)
a 0 .5 a
   a  200
CO  1 / 2O2  CO2 ; H  10 …..(ii) 2 2

adding equation (i) and (ii) we can get a  800

H  12  (10 )  22 2. (a) 4 g H 2  2 moles. Bond energy for 1 mole of

H 2  208 / 2  104 kcal.
170. (b) C  O2  CO2 ; H F  490 KJ / mol – (I)
4. (d) By definition of Hess’s law.
H 2  1 / 2O2  H 2 O; H F  240 KJ / mol – (II)
1 1
5. (c) Aim: H 2  Cl2  HCl
8 C  18 H  C8 H18 ; H F  160 KJ / mol – (III) 2 2
applying H   B. E.   B. E.
(Products) (Reactants)
(I) 8  (II) 9  (III)
1 1 
 B. E.( HCl )   B. E.( H 2 )  B. E.(Cl2 )
C 8 H 18 
25
O 2  8 CO 2  9 H 2 O 2 2 
2
1 1 
 103   (  104 )  (  58 )
H o  3920  2160  160  6240 KJ / mol  2 2 

H o  for 6 moles of octane  6240  6  103  (  52  29 )  22 kcal .

 37440 KJ / mol  37 .4 KJ 6. (c) First ionization potential of Li  5 .4 eV

3 Electron affinity of Cl  3 .61 eV

171. (d) 2 Fe  O 2  Fe 2 O 3 ; H  193 .4 k J .....(i)
2 We have H  I.P.  E. A.

1  5 .4  3.61  1.80 eV  1.80  1 .6  10 22 kJ

Mg  O 2  MgO; H  140 .2 kJ .....(ii)
2
 Thermodynamics and Thermochemistry 449
H  2.86  10 22 kJ, 18. (c) If G  ve reaction is spontaneous.
20. (b) (dS )V , E  0, (dG)T , P  0 .
for 1mol Avogadro’s number  6 .02  10 23 .
21. (b) Only high pressure favours the conversion.
H  2 . 86  10 22  6 . 02  10 23  170 kJ / mole .
22. (d) By 2× (ii) – (i) – (iii)
166
7. (b)  41 .5 kJ / mole . H 2(g)  2C(s)  C 2 H 2(g) , G   209 kJ .
4
1 1 23. (b) G  2.303 RT log K  , Here R  2 cal, T  300 K
8. (d) H 2  Cl2  HCl, H  90 KJ
2 2 10  15
K   10 ; G  2.303  2  300  log10 10
1 1 35
 H  E H  H  ECl Cl
2 2  2.303  2  300  1  1381 .8 cal
1 1 24. (a) G  H  T S (Gibb’s free energy equation)
or  90   430   240  E HCl
2 2 25. (d) G  H  T S
 E H Cl  425 kJ mol 1 . G  382 .64  (145 .6)  10 3  298
9. (b) CH 4  C  4 H, H  320  339 . 3 KJ mol 1

EC  H  90 cal 26. (d) G  H  T S ; G  E  PV  T S

For spontaneity (G  ve )
C2 H 6  2C  6 H, H  360
 G  ve , E  ve
 360  EC C  6 EC  H 27. (a) G  H  TS  31400  1273  32
 EC  C  360  320  40 cal .  31400  40736  9336 cal

10. (b) H  H  Br  Br  2 H  Br 28. (d) G  H  T S

0  30 .558  T  0 . 066
433  192 2  364
30 .558
625 728 or T   463 K
0 .066
Energy absorbed = Energy released If (dG)T , P  0 sign ' ' mean. If is reversible
Net energy released  728  625  103 kJ process
i.e.,  H  103 KJ
Critical Thinking Questions
Free energy and Work function
1. (b) Due to randomness of particles is reduced
1. (d) G at equilibrium = 0. since entropy decreases.
2. (b) For spontaneous change G  ve . 2. (c) H  nCp T
3. (a) When G  ve than the reaction is The process is isothermal therefore
spontaneous in nature.
G  0 ;  H  0
5. (acd)When H  ve and S  ve than the
reaction is non-spontaneous. 3. (d) 13 .7 kcal  57 kJ  5 . 7  10 4 J .
7. (c) Because the reaction is spontaneous . 4. (b) When strong acid and strong base neutralize each
8. (c) G = –ve. other than the value of heat generated is about
13.7 kcal.
P2
9. (a) GT  nRT ln . 5. (b) Due to fall in temperature.
P1
6. (d) q  H .
10. (a) G  0 for equilibrium. p

11. (d) At equilibrium G  0 . 7. (d) w  2.303 RT log

V2 V
. As it involves the ratio 2 ,
V1 V1
12. (a) G o   2 . 303 RT log K
volume can be used in any units. (R should be
 4.606   2.303  0.002  500 log K in joules).
log K  2, K  100 . 8. (b) 
dQ

dQ
; dE  dW  dQ ; dW  dQ  dE
dW dQ  dE
14. (d) Spontaneous change shows G  ve .
nc p dT cp
15. (b) G  H  TS , T  25  273  298 K  
nc p dT  nc v dT (c p  c v )
 11 .7  10 3  298  (105 )  19590 J  19 .59 kJ
 450 Thermodynamics and Thermochemistry
7R 7R
 {for diatomic of gas c p  }
2R 2

Enthalpy
Ea Ea > H
9. (a) C2 H 2 (g)  H 2 (g)  C2 H 4 (g)
23. (c) H
ng  1  2  1 ; H  0 . 31 KJ mol 1
P  1.5 atm , V  50 mL  0.050 L
Energy
H  E  PV

0.31  E  0.0076 ; E  0.3024 KJ 24. (b) H Neutralization  57 .1 kJ  13 .7 kcal .

10. (a) Since process is exothermic then heat is 25. (b) Backmann thermometer is used to measure
evolved due to this temperature of water low temperature.
increases. 26. (b) Heat required to rise the temperature of a
11. (a) Because randomness is decreases. body by 1K called thermal capacity of the
body.
12. (c) Conversion of graphite into diamond is an
endothermic reaction. So, heat of diamond is 27. (e) Mechanical work is important only in gases as
higher than that of graphite. But S would be they undergo appreciable change in volume.
negative for the conversion of graphite into 28. (d) It is Lavoisier and Laplace law. This is another
diamond. law of thermochemistry which was put
forward before Hess's law.
13. (c) H and S both are ve for spontaneous
change, and H  ve for endothermic 29. (a) It is also known as "constant heat summation"
reaction. law. It state that the total amount of heat
evolved or absorbed in a reaction is same
14. (a) G  H  T S is negative for spontaneity.
whether the reaction takes place in one step
15. (a) Entropy (a measure of disorder) of universe is or in a number of steps.
increasing toward maximum. This is II law of 30. (c) In this reaction n  2  4  2 so H  E .
thermodynamics.
18 .94  0 .632  0 .998  122
16. (a) For a pure substance TA and TB represent the 31. (a) Q  = 771 .1 Kcal
1 .89
same temperature. Hence A is a correct
32. (c) H  Ea for forward reaction  Ea for
choice.
backward reaction  19  9  10 kJ .
17. (a) For endothermic reaction enthalpy of products
(H P ) > enthalpy of reactant (H R ) 33. (d) Q  18 .94  0.632  0.998  1000
57 .4  x  12 .13
Hence, change in enthalpy,
x  45 .2
H  H P  H R  Positive
34. (c) Thermodynamics is a reversible process in
18. (d) Suppose the no. of gm, 1gm for each case so which surroundings are always equilibrium
the max. no of mole expected for SO 2 (g) with system.
which has to expected maximum entropy. 4 . 18
35. (a) 1 cal  4 . 18 J  4 . 18  10 7 erg   10 19 eV .
3 1 . 602
19. (b) 2 Al  O 2  Al 2 O 3 , H  1596 kJ …..(i)
2 36. (b) Order of bond energy : Cl2  Br2  F2  I2 .
3
2 Cr  O 2  Cr2 O 3 , H  1134 kJ …..(ii) 37. (c) Heat energy is also involved when one
2 allotropic form of an element is converted in
By (i) – (ii) to another. graphite is the stabler allotrope
2 Al  Cr2 O3  2Cr  Al2 O3 , H  462 kJ . because the heat of transformation of
C(diamond )  C(graphite ) .
20. (a) Bomb calorimeter is used to measure heat of
reaction. (i) C(dia )  O2(g)  CO2(g)H  94 .5kcal

21. (b) Larger the number of C and H atoms, greater (ii) C(graphite )  O2(g)  CO2(g)H  94 .0 k cal
is the heat of combustion.
H transforma tion  94 .5  (94 .0)
22. (c) The bomb calorimeter is used to measure E .
 0.5k cal .
 Thermodynamics and Thermochemistry 451
38. (b) The compound Y possess less energy than the 52. (a) G  H  TS , T  27  273  300 K
X and thus Y is more stable than X.
G  (285 .8 )  (300 )(0 .163 )  236 .9 kJ mol 1
39. (c) Both H and p are positive.

40. (a) For equilibrium G o  0 .

Assertion & Reason
41. (b) Equilibrium constant is decreases with
temperature and H is also decreases so it is 1. (b) Assertion and reason show, reaction at
–ve. equilibrium state in which G  0 , S  0 ,
42. (a) The fusion temperature of napthalene is H  0 .
minimum, because it is non-polar covalent 2. (b) It is correct that on touching the ice we feel
compound and has less fusion temperature. cold because ice absorb heat from our hand.
43. (a) The bond energy of C  H bond is y kcal mol 1 . 3. (b) Entropy of ice is less than water because
water molecules in solid state lose kinetic
H
| energy and hence their tendency of movement
44. (a) N  N  3 H  H  2N  H minimise. Hence entropy decrease in solid
945  3  436 |
H state. The reason that ice have cage like
Energy absorbed 2 (3  391 )  2346
structure is also correct but reason is not or
Energy released
correct explanation for assertion.
Net. energy released = 2346 – 2253 = 93 kJ 4. (c) During isothermal expansion of an ideal gas
i.e. ΔH = – 93 kJ . against vacuum is zero because expansion is
isothermal. The reason, that volume occupied
45. (d) If E  ve than the cell reaction will be
by the molecules of an ideal gas is zero, is
spontaneous.
false.
46. (d) All are the correct statements. 5. (a) it is fact that absolute values of internal
47. (d) CH 2  CH 2(g)  H 2(g)  H 3 C  CH 3(g) energy of substances can not be determined. It
is also true that to determine exact values of
414  4  1656 414  6  2484 constituent energies of the substance is
615  1  615 347  1  347 impossible.
6. (b) Mass and volume are extensive properties.
435  1  435 2831
2706 mass/volume is also an extensive parameter.
Here, both assertion and reason are true.
H  2706  2831  125 kJ
7. (b) The molar entropy of vaporization of water it
48. (b) It means that the heat absorbed when one differ from ethanol due to hydrogen bonding
gram molecule of HCl is formed from its according to VSEPR theory water molecule
elements at 298 K is having two lone pair of electron by which it
angular and show some polarity which is
 22 .060 k cal .
higher than that of ethanol so both assertion
49. (d) eq. (i) + eq. (ii) find the required result and and reason are correct but reason is not
explaination assertion.
divide by 2.
8. (a) The assertion that the increase in internal
50. (d) For complete neutralization of strong acid and
energy for the vaporisation of one mole of
strong base energy released is 57 .32 KJ / mol
water at 1 atm and 373 K is zero is true and
0.2  50 this is because that for all isothermal process
No. of mole of H 2 SO 4   10 2 internal energy is zero.
1000
9. (b) N 2 (g)  O2 (g) ⇌ 2 NO (g)
1
No. of mole of KOH   50  5  10  2
1000 We know that H  E  nRT

So  57 . 32  10 2  0 . 5732 KJ  573 .2 Joule . n  2  2  0 hence, nRT  0

51. (b) For Combustion reaction, H is negative,
n  (16  18 )  (25  2)  7 , so S is ve , 10.
reaction is spontaneous, hence G is –ve.
Therefore, H  E
(a) The enthalpies of neutralisation of strong
acids and strong bases are same they are 13.7
 452 Thermodynamics and Thermochemistry
Kcal. The reason is that it is heat of formation If a system undergoes a change in which
  internal energy of the system remains
of water from H and OH ions.
H   OH   H 2 O, H  13 .7 Kcal . Thus, both constant (i.e., E  0 ), then W  Q .

assertion and reason are true. This means that work done by the system
equals the heat absorbed by the system.
11. (a) Zeroth (law of temperature) can also be
summarized as two objects at different 20. (e) If a refrigerator’s door is kept open room gets
temperature in thermal contact with each heated as heat energy is released to the
other tend to move towards the same surroundings.
temperature.
21. (c) Enthalpy is zero but entropy is not zero.
12. (d) Photo chemical reactions have ve G . Vibrational motion exists even at absolute
zero.
22. (c) It may involve increase or decrease in
temperature of the system. Systems in which
such process occur, are thermally insulated
from the surroundings.

14. (e) Heat absorbed in a reaction at constant

temperature and constant volume (Qv )  E .

15. (c) Values of state functions depend only on the

state of the system and not on how it is
reached.
16. (a) The properties whose magnitude depends
upon the quantity of matter present in the
system are called extensive properties.
17. (c) Combustion reactions are always accompanied
by the evolution of heat therefore, for such
reactions the value of H is always negative.
18. (b) In an isothermal process change in internal
energy (E) is zero (as it is a fucntion of
temperature).  According to first law of
thermodynamics
 q  w  E , hence Q  W (if E  0)
 452 Thermodynamics and Thermochemistry

1. The internal energy change when a system goes (a) 2 Joule (b) 4 Joule
from state A to B is 40 kJ/mole. If the system goes
(c) Zero (d) Infinite
from A to B by a reversible path and returns to
state A by an irreversible path what would be the 8. Heat exchanged in a chemical reaction at constant
net change in internal energy temperature and constant pressure is called as
[CBSE PMT 2003]
[BHU 1998; Pb. PET 2000; MP PET 2002]
(a) 40 kJ (b) > 0 kJ
(a) Internal energy (b) Enthalpy
(c) < 40 kJ (d) Zero
2. The correct relationship is [DPMT 2002] (c) Entropy (d) Free energy
(a) H  PV  V (b) H  nRT  E 9. Which of the following statements is true[KCET 2002]
(c) E  nRT  P (d) None of these (a) E is always greater than H
3. For CaCO3 (s) ⇌ CaO(s)  CO2 (g) at 977 o C ;
(b) E is always less than H
H  176 kJ mol, then E is [BVP 2003]
(c) E may be lesser or greater or equal to H
(a) 180 kJ (b) 186.4 kJ
(c) 165.6 kJ (d) 160 kJ (d) E is always proportional to H
4. Values of H and S for five different reactions 10. Mass and energy are conserved is demonstrated
are given below. by
Reaction H (kJ mol 1 ) S ( JK 1 mol 1 ) [MH CET 2002]
I +98.0 +14.8 (a) First law of thermodynamics
II – 55.5 –84.6
(b) Law of conservation of energy
III +28.3 –17.0
(c) Law of conservation of mass
IV – 40.5 +24.6
V + 34.7 0.0 (d) Modified form of Ist law of thermodynamics
On the basis of these values predict which one of 11. The enthalpy of the reaction,
these will be spontaneous at all tempeature
1
[Kerala PMT 2004; KCET 1988,90] H 2 (g)  O 2 (g)  H 2 O(g) is H 1 and that of
2
(a) Reaction I (b) Reaction II
1
(c) Reaction III (d) Reaction IV H 2 (g )  O 2 (g)  H 2 O(l) is H 2 . Then [KCET 2004]
2
(e) Reaction V
5. Molar heat capacity of water in equilibrium with (a) H1  H 2 (b) H1  H 2  0
ice at constant pressure is [IIT JEE 1997]
(c) H1  H 2 (d) H1  H 2
(a) Zero (b) Infinity ()
12. A reaction occurs spontaneously if
(c) 40 . 45 kJ K 1 mol 1 (d) 75 . 48 J K 1
[MP PET 2002; CBSE PMT 2005]
6. Internal energy does not include
[AIIMS 1999; CPMT 2000] (a) T S  H and both H and S are +ve
(a) Nuclear energy (b) T S  H and both H and S are +ve
(b) Rotational energy
(c) T S  H and both H and S are +ve
(c) Vibrational energy
(d) T S  H and H is +ve and S is –ve
(d) Energy arising by gravitational pull
13. Which expression is correct for the work done in
7. Two moles of an ideal gas expand spontaneously
adiabatic reversible expansion of an ideal gas[AMU 2002]
into a vacuum. The work done is [AMU 2000]
 Thermodynamics and Thermochemistry 453
V2 T2 19. A cylinder of gas supplied by Bharat Petroleum is
(a) W  nRT ln (b) W  n e ln
V1 T1 14 kg
assumed to contain of butane. It a normal
20 ,000 kJ

2
family requires of energy per day for
(c) W  PV (d) W   PdV
1 cooking, butane gas in the cylinder last for ….
Days [Kerala PMT 2004]
14. If an endothermic reaction is non-spontaneous at
freezing point of water and becomes feasible at ( Hc of C4 H10  2658 KJ per mole )
its boiling point, then
(a) 15 days (b) 20 days
[AIEEE 2002]
(c) 50 days (d) 40 days
(a) H is ve , S is +ve
(e) 32 days
(b) H and S both are +ve
20. The heat of neutralization of HCl by NaOH under
(c) H and S both are –ve certain condition is – 55.9 kJ and that of HCN by
(d) H is +ve, S is –ve NaOH is –12.1 kJ. the heat of ionization of HCN
is [MP PET 2001]
JK 1 mol 1
15. What is the entropy change (in ) when
o
(a)  68 . 0 kJ mol 1 (b)  43 . 8 kJ mol 1
one mole of ice is converted into water at 0 C
(The enthalpy change for the conversion of ice to (c) 68 . 0 kJ mol 1 (d) 43 . 8 kJ mol 1
1 o
liquid water is 6.0 kJ mol at 0 C )[CBSE PMT 2003] 21. Equilibrium constant of a reaction is related to
(a) 21.98 (b) 20.13
[AIIMS 1991]
(c) 2.013 (d) 2.198
(a) Standard free energy change G o
30 .5 kJ
16. One mole of NaCl (s) on melting absorbed
(b) Free energy change G
28 . 8 JK 1
of heat and its entropy is increased by . (c) Temperature T
The melting point of NaCl is [DPMT 2004]
(d) None
(a) 1059 K (b) 30.5 K
22. The standard Gibbs free energy change G o is
(c) 28.8 K (d) 28800 K
related to equilibrium constant K p as [MP PET/PMT 1998]
17. The enthalpy change (H ) for the process
G o
N 2 H 4 (g)  2 N(g)  4 H(g) 1724 KJ mol 1  e 
in . If the (a) K p  RT ln G o
(b) K p   
 RT 
bond energy of N H bond in ammonia is
1 G o
391 KJ mol
. What is the bond energy of N  N G o 
(c) K p   (d) K p  e RT

N2H4 RT
bond is
23. The standard enthalpy or the decomposition of
[MP PMT 2004]
N 2 O5 to NO2 is 58.04 kJ and standard entropy of
(a) 160 KJ mol 1 (b) 391 KJ mol 1
this reaction is 176 .7 J / K . The standard free
(c) 1173 KJ mol 1 (d) 320 KJ mol 1 energy change for this reaction at 25 o C is [DCE 2004]
18. Liquid ammonia is used in refrigeration because (a) –5.38 kJ (b) 5.38 kJ
of its
(c) 5.38 kJ (d) –538 kJ
[DCE 2003]
24. For the equilibrium H 2 O(l) ⇌ H 2 O(g) at 1 atm and
(a) High dipole moment
298 K
(b) High heat of vaporisation
[AIIMS 2004]
(c) High basicity
(d) All of these (a) Standard free energy change is equal to zero
(G  0)
o
 454 Thermodynamics and Thermochemistry
(b) Free energy change is less than zero (G  0) S  0 . 066 k JK 1 mol 1 . Temperature at which free

(c) Standard free energy change is less than zero energy change for reaction will be zero, is [MH CET 1999]
(G o  0) (a) 373 K (b) 413 K

(d) Standard free energy change is greater than (c) 463 K (d) 493 K
zero (G  0)o

25. For reaction Ag 2 O(s)  2 Ag(s)  (1 / 2)O 2 (g) the value

of  H  30 .56 kJ mol 1 and

(SET -10)

1. (d) A 
 B
40 12. (b) For spontaneous reaction G should be
negative G  H  T S  (ve )  T (ve )
40
A 
 B
If T S  H then G will be negative and
H  40  40  0 . reaction will be spontaneous.
2. (b) H  E  nRT . 13. (b) W  PV .
3. (c) n  1  0  1 14. (b) H and S both are +ve than reaction is
E  H  nRT spontaneous.
q rev 6000
E  176  1 
8 .314
 1240  165 .6 k J. 15. (a) S    21 .98 JK 1 mol 1
1000 T 273

4. (d) A spontaneous process is accompanied by

decrease in enthalpy and increase in entropy 16. (a) NaCl (s) ⇌ NaCl (l)
means H is negative and S is positive.
Given that : H  30 .5 KJ mol 1
 H 
5. (b) C P    , At equilibrium T is constant i.e. S  28 .8 JK 1  28 .8  10 3 KJ K 1
 T  P
 T  0, thus C P   . H
By using S 
T
6. (d) E  Eele.  Enucl.  Echemical  Epotential
30 .5
  1059 K
 Ekinetic(Et  Ev  Er ) . 28 .8  10 3
H H
7. (c) An ideal gas under going expansion in vacuum | |

shows, E  0, W  0 and q  0 . 17. (a) H  N  N  H (So, 4 N  H bond present)

means their energy  391  4  1564
8. (b) H  q p . so the bond energy of N  N in N 2 H 4
9. (c) E may be greater or lesser or equal to H .  1724  1564  160 KJ / mol
 H  E  PV  E  nRT . 18. (b) Ammonia has high heat of vaporisation hence
is used in refrigeration.
10. (d) It is a modified form of Ist law of
thermodynamics. It is a conservation law of 19. (e) Calorific value of butane
mass and energy. H c 2658
   45 .8 KJ / gm
mol. wt. 58
11. (a) for reaction (i) n1  0.5
Cylinder consist 14 Kg of butane means
for reaction (ii) n2  1.5
14000 gm of butane
So, H1  H 2  1gm gives 45 .8 KJ
 Thermodynamics and Thermochemistry 437
14000 gm gives 14000  45 .8

 641200 KJ
Family need 20 ,000 KJ / day

So gas full fill the requirement for

641200
 32 .06 days
20 ,000
20. (d)
21. (a) G o  2 . 303 log k .
o
22. (d) K p  e G / RT
.

23. (d)
24. (b) For reaction H 2 O(l) ⇌ H 2 O(g)

n  1 means positive
so when  n is positive then G  0 .
25. (c) G  H  T S
G  0 at equilibrium
 H  T S or 30 .56  T  0 .066
T  463 K .

***
 Chemical Kinetics 455

Chapter

11
Chemical Kinetics

The branch of physical chemistry which deals with (3) Very slow reactions : These reactions are
the rate at which the chemical reactions occur, the extremely slow and take months together to show any
mechanism by which the chemical reactions take place measurable change.
and the influence of various factors such as
concentration, temperature, pressure, catalyst etc., on Examples
the reaction rates is called the chemical kinetics. (i) Rusting of iron :
Types of chemical reactions Fe 2 O 3  xH 2 O  Fe 2 O 3 . xH 2 O
Hydrated ferric oxide (Rust)

On the basis of reaction rates, the chemical

reactions have been classified into the following three (ii) 2 H 2  O 2   2 H 2 O
Room temperatu re

types, Rate of a reaction

(1) Very fast or instantaneous reactions : These The rate (speed or velocity) of a reaction is the
reactions occur at a very fast rate generally these change in concentration in per unit time.
reactions involve ionic species and known as ionic x dx  x 2  x 1 
or  
reactions. It is almost impossible to determine the rates t dt  t 2  t1 
of these reactions.
where  x or dx is the concentration change, i.e.,
Examples (x 2  x1 ) in the time interval  t or dt, i.e., (t 2  t1 ) .
(i) AgNO 3  NaCl  AgCl  NaNO 3 (Precipitation Concentration is generally expressed in active mass, i.e.,
(PPt.)
mole L–1
reaction)  The rate measured over a long time interval is
(ii) HCl  NaOH  NaCl H 2 O (Neutralization called average rate and the rate measured for an
(acid) (base) (Salt) infinitesimally small time interval is called
reaction) instantaneous rate and
Instantaneous rate  (Average rate)t 0
(2) Moderate reaction : These reactions proceed
with a measurable rates at normal temperature and it  For the reaction aA  bB  cC  dD
is these reactions are studied in chemical kinetics. Rate of disappearance of a reactant is negative
Mostly these reactions are molecular in nature. d [ A]
  Rate of disappearance of A
dt
Examples
d[B]
  Rate of disappearance of B
(i) Decomposition of H 2 O2 : 2 H 2 O2  2 H 2 O  O2 dt
(ii) Decomposition of N 2 O5 : 2 N 2 O5  2 N 2 O4  O2 Rate of formation of a product is positive
d[C]
 Rate of formation of C
dt
 456 Chemical Kinetics
d[D] (4) Presence of catalyst : The function of a
 Rate of formation of D
dt catalyst is to lower down the activation energy. The
 In terms of stoichiometric coefficient rate may greater the decrease in the activation energy caused by
be expressed as the catalyst, higher will be the reaction rate.
Reaction
dx 1 d [ A] 1 d [B] 1 d [C ] 1 d [D] path
    Without
dt a dt b dt c dt d dt catalyst
Ea
 The rate of reaction is always positive.
 The rate of chemical reaction decreases as the Ea Reaction
path
reaction proceeds. with
catalyst
Unit of conc. Reactants
 Unit of rate of a reaction = =mole L–1

Potential
Energy of Reaction

Unit of time
time –1
In term of gaseous reaction the unit is atm time-1
and
Rate in atm time-1= Rate in mole L1 time 1  RT
Factors affecting rate of a reaction
The rate of a chemical reaction depends on the
following things
(1) Nature of reactants
(i) Physical state of reactants : This
considerable effect over rate of reaction.
Gaseous satae  Liquid state  Solid state
 
Decreasing rate of reaction
(ii) Physical size of the reactants : Among the
solids, rate increases with decrease in particle size of
the solid.
(iii) Chemical nature of the reactants
(a) Reactions involving polar and ionic
substances including the proton transfer reactions are
usually very fast. On the other hand, the reaction in
which bonds is rearranged, or electrons transferred are
slow.
(b) Oxidation-reduction reactions, which
involve transfer of electrons, are also slow as
compared to the ionic substance.
(c) Substitution reactions are relatively much
slower.
(2) Effect of temperature : The rate of chemical
reaction generally increases on increasing the
temperature. The rate of a reaction becomes almost
double or tripled for every 10 o C rise in temperature.
Temperature coefficient of a reaction is defined as
the ratio of rate constants at two temperatures
differing by (generally 25°C and 35°C) 10°C.
k at (t  10 o C ) k 35 o C
  Temperatur e coefficien t  
k at t o C k 25 o C
(3) Concentration of reactants : The rate of a
chemical reaction is directly proportional to the
concentration of the reactants means rate of reaction
decreases with decrease in concentration.
Energy
Products
A catalyst changes the reaction
path
(5) Effect of sunlight : There are many chemical
reactions whose rate are influenced by radiations
particularly by ultraviolet and visible light. Such
reactions are called photochemical reactions. For
example, Photosynthesis, Photography, Blue printing,
Photochemical synthesis of compounds etc.
The radiant energy initiates the chemical reaction
has by supplying the necessary activation energy required
for the reaction.
Law of mass action and Rate constant
The rate at which a substance reacts is directly
proportional to its active mass and the rate at which a
reaction proceeds is proportional to the product of the
active masses of the reacting substances.
 For a reaction, aA  bB  product
 dx   dx 
Rate     [ A]a [B]b ;    k [ A]a [B]b
 dt   dt 
Where k is called rate constant or velocity
constant.
dx
When [ A]  [B]  1 mol / litre, then k
dt
Thus, rate constant k is also called specific
reaction rate.
 The value of rate constant depends on, nature
of reactant, temperature and catalyst. It is independent
of concentration of the reactants.
n 1 1 n
 litre   mol 
 Unit of rate constant     sec1     sec1
 mol   litre 
Where n  order of reaction.
Rate law : Molecularity and Order of a reaction
Molecularity is the sum of the number of molecules
of reactants involved in the balanced chemical equation.
Molecularity of a complete reaction has no significance
and overall kinetics of the reaction depends upon the
rate determining step. Slowest step is the rate-
determining step. This was proposed by Van't Hoff.
Example : NH 4 NO 2  N 2  2 H 2 O (Unimolecular)
NO  O3  NO 2  O 2 (Bimolecular)
 Chemical Kinetics 457
2 NO  O 2  2 NO 2 (Trimolecular) AB3  A  A2 B3 (fast)
The total number of molecules or atoms whose (Here, the overall order of reaction is equal to
concentration determine the rate of reaction is known as two.)
order of reaction.  Molecularity of a reaction is derived from the
Order of reaction = Sum of exponents of the conc. terms in mechanism of the given reaction. Molecularity can not be
rate law greater than three because more than three molecules may
For the reaction xA  yB  Products not mutually collide with each other.
 Molecularity of a reaction can't be zero,
The rate law is Rate  [A]x [B[y
negative or fractional. order of a reaction may be zero,
Then the overall order of reaction. n  x  y
negative, positive or in fraction and greater than three.
where x and y are the orders with respect to Infinite and imaginary values are not possible.
individual reactants.  When one of the reactants is present in the large
 If reaction is in the form of reaction mechanism excess, the second order reaction conforms to the first
then the order is determined by the slowest step of order and is known as pesudo unimolecular reaction.
mechanism. (Table 11.1)
2 A  3 B  A2 B3
A  B  AB (fast )
AB  B2  AB3 (slow) (Rate determining step)
Table : 11.1 Order and molecularity of some reaction
S. Chemical equation Molecularit Rate law Order w.r.t.
No y First Second Overal
. reacta reactant l
nt
1. aA  bB  product a+b  dx  a b a+b
   k [ A]a [B]b
 dt 
2. aA  bB  product a+b  dx  2 zero, if B is in 2
   k [ A]2 [B]0 excess
 dt 
Pt , 
3. 2 H 2 O2   2 H 2 O  O2 2  dx  1* ----- 1
(Bimolecula    k [H 2 O2 ]
 dt 
r)

4. CH 3 COOC 2 H 5  H 2 O 
H
 2  dx  1* Zero, if H2O is 1
(Bimolecula    k [CH 3 COOC 2 H 5 ] in excess
CH3COOH  C2 H5 OH  dt 
r)

5. C 12 H 22 O 11  H 2 O 
H
 2  dx  1* Zero, if H2O is 1
(Bimolecula    k [C12 H 22 O11 ] in excess
Sucrose
 dt 
C6 H12 O6  C6 H12 O6 r)
Glucose Fructose
 Zero, if OH–
6. (CH 3 )3 CCl  OH  2  dx  1* 1
(Bimolecula    k [(CH 3 )3 CCl] does not take
(CH 3 )3 COH  Cl   dt 
r) part in slow
step

7. CH 3 Cl  OH  CH 3 OH  Cl  2  dx  1 1 2
(Bimolecula    k [CH 3 Cl][OH  ]
 dt 
r)

8. C6 H 5 N 2 Cl  C6 H5 Cl  N 2 1  dx  1 ---- 1
(Unimolecul    k [C6 H 5 N 2 Cl]
 dt 
ar)

9. CH 3 CHO  CH 4  CO 1  dx  1.5 ---- 1.5
(Unimolecul    k [CH 3 CHO ]3 / 2
 dt 
ar)
10. H 2 O2  2 I   2 H   2 H 2O  I2 5  dx  1 1 2
   k [H 2 O 2 ][ I  ] (H+is medium)
 dt 
11. 2O3  3O2 2  dx  1 -1 with respect 1
   k[O3 ] [O 2 ]
2
(Bimolecula  dt  to O2
r)
 458 Chemical Kinetics
*Pseudo-unimolecular reactions.
Table : 11.2 Rate constant and other parameters of different order reactions
Orde Rate constant Unit of rate Effect on rate by (Half-life
r constant changing conc. to m period) T50=
times
0 x conc. time–1 No change a
k0 
t (mol L–1 s–1) 2k 0
1 2 .303  a  k t time–1 (s–1) m times 0 .693
k1  log10   , C  C0 e 1
t  a  x  k1
k1 t 2.303 (a  x1 )
N  N 0e , k1  log10
(t2  t1 ) (a  x 2 )
2 1 1 1 x conc–1 time–1 m2 times 1
k2      (for the case (mol L–1) s–1
t (a  x ) a  ta(a  x) k 2a
L mol–1 s–1
when each reactant has equal
concentration)
2 . 303  b(a  x ) 
k2  log 10   (for the case
t(a  b )  a(b  x ) 
when both reactants have different
concentration)
3 1  1 1  conc–2 time–1 m3 times 3
k3    2
 2 (mol L–1)–2 s–1 2k 3 a 2
2t  (a x ) a 
L2 mol–2 s–1
n 1  1 1  conc(1–n) time– mn times 2 n 1  1
kn   n 1
 n 1  ; n  2 1
(n  1)t  (a  x ) (a)  (n  1)k n (a)n 1
(mol L–1)(1–n)
s–1
L(n–1) mol(1–n)
s–1

Methods for determination of order of a reaction (2) Half-life method : This method is employed
only when the rate law involved only one concentration
(1) Integration method (Hit and Trial method)
term.
(i) The method can be used with various sets of
t 1 / 2  a 1  n ; t 1 / 2  ka 1 n ; log t1 / 2  log k  (1  n) log a
a, x and t with integrated rate equations.
A plotted graph of log t1 / 2 vs log a gives a straight
(ii) The value of k is determined and checked for
all sets of a, x and t . line with slope (1  n) , determining the slope we can
find the order n. If half-life at different concentration
(iii) If the value of k is constant, the used
is given then,
equation gives the order of reaction.
n 1
(iv) If all the reactants are at the same molar 1 1 (t1 / 2 )1  a 2 
(t1 / 2 )1  ; (t1 / 2 )2  ;  
concentration, the kinetic equations are : a1n 1
a 2n 1 (t1 / 2 )2  a1 
2 .303 a log10 (t1 / 2 )1  log10 (t1 / 2 )2  (n  1) [log10 a2  log10 a1 ]
k  log 10 (For first order
t (a  x )
log 10 (t1 / 2 )1  log 10 (t1 / 2 )2
reactions) n 1
(log 10 a 2  log10 a1 )
1 1 1 
k  (For second order
t  a a  x 
 This relation can be used to determine order of
reaction ‘n’
reactions)
Plots of half-lives Vs concentrations (t1/2  a1–n)
1  1 1 
k   2 (For third order Zero 1st order 2nd 3rd
2t   2

t1/2 

(a x ) a
t1/2 

t1/2 
t1/2 

order order order

reactions)

Conc. Conc. 1/a 1/a2

 Chemical Kinetics 459
This method can be used irrespective of the
(3) Graphical method : A graphical method
number of reactants involved e.g., consider the
based on the respective rate laws, can also be used.
reaction, n1 A  n2 B  n3 C  Products .
(i) If the plot of log( a  x ) Vs t is a straight line,
This method consists in finding the initial rate of
the reaction follows first order.
the reaction taking known concentrations of the
1
(ii) If the plot of Vs t is a straight line, the different reactants (A, B, C).
(a  x )
reaction follows second order. Suppose it is observed as follows,
1 (i) Keeping the concentrations of B and C
(iii) If the plot of Vs t is a straight line, constant, if concentration of A is doubled, the rate of
(a  x )2
reaction becomes four times. This means that, Rate
the reaction follows third order.
 [A] 2 i.e., order with respect to A is 2
(iv) In general, for a reaction of nth order, a
1 (ii) Keeping the concentrations of A and C
graph of Vs t must be a straight line.
(a  x )n 1 constant, if concentration of B is doubled, the rate of
reaction is also doubled. This means that, Rate  [B]
Plots from integrated rate equations
i.e., order with respect to B is 1
Zero order 1st order 2nd order 3rd order
Conc. [A]

(iii) Keeping the concentrations of A and B

log. [A]

1 1


constant, if concentration of C is doubled, the rate of



[ A] [ A ]2 reaction remains unaffected. This means that rate is

t t t independent of the concentration of C i.e., order with
t
respect to C is zero. Hence the overall rate law
expression will be, Rate = k[A]2 [B] [C]0
Plots of rate Vs concentrations [Rate = k(conc.)n
]  Overall order of reaction = 2 + 1 + 0 = 3.
Theories of reaction rate
Zero order 1st 2nd 3rd
Rate 
Rate 

Rate 
Rate 

order order order (1) Collision theory

(i) The basic requirement for a reaction to occur
is that the reacting species must collide with one
Conc. Conc. (Conc.) (Conc.) another. This is the basis of collision theory for
2
3
reactions.
(4) Van't Haff differential method : The rate of (ii) The number of collisions that takes place per
reaction varies as the nth power of the concentration second per unit volume of the reaction mixture is
Where ' n ' is the order of the reaction. Thus for two
known as collision frequency (Z). The value of collision
different initial concentrations C1 and C 2 equation,
frequency is very high of the order of 10 25 to 10 28 in
can be written in the form,
dC1 dC2 case of binary collisions.
 k C1n and  k C2n (iii) Every collision does not bring a chemical
dt dt
change. The collisions that actually produce the product
Taking logarithms,
are effective collisions. The effective collisions, which
 dC1 
log 10    log 10 k  n log 10 C1 …..(i) bring chemical change, are few in comparison to the
 dt  total number of collisions. The collisions that do not
 dC 2  form a product are ineffective elastic collisions, i.e.,
and log 10    log 10 k  n log 10 C 2 …..(ii) molecules just collide and disperse in different
 dt 
directions with different velocities.
Subtracting equation (ii) from (i),
 dC1   dC2  Fraction of
log10    log10   molecules
n  dt   dt  capable of
Fraction of

…..(iii)
molecules

log10 C1  log10 C 2 bringing

effective collisions
dC1 dC 2
and are determined from
dt dt
concentration Vs time graphs and the value of ' n ' can Energy E
Distribution of energies at a
be determined. definite temperature
(5) Ostwald's isolation method (Initial rate
method)
 460 Chemical Kinetics
(iv) For a collision to be effective, the following two Where f is fraction of effective collision and Z is
barriers are to be cleared, the collision frequency.
(a) Energy barrier : “The minimum amount of (vii) The physical meaning of the activation
energy which the colliding molecules must possess as to energy is that it is the minimum relative kinetic energy
make the chemical reaction to occur, is known as
which the reactant molecules must possess for
threshold energy”.
changing into the products molecules during their
 In the graph 'E' corresponds to minimum or
collision. This means that the fraction of successful
threshold energy for effective collision.
collision is equal to e  Ea / RT called Boltzmann factor.
 There is an energy barrier for each reaction. The
reacting species must be provided with sufficient energy to (viii) It may be noted that besides the
cross the energy barrier. requirement of sufficient energy, the molecules must
(b) Orientation barrier : The colliding molecules be properly oriented in space also for a collision to be
should also have proper orientation so that the old successful. Thus, if Z AB is the collision frequency, P is
bonds may break and new bonds are formed. For the orientation factor (Steric factor) then,
example, NO2 (g)  NO2 (g)  N 2 O4 (g). During this
k  PZ AB .e  Ea / RT . If we compare this equation with
reaction, the products are formed only when the
colliding molecules have proper orientation at the time Arrhenius equation. k  A e  Ea / RT
of collisions. These are called effective collisions.
We know that pre-exponential form 'A' in
Collisions not properly oriented Arrhenius equation is, A  PZ AB .

O O O Concept of activation energy

O
N O N Molecule N O N Molecule N N
s
approach s
Separate The excess energy (Over and above the average
O O O O O energy of the reactants) which must be supplied to the
NO2 + NO2
O
Collision NO2 NO2 reactants to undergo chemical reactions is called
No product activation energy (Ea ) ,
Properly oriented collisions form products

O O O O O O Ea  E(Threshold energy)  E(Reactan ts)

Molecule Bond
N N N N N N
s
approach Formatio Activation energy = Threshold energy – Average
O O O On O O kinetic energy of the reacting molecules.
NO2 Product
+ NO2 Collision N2O4
(a) Zero activation energy = Fraction of effective
Fig. 11.1
collision (f) will be very large = Very fast reaction
(v) Thus, the main points of collision theory are (Instantaneous reaction).
as follows, (b) Low activation energies = Fraction of effective
(a) For a reaction to occur, there must be collision (f) will be large = Fast reactions.
collisions between the reacting species. (c) High activation energies = Fraction of
(b) Only a certain fraction of the total number of effective collision (f) will be small = Slow reaction.
collisions is effective in forming the products. The activation energy (Ea ) depends upon the nature
(c) For effective collisions, the molecules should of chemical bonds undergoing rupture and is
possess sufficient energy as well as orientation. independent of enthalpies of reactants and products.
(vi) The fraction of effective collisions, under According to the concept of activation energy, the
ordinary conditions may vary from nearly zero to about reactants do not change directly into the products. The
one for ordinary reactions. Thus, the rate of reaction is reactant first absorb energy equal to activation energy
proportional to : and form activated complex. At this state, the molecules
must have energy at least equal to the threshold energy.
(a) The number of collisions per unit volume per
This means that the reaction involves some energy
second (Collision frequency, Z) between the reacting
barrier which must be overcome before products are
species
formed. The energy barrier is known as activation
(b) The fraction of effective collisions (Properly energy barrier.
oriented and possessing sufficient energy), f i.e.,
Threshold Activated
dx energy complex
Rate   fZ Et (Et)
dt
Energy
Ea barrier
(activation
energy)
Er Reactants Energy of
E the
(Er) reaction
Ep Products (Ep)

Progress of reaction
 Chemical Kinetics 461

log k
Ea
Slope  
2 .303 R

1/T
(2) Transition state theory
(i) According to transition state theory the Rate constants for the reaction at two different
activated complex is supposed to be in equilibrium with temperatures T1 and T2 ,
the reactant molecules. k2 1
Ea 1
log     …..(iii)
(ii) Once the transition state is formed it can  1
k1 2 .303 R
T T 2
either return to the initial reactants or proceeds to where k1 and k 2 are rate constant at temperatures
form the products.
T1 and T2 respectively (T2  T1 ) .
(iii) Assuming that once formed the transition state
proceeds to products we can say that rate is Mechanism of the reaction
proportional to concentration of transition state. (1) Reaction involving first order consecutive
Mathematically, Rate  Transition state reactions
Rate= Constant × Transition state (i) In such reactions, the reactions form a stable
(iv) The activation energy for the forward intermediate compound before they are finally
reaction, ( E af ) and the activation energy for the reverse converted into the products.
(ii) For example, reactants (R) are first converted to
reaction ( E ar ) are related to the enthalpy (H ) of the
intermediate (I) which is then converted to product (P) as
reaction by the equation H  Eaf  Ear . R 
k1
I 
k2
P
(a) For endothermic reactions, H  0, so that Therefore, the reaction takes place in two steps,
Ear  Eaf both of which are first order i.e.,

(b) For exothermic reaction, H  0, so that Step I : R 

k1
I ; Step II : I 
k2
P

Ear  Eaf .
This means that I is produced by step I and consumed
by step II. In these reactions, each stage will have its
Arrhenius equation own rate and rate constant the reactant concentration
Arrhenius proposed a quantitative relationship will always decrease and product concentration will
between rate constant and temperature as, always increase as shown in fig.
k  A e  Ea / RT …..(i) P
Concentration

The equation is called Arrhenius equation.

In which constant A is known as frequency factor. I
This factor is related to number of binary molecular
collision per second per litre. R
Ea is the activation energy. Time

T is the absolute temperature and Concentration profile of reactants (R),

intermediate (I) and products (P) as a
R is the gas constant
function of time
Both A and Ea are collectively known as (2) Reaction involving slow step : When a
Arrhenius parameters. reaction occurs by a sequence of steps and one of the
Taking logarithm equation (i) may be written as, step is slow, then the rate determining step is the slow
Ea step. For example in the reaction
log k  log A  …..(ii)
2.303 RT R 
k1
I; I 
k2
P , if k1  k 2 then I is
The value of activation energy (Ea ) increases, the converted into products as soon as it is formed, we can
value of k decreases and therefore, the reaction rate say that
decreases. d [ R ] d [ P ]
When log k plotted against 1 / T , we get a straight   k1 [R]
dt dt
line. The intercept of this line is equal to log A and
(3) Parallel reactions : In such type of reactions
 Ea
slope equal to . the reactants are more reactive, which may have
2.303 R
different orders of the reactions taking place
Therefore Ea  2.303 R  slope .
simultaneously. For example, in a system containing
 462 Chemical Kinetics
NO2 and SO 2 , NO2 is consumed in the following two (iv) The rate of photochemical reactions depend
upon the intensity of radiation’s absorbed.
reactions, 2 NO2 
 N 2 O4 ; NO2  SO 2 
k1
 NO  SO 3
k2

(v) The G values for light initiated reactions

The rate of disappearance of NO2 will be sum of
may or may not be negative.
the rates of the two reactions i.e., (vi) The temperature does not have marked effect
d[ NO2 ] on the rate of light initiated reactions.
  2k1 [ NO2 ]2  k 2 [ NO2 ][SO 2 ]
dt (2) Mechanism of some photochemical
Photochemical reaction reactions
Absorption of radiant energy by reactant (i) Photochemical combination of H2 and Cl2 : A
molecules brings in photophysical as well as mixture of H 2 and Cl 2 on exposure to light give rise to
photochemical changes. According to Einstein's law of the formation of HCl, showing a chain reaction and
photochemical equivalence, the basic principle of photo thereby producing 10 6 to 10 8 molecules of HCl per
processes, each reactant molecule is capable of photon absorbed.
absorbing only one photon of radiant energy. The
H 2  Cl 2   2 HCl
sunlight
absorption of photon by a reactant molecule may lead
to any of the photo process. The mechanism leading to very high yield of HCl
as a result of chemical change can be as follows.
Reactant molecule
Chlorine molecules absorb radiant energy to form an
Absorption of
photon (As per
excited molecule which decomposes to chlorine free
Einstein law) radicals (Cl) to give chain initiation step.
Excitation of Knock out the Light absorption step : Cl2 

hv
Cl2
*
electronic level electron from the
reactant species ........(i)
Excited molecule Photoelectric effect Chain initiation step : Cl2*  Cl  Cl
........(ii)
The chlorine free radical then combines with H 2
Photophysical Photochemical
process molecule to form HCl and H  free radical. The H  free
process
(i) Oxidation radical so formed again combines with another Cl2
(i) Fluorescence (ii) Reduction
(ii) Phosphorescence (iii) Dissociation molecule to give HCl and Cl  free radical back resulting
(iv) Double into chain propagation step.
decomposition
Chain propagation step : Cl   H 2  HCl  H 
(v) Isomeric
transformation
The chemical reactions, which are initiated as a ........(iii)
(vi) Photosensitization
result of absorption of light, are known as photochemical H   Cl 2  HCl  Cl 
reactions. In such cases, the absorbed energy is The combination of two Cl  free radicals leads to
sufficient to activate the reactant molecules to cross chain terminating step.
the energy barrier existing between the reactants and
Chain terminating step : Cl   Cl   Cl 2
products or in other words, energy associated with
........(iv)
each photon supplies activation energy to reactant
(ii) Photochemical combination of H2 and Br2 :
molecule required for the change.
The combination of H 2 and Br2 to form HBr in
(1) Characteristics of photochemical reactions
presence of light is also an example of chain reaction
(i) Each molecule taking part in a photo process
like photochemical combination of H 2 and Cl2 . Here
absorbs only one photon of radiant energy thereby
hc two Br2 molecules absorb photon, however, inspite of
increasing its energy level by hv or
 chain reaction only one molecule of HBr is formed for
(ii) Photochemical reactions do not occur in dark. each 100 photon absorbed by 100 molecules of Br2 .
(iii) Each photochemical reaction requires a H 2  Br 2   2 HBr
light

definite amount of energy which is characteristic of a

Mechanism
particular wavelength of photon. For example,
reactions needing more energy are carried out in Light absorption step : Br2  hv  Br2*
presence of UV light (lower  , more E/Photon). A ........(i)
reaction-taking place in UV light may not occur on Chain initiation step : Br2*  Br  Br
exposure to yellow light (lower  and lesser E/Photon) ........(ii)

Chain propagation step : Br *  H 2  HBr  H 
........(iii)
H *  Br2  HBr  Br 
........(iv)
Chain termination step : Br   Br   Br2 ........(v)
The lower values of HBr formation per photon of
light absorbed has been attributed to the fact that step
(III) is highly endothermic and thus before step (III)
can take place most of the bromine free radicals
recombine as per step (V) to give Br2 molecule and
thus providing less feasibility for step (IV) i.e. steps
regenerating free radicals. Also the decomposition of
HBr increases with increase in temperature.
(3) Quantum yield (or quantum efficiency) : The
quantum efficiency or yield   of a photochemical
reaction may be expressed as,
No. of molecules reacted or product formed

No. of photon absorbed
(4) Application of photochemistry :
Photochemistry has significant role in our daily life.
Some of the photochemical reactions commonly known
as cited below,
(i) Photosynthesis in plants
(ii) Photography
(iii) The formation and destruction of ozone layer
(iv) Photoetching in electronic industry
(v) Many polymerization reactions.
(vi) Modern printing technology
(vii) Free radical combinations to obtain many
compounds.
 Different reactions have different rates because
their activation energies are different. Lesser the
activation energy faster is the reaction.
1
 The reaction, NO  O2  NO2 , exhibits a small
2
negative temperature coefficient and the rate of
reaction decreases with increase of temperature.
 Fuels in contact with oxygen do not burn by
themselves. This is because they need activation energy
(provided by the flame) to initiate the reaction. Thus,
fuels are thermodynamically unstable ( G is –ve) but
kinetically stable.
 Quantum efficiency of the photochemical
reaction, H 2  Cl 2  2 HCl is very high while that
hv
of H 2  Br2 
hv
2 HBr , is very low. This is because
Chemical Kinetics 463

after the chain initiating step X 2 
hv
2X 
Cl  H 2  HCl  H is exothermic whereas
Br  H2  HBr  H is endothermic.
 Drapper’s effect : H 2  Cl2  2 HCl , Such
reactions are accompanied by the increase in the
volume. This is called Drapper’s effect. The reason is
that the reaction is exothermic and heat released
raises the temperature and gas expands resulting in
the increase in volume.
 Actinometer : A device which is used to measure
the intensity of radiation is konwn as actimometer.
e.g., Uranyl oxalate actinometer.
 Amount of the substance left after ‘n’ half lives
A0
 .
2n
 Free energy change (G) for thermochemical
reactions is always negative but remember, G for
photochemical reaction may not always be negative.
It may be +ve also because a part of the light energy
absorbed is converted into the free energy of the
products.
 Negative catalysts or inhibitors are those
substances which decrease the rate of a reaction.
 Example of fourth order reaction,
4 KClO3 ⇌ 3 KClO4  KCl
 Grothus-Draper law : When light falls on a
substance, a part of light is absorbed, a part is
reflected and a part is transmitted. only that part of
light which is absorbed causes a particular reaction
to occur.
 Stark’s Einstein law of photochemical equivalence
According to this law, every atom or molecule taking
part in photochemical reaction absorbs only one
quantum of radiaton.
 Kinetics of fast reactions can be studied by (i)
Relaxation method (ii) Flash photolysis technique
etc.
 Enzyme catalysed reactions are faster than metal
catalysed reactions, the former has lower activation
energy.
Rate of a reaction
1. The rate of a chemical reaction
[MP PMT 1973; CPMT 1982]
(a) Increases as the reaction proceeds
(b) Decreases as the reaction proceeds
 464 Chemical Kinetics
(c) May increase or decrease during the reaction
(d) Remains constant as the reaction proceeds
2. The rate of a reaction that not involve gases is not
dependent on [CPMT 1988; AFMC 1995]
(a) Pressure (b) Temperature
(c) Concentration (d) Catalyst
3. The rate at which a substance reacts depends on
its
[MP PMT 1987; BHU 1999; KCET 2005]
(a) Atomic weight (b) Equivalent weight
(c) Molecular weight (d) Active mass
4. The rate law for the reaction
RCl  NaOH (aq )  ROH  NaCl is given by Rate
 K1 [RCl] . The rate of the reaction will be[IIT 1988]
(a) Doubled on doubling the concentration of
sodium hydroxide
(b) Halved on reducing the concentration of alkyl
halide to one half
(c) Decreased on increasing the temperature of
the reaction
(d) Unaffected by increasing the temperature of
the reaction
5. If doubling the concentration of a reactant `A'
increases the rate 4 times and tripling the
concentration of `A' increases the rate 9 times,
the rate is proportional to [AIIMS 1991]
(a) Concentration of `A'
(b) Square of concentration of `A'
(c) Under root of the concentration of `A'
(d) Cube of concentration of `A'
6. The rate of chemical reaction at constant
temperature is proportional to
(a) The amount of products formed
(b) The product of masses of the reactants
(c) The product of the molar concentration of the
reactants
(d) The mean free path of the reaction
7. The concentration of a reactant decreases from
0.2 M to 0.1 M in 10 minutes. The rate of the
reaction is
(a) 0.01 M (b) 10 2
3 1
(c) 0.01 mol dm min (d) 1 mol dm 3 min 1
8. When a reaction is progressing
(a) The rate of the reaction goes on increasing
(b) The concentration of the products goes on
decreasing
(c) The concentration of the reactants goes on
decreasing
(d) The reaction rate always remains constant
 Chemical Kinetics 463
9. In a catalytic conversion of N 2 to NH 3 by Haber's 17. In the reaction 2 A  B  A2 B , if the concentration
process, the rate of reaction was expressed as of A is doubled and of B is halved, then the rate
change in the concentration of ammonia per time of the reaction will [
is 40  10 3 mol litre 1 s 1 . If there are no side (a) Increase by four times (b)Decrease by two times
reaction, the rate of the reaction as expressed in (c) Increase by two times (d) Remain the same
terms of hydrogen is (in mol litre 1 s 1 )  dc 
18. The term    in a rate equation refers to the
(a) 60  10 3 (b) 20  10 3  dt 
(c) 1.200 (d) 10 .3  10 3 [MP PMT 1996]

10. If the concentration of the reactants is increased, (a) Concentration of the reactant
the rate of reaction [MP PMT 1989] (b) Decrease in concentration of the reactant with
time
(a) Remains unaffected (b) Increases
(c) Increase in concentration of the reactant with
(c) Decreases (d) May increase or
time
decrease
(d) Velocity constant of the reaction
11. Time required for completion of ionic reactions in
19. The rate of a reaction depends upon the [Pb. PMT 1999]
comparison to molecular reactions is
(a) Volume
(a) Maximum (b) Minimum
(b) Force
(c) Equal (d) None
(c) Pressure
12. For reaction 2 A  B  products, the active mass of
(d) Concentration of reactant
B is kept constant and that of A is doubled. The
20. For a given reaction 3 A  B  C  D the rate of
rate of reaction will then [MP PET 1993]
reaction can be represented by [DCE 2000]
(a) Increase 2 times (b) Increase 4 times
1 d [ A] d [ B]  d [C ]  d [D]
(c) Decrease 2 times (d) Decrease 4 times (a)    
3 dt dt dt dt
13. In a reaction 2 A  B  A2 B , the reactant A will
1 d [ A] d [C ]
disappear at (b)    K[ A]m [ B]n
3 dt dt
[MP PET 1993] 1 d [ A] d [C ]
(a) Half the rate that B will decrease (c)    K[ A]n [B]m
3 dt dt
(b) The same rate that B will decrease (d) None of these
(c) Twice the rate that B will decrease 21. For the reaction N 2  3 H 2  2 NH 3
(d) The same rate that A2 B will form [ NH 3 ]  [ H 2 ]
if  2  10  4 mol l  1 s 1 , the value of
14. The rate of a gaseous reaction is given by the t t
expression K [ A][B] . If the volume of the reaction would be [
4 1 1 4 1 1
vessel is suddenly reduced to 1/4th of the initial (a) 1  10 mol l s (b) 3  10 mol l s
volume, the reaction rate relating to original rate 4 1 1 4
will be [Roorkee 1992]
(c) 4  10 mol l s (d) 6  10 mol l 1 s 1

(a) 1/10 (b) 1/8 22. A gaseous hypothetical chemical equation

(c) 8 (d) 16 2 A ⇌ 4 B  C is carried out in a closed vessel. The
15. A catalyst increases the rate of reaction because it concentration of B is found to increase by
[EAMCET 1992] 5  10 3 mol l 1 in 10 second. The rate of
(a) Increases the activation energy appearance of B is [AFMC 2001]
4 1 1 5
(b) Decreases the energy barrier for reaction (a) 5  10 mol l sec (b) 5  10 mol l 1 sec 1
(c) Decreases the collision diameter (c) 6  10 5 mol l 1 sec 1 (d) 4  10 4 mol l 1 sec 1
(d) Increases the temperature coefficient
23. The rate of a chemical reaction depends upon
16. For the reaction N 2 (g)  3 H 2 (g)  2 NH 3 (g) under [AFMC 2002]
certain conditions of temperature and partial (a) Time (b) Pressure
pressure of the reactants, the rate of formation of (c) Concentration (d) All of these
NH 3 is 0 . 001 kg h 1 . The rate of conversion of H 2 24. The rate of disappearance of SO 2 in the reaction
under the same conditions is
2SO 2  O2  2SO 3 is 1.28  10 3 g / sec then the rate of
[IIT 1994]
formation of SO 3 is [JIPMER 2002]
(a) 1 .82  10 4 kg / hr (b) 0.0015 kg / hr
(a) 0.64  10 3 g / sec (b) 0.80  10 3 g / sec
(c) 1.52  10 4 kg / hr (d) 1.82  10 14 kg / hr
(c) 1.28  10 3 g / sec (d) 1.60  10 3 g / sec
 464 Chemical Kinetics
25. When the concentration of A in the reaction (d) To increase the energy of the molecules of the
A  B ⇌ AB is doubled, the rate of reaction will be [MP PMT 2002] reactants
(a) Doubled (b) Decreased by half 34. The rate of a reaction [CPMT 1973]
(c) Unchanged (d) Increased by four (a) Increases with increase in temperature
times (b) Decreases with increase in temperature
26. The velocity of the chemical reaction doubles (c) Does not depend on temperature
every 10 C o
rise of temperature. If the (d) Does not depend on concentration
temperature is raised by 50 o C , the velocity of the 35. Which of the following statements is false in
reaction increases to about relation to enzyme [MP PMT 2003]
(a) 32 times (b) 16 times (a) pH affects their functioning
(c) 20 times (d) 50 times (b) Temperature affects their functioning
27. o
An increase in temperature by 10 C , generally (c) They always increase activation energy
increases the rate of a reaction by (d) Their reactions are specific
(a) 2 times (b) 10 times 36. A reaction is catalysed by ‘X ’. Here ‘X ’ [MP PMT 2003]
(c) 9 times (d) 100 times (a) Decreases the rate constant of reaction
28. The temperature coefficient for reaction in which (b) Does not affect the equilibrium constant of
food deteriorates is 2. Then food deteriorates ...... reaction
o
times as rapidly at 25 C as it does at 5 Co (c) Decreases the enthalpy of reaction
(a) Two (b) Four (d) Decreases the activation energy
(c) Six (d) Twenty 37. Which reaction characteristics are changing by
the addition of a catalyst to a reaction at constant
29. The rate of a reaction is doubled for every 10 o
temperature
rise in temperature. The increase in reaction rate
(i) Activation energy (ii) Equilibrium constant
as a result of temperature rise from 10 o to 100 o
is (iii) Reaction entropy (iv) R
[KCET 1993; Kerala PET 2002; MP PET 2003] [DCE 2003]
(a) 112 (b) 512 (a) (i) Only (b) (iii) only
(c) 400 (d) 614 (c) (i) and I(ii) only (d) All of these
30. A catalyst increases the rate of a chemical 38. The velocity constant of a reaction at 290 K was
reaction by found to be 3 .2  10 3 . At 300 K it will be[MP PMT 2004]
[MNR 1988; CPMT 1999; Pb. PMT 2000]
(a) 1 . 28  10 2 (b) 6 .4  10 3
(a) Increasing the activation energy
3
(b) Decreasing the activation energy (c) 9 .6  10 (d) 3 .2  10 4
(c) Reacting with reactants 39. In which of the following cases, does the reaction
(d) Reacting with products go farthest to completion [
2
31. Velocity constant of a reaction at 290 K was found (a) K  10 3
(b) K  10
to be 3 .2  10 3 . At 310 K it will be about[KCET 1989, 91] (c) K  10 (d) K  1
2 3
(a) 1 .28  10 (b) 9 .6  10 40. Rate of reaction [Pb. CET 2004]
(c) 6.4  10 3 (d) 3.2  10 4 (a) Decreases with increase in temperature
32. The temperature coefficient of a reaction is (b) Increases with increase in temperature
(a) Specific reaction rate at 25 C o (c) May increase or decrease with increase in
o temperature
(b) Rate of the reaction at 100 C
(c) Ratio of the rate constants at temperatures (d) Does not depend on temperature
35 o C and 25 o C 41. For the reaction 2 N 2O5(g)  4 NO2(g)  O2(g) , if
(d) Ratio of the rate constants at two concentration of NO2 in 100 seconds is increased
temperatures differing by 1 o C by 5 .2  10 3 m . Then rate of reaction will be
33. The main function of a catalyst in speeding up a [Kerala CET 2005]
reaction is
(a) 1 .3  10 5 ms 1 (b) 5  10 4 ms 1
(a) To increase the rate of the forward reaction
(b) To change the reaction path so as to decrease (c) 7.6  10 4 ms 1 (d) 2  10 3 ms 1
the energy of activation for the reaction (e) 2 .5  10 5 ms 1
(c) To reduce the temperature at which the reaction 42. A first order reaction complete its 10% in 20
can occur minutes then time required to complete its 19% is[Kerala
(a) 30 minutes (b) 40 minutes
 Chemical Kinetics 465
(c) 50 minutes (d) 38 minutes [CBSE PMT 1997]
(e) 45 minutes Exp. [A]0 [B]0 Rate (mole s 1 )

Rate law and Rate constant (1) 0.50 0.50 1 .6  10 4

(2) 0.50 1.00 3.2  10 4
1. Which of these does not influence the rate of
reaction
(3) 1.00 1.00 3 .2  10 4
[KCET 2005]
The rate equation for the above data is
(a) Nature of the reactants
(b) Concentration of the reactants (a) Rate  k [B2 ] (b) Rate  k [B 2 ]2
(c) Temperature of the reaction (c) Rate  k [ A]2 [B]2 (d) Rate  k [ A]2 [ B]
(d) Molecularity of the reaction
2. The rate law for reaction A  2 B  C  2 D will be 8. The reaction 2 NO(g)  O2 (g) ⇌ 2 NO2 (g) is of first
(a) Rate  K[ A][B] (b) Rate  K[ A][2B] order. If volume of reaction vessel is reduced to
1/3, the rate of reaction would be
[C ][ D] 2
(c) Rate  K[ A][B]2 (d) Rate  K (a) 1/3 times (b) 2/3 times
[ A][ B]2
(c) 3 times (d) 6 times
3. In the reaction 2 N 2O5  4 NO2  O2 , initial
9. For a reaction 2 A  B  Products, doubling the
pressure is 500 atm and rate constant K is
initial concentration of both the reactants
3 .38  10 5 sec 1 . After 10 minutes the final increases the rate by a factor of 8, and doubling
pressure of N 2O5 is [Orissa JEE 2005] the concentration of B alone doubles the rate. The
rate law for the reaction is
(a) 490 atm (b) 250 atm
(c) 480 atm (d) 420 atm [MP PET 2001]

4. The rate law for the reaction (a)   k[ A][B] 2

(b)   k[ A] [B] 2


Sucrose + Water   Glucose + Fructose is
[H ]
(c)   k[ A][B] (d)   k[ A]2 [B]2
given by 10. For a reactions A  B  product, it was found that
(a) Rate  K [sucrose] [water] rate of reaction increases four times if
concentration of ‘A’ is doubled, but the rate of
(b) Rate  K [sucrose] [water] 0
reaction remains unaffected. If concentration of
(c) Rate  K [sucrose] 0 [water] ‘B’ is doubled. Hence, the rate law for the reaction
is [MP PET/PMT 1998; MP PMT 2003]
(d) Rate  K [sucrose] 1 / 2 [water] 1 / 2
d[ A] (a) rate  k[ A][B] (b) rate  k[ A]2
5. A  2 B  C  D . If   5  10  4 mol l 1 s 1 1, then
dt (c) rate  k[ A]2 [B]1 (d) rate  k[ A]2 [B]2
d [B]
 is [DPMT 2005] 11. Velocity constant K of a reaction is affected by
dt
(a) Change in the concentration of the reactant
(a) 2 .5  10 4 mol l 1 s 1 (b) 5 . 0  10 4 mol l 1 s 1
(b) Change of temperature
(c) 2 .5  10  3 mol l 1 s 1 (d) 1 . 0  10 3 mol l 1 s 1 (c) Change in the concentration of the product
6. The data for the reaction A  B  C is[CBSE PMT 1994] (d) None of the above
Exp. [A]0 [B]0 Initial rate 12. Point out the wrong statement :

(1) 0.012 0.035 0.10 For a first order reaction

(2) 0.024 0.070 0.80 (a) Time for half-change (t1 / 2 ) is independent of

(3) 0.024 0.035 0.10 initial concentration

(4) 0.012 0.070 0.80 (b) Change in the concentration unit does not
change the rate constant (K )
The rate law corresponds to the above data is (c) Time for half-change  rate constant  0 . 693
(a) Rate  k [B]3 (b) Rate  k [B]4 (d) The unit of K is mole 1
min 1
(c) Rate  k [ A][ B]3 (d) Rate  k [ A]2 [B]2 13. The rate constant of a reaction depends on
[CPMT 1989; DPMT 2001]
7. The experimental data for the reaction
2 A  B2  2 AB is (a) Temperature (b) Mass
 466 Chemical Kinetics
(c) Weight (d) Time 21. Rate constant for a reaction H 2  I2  2 HI is 49,
14. In a first order reaction the concentration of then rate constant for reaction 2 HI  H 2  I2 is [Bihar MEE
reactant decreases from 800 mol / dm 3 to (a) 7 (b) 1/49
50 mol / dm 3 is 2  10 2 sec . The rate constant of (c) 49 (d) 21
1 (e) 63
reaction in sec is
[IIT-JEE (Screening) 2003] 22. The reaction
1
(a) 2  10 4 (b) 3.45  10 5 N 2 O5 (in CCl4 solution)  2 NO2 (solution)  O 2 (g )
2
(c) 1 .386  10 2 (d) 2  10 4 is of first order in N 2 O5 with rate constant
15. For a reaction A  B , the rate of reaction 1 1
6 .2  10 s . What is the value of rate of reaction
quadrupled when the concentration of A is
when [ N 2 O 5 ]  1 .25 mole l 1 [AFMC 1998]
doubled. The rate expression of the reaction is
r  K( A)n . when the value of n is (a) 7 . 75  10 1 mole l 1 s 1 (b) 6 .35  10 3 mole l 1 s 1
(a) 1 (b) 0 (c) 5 .15  10 5 mole l 1 s 1 (d) 3 . 85  10 1 mole l 1 s 1
(c) 3 (d) 2 23. A reaction that is of the first order with respect to
16. The velocity constant of a reaction is K. Which of reactant A has a rate constant 6 min 1 . If we start
the following statements is not true regarding K with [ A]  0 .5 mol l 1 , when would [A] reach the
(a) K is a constant for a reaction at a given value 0.05mol l 1 [KCET 2000]
temperature
(a) 0.384 min (b) 0.15 min
(b) The value of K changes when the temperature
(c) 3 min (d) 3.84 min
changes
24. The rate constant for the reaction,
(c) K is the velocity of the reaction at unit
2 N 2 O5  4 NO2 O2 is 3  10 5 sec 1 . If the rate is
concentrations of the reactant
2 .40  10 5 mol litre -1 sec 1 . Then the concentration
(d) K is a constant for all reactions
of N 2 O5 (in mol litre-1) is
17. For the following reaction scheme
(homogeneous), the rate constant has units : [IIT Screening 2000]
A  B 
K
C [MP PET 1999] (a) 1.4 (b) 1.2
(c) 0.04 (d) 0.8
(a) sec 1 mole (b) sec 1
25. For the reaction 2 N 2 O5  4 NO2  O2 rate of
1 1 4
(c) sec litre mole (d) sec reaction and rate constant are 1 .02  10 and
18. Which of the following oxides of nitrogen will be 3 .4  10 5 sec 1 respectively. The concentration of
the most stable one [NCERT 1978] N 2 O5 at that time will be

(a) 2 NO2 (g) ⇌ N 2 (g)  2O 2 (g); K  6 . 7  10 16 mol l 1 [BHU 2001]

(a) 1.732 (b) 3
(b) 2 NO (g) ⇌ N 2 (g)  O 2 (g); K  2 . 2  10 30 mol l 1 4
(c) 1 .02  10 (d) 3 .4  10 5
(c) 2 N 2 O5 (g) ⇌ 2 N 2 (g)  5 O 2 (g); K  1 . 2  10 34 mol l 5 26. The rate law of the reaction 2 N 2 O5  4 NO2  O2 is
1
(d) 2 N 2 O(g) ⇌ 2 N 2 (g)  O 2 (g); K  3 .5  10 33
mol litre [MP PET 2002]
(a) r  K[N 2 O5 ] (b) r  K[ N 2 O 5 ]2
19. The rate of reaction is determined by slow step
reaction. The step is called (c) r  K[ N 2 O 5 ]0 (d) r  K[ NO 2 ]4 [O 2 ]
(a) Reaction rate (b) Activation step 27. If R  K[ NO ]2 [O 2 ], rate constant may be increased
(c) Rate determining step (d) None of the above by
20. The rate of the reaction [BHU 2003]
CCl3 CHO  NO  CHCl 3  NO  CO is given by Rate (a) Increasing temperature
 K [CCl3 CHO][NO] . If concentration is expressed (b) Decreasing temperature
(c) Increasing concentration of O 2
in moles/litre, the units of K are [MP PET 1993]
2 1 (d) Increasing concentration of NO
2
(a) litre mole sec (b) mole litre 1 sec 1
28. The value of rate constant A  B  products
1
(c) litre mole sec 1 (d) sec 1 depends on
[BHU 2003]
(a) Concentration of A and B
 Chemical Kinetics 467
(b) Pressure (a) litre sec 1 (b) litre mole 1
sec 1
(c) Temperature
(c) mole litre 1 sec 1 (d) mole sec 1
(d) All of these
29. The rate constant of a reaction depends upon[BHU 2004] 37. Which of the following rate laws has an overall
order of 0.5 for reaction involving substances x ,
(a) Extent of reaction
y and z
(b) Time of reaction
(c) Temperature of the system [AIIMS 1983]

(d) Concentration of the system (a) Rate  K(C x )(C y )(C z )

30. The rate equation for the reaction 2 A  B  C is (b) Rate  K(C x )0.5 (C y )0.5 (C z )0.5
found to be: rate  k [ A][ B] . The correct statement
in relation to this reaction is that the [AIEEE 2004] (c) Rate  K(C x )1.5 (C y )1 (C z )0
(a) Rate of formation of C is twice the rate of (d) Rate  K(C x )(C z )n /(C y )2
disappearance of A
(b) t1 / 2 is a constant 38. The rates of a certain reaction (dc/dt) at different
times are as follows
(c) Unit of k must be s 1 Time Rate (mole litre–1 sec –1 )
(d) Value of k is independent of the initial
0 2.8  10 2
concentrations of A and B
31. The specific rate constant of a first order reaction 10 2.78  10 2
depends on the 20 2 .81  10 2
[IIT 1981, 83; DPMT 1991; Bihar MEE 1995; KCET 1998]
30 2.79  10 2
(a) Concentration of the reactants
The reaction is [NCERT 1978]
(b) Concentration of the products
(a) Zero order (b) First order
(c) Time of reaction
(c) Second order (d) Third order
(d) Temperature of reaction
39. For a chemical reaction A  B it is found that the
32. If the concentration is expressed in moles per
litre, the unit of the rate constant for a first order rate of reaction doubles, when the concentration
reaction is of A is increased four times. The order in A for
[MNR 1986; MP PET 1994, 2000, 01;Bihar MEE 1996;
this reaction is
CPMT 1997; MP PMT 1995, 96, 99;AFMC 2002] [NCERT 1979; AIIMS 1997; J & K CET 2005]

(a) mole litre 1

sec 1
(b) mole litre 1 (a) Two (b) One
1
(c) Half (d) Zero
(c) sec (d) mole 1 litre 1 sec 1
40. The following data are for the decomposition of
33. The dimension of rate constant of a second order ammonium nitrate in aqueous solution
reaction involves [NCERT 1982]
Volume of N 2 in cc Time (minutes)
(a) Neither time nor concentration
(b) Only time 6.25 10
(c) Time and concentration 9.50 15
(d) Time and square of concentration 11.42 20
34. The unit of rate constant of second order reaction 13.65 25
is usually expressed as 35.05 Finally
[NCERT 1983, 84; MNR 1983; MP PMT 1994, 99] The order of the reaction is [
(a) mole litre sec 1 (b) mole 1
litre 1 sec 1 (a) Zero (b) One
(c) mole litre 1 sec 1 (d) mole 1
litre sec 1 (c) Two (d) Three
35. A zero order reaction is one whose rate is 41. The hydrolysis of ethyl acetate is a reaction of
independent of [MP PMT 1987]
[NCERT 1981] H
CH 3 COOEt  H 2 O 
 CH 3 COOH  EtOH
(a)Temperature of the reaction
(a) First order (b) Second order
(b)The concentrations of the reactants
(c) Third order (d) Zero order
(c)The concentration of the products
42. The rate of reaction between A and B increases
(d)The material of the vessel in which the
by a factor of 100, when the concentration of A is
reaction is carried out
increased 10 folds. The order of reaction with
36. The unit of rate constant for a zero order reaction respect to A is
is [CPMT 1985]
[NCERT 1981; MP PMT 2000; RPET 2000]
(a) 10 (b) 1
 468 Chemical Kinetics
(c) 4 (d) 2 (b) The sum of powers to which the concentration
43. Which of the following is a first order reaction terms are raised in the velocity equation
[MP PMT 1987] (c) The least number of molecules of the
(a) NH 4 NO2  N 2  2 H 2 O reactants needed for the reaction

(b) 2 HI  H 2  I2 (d) The number of reactants which take part in

the reaction
(c) 2 NO2  2 NO  O2
52. Catalyst decomposition of hydrogen peroxide is a
(d) 2 NO  O2  2 NO2 ........ order reaction
44. The inversion of cane sugar is represented by (a) First (b) Second
C12 H 22O11  H 2 O  C6 H12O6  C6 H12O6 (c) Third (d) Zero

It is a reaction of 53. The half life of a first order reaction is

[AFMC 1982; MP PMT 1993; RPET 2000] (a) Independent of the initial concentration of the
(a) Second order (b) Unimolecular reactant
(c) Pseudo unimolecular (d) None of the three (b) Directly proportional to the initial
concentration of the reactants
45. Which one of the following formula represents a
first order reaction [MP PMT 1999] (c) Inversely proportional to the initial
concentration of the reactant
x 1  1 1 
(a) K  (b) K    2 (d) Directly proportional to the square of the
t 2 t  (a  x ) 2
a 
initial concentration of the reactant
2 .303 a 1 x 54. The decomposition of N 2 O5 is a first order
(c) K  log 10 (d) K 
t (a  x ) t a(a  x ) 1
reaction represented by N 2 O5  N 2 O 4 
O2 .
46. The first order rate constant for the 2
decomposition of N 2 O5 is 6 .2  10 4 sec 1 . The half After 15 minutes the volume of O 2 produced is
life period for this decomposition in seconds is 9 ml and at the end of the reaction 35 ml . The rate
[MNR 1991; MP PET 1997; UPSEAT 2000] constant is equal to
(a) 1117.7 (b) 111.7 [MP PET 1995]
(c) 223.4 (d) 160.9 1 35 1 44
(a) ln (b) ln
47. A first order reaction which is 30% complete in 15 44 15 26
30 minutes has a half-life period of [AIIMS 1998]
1 44 1 35
(a) 24.2 min (b) 58.2 min (c) ln (d) ln
15 35 15 26
(c) 102.2 min (d) 120.2 min
55. The unit of specific reaction rate constant for a
48. The order of a reaction which has the rate first order (if the concentration expressed in
dc
expression  K[ E]3 / 2 [D]3 / 2 is molarity) would be
dt
[MNR 1988; UPSEAT 2000, 01]
(a) 3/2 (b) 3 1 1
(a) mole litre s (b) mole litre 1
(c) 2 (d) 0
(c) mole s 1 (d) s 1
49. The reaction 2 N 2 O5 ⇌ 2 NO2  O2 follows first
56. A first order reaction requires 30 minutes for
order kinetics. Hence, the molecularity of the
50% completion. The time required to complete
reaction is
the reaction by 75% will be
(a) Unimolecular
(a) 45 minutes (b) 15 minutes
(b) Pseudo–unimolecular
(c) 60 minutes (d) None of these
(c) Bimolecular
57. Inversion of canesugar in dilute acid (conversion
(d) None of the above
into glucose and fructose) is a
50. A reaction involving two different reactants
(a) Unimolecular reaction
[KCET 1989; AIEEE 2005]
(b) Bimolecular reaction
(a) Can never be a second order reaction
(c) Trimolecular reaction
(b) Can never be a unimolecular reaction
(c) Can never be a bimolecular reaction (d) Pseudo-unimolecular reaction

(d) Can never be a first order reaction 58. The half life period of a first order reaction[AMU 2000]
51. By “the overall order of a reaction”, we mean 0 .693 0 .693
(a) (b)
t K
(a) The number of concentration terms in the
equation for the reaction
 Chemical Kinetics 469

(c)
2 .303
(d)
0 .303 (a) T  an 1 (b) T  a n
t K1 1 1
(c) T  n (d) T  n 1
59. The order of a reaction is said to be 2 with respect a a
to a reactant X, when [DPMT 2000] 67. In presence of HCl , sucrose gets hydrolysed into
(a) The rate of the reaction is proportional to [X] glucose and fructose. The concentration of
(b) The rate of the reaction is proportional [X ]2 sucrose was found to reduce form 0.4 M to 0.2 M
in 1 hour and 0.1 M in 2 hours. The order of the
(c) Two molecules of X are present in the reaction is
stoichiometric equation
(a) Zero (b) One
(d) The reaction occurs in two steps
(c) Two (d) None of these
60. Decay constant of a reaction is 1.1  10 9 / sec , then 68. The time of half change of a first order reaction in
the half life of the reaction is ....... initial concentration
(a) 1.2  10 8 (b) 6 . 3  10 8 (a) Proportional to
(c) 3 .3  10 8
(d) 2 . 1  10 8 (b) Inversely proportional to
61. If the half life period of a reaction is inversely (c) Independent of
proportional to the initial concentration, the
(d) Equal to
order of the reaction is
(a) Zero (b) One 69. Half life period of a first order reaction is 138.6
minutes. The velocity constant of the reaction is
(c) Two (d) Three
(a) 0 . 05 min 1 (b) 0 . 00005 min 1
62. Which one of the following statements is wrong
(a) Molecularity of a reaction is always a whole (c) 0 . 005 min 1 (d) 200 min 1
number
70. An example of a pseudo –unimolecular reaction is
(b) Order and molecularity of a reaction need not
be same (a) Dissociation of hydrogen iodide

(c) Order of a reaction may be zero (b) Hydrolysis of methyl acetate in dilute solution
(d) Order of a reaction depends upon the (c) Dissociation of phosphorus pentachloride
mechanism of the reaction (d) Decomposition of hydrogen peroxide
63. The velocity constant of first order reaction is 71. About half life period of a first order reaction,
expressed in the units which one of the following statements is
(a) Concentration per unit time generally false
(b) Time per unit concentration (a) It is independent of initial concentration
(c) Per unit time (b) It is independent of temperature
(d) Unit time per unit concentration (c) It decreases with the introduction of a
64. For reation, A  B  products, it is found that the catalyst
rate of the reaction is proportional to the (d) It increases with increase of temperature
concentration of A, but it is independent of the 72. Decomposition of nitrogen pentoxide is known to
concentration of B, then be a first order reaction 75 percent of the oxide
(a) The order of the reaction 2 and molecularity 1 had decomposed in the first 24 minutes. At the
(b) Molecularity of the reaction is 2 but order is 1 end of an hour, after the start of the reaction, the
(c) Order is 2 and molecularity is 2 amount of oxide left will be
(d) Order of the reaction is 2 but molecularity is 0 (a) Nil (b) About 1%
65. For a zero order reaction (c) About 2% (d) About 3%
(a) The concentration of the reactant does not 73. A reaction 2 A  products is found to follow zero
change during the reaction oder kinetics, then
(b) The concentration change only when the dx dx
(a)  k [A]2 (b)  k [A]0
temperature changes dt dt
(c) The rate remains constant throughout dx dx
(d) The rate of the reaction is proportional to the (c)  k[A] (d)  k [2 A ]
dt dt
concentration
74. The alkaline hydrolysis of ethyl acetate is
66. If ‘a’ is the initial concentration and ‘n’ is the
represented by the equation
order of the reaction and the half life period is ‘T’,
then CH 3 COOC 2 H 5  NaOH  CH 3 COONa  C2 H 5 OH
[MH CET 2000] Experimentally it is found that for this reaction
 470 Chemical Kinetics
dx 83. Value of velocity constant for first order reaction
 k [CH 3 COOC 2 H 5 ][ NaOH ]
dt is 3 .46  10 3 min 1 , the time for half change is
Then the reaction is [JIPMER 1999] (a) 100 minutes (b) 400 minutes
(a) Bimolecular and of first order (c) 200 minutes (d) 346 minutes
(b) Bimolecular and of second order 84. The unit of the velocity constant in case of zero
(c) Pseudo–bimolecular order reaction is [CPMT 1994]
(d) Pseudo–unimolecular (a) Conc .  time 1 (b) Conc . 1  time
75. For the reaction 2 HI ⇌ H 2  I2 , the rate of the (c) Conc . 1  time 1 (d) Conc.  (time)2
2
reaction is proportional to [HI] . This means that
85. For the reaction H 2 (g)  Br2 (g)  2 HBr(g) , the
the reaction is
experimental data suggest, rate  K[H 2 ][ Br 2 ] 1/2
.
[AMU 1985; MP PET 2000]
The molecularity and order of the reaction are
(a) Unimolecular (b) Bimolecular respectively
(c) Of first order (d) Of second order [CPMT 1988; MP PET 1993]
76. Inversion of sucrose is [AMU 1988; MP PET 2000] 3 3 3
(a) 2, (b) ,
(a) Zero order reaction (b) First order reaction 2 2 2
(c) Second order reaction (d)Third order reaction 1
(c) 1, 1 (d) 1,
77. The one which is unimolecular reaction is 2

[MP PMT 1999; UPSEAT 2001] 86. The incorrect order indicated against the rate of
reaction A  B 
K
C is [BHU 1990]
1
(a) 2 HI  H 2  I2 (b) N 2 O5  N 2 O 4  O2 Rate Order
2
d[C]
(c) H 2  Cl2  2 HCl (d) PCl3  Cl2  PCl5 (a)  K [ A] 1
dt
78. Integrated velocity equation for first order d[C]
reaction is (b)  K[ A][B] 2
dt
(a) [ A]o  [ A] e  Kt (b) K  [ A]o e  A / t d [ A]
(c)  K [ A][B]0 2
[ A ]o [ A ]o dt
(c) Kt  2 . 303 log (d) log  2 . 303 Kt
[ A] [ A] d [ A]
(d) K [ A] 1
dt
79. If the surface area of the reactants increases, then
order of the reaction 87. Which of the following statements regarding the
molecularity of a reaction is wrong[CBSE PMT 1989]
(a) Increases
(a) It is the number of molecules of the reactants
(b) Decreases taking part in a single step chemical reaction
(c) Remain constant (b) It is calculated from the reaction mechanism
(d) Sometimes increases and sometimes dereases (c) It may be either a whole number or fractional
80. Half life period t1 / 2 for first order reaction is (d) It depends on the rate determining step in the
reaction
1 .303 log 2 88. Diazonium salt decomposes as
(a) K (b)
K
C 6 H 5 N 2 Cl   C 6 H 5 Cl  N 2
2 .303 log 2 9
(c) (d) At 0 o C , the evolution of N 2 becomes two times
K K
faster when the initial concentration of the salt is
81. Molecularity of reaction of inversion of sugar is
doubled. Therefore, it is [MNR 1994; UPSEAT 2002]
(a) 3 (b) 2 (a) A first order reaction
(c) 1 (d) 0 (b) A second order reaction
82. For any reaction, if we plot a graph between time (c) Independent of the initial concentration of the
‘t’ and log( a  x ) , a simple line is obtained. The salt
order of reaction is (d) A zero order reaction
(a) Zero (b) One 89. In the reaction A  B  Products, if B is taken in
(c) Two (d) Three excess, then it is an example of [EAMCET 1992]
(a) Second order reaction
 Chemical Kinetics 471
(b) Zero order reaction 97. The order of a reaction with rate equals
(c) Pseudounimolecular reaction kC A3 / 2 C B1 / 2 is
(d) First order reaction [MP PET 1996, 2001]
90. The half life of a first order reaction is 69 .35 sec . (a) 2 (b) 1
The value of the rate constant of the reaction is[CBSE PMT 1990] 1 3
(c)  (d)
1 1 2 2
(a) 1 . 0 s (b) 0 . 1 s
98. If the rate expression for a chemical reaction is
(c) 0 . 01 s 1 (d) 0 . 001 s 1
given by Rate  k[ A]m [B]n [MP PMT 1996]
1
91. The half life for the reaction N 2 O5 ⇌ 2 NO 2  O 2 (a) The order of the reaction is m
2
(b) The order of the reaction is n
in 24 hrs at 30 o C . Starting with 10 g of N 2 O5 how
(c) The order of the reaction is m  n
many grams of N 2 O5 will remain after a period of
(d) The order of the reaction is m  n
96 hours
99. The half-life period of a first order reaction is 100
[KCET 1992]
sec. The rate constant of the reaction is
(a) 1.25 g (b) 0.63 g [MP PMT 1997; MP PET 2001]
(c) 1.77 g (d) 0.5 g (a) 6 .93  10 3 sec 1 (b) 6 .93  10 4 sec 1
92. The half life of a first order reaction is 10 (c) 0 .693 sec 1 (d) 69 . 3 sec 1
minutes. If initial amount is 0.08 mol / litre and
100. For the first order reaction with rate constant
concentration at some instant is 0.01 mol / litre, k , which expression gives the half-life period ?
then t  [Roorkee 1990] (Initial concentration  a ) [MP PET/PMT 1998]
(a) 10 minutes (b) 30 minutes 12 1
(a) (b)
(c) 20 minutes (d) 40 minutes k ka
93. Half life period of second order reaction is[MP PMT 1994] 0 .693 3
(c) (d)
(a) Proportional to the initial concentration of k 2k a 2
reactants 101. The rate constant of a first order reaction whose
(b) Independent of the initial concentration of half-life is 480 seconds, is [MP PET 1999]
reactants (a) 2 .88  10 3 sec 1 (b) 1 .44  10 3 sec 1
(c) Inversely proportional to initial concentration (c) 1 .44 sec 1 (d) 0.72  10 3 sec1
of reactants
102. The conversion of A  B follows second order
(d) Inversely proportional to square of initial
kinetics. Doubling the concentration of A will
concentration of reactants
increase the rate of formation of B by a factor
94. The reaction 2H 2 O2  2 H 2 O  O2 is a
[MP PET 1999; DCE 1999; KCET 2001; BCECE 2005]
[Manipal MEE 1995] (a) 1 / 4 (b) 2
(a) Zero order reaction (b) First order reaction
(c) 1 / 2 (d) 4
(c) Second order reaction (d)Third order reaction
103. The reaction 2 FeCl3  SnCl 2  2 FeCl2  SnCl 4 is an
95. In a reaction involving hydrolysis of an organic
chloride in presence of large excess of water example of [CBSE PMT 1996; MP PET 1999]

RCl  H 2 O  ROH  HCl [MP PET 1995] (a) First order reaction
(b) Second order reaction
(a) Molecularity is 2, order of reaction is also 2
(c) Third order reaction
(b) Molecularity is 2, order of reaction is 1
(d) None of these
(c) Molecularity is 1, order of reaction is 2
(d) Molecularity is 1, order of reaction is also 1 104. If reaction between A and B to give C shows
first order kinetics in A and second order in B ,
96. The thermal decomposition of a compound is of the rate equation can be written as [MP PET 1999]
first order. If a sample of the compound
decomposes 50% in 120 minutes, in what time (a) Rate  k [ A][B]1 / 2 (b) Rate  k [ A]1 / 2 [B]
will it undergo 90% decomposition
(c) Rate  k [ A][ B] 2 (d) Rate  k[ A]2 [B]
[MP PET 1996]
(a) Nearly 240 minutes (b) Nearly 480 minutes 105. For a first order reaction, the half-life period is
independent of
(c) Nearly 450 minutes (d) Nearly 400 minutes
[CBSE PMT 1999]
(a) Initial concentration
 472 Chemical Kinetics
(b) Cube root of initial concentration 113. For a first order reaction, rate constant is
(c) First power of final concentration 0 . 6932 hr 1 , then half-life for the reaction is[Bihar MEE 199
(d) Square root of final concentration (a) 0.01 hr (b) 1 hr
106. Order of a reaction can have [DPMT 1996]
(c) 2 hr (d) 10 hr
(a) ve values (b) Whole number
values (e) 0.1 hr
(c) Fractional values (d) All of the above 114. The rate constant of a reaction is 0 .69  10 1 min 1
107. The order of the reaction occurring by following and the initial concentration is 0 . 2mol l 1 . The
mechanism should be [JIPMER 1997] half-life period is
(i) A2  A  A (fast) [AIIMS 1998]
(ii) A  B2  AB  B (slow) (a) 400 sec (b) 600 sec
(iii) A  B  (fast) (c) 800 sec (d) 1200 sec
1 1 115. The rate constant of a first order reaction is
(a) 1 (b) 3 3  10 6 per second. If the initial concentration is
2 2
0.10 m, the initial rate of reaction is
(c) 2 (d) None of these
[AFMC 1999 Pb. PMT 1999, 2000; BHU 1999;
108. For the reaction A  B , the rate law expression is
AIIMS 1999; KCET 2000; DCE 2004]
: Rate  k [A]
5 1
(a) 3  10 ms (b) 3  10 6 ms 1
Which of the following statements is incorrect
[Pb. PMT 1998] (c) 3  10 8 ms 1 (d) 3  10 7 ms 1

(a) The reaction is said to follow first order 116. Certain bimolecular reactions which follow the
kinetics first order kinetics are called
(b) The half life of the reaction will depend on the (a) First order reactions
initial concentration of the reactant (b) Unimolecular reactions
(c) k is constant for the reaction at a constant (c) Bimolecular reactions
temperature (d) Pseudounimolecular reactions
(d) The rate law provides a simple way of 117. The rate law of the reaction A  2 B  Product is
predicting the concentration of reactants and
d[dB]
products at any time after the start of the given by  k [B 2 ] . If A is taken in excess, the
dt
reaction
order of the reaction will be [AMU (Engg.) 1999]
109. If initial concentration is reduced to its 1/4th in a
zero order reaction, the time taken for half of the (a) 1 (b) 2
reaction to complete (c) 3 (d) 0
[BHU 1998] 118. For a first order reaction A  product, the rate of
(a) Remains same (b) Becomes 4 times reaction at [ A]  0 .2 mol l 1 is 1 .0  10 2 mol l 1 min 1 .
(c) Becomes one-fourth (d) Doubles The half life period for the reaction is[Roorkee 1999]
110. For a reaction whose rate expression is :
(a) 832 s (b) 440 s
Rate  k[ A]1 / 2 [B]3 / 2 , the order would be[Pune CET 1998] (c) 416 s (d) 13.86 s
(a) 1.5 (b) 2 119. For the reaction A  B  products, doubling the
(c) 3 (d) 1 concentration of A the rate of the reaction is
doubled, but on doubling the concentration of B
111. For the reaction A  B , the rate increases by a
rate remains unaltered. The over all order of the
factor of 2.25 when the concentration of A is
reaction is [JIPMER 1999]
increased by 1.5. What is the order of the reaction[KCET 1998]
(a) 1 (b) 0
(a) 3 (b) 0
(c) 2 (d) 1 (c) 2 (d) 3
120. Which among the following is a false statement
112. For the reaction H 2  Cl 2   2 HCl
Sunlight
taking
[KCET 1999]
place on water, the order of reaction is
[KCET 1998; AIIMS 2002; Pb. PMT 2002] (a) Half life of a third order reaction is inversely
proportional to the square of initial
(a) 1 (b) 2
concentration of the reactant.
(c) 3 (d) 0
 Chemical Kinetics 473
(b) Molecularity of a reaction may be zero or 128. 75% of a first order reaction is completed in 30
fractional minutes. What is the time required for 93.75% of
0.693 the reaction (in minutes) [KCET 2001]
(c) For a first order reaction t1 / 2 
K (a) 45 (b) 120

(d) Rate of zero order reaction is independent of (c) 90 (d) 60

initial concentration of reactant 129. A First order reaction is half completed in 45
121. After how many seconds will the concentration of minutes. How long does it need 99.9% of the
the reactants in a first order reaction be halved, if reaction to be completed
the decay constant is 1.155  10 -3 sec 1 [CBSE PMT 2000] [AIIMS 2001]

(a) 100 sec (b) 200 sec (a) 5 hours (b) 7.5 hours
(c) 10 hours (d) 20 hours
(c) 400 sec (d) 600 sec
130. A substance ‘A’ decomposes by a first order
122. What is the order of a reaction which has a rate
reaction starting initially with [A] =2.00m and
expression rate  K[ A]3 / 2 [B]1 [DCE 2000]
after 200 min [A] = 0.15m. For this reaction what
(a) 3/2 (b) 1/2 is the value of k [AIIMS 2001]

(c) 0 (d) None of these (a) 1 .29  10 2 min 1 (b) 2 .29  10 2 min 1
123. Which of the following expression is correct for (c) 3 .29  10 2 min 1 (d) 4 .40  10 2 min 1
first order reaction? (CO ) refers to initial
131. Which of the following statements about zero
concentration of reactant order reaction is not true [
[DCE 2000] 1
(a) Its unit is sec
(a) t1 / 2  CO (b) t1 / 2  CO 1 (b) The graph between log (reactant) versus rate
2 of reaction is a straight line
(c) t1/2  CO (d) t1 / 2  CO 0

(c) The rate of reaction increases with the

124. For a reaction 2 NO(g)  Cl2 (g) ⇌ 2 NOCl(g) . When decrease in concentration of reactants
concentration of Cl2 is doubled, the rate of (d) Rate of reaction is independent of
reaction becomes two times of the original. When concentration of reactants
the concentration of NO is doubled the rate 132. The given reaction 2 NO  O2  2 NO2 is an
becomes four times. What is the order of the example of
reaction [MP PMT 2000]
[CBSE PMT 2001; JIPMER 2002]
(a) 1 (b) 2 (a) First order reaction (b) Second order
(c) 3 (d) 4 reaction
125. The rate constant for a second order reaction is (c) Third order reaction (d) None of these
8  10 5 M 1min 1 . How long will it take a 1M 133. Order of a reaction is decided by [KCET 2002]
solution to be reduced to 0.5 M [MH CET 2001] (a) Pressure
(a) 8  10 5 min (b) 8 .665  10 3 min (b) Temperature
(c) Molecularity
(c) 4  10 5 min (d) 1 .25  10 4 min
(d) Relative concentration of reactants
126. The rate for a first order reaction is
134. From the following which is a second order
0 .6932  10 2 mol l 1min 1
and the initial
reaction
concentration of the reactants is 1M, T1 / 2 is equal
[AMU 2002]
to [JIPMER (Med.) 2001] 4 1
(a) K  5.47  10 sec
(a) 6 . 932 min (b) 100 min 3
(b) K  3 .9  10 mole lit sec 1
(c) 0 .6932  10 3 min (d) 0.6932  10 2 min
(c) K  3 .94  10 4 lit mole -1 sec 1
1
127. For a given reaction t1 / 2  . . The order of the
Ka (d) K  3 .98  10 5 lit mole -2 sec 1
reaction is
135. For the reaction A  2 B  C, rate is given by R
[KCET 2001]
 [ A][B]2 then the order of the reaction is [AIEEE 2002]
(a) 1 (b) 0
(a) 3 (b) 6
(c) 3 (d) 2
(c) 5 (d) 7
 474 Chemical Kinetics
136. Units of rate constant of first and zero order (a) The reaction is unimolecular
reactions in terms of molarity M unit are (b) The reaction is bimolecular
respectively [AIEEE 2002]
(c) T1 / 2  a 0
(a) sec 1 , M sec 1 (b) sec 1 , M
(d) None of these
(c) M sec 1 , sec 1 (d) M , sec 1 146. Which equation is correct for first order reactions
137. The reaction 2 N 2 O5 ⇌ 2 N 2 O4  O2 is [MP PMT 2002] [MP PMT 2003]
1
(a) Bimolecular and second order (a) t1 / 2  C (b) t1 / 2  C
(b) Unimolecular and first order
(c) t1 / 2  C 0 (d) t1 / 2  C 1 / 2
(c) Bimolecular and first order
147. For the reaction system 2 NO(g)  O2 (g)  2 NO2 (g)
(d) Bimolecular and zero order
138. The half-life period for a first order reaction is volume is suddenly produced to half its value by
693 seconds. The rate constants for this reaction increasing the pressure on it. If the reaction is of
would be first order with respect to O 2 and second order
[MP PET 2002] with respect to NO , the rate of reaction will [AIEEE 2003]
(a) 0 .1sec 1 (b) 0 .01 sec 1 (a) Diminish to one fourth of its initial value
(c) 0 .001 sec 1 (d) 0 .0001 sec 1 (b) Diminish to one eighth of its initial value
139. For an elementary reaction, 2A + B  C + D the (c) Increase to eight times of its initial value
molecularity is [Kurukshetra CEE 2002] (d) Increase to four times of its initial value
(a) Zero (b) One 148. If the rate of the reaction is equal to the rate
(c) Two (d) Three constant, the order of the reaction is [CBSE PMT 2003]
140. If the order of the reaction x  y 
hv
 x y is zero, (a) 3 (b) 0
it means that the rate of [Kurukshetra CEE 2002] (c) 1 (d) 2
(a) Reaction is independent of temperature 149. The reaction A  B follows first order kinetics.
(b) Formation of activated complex is zero The time taken for 0.8 mole of A to produce 0.6
(c) Reaction is independent of the concentration of mole of B is 1 hour. What is the time taken for
reacting species conversion of 0.9 mole of A to produce 0.675 mole
(d) Decomposition of activated complex is zero of B [CBSE PMT 2003]

141. For a first order reaction velocity constant, (a) 2 hours (b) 1 hour
3 1
K  10 s . Two third life for it would be[MP PET 2001; UPSEAT
(c) 2003]
0.5 hour (d) 0.25 hour
(a) 1100 s (b) 2200 s 150. The unit of velocity constant in case of zero order
(c) 3300 s (d) 4400 s reaction is
142. In a reaction, the concentration of reactant is [MP PMT 2004]
increased two times and three times then the 1
(a) Concentration  Time (b) Concentrat ion -1  Time -1
increases in rate of reaction were four times and
nine times respectively, order of reaction is (c) Concentrat
[UPSEATion  Time 2
2003] (d) Concentrat ion -1  Time
(a) Zero (b) 1 151. Which one of the following is wrongly matched
(c) 2 (d) 3 [KCET 2004]
143. For a chemical reaction....can never be a fraction (a) Saponification of CH 3 COOC 2 H5 – Second order
[EAMCET 2003]
reaction
(a) Order (b) Half-life
(b) Hydrolysis of CH 3 COOCH 3 – Pseudo uni-
(c) Molecularity (d) Rate constant
molecular
144. 75% of a first order reaction was completed in 32
minutes when was 50% of the reaction completed reaction
[AMU 1999; Kerala (Med.) 2003] (c) Decomposition of H 2 O2 – First order reaction
(a) 16 min. (b) 24 min.
(d) Combination of H 2 and Br2 to give HBr – Zero
(c) 8 min. (d) 4 min.
order
145. The decomposition of N 2 O5 occurs as,
reaction
2 N 2 O5  4 NO2  O2 , and follows Ist order kinetics,
hence 152. Which of the following is an example of pseudo
[BVP 2003]
unimolecular reaction [Pb. CET 2001]
 Chemical Kinetics 475

(a) CH 3 COOCH 3  H 2 O 
H
 CH 3 COOH  CH 3 OH 161. Which is correct about zero order reaction
[JEE Orissa 2004]

(b) CH 3 COOCH 3  H 2 O 
OH
 CH 3 COOH  CH 3 OH (a) Rate of reaction depends on decay constant
(c) 2 FeCl3  SnCl 2  SnCl4  2FeCl2 (b) Rate of reaction is independent of
concentration
(d) NaOH  HCl  NaCl  H 2O (c) Unit of rate constant is concentration–1
153. Hydrolysis of DDT is a first order reaction, its (d) Unit of rate constant is concentration–1 time–1
half life is 10 years. Time to hydrolyse 10 g DDT 162. Decay of 235
is .....order reaction[JEE Orissa 2004]
92 U
to half is [BVP 2004]
(a) Zero (b) First
(a) 100 years (b) 50 years
(c) Second (d) Third
(c) 5 years (d) 10 years 163. The half-life of 2 sample are 0.1 and 0.4 seconds.
154. In a first order reaction, the concentration of the Their respective concentration are 200 and 50
reactant, decreases from 0.8 M to 0.4 M in 15 respectively. What is the order of the reaction [JEE Orissa
minutes. The time taken for the concentration to (a) 0 (b) 2
change from 0.1 M to 0.025 M is [AIEEE 2004] (c) 1 (d) 4
(a) 7.5 minutes (b) 15 minutes 164. The following statements(s) is(are) correct[IIT 1999]
(c) 30 minutes (d) 60 minutes (a) A plot of log K p versus 1 / T is linear
155. In the first order reaction, the concentration of
the reactant is reduced to 25% in one hour. The (b) A plot of log [ X ] versus time is linear for a first
half life period of the reaction is [DCE 2004] order reaction X  P
(a) 2 hr (b) 4 hr (c) A plot of log P versus 1 / T is linear at constant
(c) 1/2 hr (d) 1/4 hr volume
156. For a reaction, X (g)  Y (g)  Z(g) the half life (d) A plot of P versus 1 / V is linear at constant
period is 10 min. In What period of time would temperature
the concentration of X be reduced to 10% of 165. For a first order reaction [IIT 1998]
original concentration [DCE 2004]
(a) The degree of dissociation is equal to (1  e kt )
(a) 20 min (b) 33 min
(c) 15 min (d) 25 min (b) A plot of reciprocal concentration of the
reactant vs time gives a straight line
157. A first order reaction with respect to the reactant
(c) The time taken for the completion of 75%
A has a rate constant of 6 sec 1 . If we start with
reaction is thrice the t1 / 2 of the reaction
[A] = 0.5 mol/litre, then in what time the
concentration of A becomes 0.05 mol/litre (d) The pre-exponential factor in the Arrhenius
[DCE 2004] equation has the dimension of time T 1
(a) 0.384 sec (b) 0.214 sec 166. For reaction a A  x P , when [ A]  2.2 mM , the
(c) 3.84 sec (d) 0.402 sec rate was found to be 2 . 4 mM s 1 . On reducing
158. Order of radioactive disintegration reaction is concentration of A to half, the rate changes to
[JEE Orissa 2004] 0 . 6 mM s 1 . The order of reaction with respect to A
(a) Zero (b) First is [AIIMS 2005]
(c) Second (d) Third (a) 1.5 (b) 2.0
159. The rate of a first order reaction is (c) 2.5 (d) 3.0
1 .5  10 2 molL 1 min 1 at 0.5 M concentration of the
167. Which one of the following statement for order of
reactant. The half life of the reaction is[CBSE PMT 2004] reaction is not correct [IIT 2005]
(a) 8.73 min (b) 7.53 min (a) Order can be determined experimentally.
(c) 0.383 min (d) 23.1 min (b) Order of reaction is equal to sum of the
160. A first order reaction was started with a powers of concentration terms in differential
decimolar solution of the reactant, 8 minutes and rate law.
20 seconds later its concentration was found to be (c) It is not affected with the stoichiometric
M / 100 . So the rate of the reaction is [Kerala PMT 2004] coefficient of the reactants.
(a) 2 .303  10 5 sec 1 (b) 2 .303  10 4 sec 1 (d) Order cannot be fractional.
3 1 5 1
(c) 4 .606  10 sec (d) 2 .606  10 sec
4 1
(e) 2 .603  10 sec
 476 Chemical Kinetics
168. t 1 can be taken as the time taken for the (b) The increase in the number of activated
4 molecules
3 (c) The shortening of the mean free path
concentration of a reactant to drop to of its
4
(d) The lowering of the activation energy
initial value. If the rate constant for a first order
reaction is K , the t 1 can be written as 2. Which of the following statements is not true
4 according to collision theory of reaction rates
[AIEEE 2005] (a) Collision of molecules is a precondition for
(a) 0.10 / K (b) 0.29 / K any reaction to occur
(c) 0.69 / K (d) 0.75 / K (b) All collisions result in the formation of the
products
169. For a first order reaction A  B the reaction rate
at reactant concentration of 0 . 01 M is found to be (c) Only activated collisions result in the
2 .0  10 5 mol L1 s1 . The half life period of the formation of the products

reaction is (d) Molecules which have acquired the energy of

activation can collide effectively
[CBSE PMT 2005]
(a) 220 s (b) 30 s 3. According to the collision theory of chemical
reactions
(c) 300 s (d) 347 s
(a) A chemical reaction occurs with every
170. The rate of reaction between two reactants A and
molecular collision
B decreases by a factor of 4 if the concentration of
reactant B is doubled. The order of this reaction (b) Rate is directly proportional to the number of
with respect to reactant B is collisions
[CBSE PMT 2005]per second
(a) – 1 (b) – 2 (c) Reactions in the gas phase are always of zero
(c) 1 (d) 2 order

171. If a substance with half life 3 days is taken at (d) Reaction rates are of the order of molecular
other place in 12 days. What amount of substance speeds
is left now [AFMC 2005] 4. According to the collision theory of reaction rates,
(a) 1/4 (b) 1/8 rate of reaction increases with temperature due
to
(c) 1/16 (d) 1/32
(a) Greater number of collisions
172. The half-life of a first order reaction having rate
constant K = 1.7  10-5 s-1 is (b) Greater velocity of the reacting molecules
[BHU 2005]
(a) 12.1 h (b) 9.7 h (c) Greater number of molecules have activation
energy
(c) 11.3 h (d) 1.8 h
(d) None of the above
173. For the reaction A  B  C , it is found that
doubling the concentration of A increases the rate 5. The reaction rate at a given temperature becomes
by 4 times, and doubling the concentration of B slower, then
doubles the reaction rate. What is the overal [MP PMT 1993; DPMT 2000]
order of the reaction. [KCET 2005]
(a) The free energy of activation is higher
(a) 4 (b) 3/2
(b) The free energy of activation is lower
(c) 3 (d) 1
(c) The entropy changes
174. Which of the following reactions end in finite
time (d) The initial concentration of the reactants
[DPMT 2005]
remains constant

(a) 0 order (b) 1st order 6. A rise in temperature increases the velocity of a
reaction. It is because it results in
(c) 2nd order (d) 3rd order
(a) An increased number of molecular collisions

Collision theory, Energy of activation (b) An increased momentum of colliding

molecules
and Arrhenius equation
(c) An increase in the activation energy

1. A large increase in the rate of a reaction for a rise (d) A decrease in the activation energy
in temperature is due to[EAMCET 1980; MP PET 1995] 7. The number of collisions depend upon
(a) The decrease in the number of collisions (a) Pressure (b) Concentration
 Chemical Kinetics 477
(c) Temperature (d) All the above (a) Reaction energy (b) Collision energy
8. If Ef and Er are the activation energies of (c) Activation energy (d) Threshold energy
forward and reverse reactions and the reaction is 15. Activation energy is
known to be exothermic, then (a) The amount of energy to be added to the
actual energy of a molecule so that the
(a) E f  Er
threshold energy is reached
(b) E f  Er (b) The amount of energy the molecule must
contain so that it reacts
(c) E f  Er (c) The energy which a molecule should have in
order to enter into an effective collision
(d) No relation can be given between E f and Er
(d) The average kinetic energy of the molecule
as data are not sufficient
16. The reason for almost doubling the rate of
9. According to Arrhenius theory, the activation reaction on increasing the temperature of the
energy is reaction system by 10 oC is
(a) The energy it should possess so that it can [J & K 2005]
enter into an effective collision (a) The value of threshold energy increases
(b) The energy which the molecule should possess (b) Collision frequency increases
in order to undergo reaction (c) The fraction of the molecule having energy
(c) The energy it has to acquire further so that it equal to threshold energy or more increases
can enter into a effective collison (d) Activation energy decreases
(d) The energy gained by the molecules on 17. The activation energy for a simple chemical
colliding with another molecule reaction A  B is Ea in forward direction. The
activation energy for reverse reaction
10. The energy of activation is
(a) Is always double of Ea
(a) The energy associated with the activated
molecules (b) Is negative of Ea

(b) Threshold energy – energy of normal (c) Is always less than Ea

molecules (d) Can be less than or more than Ea
(c) Threshold energy + energy of normal 18. Arrhenius equation is
molecules
d ln K d ln K
(a)  E * / RT (b)  E * / RT 2
(d) Energy of products – energy of reactants dT dT
11. Which one of the following does not represent d ln K d ln K
(c)  E * / RT 2 (d)  E * / RT
Arrhenius equation dT dT
(a) k  Ae  E / RT 19. Activation energy of any reaction depends on
(a) Temperature
E
(b) log e k  log e A  (b) Nature of reactants
RT
(c) Number of collisions per unit time
E
(c) log10 k  log10 A  (d) Concentration of reactants
2.303 RT
20. Relation between rate constant and temperature
(d) k  AE  RT by Arrhenius equation is
E E
12. On increasing the temperature, the rate of the (a) log e A  log e K  a (b) log K  A a
RT RT
reaction increases because of [MP PMT 1997]
E
(a) Decrease in the number of collisions (c) log e K  log e A  a2 (d) log A  RT ln Ea  ln K
(b) Decrease in the energy of activation RT
21. An endothermic reaction A  B has an activation
(c) Decrease in the number of activated molecules
energy 15 kcal/ mole and energy of reaction
(d) Increase in the number of effective collisions
5 kcal/ mole . The activation energy of the reaction
13. Energy of activation of a reactant is reduced by
B  A is [Pb. CET 1985]
(a) Increased temperature (b)Reduced temperature
(a) 20 kcal/mole (b) 15 kcal/mole
(c) Reduced pressure (d) Increased pressure
(c) 10 kcal/mole (d) None of these
14. The minimum energy a molecule should possess
22. Which of the following plots is in accordance with
in order to enter into a fruitful collision is known
the Arrhenius equation
as
[Kurukshetra CEE 2002]
log K
K
1/T 1/T

log log
 478 Chemical Kinetics
30. In respect of the equation k  Ae  Ea / RT in chemical
(a) (b) kinetics, which one of the following statement is
correct
[AIEEE 2003]
(a) k is equilibrium constant
(c) (d) (b) A is adsorption factor
(c) Ea is energy of activation
23. The Arrhenius equation expressing the effect of
(d) R is Rydberg’s constant
temperature on the rate constant of a reaction is[MP PET 1997]
31. The rate constant is doubled when temperature
(a) k  e  Ea / RT (b) k  Ea / RT
increases from 27°C to 37°C. Activation energy in
Ea  Ea / RT kJ is
(c) k  log e (d) k  Ae
RT [JEE Orissa 2004]
24. For a reaction, activation energy (Ea )  0 and rate
(a) 34 (b) 54
constant (K)  3.2  10 6 s 1 at 300 K. What is the
(c) 100 (d) 50
value of the rate constant at 310 K [KCET (Med.) 1999]
32. The activation energy of a reaction is zero. The
(a) 3 .2  10 12 s 1 (b) 3 .2  10 6 s 1
rate constant of this reaction
(c) 6 .4  10 12 s 1 (d) 6 . 4  10 6 s 1
(a) Increases with increase of temperature
25. Activation energy is given by the formula[DCE 1999]
(b) Decreases with an increase of temperature
K Ea  T2  T1 
(a) log 2    (c) Decreases with decrease of temperature
K1 2 .303 R  T1 T2 
(d) Is independent of temperature
K Ea  T2  T1 
(b) log 1     33. The rate constant is given by the equation
K2 2 .303 R  T1 T2 
k  pze  E / RT . Which factor should register a
K1 Ea  T1  T2 
(c) log    decrease for the reaction to proceed more rapidly [MP PET
K2 2 .303 R  T1 T2 
(a) T (b) Z
(d) None of these
(c) E (d) p
26. A reaction having equal activation energies for
forward and reverse reaction has [MP PMT 2002] 34. An endothermic reaction with high activation
(a) H  0 (b) S  0 energy for the forward reaction is given by the
(c) Zero order (d) None of these diagram: [AIIMS 2005]
27. Collision theory is applicable to [MP PMT 2002]
Potential

Potential
energy

energy

(a) First order reactions (b) Zero order reactions

R P
(c) Bimolecular reactions (d)Intra molecular reactions R
(a) (b) P
28. A graph plotted between log K vs 1/T for
Reaction Reaction
calculating activation energy is shown by [MP PET 2002] coordinate coordinate
Potential

Potential
energy

energy

P P
log K log K R
R
(a) (b) (c) (d)
1/T Reaction Reaction
1/T coordinate coordinate
35. Consider an endothermic reaction X  Y with the
activation energies Eb and E f for the backward
log K log K
and forward reactions, respectively, in general[AIEEE 200
(c) (d) (a) Eb  E f
1/T 1/T

29. The rate constant of a reaction at temperature (b) Eb  E f

200K is 10 times less than the rate constant at
(c) Eb  E f
400 K. What is the activation energy (E a ) of the
reaction (R = gas constant) (d) There is no definite relation between Eb and
[EAMCET 2003] Ef
(a) 1842.4 R (b) 921.2 R
(c) 460.6 R (d) 230.3 R
 Chemical Kinetics 479
36. Temperature dependent equation can be written d ( A) 1 d ( A)
(a)  2 (b) 
as dt 3 dt
[Orrisa JEE 2005] 2 d ( A) 3 d ( A)
(c)  (d) 
(a) ln k  ln A  e Ea / RT
(b) ln k  ln A  e E a / RT 3 dt 2 dt
3. The differential rate law for the reaction
(c) ln k  ln A  e RT / Ea (d) All of these H 2  I2  2 HI is [AIEEE 2002]
d [H 2 ] d [I2 ] 1 d [HI ]
Photochemical reactions (a)   
dt dt 2 dt
d [H 2 ] d [HI ] 1 d [HI ]
1. The formation of starch in plants results from (b)  
dt dt 2 dt
(a) Photosynthesis (b) Photolysis 1 d [H 2 ] 1 d [I2 ] d [HI ]
(c)  
2 dt 2 dt dt
(c) Flash photolysis (d) None of the above
d[H 2 ] d[I2 ] d [HI ]
2. The photolysis of water gives the substance (d)  2  2 
dt dt dt
4. The rate law for a reaction between the
(a) OH   H  (b) H 2  OH 
substances A and B is given by, rate  k[ A]n [B]m .
(c) H 2  O2 (d) H 2 O  H 2 O2 On doubling the concentration of A and halving
the concentration of B, the ratio of the new rate to
3. The law of photochemical equivalence was given by the earlier rate of the reaction will be as [
(a) Drapper (b) Grauths 1
(a) (m  n) (b) (m  n)
2
(c) Einstein (d) Labbert
(c) (n  m ) (d) 2 (n  m )
4. If ‘I’ is the intensity of absorbed light and C is the 1
5. If we plot a graph between log K and by
concentration of AB for the photochemical process T
AB  hv  AB *, the rate of formation of AB* is Arrhenius equation, the slope is [UPSEAT 2001]
directly proportional to [IIT Screening 2001] Ea Ea
(a)  (b) 
R R
(a) C (b) I
Ea Ea
(c)  (d) 
(c) I 2 (d) C.I 2 .303 R 2.303 R
6. For an endothermic reaction, where H
represents the enthalpy of the reaction in kJ / mol ,
the minimum value for the energy of activation
will be [IIT 1992]
(a) Less than H (b) Zero
(c) More than H (d) Equal to H
7. The rate constant (K ) of one reaction is double of
1. For the reaction H 2 (g)  I2 (g) ⇌ 2 HI (g) , the rate of the rate constant (K ) of another reaction. Then
reaction is expressed as[CBSE PMT 1997; AIEEE 2002] the relationship between the corresponding

[I 2 ] [H 2 ] 1 [HI ] activation energies of the two reactions ( Ea and
(a)   
t t 2 t E a  ) will be
[I2 ] [H 2 ] [HI ] [MP PET 1994; UPSEAT 2001]
(b)      
t t 2 t (a) E a  E a (b) E a  E a
[H 2 ] 1 [I 2 ] [HI ] (c) E a   E a  (d) E a   4 E a 
(c)  
t 2 t t 8. The rate constant, the activation energy and the
(d) None of these arrhenius parameter of a chemical reaction at
25 o C are 3 .0  10 4 s 1 , 104 . 4 kJ mol 1 and
d (B )
2. If 3 A  2 B, then the rate of reaction of  is 6 .0  10 14 s 1 respectively. The value of the rate
dt
constant as T   is
equal to [IIT 1996]
[CBSE PMT 2002] (a) 2 .0  10 18 s 1 (b) 6 .0  10 14 s 1
(c) Infinity (d) 3 .6  10 30 s 1
 480 Chemical Kinetics
9. The H value of the reaction H 2  Cl2 ⇌ 2 HCl is 15. For the reaction CH 3 COOCH 3  H 2 O 
H



44 .12 kcal. If E1 is the activation energy of the CH 3 COOH  CH 3 OH The progress of the process of
products, then for the above reaction[EAMCET 1997] reaction is followed by
(a) E1  E2
(a) Finding the amount of methanol formed at
(b) E1  E2 different intervals
(c) E1  E2 (b) Finding the amount of acetic acid formed at
(d) H is not related to E1 and E 2 different intervals
(c) Using a voltmeter
(e) None is correct
10. The temperature dependence of rate constant (k ) (d) Using a polarimeter
of a chemical reaction is written in terms of 16. Half life of a reaction is found to be inversely
proportional to the cube of its initial
Arrhenius equation, K  A.e  E*/ RT . Activation
concentration. The order of reaction is
energy ( E * ) of the reaction can be calculated by
[KCET 2002]
plotting [CBSE PMT 2003]
(a) 2 (b) 5
1
(a) log k vs (b) k vs T (c) 3 (d) 4
log T
17. The integrated rate equation is Rt  log C0  log C t .
1 1
(c) k vs (d) log k vs The straight line graph is obtained by plotting [AIEEE 2002
log T T
1
(a) time v/s logCt (b) v / s Ct
11. Activation energy of a chemical reaction can be time
determined by[CBSE PMT 1998; AFMC 1999; BHU 2000] 1 1
(a) Changing concentration of reactants (c) time v / s C t (d) v/s
time Ct
(b) Evaluating rate constant at standard
18. For which order reaction a straight line is
temperature
obtained along with x–axis by plotting a graph
(c) Evaluating rate constants at two different between half life (t1 / 2 ) and initial concentration 'a'
temperatures
(a) 1 (b) 2
(d) Evaluating velocities of reaction at two
(c) 3 (d) 0
different temperatures
19. The reaction, X  product follows first order
12. The activation energy for a reaction is
kinetics. In 40 minutes the concentration of X
9.0 K cal/mol . The increase in the rate constant
changes from 0.1 M to 0.025 M Then the rate of
when its temperature is increased from 298K to reaction when concentration of X is 0.01 M
308K is [JIPMER 2000]
(a) 1 . 73  10 4 M min 1 (b) 3 . 47  10 5 M min 1
(a) 63% (b) 50%
(c) 100% (d) 10% (c) 3 . 47  10 4 M min 1 (d) 1 . 73  10 5 M min 1
13. Which of the following is the fastest reaction 20. A Substance undergoes first order decomposition.
[Pb. CET 2002] The decomposition follows two parallel first order
1 250 C 1 500 C reactions as
(a) C  O 2   CO (b) C  O 2   CO
2 2 k1 B
1 750 C 1 1000 C
k1= 1.26  10–4 s–
(c) C  O 2   CO (d) C  O 2   CO A 1
2 2 k1= 3.8  10–5 s–1
k2 C
14. The rate constant k, for the reaction N 2 O5 (g) 
1 The percentage distribution of B and C are
0 2 (g) is 2 .3  10 2 s 1 . Which equation
2 NO 2 (g) 
2 [Kerala PMT 2004]
given below describes the change of [ N 2O5 ] with (a) 75% B and 25% C (b) 80% B and 20% C
time? [ N 2 O 5 ]0 and [ N 2 O5 ]t correspond to (c) 60% B and 40% C (d) 90% B and 10% C
concentration of N 2 O 5 initially and at time, t [AIIMS 2004]
(e) 76.83% B and 23.17% C
(a) [N 2O5 ]t  [N 2O5 ]0  kt

(b) [ N 2 O5 ]0  [ N 2 O5 ]t e kt
(c) log10[N 2 O5 ]t  log10[N 2 O5 ]0  kt
[N 2 O5 ]0
(d) In  kt
[N 2 O5 ]t
 Chemical Kinetics 481
Read the assertion and reason carefully to mark the 7. Assertion : The photochemical reactions
correct option out of the options given below : H 2  Cl2  2 HCl and
(a) If both assertion and reason are true and the H 2  Br2  2 HBr have equal quantum
reason is the correct explanation of the assertion. efficiencies.
(b) If both assertion and reason are true but reason is
Reason : Both the reactions proceed by
not the correct explanation of the assertion.
similar mechanism.
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false. 8. Assertion : Vision is not a photochemical
(e) If assertion is false but reason is true. reaction.

Reason : Halogenation of alkenes is a

1. Assertion : Instantaneous rate of reaction is
equal to dx / dt . photochemical reaction.
Reason : It is the rate of reaction at any 9. Assertion : Glow worm shows
particular instant of time. chemiluminescence.
2. Assertion : Molecularity has no meaning for a
complex reaction. Reason : Glow worm emits light due to
Reason : The overall molecularity of a oxidation of protein, luciferin
complex reaction is equal to the present in it.
molecularity of the slowest step. 10. Assertion : The rate of reaction is always
3. Assertion : If in a zero order reaction, the negative.
concentration of the reactant is
Reason : Minus sign used in expressing the
doubled, the half-life period is also
rate shows that concentration of
doubled.
product is decreasing.
Reason : For a zero order reaction, the rate of
11. Assertion : The kinetic of the reaction
reaction is independent of initial
mA  nB  pC  m ' X  n' Y  p ' Z obeys
concentration.
the rate expression as
4. Assertion : If the activation energy of a
dx
reaction is zero, temperature will  k [ A]m [ B]n .
dt
have no effect on the rate constant.
Reason : The rate of the reaction does not
Reason : Lower the activation energy, faster depend upon the concentration of C.
is the reaction.

5. Assertion : According to steady state

hypothesis, in a multistep reaction,
the change in concentration with
time for reactive intermediates is
zero.

Reason : The intermediates are so reactive

that after a brief initial period their
concentrations rise from zero to a
small value and remains constant
for most of the duration of the
reaction.

6. Assertion : Half-life period of a reaction of first

order is independent of initial
concentration.

Reason : Half-life period for a first order

2 .303
reaction t1 / 2  log 2 .
K
 480 Chemical Kinetics
116 d 117 b 118 d 119 a 120 b

121 d 122 b 123 d 124 c 125 d

126 b 127 d 128 d 129 b 130 a

131 ac 132 c 133 d 134 c 135 a

136 a 137 c 138 c 139 d 140 c

Rate of a reaction
141 c 142 c 143 c 144 a 145 c

146 c 147 c 148 b 149 b 150 a

1 b 2 a 3 d 4 b 5 b

6 c 7 c 8 c 9 a 10 b 151 d 152 a 153 d 154 c 155 c

11 b 12 b 13 c 14 d 15 b 156 b 157 a 158 b 159 d 160 c

16 b 17 c 18 b 19 d 20 a 161 b 162 b 163 b 164 abd 165 ad

21 b 22 a 23 d 24 c 25 a 166 b 167 d 168 b 169 d 170 b

26 a 27 a 28 b 29 b 30 b 171 c 172 c 173 c 174 a

31 a 32 c 33 b 34 a 35 c

36 d 37 a 38 b 39 a 40 c Collision theory, Energy of activation

41 a 42 b and Arrhenius equation

Rate law and Rate constant 1 b 2 b 3 b 4 c 5 a

6 d 7 d 8 b 9 c 10 b
1 d 2 c 3 a 4 b 5 a 11 d 12 d 13 a 14 d 15 a
6 a 7 a 8 c 9 b 10 b 16 b 17 d 18 b 19 b 20 a
11 b 12 d 13 a 14 c 15 d 21 c 22 a 23 d 24 b 25 a
16 d 17 c 18 a 19 c 20 c 26 ab 27 c 28 b 29 b 30 c
21 b 22 a 23 a 24 d 25 b 31 b 32 d 33 c 34 c 35 a

26 a 27 a 28 c 29 c 30 d 36 a

31 d 32 c 33 c 34 d 35 b

36 c 37 c 38 a 39 c 40 b Photochemical reaction
41 a 42 d 43 a 44 c 45 c

46 a 47 b 48 b 49 c 50 b 1 a 2 a 3 c 4 b

51 b 52 a 53 a 54 d 55 d
56 c 57 d 58 b 59 b 60 b
Critical Thinking Questions
61 c 62 d 63 c 64 b 65 c
1 a 2 c 3 a 4 d 5 c
66 d 67 b 68 c 69 c 70 b
6 c 7 c 8 b 9 a 10 d
71 d 72 d 73 b 74 b 75 d
11 c 12 a 13 d 14 d 15 b
76 b 77 b 78 c 79 c 80 c
16 d 17 a 18 b 19 c 20 e
81 b 82 b 83 c 84 a 85 a
86 c 87 c 88 a 89 c 90 c
Assertion & Reason
91 b 92 b 93 c 94 b 95 b
96 d 97 b 98 c 99 a 100 c
1 b 2 b 3 b 4 b 5 a
101 b 102 d 103 c 104 c 105 a
6 a 7 d 8 e 9 a 10 d
106 d 107 a 108 b 109 c 110 b
11 a
111 c 112 d 113 b 114 b 115 d
 Chemical Kinetics 481
19. (d) The rate of a reaction depends upon
concentration of reactant.
1 d[ A] d[B] d[C] d (D)
20. (a)     .
3 dt dt dt dt
21. (b) N 2  3H 2 ⇌ 2NH 3

[ N 2 ] 1 [H 2 ] 1 [ NH 3 ]
Rate of a reaction  
t 3 t 2 t
[H 2 ] 3 [ NH 3 ] 3
1. (b) Rate of reaction continuously decreases with      2  10 4
time. t 2 t 2

2. (a) The rate of reaction depends upon conc. of  3  10 4 mol litre 1 sec 1
reactant, surface area of reactant,
temperature, presence of light and catalyst. 22. (a) Increase in concentration of B  5  10 3 mol l 1
3. (d) According to law of mass action. Time  10 sec
4. (b) R  K[RCl ] , if [RCl] =1/2, then rate = R/2. Increase of conc. B
Rate of appearance of B 
Time taken
5. (b) 2  4 , 3  9
2 2

(c) The rate of chemical reaction  The product 5  10 3 mol l 1

6.   5  10 4 mol l 1 Sec 1

of the molar conc. of the reactants (at 10 sec

constant T)
24. (c) The rate of formation of SO 3 is
dx  0 .2  0 .1  0 .1 3
7. (c) Rate of reaction =    10 1 .28  10 g / sec .
dt  10 
K t  10 rt  10
 0 .01 mol dm 3 min 1 26. (a)   2 ; For an increase of
Kt rt
8. (c) As reaction progressing the concentration of temperature to 50 o C , i.e. 5 times, the rate
the reactants decreases and the concentration increases by 2 5 times, i.e. 32 times.
of the product increases.
K t  10 rt  10
 d(N 2 ) 1 d (H 2 ) 1 d ( NH 3 ) 3 28. (b)   2.
9. (a)   =  40  10  3 Kt rt
dt 3 dt 2 dt 2
For an increase of temperature to 20 C i.e. 2
 60  10 3.
times, the rate increase by 2 2 times, i.e. 4
10. (b) Greater are the concentrations of the times.
reactants, faster is the reaction. Conversely,
as the concentrations of the reactants k t  10 rt  10
29. (b)  2
decreases, the rate of reaction also decreases. Kt rt
11. (b) Ionic reactions are very fast reactions i.e. take For an increase of temperature to 90 o C i.e. 9
place instantaneously.
times, the rate increases by 2 9 times i.e. 512.
12. (b) Rate = K( A)2 (B)1 on doubling the active mass 30. (b) Catalyst increases the rate by decreasing the
of A the rate of reaction increase 4 times. activation energy.
13. (c) ‘A’ will disappear at twice the rate at which 31. (a) For 10K rise in temperature, the rate of
‘B’ will decrease. reaction nearly doubles.
1 K 35 o C
14. (d) When volume is reduced to , concentrations K 308 k
4 32. (c) Temperature coefficient   2 and
K 25 o C K 298 k
become four times.
3 for most reactions.
dN 2 1 dH 2 1 dNH 3
16. (b)   33. (b) Catalyst decrease energy of activation.
dt 3 dt 2 dt
dH 2 3 34. (a) Thus both rate and rate constant K increase
  0 .001  0 .0015 kg hr 1 . with temperature, r  k (reactant)n and
dt 2
k  Ae  Ea / RT
dc
18. (b)  refers as decrease in concentration of
dt 35. (c) Enzymes does not always increase activation
the reactant with time. energy.
 482 Chemical Kinetics
36. (d) Catalyst reduce the activation energy for 1 d[B] 5  10 4
reaction and thus increase the rate of    2.5  10 4 mol 1 sec 1
2 dt 2
reaction.
8. (c) For following
37. (a) Catalyst affect only activation energy. It reaction, 2 NO(g)  O 2 (g)  2 NO 2 (g)
brings down the activation energy of reaction.
1
38. (b) As we know that the velocity constant become When the volume of vessel change into
3
double by increasing the temperature by 10°C then concentration of reactant become three
so if at 290 K, velocity constant  3 .2  10 3 times.
then at 300 K, velocity constant The rate of reaction for first order reaction 
3 3
 2(K 290 )  2  3.2  10  6 .4  10 . concentration. So rate of reaction will
increases three times.
39. (a) Higher the value of rate constant so, faster the
9. (b) 2 A  B  Products
reaction rate.
According to question : Rate of reaction of
40. (c) Rate of reaction may increase or decrease
‘A’  [B] as increase in rate is double when [B]
with increase in temperature. If reaction is
is doubled.
exothermic, rate decreases with increasing
Rate of reaction  [A] [B] as increase in rate
temperature while that of endothermic
is 8 times when concentration of both
reactions increase with increasing
reactant is doubled. It means that order of
temperature.
reaction is 3 and overall rate reaction should
41. (a) 2 N 2 O5(g)  4 NO 2(g)  O 2(g)
be r  K[ A]2 [B]
Rate of reaction with respect to NO2
10. (b) Let the rate of reaction depends on xth power
1 d[ NO 2 ] 1 5.2  10 3 of [A]. Then
    1 .3  10 5 ms 1
4 dt 4 100 r1  k [ A] x and r2  k [2 A] x
2.303 90 2
42. (b) In first phase, K  log .....(i) r1 [ A] x 1 1
20 100      ( r2  4 r1 )
r2 [2 A] x 4 2
2.303 81
In second phase K  log .....(ii)  x  2 . As the reaction rate does not depend
t 100
upon the concentration of B. Hence, the
2 .303 90 2 .303 81
From eq. (i) log  log correct rate law will be rate  K[ A]2 [B]o or
20 100 t 100
20 (log 81  log 100 )  K[A]2
t 11. (b) Velocity constant ‘K’ is characteristic constant
(log 90  log 100 )
of a reaction and depends only on
20 (1 . 908  2) 20  (0 .092 )
  = 40 minutes temperature and catalyst.
(1 . 954  2) (0 . 046 )
12. (d) Unit of K for Ist order reaction is Time 1 .
Rate law and Rate constant 13. (a) K  Ae  Ea / RT by this equation it is clear that
rate constant of a reaction depends on
1. (d) Molecularity of the reaction does not temperature
influence the rate of reaction. 2.303 a
14. (c) k  log 10 ;
2. (c) The rate law for an reaction can be given by; t ax
rate = K( A)(B)2 , i.e. the powers are raised t  2  10 2 , a  800 , a  x  50
which are given as coefficient of reactant. 2.303 800 2 .303
3. (a) p 0  500 atm k log10  log10 16
2  10 2
50 2  10 2
2.303 p
K log 10 0 
2 .303
log 10 2 4 
2 .303
 4  0 .301
t pt 2  10 2 2  10 4
2.303 500  1 .38  10 2 s 1
3.38  10  5  log
10  60 pt
15. (d) Rate of reaction is quadrupled on doubling the
500 00 concentration. Thus r  [A]2 .
or 0.00880  log   490 atm
pt 1.02
16. (d) K is not constant for all the reaction.
4. (b) It is a pseudo-unimolecular reaction.
19. (c) Rate determining step is a slow step by which
5. (a) A  2 B  C  D rate of reaction can be determined.
d [ A]
 5  10 4 20. (c) It is a second order reaction and the unit of k
dt for second order reaction is litre mol 1 sec 1 .
 Chemical Kinetics 483
21. (b) For reversible reaction rate constant is also 2.303 V
40. (b) K  log gives constant value of K.
reverse. t V  Vt
22. (a) Rate  K ( N 2 O 5 )  6 .2  10 1  1 .25 With the given date. Hence it is 1st order.
 7 . 75  10 1 mol l 1 s 1 42. (d) r  K[ A]n , 100 r  K[10 A]n
n
23. (a) We know that for first order kinetics 1  1 
Thus    or n = 2
2 .303 a 100  10 
k log
t ax 43. (a) It is a standard example of first order because
1 2 .303 0 .5 in that reaction rate of reaction affected by
(a  x )  0 .05 mol l , 6  log
t 0 .05 only one concentration term.
2 .303 0 .5 2 .303 44. (c) Inversion of cane sugar is a Pseudo
or t  log   0 .384 min unimolecular reaction.
6 0 .05 6
24. (d) Rate = hence 45. (c) For 1st order reaction
K(N 2O5 )
2 . 303 a
2 .4  10 5  3 .0  10 5 ( N 2 O5 ) K log 10
t (a  x )
or (N 2 O5 )  0 . 8 mol l 1 0 .693 0 .693
46. (a) t1 / 2    1117 .7 sec.
25. (b) R  K[A] , 1 .02  10 4
 3 . 4  10 5
, [N 2 O5 ] k 6 .2  10  4
2 .303 a
1 .02  10 4 47. (b) k  log
or (N 2 O5 )  5
,K  3 t ax
3 .4  10
0.693 2.303 100
26. (a) Rate law for the reaction  log
T t 100  30
2 N 2O5  4 NO2  O2
 T  58 .2 min.
is r  k[ N 2 O5 ] first order reaction.
3 3 33 6
28. (c) Rate constant depends on temperature only. 48. (b) Order of reaction =    3
2 2 2 2
29. (c) According to Arhenius concept 49. (c) Two molecules are taking part in elementary
Rate constant K  Ae Ea / RT , Hence rate constant step.
depends only upon temperature of the system. 50. (b) Because two molecules are taking part in
30. (d) For 2 A  B  C elementary step.
51. (b) The overall order of a reaction is sum of
Rate  K[ A][B]
powers T raised on concentration terms in
Value of rate constant K  Ae  Ea / RT here K is order to write rate expression.
independent of the initial concentration of A 52. (a) It is a first order reaction as is clear from rate
and B. law expression, r  k(H 2O2 )
31. (d) The specific rate constant of a first order 53. (a) For Ist order reaction half life is independent
reaction depends upon the temperature of of concentration.
reaction.
1  a  1  35 
32. (c) Unit of K for first order reaction  sec 1 54. (d) K  log e   log e  
t  a  x  15  35  9 
35. (b) The rate of zero order reaction is not depend
1  35 
on the concentration of the reactants.  log e  
36. (c) The unit of K for zero order reaction
15  26 
 mole litre 1 sec 1 . 0 .693 2 .303  100 
56. (c) k   0 .0231 ; t  log 
37. (c) Order of reaction is sum of the power raised 30 k  100  75 
on concentration terms to express rate 2.303
expression. t log 4  60 minutes
0 .0231
38. (a) The concentration of reactant does not change
57. (d) Rate  K (sugar )(H 2 O)o
with time for zero order reaction (unit of K
suggests zero order) since reactant is in a
58. (b) Derive t1 / 2 from K t  2 .303 log
, putting
excess. ax
m
1 1 t
1 a
and x  . Therefore it is
0 .693
39. (c) r  K[ A]m also 2 r  K[4 A] m ,   .
2 4 2 2 K
1 59. (b) r  [X ]2 or r  k [X ]2
m 
2 0 .693 0 .693
60. (b) t1 / 2  ,  6 .3  10 8 sec.
k 1 .1  10 9
 484 Chemical Kinetics
1 3
61. (c) t1 / 2  for II order reaction. 85. (a) The order of reaction is and molecularity is
(a) 2
62. (d) Order of reaction is an experimental value, 2.
while molecularity is a theoretical value. 87. (c) Molecularity can never be fractional.
63. (c) K for 1st order reaction = per unit time i.e. 88. (a) As doubling the initial conc. doubles the rate
of reaction, order = 1.
Time 1 .
89. (c) When B is in excess, it becomes a pseudo-
64. (b) R  K[ A][B]0 so molecularity is two and order unimolecular reaction.
is two. 0.693 0.693
90. (c) k    9.99  10  3  0.01 s 1
65. (c) Rate of zero order reaction is independent of t1 / 2 69 .35
the concentration of the reactant and remains
0 .693 1 2 .303 10
constant throughout the reaction. 91. (b) k  hr  log
24 96 ax
1
66. (d) t1 / 2  10
(a)n 1 or log  1 .2036 or 1 – log (a – x) =
ax
1 1.2036
67. (b) t1 / 2   reaction is of first order.
(Co )n 1 or log( a  x )  0 .2036  1.7964
68. (c) For Ist order reaction half life is independent or (a  x )  antilog 1 .7964  0.6258 gm
of concentration.
92. (b) 0 .08 mol l 1 to 0 .01 mol l 1 involves 3 half-life.
0.693 0.693
69. (c) K  ,K  0.005 min 1 So the t is 30 minutes
t1 / 2 138 .6 min
93. (c) t1 / 2 of II order reaction is inversely

70. (b) CH 3 COOCH 3  H 2 O 
H
 CH 3 COOH CH3OH proportional to initial concentration of
It is a pseudo-unimolecular reaction. reactants.
94. (b) As r  k(H 2O2 ) , it is a reaction of 1st order.
1
71. (d) t1 / 2  and K  t
K 97. (b) r  k (C A )3 / 2 (C B )1 / 2
dx
 K( A)o 3  1 2
73. (b) For zero order reactions Order =      1
dt 2  2 2
74. (b) It is an bimolecular and second order
98. (c) If rate  K( A)m (B)n , then order of reaction
reaction.
 m n .
dx
75. (d)  (HI )2 , then order of reaction = 2 0.693 0.693
dt 99. (a) k    6.93  10  3 sec 1
t1 / 2 100 sec
76. (b) Rate = K (Sucrose )(H 2 O)o
0 .693
100. (c) t1 / 2 
77. (b) Because in this reaction one molecule of N 2 O5 k
is used. 0 .693 0 .693
101. (b) t1 / 2  ,k  1.44  10  3 sec1 .
78. (c) Integrated velocity equation for first order k 480
2 . 303 ( A)o
reaction is: k  log 102. (d) r  k (A)2 , when concentration is doubled
t ( A)
r  k (2 A)2  k 4 ( A)2 the rate becomes 4 times.
2 .303 log 2 0 .693
80. (c) t1 / 2   103 (c) r  K[FeCl 3 ]2 [SnCl 2 ]1 . Order  2  1  3
K K
81. (b) Inversion of sugar is a pseudo-unimolecular 105. (a) t1 / 2 for I order reaction independent of initial
reaction. concentration.
82. (b) For Ist order reaction 107. (a) The rate will be given by slowest step. Thus
kt [ A][ A]
log(a  x )  log a  r  K[ A][B2 ] . Kc  or [ A]  [K c ]1 / 2 [ A2 ]1 / 2
2 .303 [ A2 ]
y  c  mx
r  K  [K c ]1 / 2 [ A2 ]1 / 2 [B2 ]  K[ A2 ]1 / 2 [B] . Thus order
0 .693 0 .693
83. (c) t1 / 2    200 min is 0 .5  1  1 .5
k 3 .46  10  3 108. (b) For Ist order reaction half life is independent
1 moles l 1 of concentration.
84. (a)  (conc.)   moles l 1time 1 for zero
Time Time 110. (b) Rate = K[ A]1 / 2 [B]3 / 2
order reaction. 1 3 4
 O.R.    2
2 2 2
 Chemical Kinetics 485
112. (d) The rate of this photochemical reaction is 2 . 303  a  2 . 303  100 
independent of the concentration, therefore, it 128. (d) k  log ; k  log 
t  a  x  30  100  75 
is zero order reaction.
2 .303  100 
0.693 0.693 k log  Put the value of K
113. (b) t1 / 2    1 hr . t  100  93 .75 
k 0.6932 hr 1
from above equation we get the value of t
114. (b) The unit of rate constant shows that reaction
therefore  t  60 min .
is of first order. For first order reaction, half
life is independent of initial conc. of the 0.693 2.303 a
129. (b) k  min 1  log or
reactant. Thus, 45 t99 .9% a  0.999 a
0 .693 0 .693  60 2 .303  45
t1 / 2  1
  600 sec t99 .9%  log 10 3  448 min  7 .5 hrs
0 .69  10 0 .69  10 1 0 .693
115. (d) Given : Rate constant of the first order 130. (a) Given A(a) = 2.00 m, t = 200 min and a(a-x) =
reaction (K )  3  10 6 per sec and initial 0.15 m we know
concentration [ A]  0.10 M . We know that 2.303 a 2 .303 2.00
k log  log
initial rate constant t ax 200 0.15
K[ A]  3  10 6  0.10  3  10 7 ms 1 . 2 .303
  (0 .301  0 .824 )  1 .29  10  2 min 1
116. (d) It is the characteristic of pseudo-unimolecular 200
reactions. 131. (a,c) The unit for zero order reaction is
117. (b) It is a second order reaction. mol litre 1time 1
118. (d) r  K [reactant] 132. (c) It is a third order reaction because
2
1.0  10 Rate  K[NO] 2 [O 2 ] 1  O.R.  2  1  3
K   0.05
0.2 133. (d) Order of a reaction is decided by relative
0 .693 concentration of reactants.
t1 / 2   13 .86 s
0 .05 134. (c) Unit of rate constant for second order reaction
119. (a) For first order reactions rate is depend on the is mol 1litre time 1
concentration of one reactant.
120. (b) Molecularity of a reaction never become zero 135. (a) R  K[ A]2 [B] order of reaction  2  1  3
or fraction. 136. (a) Units of 1st rate constant order reaction are
121. (d) t 
2.303 a sec 1 and for zero order reaction, these are
log
k ax mol litre 1 sec 1 i.e. M sec 1 .
2 .303 100
t log  600 sec 137. (c) This reaction is bimolecular and first order of
1 .155  10  3 100  50 reaction.
122. (b) Rate = K[ A]3 / 2 [B]1 0 .693
138. (c) t1 / 2  Given t1 / 2  693 sec
3 1 k
 O.R.   (1) 
2 2
0 .693 693  10 3
693  , k ; k  10 3  0 . 001 sec 1 .
123. (d) t1 / 2  (CO ) o
i.e. half life for Ist order is k 693
independent of initial concentration. 139. (d) 2 A  B  C  B
124. (c) 2 NO(g)  Cl2(g)  2 NOCl(g)
Rate = k[ A]2 [B]1
Rate = K[ NO ] [Cl 2 ] ,  O. R.  2  1  3
2 1
 O.R.  2  1  3 and molecularity is 3[2 A  B] .
1 1 1 1
125. (d) 8  10  5     ; 8  10  5  [2  1] 140. (c) In photochemical reactions the rate of
t  0 .5 1  t reaction is independent of the concentration
1 of reacting species.
t  0 .125  10 5  1 .25  10 4 min.
8  10  5 2 .303 a
141. (c) We know that k  log
0 .693  10 2 t ax
126. (b) r  k[reactant ]1 k  also 2 . 303 a 2 . 303
1 10  3  log , 10  3  log 3
t 2a t
0 .693 0 .693 (a  )
t1 / 2    100 min . 3
k 0 .693  10  2
2 .303 2 .303  0 .4771
127. (d) t1 / 2 
1
for second order reactions. 10  3   0 .4771 , t   3300 sec
Ka t 10  3
R'
142. (c) R  K( A)2 , R '  K(2 A)2 ,  4
R
 486 Chemical Kinetics
R' 2 .303  10  log 2 2 .303  10  0 .301
R  K( A)2 , R '  K(3 A)2 , 9    10 years .
R .693 0 .693
2 . 303  a  154. (c) The concentration of the reactants decrease
144. (a) k  log  from 0.8 to 0.4 in 15 min i.e., T1 / 2  15 min,
t ax 
concentration from 0.1m to 0.025 will fall in 2
2 . 303  100  half lives so total time taken
k log  .… (i)
32  100  75   2  T1 / 2  2  15  30 min.
2 . 303  100  155. (c) K 
2.303 100 2.303

100
k log  ….(ii) log log
t  100  50  1 hr 25 t 50
1
from the two equation (i) and (ii),  log 4  log 2
t  16 minutes. t
1 1
146. (c) The relation between half – life period and  2 log 2  log 2 ; t  hr .
initial concentration (c) for a nth order t 2
1 156. (b) x (g)  y(g)  z(g)
reaction is given by t1 / 2  n 1 for first order
C The reaction is a first order reaction hence,
1 0.693 2.303 a 0 .693
reaction (n  1) . t1 / 2  1 1 or t1 / 2  C 0 . K  log 
C t1 / 2 t ax 10 min
2.303 a 0 .693 2 .303
147. (c) R  k [ NO ]2 [O2 ] , R '  k [2 NO ]2 [2 O 2 ]  log   log 10
t a / 10 10 t
R '  k  4[ NO ]2 [O2 ]  k  8[ NO ]2 [O2 ] 2 .303  10
 t  33 min .
.693
R ' k  8[ NO ]2 [O 2 ]
 8 2 .303 a
R k [ NO ]2 [O 2 ] 157. (a) For the first order reaction t  log
K ax
148. (b) For zero order reaction r  k . Given: a  0.5 mol / litre; a  x  0.05 , mol / litre

149. (b) k 
2 .303
log
0 .8
 2 .303 log
4 K  6 sec 1 .
t 0.6 3 2 .303 0.5 2 .303 2.303
t log  log 10   0.384 sec .
2 .303 0 .9 2.303 4 6 0 .05 6 6
t log  log ; t  1 hour.
k 0.675 k 3 158. (b) The radioactive disintegration reactions are of
150. (a) For zero order reaction first order because in this rate of
dx Concentrat ion disintegration depends on the concentration
Velocity constant   term of radioactive material only.
dt Time
 dx 
Unit  concentrat ion  time -1 . 159. (d) Rate    K . c ; 1.5  10 2  K  0.5
 dt 
151. (d) H 2  Br2 ⇌ 2 HBr is a 1.5 order reaction
1.5  10 2
i.e., K  [H 2 ][Br2 ]1 / 2 . For first order K   3  10  2 min ute 1
0.5
152. (a) When in any chemical reaction, one of the .693 .693
reactant is present in large excess, then the t1 / 2    23 .1 min ute .
K 3  10  2
second order reaction becomes first order 2 .303 a
reaction and is known as pseudo unimolecular 160. (c) For first order reaction K  log
t ax
reaction e.g.,
1 1
 Given: a   .1m ; a  x   .01 m ; t = 500
CH 3 COOCH 3  H 2 O 
H
 CH 3 COOH  CH 3 OH 10 100
in this reaction molecularity is 2 but order of sec
reaction is found to be first order 2 .303 .10 2 .303
 K log  log 10
experimentally, so it is an example of pseudo 500 .01 500
unimolecular reaction. 2 .303
  0 .004606  4 .6  10  3 sec1 .
0.693 0 .693 500
153. (d) K  
t1 / 2 10 years 161. (b) For zero order reaction, rate of reaction is
If initial concentration a  10 gm and final independent of concentration R  K[Reactant]0
a 162. (b) The radioactive disintegration reactions are of
concentration x   5 gm first order because in this rate of
2
disintegration depends on the concentration
2 . 303 a 2 .303 10
then, t  log   10  log term of radioactive material only.
K ax .693 5
 Chemical Kinetics 487
1 n n 1
0 . 1 (200 )1  n 1 4  1  However on doubling the concentration of B ,
163. (b) t1 / 2  a1  n        rate of reaction increases two times. Rate  [B]
0 .4 (50 )1  n 4 1  4 
Thus, overall order of reaction = 2 + 1= 3.
1 1
 1
 n 1  n  1  1 ; n  2 . 174. (a) In case of zero order reaction, the
4 4
concentration of reactant decreases linearly
d ln k H o with time, as its rate is independent of the
164. (abd) By Vant’s Hoff equation, 
dt RT 2 concentration of the reactants.
H o
or ln k p    I . Hence (a) is correct (b) is Collision theory, Energy of activation
RT
also correct as plot of log (X) vs time is linear. and Arrhenius equation
(c) is wrong because p  T at constant
volume. (d) is correct by Boyle’s law. 1. (b) The increase in collision frequency brings in
165. (ad) (a) is correct because an increase in effective collisions and thus
rate of reaction increases.
degree of dissociation  1  e kt at any time t.
(b) is wrong because plot of log [A] vs t is a 2. (b) All collisions are not effective and does not
straight line result in the formation of the products
(c) is wrong because time taken for 75% 3. (b) The increase in collision frequency brings in
reaction is two half life. an increase in effective collisions and thus
(d) is correct because in k  Ae  E a / RT , Ea / RT is rate of reaction increases.
4. (c) The increase in collision frequency brings in
dimensionless hence A has the unit of K.
an increase in effective collisions and thus
166. (b) aA  xP
rate of reaction increases.
Rate of reaction = [A]a
5. (a) Slower reaction rate indicates higher energy
Order of reaction = a
of activation.
[A]1 = 2.2 mM, r1 = 2.4 m M s–1 ...(i)
6. (d) Energy of activation decreases, rate of
2 .4
[A]2 = 2.2/2 mM, r1 = 0.6 m M s–1 or, ...(ii) reaction will increases.
4
7. (d) Number of collision depend upon pressure,
On reducing the concentration of A to half, the concentration and temperature.
rate of reaction is decreased by four times.
9. (c) The definition of activation energy.
Rate of reaction = [A]2
10. (b) Activation energy is the energy needed by
Order of reaction = 2.
reactant molecules to gain threshold energy
167. (d) Order of a reaction can be fractional.
level.
2 . 303 1 0 .29
168. (b) t1 / 4  log  . 11. (d) All other are different forms of Arrhenius
K 1 K
1 equation.
4
12. (d) Increase in the rate of reaction is determined
169. (d) R  K[A] by the increase in the number of effective
2  10 5  K  10 2 collisions.
K  2  10 3 sec 1 13. (a) Energy of activation reduced by increasing
temperature.
.693 .693 693
t1 / 2     347 sec 14. (d) The definition of threshold energy.
K 2  10  3 2
n 15. (a) The definition of activation energy.
1 1
170. (b) R  k [B]n ; R  k [2 B]n ; 4    ; 4  2 n ; 16. (b) When the temperature is increased, heat
4 2 energy is supplied which increases the kinetic
n  2 . energy of the reacting molecules. this will
171. (c) T  t1 / 2  n i.e. 12  3  n  n  4 increase the number of collisions and
n 4 ultimately the rate of reaction will be
1 N 1 1 enhanced.
N  N0      
 
2 N 0  
2 16 17. (d) In exothermic and endothermic reactions will
172. (c) K  1.7  10 s 5 1 be more and less than Ea respectively.
0 .693 0 .693 19. (b) The value of activation energy for a chemical
t1 / 2    10 5  11 .32 h reaction primarily dependent on the nature of
K 1.7
reacting species.
173. (c) A  B  C
E
On doubling the concentration of A rate of 20. (a) Arrhenius equation is log k  log A  a
RT
reaction increases by four times. Rate  [A]2
 488 Chemical Kinetics
1 4. (b) In photochemical reaction the rate of
22. (a) A graph plotted between log k vs for
T formation of product is directly proportional
calculating activation energy. to the intensity of absorbed light.
24. (b) When Ea  0 rate constant is independent of
temperature. Critical Thinking Questions
25. (a) It is modified form of Arrhenius equation.
1 1. (a) For the given reaction :
28. (b) A graph plotted between log k Vs for
T [I2 ] [H 2 ] 1 [HI ]
  
calculating activation energy is shown as t t 2 t
from Arrhenius equation 1 d [ A ] 1 d [ B] d[B] 2 d[ A]
log k 2. (c)    
EA 3 dt 2 dt dt 3 dt
log k  log A  1/T
2.303 RT 3. (a) Concentration of reactants decreases while
30. (c) It is Arrhenius equation. concentration of product increases.
K2 Ea 1 1  4. (d) R  K( A)n (B)m
31. (b) log    
K1 2 .303 R  1
T T2  m
B
K2 R '  K(2 A)n    K( A)n 2n (B)m 2 m
If 2 2
K1
R ' K( A)n (B)m 2n m
Ea  1 1   K( A)n (B)m 2n m ,   2n m
log 2   K( A)n (B)m
2.303  8.314  300 310 
R

 300  310  Ea
E a  .3010  2 .303  8 . 314  5. (c) ln K  ln 
is Arrhenius equation. Thus
 RT
 10 
plots of ln K vs 1/T will give slope   Ea / RT
1
 53598 .59 Jmol  54 kJ . or  Ea / 2.303 R .
32. (d) When Ea  0 , the rate of reaction becomes
6. (c) For a reaction E a for forward reaction  Ea
independent of temperature.
for backward reaction + H .
(Ea = Energy of activation).
7. (c) As K '  K ", Ea'  Ea" (Greater the rate constant,
33. (c) When k increases, rate of reaction also less is the activation energy).
pz
increases, k  E / RT for k to increase p, z, T 8. (b) T2  T (say ), T  25 o C  298 K ,
e
should increase and E should decrease. Ea  104 .4 kJ mol 1  104 .4  10 3 J mol 1
( e  2.7 ). K1  3  10 4 , K 2  ,
34. (c) Endothermic reactions are those which K2 Ea 1 1
involve absorption of heat. High activation log    
energy means potential energy of product
K1 2 .303 R  T1 T2 
must be much greater than reactants. K2 104 . 4  10 3 J mol 1
log 4

35. (a) For endothermic reaction H = +ve 3  10 2 . 303  (8 . 314 J k 1 mol 1 )
Then from equation  1 1 1
H  EaF. R.  EaB. R. ; E B. R.  E F. R.  298 K  T  As T  , T  0
 

36. (a) Arrhenius suggested an equation which K2 104 .4  10 3 J mol 1

 log 4

describes rate constant (K) as a function of 3  10 2.303  8 .314  298
temperature. K2 K2
log  18 .297 ,  1 .98  10 18 or
K  Ae  Ea / RT 3  10  4 3  10  4
K 2  (1 .98  10 18 )  (3  10 4 )  6  10 14 s 1
ln K  ln A  e Ea / RT
9. (a) Because reaction is exothermic
Photochemical reactions 10. (d) k  Ae  E
0
/ RT
log K  log A  E o / RT  log K Vs
1
.
y c mx T
2. (a) H 2 O 
 OH  H
Photolysis  
K2 Ea  T2  T1 
11. (c) log   
K1 2 .303 R  T1T2 
3. (c) Stark - Einstein was given the law of
photochemical equivalence.
 Chemical Kinetics 489
K 2 Ea  T2  T1  1. (b) Instantaneous rate of a reaction is equal to
12. (a) 2 .303 log    small change in concentration (dx ) during a
K1 R  T1T2 
small interval of time (dt ) at that particular
K2 9 . 0  10 3  308  298 
log  instent of time divided by the time interval.
K1 2 . 303  2  308  298  2. (b) Molecularity of a reaction can be defined only
K2 1.63 K 1  K 1 for an elementary reaction because complex
 1.63 ; K 2  1.63 K1 ;  100  63 .0%
K1 K1 reaction does not take place in one single step
and it is almost impossible for all the total
13. (d) Combustion is an exothermic process, which
molecules of the reactants to be in a state of
is expected to be favoured by low
encounter simultaneously.
temperature, but it is not true. Combustion
3. (b) For a zero order reaction, t1 / 2  [ A0 ] / 2 K .
include burning of particles which takes place
at higher temperature. Thus at high 4. (b) According to Arrhenius equation,
temperature due to combustion of more K  Ae  Ea / RT when Ea  0, K  A .
particles, the reaction proceeds at higher rate.
2 . 303 a
14. (d) Rate constant  2 .3  10 2 sec 1 6. (a) For a first order reaction, K  log ,
t ax
It means it is a first order reaction (because where a is initial concentration, and x is the
unit of rate constant is sec–1) amount reacted in time t. For half-life
For first order reaction K  ln
1 a x  a / 2 , t  t1 / 2
t ax 2.303 a
a [ N 2 O5 ]0 K log
Kt  ln  ln K aa/2
ax [ N 2 O5 ]t 2 . 303 0 . 693
t1 / 2  log 2  .
15. (b) Because as reaction progresses the amount of K K
acetic acid increases. 7. (d) H 2  Cl2  2 HCl has much higher quantum
16. (d) Half life of a reaction is found to be inversely
efficiency than H 2  Br2  2 HBr . The first step
proportional to the cube of initial
concentration. The order of reaction is 4. of secondary process of H 2  Cl2  2 HCl is
17. (a) It is similar to y  mx  c exothermic while the same for
H 2  Br2  2 HBr is endothermic.
18. (b) r  K[ A] , 100 r  K[10 A]
n n

n
8. (e) Vision is a fast photochemical reaction in
1  1  which the compound, retinal, present in the
Thus    or n = 2
100  10  eye undergoes isomerisation by absorbing a
19. (c) Concentration will fall from 0.1 M photon of light.
concentration to 0.025 M concentration 9. (a) The emission of cold light during a chemical
within 2 half lives. reaction is called chemiluminescence.
2  T1 / 2  40 min 10. (d) The rate reaction is never negative. Minus
sign used in expressing the rate only shows
 T1 / 2  20 min that the concentration of the reactant is
0 .693 decreasing.
Rate of reaction = K . c  .c
T1 / 2 dx
11. (a) Rate expression  K [ A]m [ B]n
0.693 dt
  10  2 M / min  3.47  10 4 M / min 1 . Shows that the total order of reactions is
20
m  n  O  m  n as the rate of reaction is
K1
20. (e) % distribution of B   100 independent of concentration of C, i.e. the
K1  K 2 order with respect to C is zero. This is the
1.26  10 4 reason that C does not figure in the rate
  100 expression.
1.26  10  4  3.8  10  4
B%  76 .83 %
K2
%Distribution of C   100
K1  K 2
3.8  10 4
  100
1.26  10  4  3.8  10  4
C%  23 .17 %

Assertion and Reason

 Chemical Kinetics 489

1. The temperature coefficient of most of the (c) Nuclear energy

reactions lies between [MP PET 1999] (d) Activation energy
(a) 1 and 3 (b) 2 and 3 6. The minimum energy necessary to permit a
(c) 1 and 4 (d) 2 and 4 reaction is

2. The influence of temperature on the rate of [NCERT 1989]

reaction can be found out by [AFMC 2001] (a) Internal energy
(a) Clapeyron–Claussius equation (b) Threshold energy
(b) Gibbs–Helmholtz equation (c) Activation energy
(c) Arrhenius equation (d) Free energy
(d) Vander Waal's equation 7. The formation of gas at the surface of tungsten
3. The mechanism for the reaction is given below due to adsorption is the reaction of order[AIEEE 2002]
2P  Q  S  T (a) 0
P  Q  R  S (slow) (b) 1
P  R  T (fast) (c) 2
The rate law expression for the reaction is (d) insufficient data
[Kurukshetra CEE 2002] 8. The time of completion of 90% of a first order
(a) r  k[P] [Q]
2
(b) r  k [P][Q] reaction is approximately [

(a) 1.1 times that of half life

(c) r  k [ A][R] (d) r  k [P]2
(b) 2.2 times that of half life
4. Consider the following energy profile for the
reaction. X  Y  R  S . Which of the following (c) 3.3 times that of half life
deductions about the reaction is not correct (d) 4.4 times that of half life
100
80 9. In a photochemical reaction, the ratio of number
60
of dissociate molecules and number of quanta of
40
20 x+y
absorbed energy is called
0
Reaction (a) Einstein
Pathway
(a) The energy of activation for the backward (b) Quantum efficiency
reaction is 80 kJ
(c) Quantum constant
(b) The forward reaction is endothermic
(d) Planck constant
(c) H for the forward reaction is 20 kJ
10. A reaction rate constant is given by
(d) The energy of activation for the forward
k  1 .2  10 14 e (25000 / RT )
sec 1
reaction is 60 kJ
It means [MP PET 1995]
5. The minimum energy required for molecules to
enter into the reaction is called (a) log k versus log T will give a straight line with
[KCET 1986; EAMCET 1992; MP PMT 1993; MP PET 1994] slope as – 25000
(a) Potential energy (b) log k versus T will give a straight line with
(b) Kinetic energy slope as – 25000
 490 Chemical Kinetics
(c) log k versus log 1 / T will give a straight line (d) log k versus 1 / T will give a straight line
with slope as – 25000

(SET -11)

K 35 o C 7. (a) The order of reaction for the formation of gas

1. (b) Temperature coefficient = = between 2
K 25 o C at the surface of tungsten due to adsorption is
zero .
and 3.
8. (c) For a first order reaction
2. (c) Arrihenius equation is : K  Ae  E a / RT 2 . 303 a
K log
3. (b) The rate law expression for the reaction is t (a  x )
r  k [P][Q] . 2 . 303  t1 / 2
2 . 303 100 100
t log   log
4. (a) Ea of backward reaction  80  40  40 kJ k (100  90 ) 0 . 593 10

Hence (a) statement is wrong.

 3.3  t1 / 2  log 10  3.3 t1 / 2

5. (d) The energy necessary for molecules to 9. (b) It is also known as Quantum yield and indicated
undergoes chemical reaction is known as by  .
Activation energy. 10. (d) According to the Arrihenius equation a
6. (b) Molecules undergoing reaction should cross straight line is to be `obtained by plotting the
over the minimum energy barrier or energy logarithm of the rate constant of a chemical
level known as threshold energy. reaction (log K) against 1/T.

***

Electrochemistry is the branch of physical
chemistry which deals with the relationship between
electrical energy and chemical changes taking place in
redox reactions
Electrolytes and Electrolysis
(1) Definition : “The substances whose aqueous
solution undergo decomposition into ions when electric
current is passed through them are known as
electrolytes and the whole process is known as
electrolysis or electrolytic decomposition.”
Solutions of acids, bases, salts in water and fused
salts etc. are the examples of electrolytes. Electrolytes
may be weak or strong. Solutions of cane sugar,
glycerine, alcohol etc., are examples of non-
electrolytes.
(2) Electrolytic cell or Voltameter : The device
in which the process of electrolysis or electrolytic
decomposition is carried out is known as electrolytic
cell or voltameter.
(i) Voltameter convert electrical energy into
chemical energy.
(ii) The electrode on which oxidation takes place
is called anode (or +ve pole) and the electrode on
which reduction takes place is called cathode (or –ve
pole)
(iii) During electrolysis in voltameter cations are
discharged on cathode and anions on anode.
Electrochemistry 491
Flow of electrons
Anode Cathod
Flow of e
current
Chapter
12
Electrochemistry
(iv) In voltameter, outside the electrolyte
electrons flow from anode to cathode and current flow
from cathode to anode.
For voltameter, E cell  ve and ΔG   ve.
(v) The anions on reaching the anode give up
their electrons and converted into the neutral atoms.
At anode : A–  A  e  (Oxidation)
(vi) On the other hand cations on reaching the
cathode take up electrons supplied by battery and
converted to the neutral atoms.
At cathode : B  e   B (Reduction)
This overall change is known as primary change
and products formed is known as primary products.
The primary products may be collected as such or
they undergo further change to form molecules or
compounds. These are called secondary products and
the change is known as secondary change.
(3) Preferential discharge theory : According to
this theory “If more than one type of ion is attracted
towards a particular electrode, then the ion is discharged
one which requires least energy or ions with lower
discharge potential or which occur low in the
electrochemical series”.
The potential at which the ion is discharged or
deposited on the appropriate electrode is termed the
 492 Electrochemistry
discharge or deposition potential, (D.P.). The values of For cations : Li  , K  , Na , Ca 2  , Mg 2  , Al 3  , Zn 2  ,
discharge potential are different for different ions.
Fe 2 , Ni2  , H  , Cu 2  , Hg 2  , Ag  , Au 3  .
The decreasing order of discharge potential or the
increasing order of deposition of some of the ions is For anions : SO 42  , NO 3 , OH  , Cl  , Br  , I  .
given below,

Table : 12.1 Products of electrolysis of some electrolytes

Electrolyte Electrode Product at cathode Product at anode

 
Aqueous NaOH Pt or Graphite 2 H  2e  H 2 2OH  
1
O 2  H 2 O  2e 
2
Fused NaOH Pt or Graphite Na  e   Na 2OH  
1
O2  H 2 O  2 e 
2
Aqueous NaCl Pt or Graphite 2 H   2e   H 2 2Cl   Cl 2  2e 
Fused NaCl Pt or Graphite Na  e   Na 2Cl   Cl 2  2e 
Aqueous CuSO4 Pt or Graphite Cu 2  2e   Cu 2OH  
1
O 2  H 2 O  2e 
2
Aqueous CuSO4 Cu electrode Cu 2  2e   Cu Cu oxidised to Cu 2  ions
Dilute H2SO4 Pt electrode 2 H   2e   H 2 2OH  
1
O2  H 2 O  2e 
2
Conc. H2SO4 Pt electrode 2 H   2e   H 2 Peroxodisulphuric
acid (H 2 S 2O8 )
Aqueous AgNO3 Pt electrode Ag   e   Ag 2OH  
1
O2  H 2 O  2e 
2
Aqueous AgNO3 Ag electrode Ag   e   Ag Ag oxidised to Ag  ions
(4) Application of electrolysis : Electrolysis has electroplati
wide applications in industries. Some of the important ng
applications are, as follows, With copper Cu Object CuSO 4  dilute H 2 SO 4
(i) Production of hydrogen by electrolysis of
With silver Ag Object K[ Ag(CN )2 ]
water.
(ii) Manufacture of heavy water (D2O) . With nickel Ni Object Nickel
ammonium
(iii) The metals like Na , K, Mg, Al, etc., are
sulphate
obtained by electrolysis of fused electrolytes.
With gold Au Object K[ Au(CN )2 ]
(iv) Non-metals like hydrogen, fluorine, chlorine
are obtained by electrolysis. With zinc Zn Iron ZnSO 4
(v) In this method pure metal is deposited at objects
cathode from a solution containing the metal ions With tin Sn Iron SnSO 4
Ag, Cu etc. objects
(vi) Compounds like NaOH, KOH, Thickness of coated layer : Let the dimensions of
Na2CO3 , KClO3 , white lead, KMnO4 etc. are synthesised metal sheet to be coated be (a cm  b cm).
by electrosynthesis method. Thickness of coated layer  c cm
(vii) Electroplating : The process of coating an
Volume of coated layer  (a  b  c) cm 3
inferior metal with a superior metal by electrolysis is
known as electroplating. The aim of electroplating is, to Mass of the deposited substance  Volume  density
prevent the inferior metal from corrosion and to make  (a  b  c)  dg
it more attractive in appearance. The object to be It E
 (a  b  c)  d 
plated is made the cathode of an electrolytic cell that 96500
contains a solution of ions of the metal to be deposited. Using above relation we may calculate the
thickness of coated layer.
For Anode Cathode Electrolyte

Faraday's laws of electrolysis
The laws, which govern the deposition of
substances (In the form of ions) on electrodes during
the process of electrolysis, is called Faraday's laws of
electrolysis. These laws given by Michael Faraday in
1833.
(1) Faraday's first law : It states that,
“The mass of any substance deposited or liberated
at any electrode is directly proportional to the quantity
of electricity passed.”i.e., W  Q
Where,
W = Mass of ions liberated in gm,
Q  Quantity of electricity passed in Coulombs
= Current in Amperes (I) × Time in second (t)
 W  I  t or W  Z  I  t
In case current efficiency () is given, then
 If in any reaction, n moles of electrons are
W  ZIt
100
where, Z  constant, known as electrochemical
equivalent (ECE) of the ion deposited.
When a current of 1 Ampere is passed for 1 second
(i.e., Q  1 ), then, W  Z
Thus, electrochemical equivalent (ECE) may be
defined as “the mass of the ion deposited by passing a
current of one Ampere for one second (i.e., by passing
Coulomb of electricity)”. It's unit is gram per coulomb.
Coulomb is the unit of electrical charge.
96500 Coulombs  6 .023  10 23 electrons = 1 mole
electrons.
6.023  10 23
1 Coulomb   6.28  10 18 electrons,
96500
or 1 electronic charge  1 .6  10 19 Coulomb.
(2) Faraday's second law : It states that,
“When the same quantity of electricity is passed
through different electrolytes, the masses of different
ions liberated at the electrodes are directly proportional
to their chemical equivalents (Equivalent weights).” i.e.,
W1 E Z1 It E1 Z1 E
 1 or  or  1 ( W  ZIt)
W2 E2 Z2 It E2 Z2 E2
Thus the electrochemical equivalent (Z) of an
element is directly proportional to its equivalent
weight (E), i.e.,
E  Z or E  FZ or E  96500  Z
Electrochemistry 493
(3) Faraday's law for gaseous electrolytic product
For the gases, we use
It Ve
V
96500
where, V  Volume of gas evolved at S.T.P. at an
electrode
Ve  Equivalent volume = Volume of gas evolved at
an electrode at S.T.P. by 1 Faraday charge
(4) Quantitative aspects of electrolysis : We know
that, one Faraday (1F) of electricity is equal to the
charge carried by one mole (6.023  10 23 ) of electrons.
So, in any reaction, if one mole of electrons are
involved, then that reaction would consume or produce
1F of electricity. Since 1F is equal to 96,500 Coulombs,
hence 96,500 Coulombs of electricity would cause a
reaction involving one mole of electrons.
involved, then the total electricity (Q ) involved in the
reaction is given by, Q  nF  n  96 ,500 C
Thus, the amount of electricity involved in any
reaction is related to,
(i) The number of moles of electrons involved in
the reaction,
(ii) The amount of any substance involved in the
reaction.
Therefore, 1 Faraday or 96,500 C or 1 mole of
electrons will reduce,
(a) 1 mole of monovalent cation,(b) 1/2mole of
divalent cation,
(c) 1/3 mole of trivalent cation, (d) 1/n mole of n
valent cations.
Metallic and Electrolytic conductors
All substances do not conduct electrical current.
The substances, which allow the passage of electric
current, are called conductors. The best metal
conductors are such as copper, silver, tin, etc. On the
other hand, the substances, which do not allow the
passage of electric current through them, are called
non-conductors or insulators. Some common examples
of insulators are rubber, wood, wax, etc.
The conductors are broadly classified into two
types,
Metallic and electrolytic conductors.

where, F  Faraday constant  96500 C mol 1 Metallic conduction Electrolytic conduction

So, 1 Faraday = 1F =Electrical charge carried out (i) It is due to the flow of (i) It is due to the flow of
electrons. ions.
by one mole of electrons.
(ii) It is not accompanied by (ii) It is accompanied by
1F = Charge on an electron × Avogadro's number. decomposition of the decomposition of the
1F = e   N  (1.602  10 19 c)  (6.023  10 23 mol 1 ). substance.(Only physical substance. (Physical as
changes occurs) well as chemical change
Number of electrons passed occur)
Number of Faraday 
6.023  10 23 (iii) It does not involve (iii) It involves transfer of
 494 Electrochemistry
transfer of matter. matter in the form of ions. Thus, resistivity is defined as the resistance of a
(iv) Conductivity decreases (iv) Conductivity increases conductor of 1 cm length and having area of cross-
with increase in temperature. with increases in
section equal to 1 cm 2 .
temperature and degree of
hydration due to decreases Units : The units of resistivity are
in viscosity of medium. 2
a cm
  R.  Ohm  Ohm. cm
The electrolyte may, therefore, be defined as the l cm
substance whose aqueous solution or fused state Its SI units are Ohm metre ( m). But quite often
conduct electricity accompanied by chemical
Ohm centimetre ( cm) is also used.
decomposition. The conduction of current through
electrolyte is due to the movement of ions. (4) Conductance : It is a measure of the ease with
On the contrary, substances, which in the form of which current flows through a conductor. It is an
their solutions or in their molten state do not conduct additive property. It is expressed as G. It is reciprocal
electricity, are called non-electrolytes. of the resistance, i.e.,
Electrolytic conduction G
1
When a voltage is applied to the electrodes dipped R
into an electrolytic solution, ions of the electrolyte Units : The units of conductance are reciprocal
move and, therefore, electric current flows through the Ohm (ohm 1 ) or mho. Ohm is also abbreviated as  so
electrolytic solution. The power of the electrolytes to
that Ohm 1 may be written as  1 .
conduct electric current is termed conductance or
According to SI system, the units of electrical
conductivity.
(1) Ohm's law : This law states that the current conductance is Siemens, S (i.e., 1S  1  1 ).
flowing through a conductor is directly proportional to (5) Conductivity : The inverse of resistivity is
the potential difference across it, i.e., I  V called conductivity (or specific conductance). It is
where I is the current strength (In Amperes) and V represented by the symbol,  (Greek kappa). The
is the potential difference applied across the conductor IUPAC has recommended the use of term conductivity
(In Volts) over specific conductance. It may be defined as, the
V conductance of a solution of 1 cm length and having 1 sq.
or I  or V  IR
R cm as the area of cross-section. In other words,
where R is the constant of proportionality and is conductivity is the conductance of one centimetre cube of
known as resistance of the conductor. It is expressed in a solution of an electrolyte.
Ohm's and is represented as . The above equation is 1
known as Ohm's law. Ohm's law may also be stated as, Thus,  

“the strength of current flowing through a
conductor is directly proportional to the potential Units : The units of conductivity are
difference applied across the conductor and inversely 1
  Ohm 1 cm–1 or  1 cm 1
proportional to the resistance of the conductor.” Ohm . cm
(2) Resistance : It measures the obstruction to
In SI units, l is expressed in m area of cross-
the flow of current. The resistance of any conductor is
directly proportional to the length (l) and inversely section in m 2 so that the units of conductivity are
proportional to the area of cross-section (a) so that S m 1 .
l l (6) Molar conductivity or molar conductance :
R or R  ρ
a a Molar conductivity is defined as the conducting power
where  (rho) is the constant of proportionality of all the ions produced by dissolving one mole of an
and is called specific resistance or resistivity. The electrolyte in solution.
resistance depends upon the nature of the material. It is denoted by  (lambda). Molar conductance is
Units : The unit of resistance is ohm (). In terms related to specific conductance (  ) as,

of SI, base unit is equal to (kgm 2 ) / (s 3 A 2 ). 


M
(3) Resistivity or specific resistance : We know
that resistance R is where, M is the molar concentration.
l If M is in the units of molarity i.e., moles per litre
R ; Now, if l  1 cm , a  1 cm 2 then R   1
a (mol L ), the  may be expressed as,
 Electrochemistry 495
  1000 determination of the conductance of a solution involves

M the measurement of its resistance.
For the solution containing 1 gm mole of (ii) Calculation of conductivity : We have seen
electrolyte placed between two parallel electrodes of 1 that conductivity () is reciprocal of resistivity (  ) , i.e.,
sq. cm area of cross-section and one cm apart, 1 a
 and   R
Conductance(G)  Conductivity  Molar conductivity()  l
But if solution contains 1 gm mole of the 1l l
electrolyte therefore, the measured conductance will be      or   G 
R a a
the molar conductivity. Thus,
where G is the conductance of the cell, l is the
Molar conductivi ty()  100  Conductivi ty
distance of separation of two electrodes having cross
In other words, ()    V section area a cm 2 .
where V is the volume of the solution in
l
cm 3 containing one gram mole of the electrolyte. The quantity   is called cell constant and is
a
If M is the concentration of the solution in mole per
expressed in cm 1 . Knowing the value of cell constant
litre, then
and conductance of the solution, the specific
M mole of electrolyte is present in 1000 cm 3 conductance can be calculated as,
1000   G  Cell constant
1 mole of electrolyte is present in  cm 3 of
M i.e., Conductivi ty  Conductanc e  Cell constant
solution
Factors affecting the electrolytic conductance
Thus,     Volume in cm 3 containing 1 mole of
electrolyte. In general, conductance of an electrolyte depends
upon the following factors,
  1000
or  
M (1) Nature of electrolyte : The conductance of an
Units of Molar Conductance : The units of molar electrolyte depends upon the number of ions present in
conductance can be derived from the formula , the solution. Therefore, the greater the number of ions
in the solution the greater is the conductance. The
  1000
 number of ions produced by an electrolyte depends
M
upon its nature. The strong electrolytes dissociate
The units of  are S cm 1 and units of  are, almost completely into ions in solutions and, therefore,
cm 3 their solutions have high conductance. On the other
Λ  S cm 1   S cm 2 mol 1  S cm 2mol 1
mol hand, weak electrolytes, dissociate to only small
According to SI system, molar conductance is extents and give lesser number of ions. Therefore, the
expressed as S m 2mol 1 , if concentration is expressed as solutions of weak electrolytes have low conductance.
mol m 3 . (2) Concentration of the solution : The molar
(7) Equivalent conductivity : It is defined as the conductance of electrolytic solution varies with the
conducting power of all the ions produced by dissolving concentration of the electrolyte. In general, the molar
one gram equivalent of an electrolyte in solution. conductance of an electrolyte increases with decrease
It is expressed as  e and is related to specific in concentration or increase in dilution.
conductance as The molar conductance of strong electrolyte
  1000 1000 ( HCl, KCl, KNO3 ) as well as weak electrolytes
e    (M is Molarity of the
C M ( CH 3 COOH , NH 4 OH ) increase with decrease in
solution)
where C is the concentration in gram equivalent concentration or increase in dilution. The variation is
per litre (or Normality). This term has earlier been however different for strong and weak electrolytes.
quite frequently used. Now it is replaced by molar The variation of molar conductance with
conductance. The units of equivalent conductance are concentration can be explained on the basis of
Ohm 1 cm 2 (gm equiv )1 . conducting ability of ions for weak and strong
(8) Experimental measurement of conductance electrolytes.
(i) The conductance of a solution is reciprocal of For weak electrolytes the variation of  with
the resistance, therefore, the experimental dilution can be explained on the bases of number of
ions in solution. The number of ions furnished by an
 496 Electrochemistry
electrolyte in solution depends upon the degree of
dissociation with dilution. With the increase in
dilution, the degree of dissociation increases and as a
result molar conductance increases. The limiting value
of molar conductance (0 ) corresponds to degree of
dissociation equal to 1 i.e., the whole of the electrolyte
dissociates.
Thus, the degree of dissociation can be calculated
at any concentration as,

c transference number or Hittorf number may be denoted

0
where  is the degree of dissociation,
c is the molar conductance at concentration C
and
0 is the molar conductance at infinite dilution.
For strong electrolytes, there is no increase in
the number of ions with dilution because strong
electrolytes are completely ionised in solution at all
concentrations (By definition). However, in
concentrated solutions of strong electrolytes there are
strong forces of attraction between the ions of opposite
charges called inter-ionic forces. Due to these inter-
ionic forces the conducting ability of the ions is less in
concentrated solutions. With dilution, the ions become
far apart from one another and inter-ionic forces
decrease. As a result, molar conductivity increases with
dilution. When the concentration of the solution
becomes very-very low, the inter-ionic attractions
become negligible and the molar conductance
approaches the limiting value called molar conductance
at infinite dilution. This value is characteristic of each
electrolyte.
(3) Temperature : The conductivity of an
electrolyte depends upon the temperature. With
increase in temperature, the conductivity of an
electrolyte increases.
Migration of ions
Electricity is carried out through the solution of
an electrolyte by migration of ions. Therefore,
(1) Ions move toward oppositely charged
electrodes at different speeds.
(2) During electrolysis, ions are discharged or
liberated in equivalent amounts at the two electrodes,
no matter what their relative speed is.
(3) Concentration of the electrolyte changes
around the electrode due to difference in the speed of
the ions.
(4) Loss of concentration around any electrode is
proportional to the speed of the ion that moves away
from the electrode, so
Loss around anode Speed of cation

Loss around cathode Speed of anion
The relation is valid only when the discharged ions
do not react with atoms of the electrodes. But when the
ions combine with the material of the electrode, the
concentration around the electrode shows an increase.
Transport number or Transference number
(1) Definition : “The fraction of the total current
carried by an ion is known as transport number,
by sets symbols like t+ and t– or tc and ta or nc and na”.
From this definition,
Current carried by an anion
ta 
Total current passed through the solution
Current carried by a cation
tc 
Total current passed through the solution
evidently, ta  tc  1.
(2) Determination of transport number :
Transport number can be determined by Hittorf's
method, moving boundary method, emf method and
from ionic mobility.
(3) Factors affecting transport number
A rise in temperature tends to bring the transport
number of cation and anion more closer to 0.5
(4) Transport number and Ionic mobility : Ionic
mobility or Ionic conductance is the conductivity of a
solution containing 1 g ion, at infinite dilution, when
two sufficiently large electrodes are placed 1 cm apart.
Ionic mobilities (a or c )  speeds of ions (uaor uc )
Unit of ionic mobility is Ohm–1 cm2 or V–1S-1cm2
Ionic mobility and transport number are related
as,
a orc  ta or tc  
Absolute ionic mobility is the mobility with which
the ion moves under unit potential gradient. It's unit is
cm sec 1 .
Ionic mobility
Absolute ionic mobility 
96,500
Kohlrausch's law
(1) Kohlrausch law states that, “At time infinite
dilution, the molar conductivity of an electrolyte can be
expressed as the sum of the contributions from its
individual ions” i.e., m         , where,   and
  are the number of cations and anions per formula
unit of electrolyte respectively and,   and   are the
molar conductivities of the cation and anion at infinite
dilution respectively. The use of above equation in
 Electrochemistry 497
expressing the molar conductivity of an electrolyte is We know, that at any concentration C, the degree
illustrated as, of ionisation ( ) is given by,   cm / m
The molar conductivity of HCl at infinite dilution
C(cm / m ) 2 C(cm ) 2
can be expressed as, Then, K  ; Thus,
[1  (cm / m )] m (m  cm )
HCl   H  H    Cl  Cl  ; For HCl, H  1 and
knowing m and cm at any concentration, the
 Cl   1 . So, HCl  (1  H  )  (1  Cl  ) ; Hence, ionisation constant (K) of the electrolyte can be
HCl  H   Cl  determined.
(iv) Determination of the solubility of a
(2) Applications of Kohlrausch's law : Some
sparingly soluble salt : The solubility of a sparingly
typical applications of the Kohlrausch's law are described
soluble salt in a solvent is quite low. Even a saturated
below,
solution of such a salt is so dilute that it can be
(i) Determination of m for weak electrolytes : assumed to be at infinite dilution. Then, the molar
The molar conductivity of a weak electrolyte at infinite conductivity of a sparingly soluble salt at infinite
dilution (m ) cannot be determined by extrapolation dilution (m ) can be obtained from the relationship,

method. However, m values for weak electrolytes can
be determined by using the Kohlrausch's equation.
CH 3 COOH  CH 3 COONa  HCl  NaCl
(ii) Determination of the degree of ionisation of
a weak electrolyte : The Kohlrausch's law can be used
for determining the degree of ionisation of a weak
electrolyte at any concentration. If
m        ........(i)
The conductivity of the saturated solution of the
sparingly soluble salt is measured. From this, the
conductivity of the salt ( salt) can be obtained by using
the relationship,  salt   sol   water , where,  water is the
conductivity of the water used in the preparation of the
 cm is the molar saturated solution of the salt.

conductivity of a weak electrolyte at any concentration 1000  salt

salt  ........(ii)
C and,  m is the molar conductivity of a electrolyte at Cm
infinite dilution. Then, the degree of ionisation is given From equation (i) and (ii) ;
c cm
by,  c  m  1000  salt
 m (       )

Cm  , Cm is the molar concentration
(       )
Thus, knowing the value of cm , and m (From of the sparingly soluble salt in its saturated solution.
the Kohlrausch's equation), the degree of ionisation at Thus, Cm is equal to the solubility of the sparingly
any concentration ( c ) can be determined. soluble salt in the mole per litre units. The solubility of
the salt in gram per litre units can be obtained by
(iii) Determination of the ionisation constant of
multiplying Cm with the molar mass of the salt.
a weak electrolyte : Weak electrolytes in aqueous
solutions ionise to a very small extent. The extent of Electrochemical or Galvanic cell
ionisation is described in terms of the degree of
“Electrochemical cell or Galvanic cell is a device in
ionisation ( ). In solution, the ions are in dynamic
which a spontaneous redox reaction is used to convert
equilibrium with the unionised molecules. Such an chemical energy into electrical energy i.e. electricity can
equilibrium can be described by a constant called be obtained with the help of oxidation and reduction
ionisation constant. For example, for a weak reaction”.
electrolyte AB, the ionisation equilibrium is, AB ⇌
 
(1) Characteristics of electrochemical cell :
A  B ; If C is the initial concentration of the Following are the important characteristics of
electrolyte AB in solution, then the equilibrium e–
electrochemical cell, e–
concentrations of various species in the solution are,
Voltmeter Salt bridge
[ AB ]  C(1   ), [ A  ]  C  and [B  ]  C Cu
Zn anode
cathode
Then, the ionisation constant of AB is given by,
[ A  ][B  ] C  .C  C 2
K   Porous
[ AB] C(1   ) (1   )
ZnSO4plug
CuSO4
Fig. 12.1
 498 Electrochemistry
(i) Electrochemical cell consists of two vessels,
two electrodes, two electrolytic solutions and a salt
bridge.
(ii) The two electrodes taken are made of
different materials and usually set up in two separate
vessels.
(iii) The electrolytes are taken in the two
different vessels called as half - cells.
(iv) The two vessels are connected by a salt
bridge/porous pot.
(v) The electrode on which oxidation takes place
is called the anode (or – ve pole) and the electrode on
which reduction takes place is called the cathode (or +
ve pole).
(vi) In electrochemical cell, ions are discharged
only on the cathode.
(vii) Like electrolytic cell, in electrochemical cell,
from outside the electrolytes electrons flow from anode
to cathode and current flow from cathode to anode.
(viii) For electrochemical cell,
Ecell  ve, G  ve.
(ix) In a electrochemical cell, cell reaction is
exothermic.
(2) Salt bridge and its significance
(i) Salt bridge is U – shaped glass tube filled with
a gelly like substance, agar – agar (plant gel) mixed
with an electrolyte like KCl, KNO3, NH4NO3 etc.
(ii) The electrolytes of the two half-cells should
be inert and should not react chemically with each
other.
(iii) The cation as well as anion of the electrolyte
should have same ionic mobility and almost same
transport number, viz. KCl, KNO3 , NH 4 NO3 etc.
(iv) The following are the functions of the salt
bridge,
(a) It connects the solutions of two half - cells
and completes the cell circuit.
(b) It prevent transference or diffusion of the
solutions from one half cell to the other.
(c) It keeps the solution of two half - cells
electrically neutral.
(d) It prevents liquid – liquid junction potential
i.e. the potential difference which arises between two
solutions when they contact with each other.
(3) Representation of an electrochemical cell
The cell may be written by arranging each of the
pair left – right, anode – cathode, oxidation – reduction,
negative and positive in the alphabetical order as,
Left Bridge Right
Anode Cathode
Reductio
Oxidation
n the same electrolytic solution. M (Hg C1 ) | M n | Zn(Hg C 2 )
Negative Positive
(4) Reversible and irreversible cells : A cell is said
to be reversible if the following two conditions are
fulfilled
(i) The chemical reaction of the cell stops when
an exactly equal external emf is applied.
(ii) The chemical reaction of the cell is reversed
and the current flows in opposite direction when the
external emf is slightly higher than that of the cell. Any
other cell, which does not obey the above two
conditions, is termed as irreversible. Daniell cell is
reversible but Zn| H 2 SO 4 | Ag cell is irreversible in
nature
(5) Types of electrochemical cells : Two main
types of electrochemical cells have been reported, these
are,
(i) Chemical cells : The cells in which electrical
energy is produced from the energy change
accompanying a chemical reaction or a physical process
are known as chemical cells. Chemical cells are of two
types,
(a) Chemical cells without transference : In this
type of chemical cells, the liquid junction potential is
neglected or the transference number is not taken into
consideration. In these cells, one electrode is reversible
to cations while the other is reversible to the anions of
the electrolyte.
(b) Chemical cells with transference : In this type
of chemical cells, the liquid-liquid junction potential or
diffusion potential is developed across the boundary
between the two solutions. This potential develops due
to the difference in mobilities of  ve and  ve ions of
the electrolytes.
(6) Concentration cells : “A cell in which
electrical energy is produced by the transference of a
substance from a system of high concentration to one at
low concentration is known as concentration cells”.
Concentration cells are of two types.
(i) Electrode concentration cells : In these cells,
the potential difference is developed between two
electrodes at different concentrations dipped in the
same solution of the electrolyte. For example, two
hydrogen electrodes at different gaseous pressures in
the same solution of hydrogen ions constitute a cell of
this type.
Pt, H 2 (pressure p1 ) H 2 (pressure p 2 ) Pt
| H | ;
Anode Cathode
0 .0591 (p )
Ecell  log 1 at 25 o C If p1  p2 , oxidation occurs
2 (p2 )
at L. H. S. electrode and reduction occurs at R. H. S.
electrode.
In the amalgam cells, two amalgams of the same
metal at two different concentrations are immersed in
 Electrochemistry 499
The emf of the cell is given by the expression, Some Commercial cell (Batteries)
0.0591 C
Ecell  log 1 at 25 o C One of the main use of galvanic cells is the
n C2 generation of portable electrical energy. These cells are
(ii) Electrolyte concentration cells : In these also popularly known as batteries. The term battery is
cells, electrodes are identical but these are immersed in generally used for two or more Galvanic cells
solutions of the same electrolyte of different connected in series. Thus, a battery is an arrangement
concentrations. The source of electrical energy in the of electrochemical cells used as an energy source. The
cell is the tendency of the electrolyte to diffuse from a basis of an electrochemical cell is an oxidation –
solution of higher concentration to that of lower reduction reaction.
concentration. With the expiry of time, the two
Types of commercial cells : There are mainly two
concentrations tend to become equal. Thus, at the start
types of commercial cells,
the emf of the cell is maximum and it gradually falls to
zero. Such a cell is represented in the following manner (1) Primary cells : In these cells, the electrode
reactions cannot be reversed by an external electric P
( C 2 is greater then C1 ).
energy source. In these cells, reactions occur only once
M | M  n (C1 )| | M n  (C 2 )| M and after use they become dead. Therefore, they are
not chargeable. Some common example are, dry cell,
Zn | Zn 2  (C1 ) Zn 2  (C2 )| Zn
or || mercury cell, Daniell cell and alkaline dry cell
Anode Cathode
(i) Voltaic cellCu rod – + Zn rod
The emf of the cell is given by the following
expression,
0 . 0591 C Dil. H2SO4
Ecell  log 2( R . H .S ) e at 25o C
n C1( L. H . S .)
Local action
Cu
Polarisatio
The concentration cells are used to determine the
n Zn
solubility of sparingly soluble salts, valency of the
cation of the electrolyte and transition point of the two Fig. 12.2
allotropic forms of metal used as electrodes, etc. Cathode : Cu rod Anode : Zn rod
(7) Heat of reaction in an electrochemical cell : Electrolyte : dil. H2SO4 Emf : 1.08 V
Let n Faraday charge flows out of a cell of emf E, then At cathode : Cu 2   2e   Cu
 G  nFE …….(i) At Anode : Zn  Zn2   2e 
Gibbs – Helmholtz equation from thermodynamics Over all reaction : Zn  Cu 2   Zn 2   Cu
may be given as
(ii) Daniel cell Electrons flow
e–
 G  e–
G  H  T   …….(ii) – Key +
 T  P
Ammeter Current

Anode (Zn) Salt bridge Cathode (Cu)

From equation (i) and (ii) we get,
 (nFE)   E 
 nFE  H  T    H  nFT  T  Cotton Plugs
 T  P  P
Zn2+ Cu2+
 E 
H  nFE  nFT  
 T  P
1M ZnSO4 (aq) Fig. 12.3 1M CuSO4 (aq)
 E  (Depolariser)
where   = Temperature coefficient of cell
 T  P Cathode : Cu rod Anode : Zn rod
Electrolyte : dil. H2SO4 Emf : 1.1 V
 E 
Case I: When   = 0, then H  nFE At cathode : Cu 2   2e   Cu
 T  P
At Anode : Zn  Zn2   2e 
 E 
Case II: When   > 0, then nFE  H , i.e. Over all reaction : Zn  Cu 2   Zn 2   Cu
 T 
(iii) Lechlanche cell (Dry cell)
process inside the cell is endothermic.
+ Seal
 E  Graphite (cathode)
Case III: When   < 0, then nFE  H , i.e.,
 T  MnO2 +C
(Depolariser)
process inside the cell is exothermic. Paste of NH4Cl+ZnCl2

–
Zinc
Fig. 12.4 anode
 500 Electrochemistry

Cathode : Mercury (II) oxide Anode :

Cathode : Graphite rod Anode : Zn pot
Electrolyte : Paste of NH 4 Cl  ZnCl2 in starch
Emf : 1.2 V to 1.5 V
At cathode : NH 4  MnO 2  2e   MnO (OH )  NH 3
At Anode : Zn  Zn 2   2e 
Over all reaction :
Zn  NH 4  MnO 2  Zn 2   MnO (OH )  NH 3
(iv) Mercury cell
Zn rod
Electrolyte : Paste of KOH  ZnO Emf :
1.35 V
At cathode : HgO(s)  H 2 O(l)  2e   Hg (l)  2OH (aq )
At Anode : Zn (s )  20 H (aq )  ZnO (s )  H 2 O (l)  2 e 
(amalgam )
Over all reaction : Zn(s)  HgO(s)  ZnO(s)  Hg(l)
(2) Secondary cells : In the secondary cells, the
reactions can be reversed by an external electrical
energy source. Therefore, these cells can be recharged
by passing electric current and used again and again.
These are also celled storage cells. Examples of
secondary cells are, lead storage battery and nickel –
cadmium storage cell.

In charged Lead storage cell Alkali cell

Ni(OH)2
+ – + –
Glass
Fe(OH)2
vessel
PbO2 Perforated
steel grid
Pb
KOH 20%
dil. H2SO4 + Li(OH), 1%

Positive Perforated lead plates coated with PbO2 Perforated steel plate coated with Ni(OH)4
electrode
Negative Perforated lead plates coated with pure lead Perforated steel plate coated with Fe
electrode
Electrolyte dil. H2SO4 20% solution of KOH + 1% LiOH
During charging Chemical reaction Chemical reaction
At anode : PbSO4 + 2H+ + 2e–  Pb + H2SO4 At anode : Ni (OH)2 + 2OH+ – 2e– 
At cathode : PbSO4 + SO4– – + 2H2O – 2e–  Ni(OH)4
PbO2 At cathode : Fe(OH)2 + 2K+ + 2e–  Fe +
+ 2KOH
2H2SO4 Emf of cell : When cell is fully charged
Specific gravity of H2SO4 increases and when then E = 1.36 volt
specific gravity becomes 1.25 the cell is fully
charged.
Emf of cell: When cell is fully charged then E =
2.2 volt
During Chemical reaction Chemical reaction
discharging At anode : Pb + SO4– – – 2e–  PbSO4 At anode : Fe + 2OH– – 2e–  Fe(OH)2
At cathode : PbO2 + 2H+ + 2e– + H2SO4  PbSO4 At cathode : Ni(OH)4 + 2K+ + 2e– 
+ Ni(OH)2 +
2H2O 2KOH
Specific gravity of H2SO4 decreases and when Emf of cell : When emf of cell falls below
specific gravity falls below 1.18 the cell 1.1 V it requires charging.
requires recharging.

Emf of cell : When emf of cell falls below 1.9
volt the cell requires recharging.
Efficiency 80%
Fuel cells
These are Voltaic cells in which the reactants are
continuously supplied to the electrodes. These are
designed to convert the energy from the combustion of
fuels such as H 2 , CO, CH 4 , etc. directly into electrical
energy. The common example is hydrogen-oxygen fuel
cell as described below,
In this cell, hydrogen and oxygen are bubbled
through a porous carbon electrode into concentrated
aqueous sodium hydroxide or potassium hydroxide.
Hydrogen (the fuel) is fed into the anode compartment
where it is oxidised. The oxygen is fed into cathode
compartment where it is reduced. The diffusion rates of
the gases into the cell are carefully regulated to get
maximum efficiency. The net reaction is the same as
burning of hydrogen and oxygen to form water. The
reactions are
At anode : 2[H 2 (g)  2OH  ](aq )  2 H 2 O(l)  2e 
At cathode : O2 (g)  2 H 2 O(l)  4 e   4 OH  (aq )
Overall reaction
2 H 2 (g)  O 2 (g)  2 H 2 O(l)
Each electrode is made of porous compressed
carbon containing a small amount of catalyst
(Pt, Ag or CoO) . This cell runs continuously as long as
the reactants are fed. Fuel cells convert the energy of
the fuel directly into electricity EMF of fuel cell is 1.23
V. This cell has been used for electric power in the
Apollo space programme. H2OThe important advantages of
fuel cells are Anode – + Cathode
Porous carbon electrode
OH–
H2 O2
Electrolyte
Fig. 12.6
(1) High efficiency : The fuel cells convert the
energy of a fuel directly into electricity and therefore,
they are more efficient than the conventional methods
of generating electricity on a large scale by burning
hydrogen, carbon fuels. Though we expect 100 %
efficiency in fuel cells, so far 60 – 70% efficiency has
been attained. The conventional methods of production
of electrical energy involve combustion of a fuel to
liberate heat which is then used to produce electricity.
The efficiency of these methods is only about 40%.
(2) Continuous source of energy : There is no
electrode material to be replaced as in ordinary
Electrochemistry 501
60%
battery. The fuel can be fed continuously to produce
power. For this reason, H 2  O2 fuel cells have been used
in space crafts.
(3) Pollution free working : There are no
objectionable byproducts and, therefore, they do not
cause pollution problems. Since fuel cells are efficient
and free from pollution, attempts are being made to get
better commercially practical fuel cells.
Electrode Potential
(1) When a metal (M) is placed in a solution of its
ions (M++), either of the following three possibilities
can occurs, according to the electrode potential
solution pressure theory of Nernst.
(i) A metal ion M n+ collides with the electrode,
and undergoes no change.
(ii) A metal ion M n+ collides with the electrode,
gains n electrons and gets converted into a metal atom
M, (i.e. the metal ion is reduced).
:
M n  (aq)  ne   M (s)
(iii) A metal atom on the electrode M may lose an
electrons to the electrode, and enter to the solution as
M n , (i.e. the metal atom is oxidised).
M (s)  M n  (aq)  ne  .
Thus, “the electrode potential is the tendency of an
electrode to lose or gain electrons when it is in contact
with solution of its own ions.”
(2) The magnitude of electrode potential depends
on the following factors,
(i) Nature of the electrode, (ii) Concentration of
the ions in solution, (iii) Temperature.
(3) Types of electrode potential : Depending on
the nature of the metal electrode to lose or gain
electrons, the electrode potential may be of two types,
(i) Oxidation potential : When electrode is
negatively charged with respect to solution, i.e., it acts
as anode. Oxidation occurs. M  M n   ne 
(ii) Reduction potential : When electrode is
positively charged with respect to solution, i.e. it acts
as cathode. Reduction occurs. M n   ne   M
(4) Standard electrode potential : “If in the half
cell, the metal rod (M) is suspended in a solution of one
molar concentration, and the temperature is kept at 298
K, the electrode potential is called standard electrode
potential, represented usually by E o ”. ‘or’
The standard electrode potential of a metal may
be defined as “the potential difference in volts developed
in a cell consisting of two electrodes, the pure metal in
 502 Electrochemistry
contact with a molar solution of one of its ions and the couple the electrode with another electrode whose
normal hydrogen electrode (NHE)”. potential is known. This electrode is termed as
Standard oxidation potential for any half - cell  – (Standard reduction potential ) reference electrode or reference half - cells. Various
Standard reduction potential for any half - cell  – (Standard reduction potential ) types of half – cells have been used to make complete
(5) Reference electrode or reference half - cells cell with spontaneous reaction in forward direction.
These half – cells have been summarised in following
It is not possible to measure the absolute value of
table,
the single electrode potential directly. Only the
difference in potential between two electrodes can be
measured experimentally. It is, therefore, necessary to
Table : 12.2 Various Types of Half – cells
Type Example Half – cell reaction Q= Reversibl Electrode Potential
e to (oxidn), E =
Gas ion half - cell Pt(H 2 )| H  (aq) 1
H 2 (g)  H  (aq)  e  [H  ] H E0  0.0591 log[H  ]
2
Pt(Cl 2 )| Cl  (aq) 1 Cl  E0  0.0591 log[Cl  ]
1
Cl (aq)  Cl 2 (g)  e 
 [Cl  ]
2
Metal – metal ion Ag | Ag  (aq) Ag(s)  Ag  (aq)  e  [ Ag  ] Ag  E0  0.0591 log[ Ag  ]
half – cell
Metal insoluble Ag, AgCl | Cl  (aq) Ag(s)  Cl  (aq)  AgCl (s)  e  1 Cl  E0  0.0591 log[Cl  ]
salt anion half – [Cl  ]
cell
Calomel electrode Hg, Hg 2Cl 2 | Cl  (aq) 2 Hg(l)  2Cl  (aq)  1 Cl  E0  0.0591 log[Cl  ]
[Cl  ]2
Hg 2Cl 2 (s)  2e 
Metal – metal Hg, HgO | OH  (aq) Hg(l)  2OH  (aq)  1 OH  E0  0.0591 log[OH  ]
oxide hydroxide  [OH  ]2
HgO(s)  H 2O(l)  2e
half - cell
Oxidation – Pt | Fe 2  , Fe 3  Fe 2  (aq)  Fe 3  (aq)  e  [Fe 3  ] Fe 2  , Fe3  [Fe 3  ]
(aq) (aq) E 0  0 .0591 log
reduction half – [Fe 2  ] [Fe 2  ]
dell

Cell potential or EMF of the cell 0

Ecell  Reduction potential of cathode – Reduction potential of anode
(1) “The difference in potentials of the two half – cells
 E Cathode
0
 E Anode
0
 Eright
o
 Eleft
o
of a cell known as electromotive force (emf) of the cell or
cell potential.” (iii) When oxidation potentials of both electrodes
The difference in potentials of the two half – cells are taken into account
of a cell arises due to the flow of electrons from anode o
Ecell  Oxidation potential of anode – Oxidation
to cathode and flow of current from cathode to anode.
potential of cathode  Eox
0
(anode )  Eox
0
(cathode )
Flow of electrons
Anode Cathode (3) Difference between emf and potential difference
Flow of current
(2) The emf of the cell or cell potential can be Emf Potential difference
calculated from the values of electrode potentials of It is the potential It is the difference of the
two the half – cells constituting the cell. The following difference between two electrode potentials of
three methods are in use : electrodes when no the two electrodes when
(i) When oxidation potential of anode and current is flowing in the the cell is under
reduction potential of cathode are taken into account circuit. operation.
0
E cell  Oxidation potential of anode + Reduction It is the maximum It is always less then the
voltage that the cell can maximum value of
potential of cathode  E ox
0
(anode )  E red
0
(cathode )
deliver. voltage which the cell
(ii) When reduction potentials of both electrodes can deliver.
are taken into account
 Electrochemistry 503
It is responsible for the It is not responsible for At 298 K, the Nernst equation for the M n / M
steady flow of current in the steady flow of electrode can be written as,
the cell. current in the cell.
0.0591 1
EM n  / M  EM
0
n
/M
 log n 
(4) Cell EMF and the spontaneity of the reaction : n [M (aq)]
We know, G  nFEcell
For an electrode (half - cell) corresponding to the
Nature of o electrode reaction,
ΔG(or ΔG ) E cell (or E ocell )
reaction Oxidised form  ne   Reduced form
Spontaneous – + The Nernst equation for the electrode is written
Equilibrium 0 0 as,

Non – spontaneous + – 2 . 303 RT [Reduced form ]

Ehalf  cell  Ehalf
0
 cell  log
nF [Oxidised form]
Nernst's equation
(1) Nernst’s equation for electrode potential At 298 K, the Nernst equation can be written as,

The potential of the electrode at which the 0 . 0591 [Reduced form ]

Ehalf  cell  Ehalf
0
 cell  log
reaction, n [Oxidised form]

M n  (aq)  ne   M (s) (2) Nernst’s equation for cell EMF

takes place is described by the equation, For a cell in which the net cell reaction involving
RT [M (s)] n electrons is, aA  bB  cC  dD
EM n  / M  EM
0
n  ln
/M nF [M n  (aq.)] The Nernst equation is written as,
RT [C] c [D]d
2.303 RT [M (s)] Ecell  Ecell
0
 ln
or EM n  / M  0
EM n
/M
 log n  nF [ A]a [B]b
nF [M (aq)]
0
Where, E cell  E cathode
0
 E anode
0
.
above eq. is called the Nernst equation.
o
Where, The E cell is called the standard cell potential.

E M n  / M = the potential of the electrode at a given 2 . 303 RT [C ]c [D]d

or Ecell  Ecell
o
 log
nF [ A]a [B]b
concentration,
At 298 K, above eq. can be written as,
0
EM n = the standard electrode potential
/M 0 .0592 [C ]c [D]d
or Ecell  Ecell
o
 log
R = the universal gas constant, 8 .31 J K 1 mol 1 n [ A]a [B]b
It may be noted here, that the concentrations of A,
T= the temperature on the absolute scale, B, C and D referred in the eqs. are the concentrations at
n = the number of electrons involved in the the time the cell emf is measured.
electrode reaction, (3) Nernst’s equation for Daniells cell :
Daniell’s cell consists of zinc and copper electrodes.
F = the Faraday constant : (96500 C),
The electrode reactions in Daniell’s cell are,
[M (s)] = the concentration of the deposited metal,
At anode : Zn(s)  Zn 2  (aq)  2e 
[M n (aq)] = the molar concentration of the metal At cathode : Cu 2  (aq)  2e   Cu(s)
ion in the solution,
Net cell reaction :
The concentration of pure metal M(s) is taken as 2 2
Zn(s)  Cu (aq)  Cu(s)  Zn (aq)
unity. So, the Nernst equation for the M n / M Therefore, the Nernst equation for the Daniell’s
electrode is written as, cell is,
2.303 RT 1 2 . 303 RT [Cu (s)][ Zn 2  (aq )]
EM n  / M  EM
0
 log n  Ecdll  Ecell
0
 log
[ Zn(s)][Cu 2  (aq )]
n
/M nF [M (aq)] 2F
 504 Electrochemistry
Since, the activities of pure copper and zinc (1) The standard reduction potentials of a large
metals are taken as unity, hence the Nernst equation number of electrodes have been measured using
for the Daniell’s cell is, standard hydrogen electrode as the reference electrode.
2 . 303 RT [ Zn 2  (aq ] These various electrodes can be arranged in increasing
Ecdll  Ecell
0
 log or decreasing order of their reduction potentials. The
2F [Cu 2  (aq )]
arrangement of elements in order of increasing
The above eq. at 298 K is, reduction potential values is called electrochemical
0 . 0591 [ Zn 2  (aq ] series.It is also called activity series, of some typical
Ecdll  Ecell
o
 log V electrodes.
2 [Cu 2  (aq )]
(2) Characteristics of Electrochemical series
0
For Daniells cell, E cell  1 .1 V (i) The negative sign of standard reduction
(4) Nernst's equation and equilibrium constant potential indicates that an electrode when joined with
SHE acts as anode and oxidation occurs on this
electrode. For example, standard reduction potential of
For a cell, in which the net cell reaction involving zinc is –0.76 volt, When zinc electrode is joined with
n electrons is, aA  bB  cC  dD SHE, it acts as anode (–ve electrode) i.e., oxidation
occurs on this electrode. Similarly, the +ve sign of
standard reduction potential indicates that the
The Nernst equation is
electrode when joined with SHE acts as cathode and
RT [C]c [D]d reduction occurs on this electrode.
ECell  Ecell
0
 ln .....(i)
nF [ A]a [B]b (ii) The substances, which are stronger reducing
agents than hydrogen are placed above hydrogen in the
At equilibrium, the cell cannot perform any useful series and have negative values of standard reduction
work. So at equilibrium, ECell is zero. Also at potentials. All those substances which have positive
values of reduction potentials and placed below
equilibrium, the ratio
hydrogen in the series are weaker reducing agents than
 [C ]c [D]d  hydrogen.
[C ]c [D]d
a
 a b
b   Kc (iii) The substances, which are stronger oxidising
[ A] [ B]  [ A] [B]  equilibriu m
agents than H  ion are placed below hydrogen in the
Relationship between potential, Gibbs energy series.
and equilibrium constant (iv) The metals on the top (having high negative
value of standard reduction potentials) have the
The electrical work (electrical energy) is equal to
tendency to lose electrons readily. These are active
the product of the EMF of the cell and electrical charge
metals. The activity of metals decreases from top to
that flows through the external circuit i.e.,
bottom. The non-metals on the bottom (having high
Wmax  nFEcell ......(i)
positive values of standard reduction potentials) have
According to thermodynamics the free energy the tendency to accept electrons readily. These are
change (G) is equal to the maximum work. In the cell active non-metals. The activity of non-metals increases
work is done on the surroundings by which electrical from top to bottom.
energy flows through the external circuit, So Table : 12.3 Standard reduction electrode potentials at
Wmax,  G 298K
......(ii) Element Electrode Reaction Standard
(Reduction) Electrode
from eq. (i) and (ii) G  nFE cell
Reduction
In standard conditions G 0   nFE cell
0 potential E0,
volt
Where G 0  standard free energy change
Li Li++ e– = Li –3.05
2 .303
But 0
E cell  RT log K c K K++ e– = K –2.925
nF Ba Ba+++ 2e = Ba –2.90
2 .303 Sr+++ 2e = Sr
 G 0  nF  RT log K c
Sr –2.89
nF Ca Ca 2   2e   Ca –2.87
tendency to accept electrons Increasing

G   2.303 RT log K c or G  G  2 .303 RT log Q

0
Na Na   e   Na –2.714
rength as reducing agent Increasing

Mg 2  –2.37
G 0   RT ln K c (2 .303 log X  ln X ) Mg  2e  Mg
Al Al 3   3 e   Al –1.66
strength as oxidising agent

Electrochemical series
ndency to lose electrons
 Electrochemistry 505
Mn Mn+++ 2e = Mn –1.18 negative like alkali metals, alkaline earth metals are
Zn Zn2+ +2e–=Zn –0.7628 strongly electropositive in nature.
Cr Cr3++3 e– = Cr –0.74 (b) Moderately electropositive metals : Metals having
Fe Fe2++ 2e– = Fe –0.44 values of reduction potentials between 0.0 and about –
Cd Cd2++2e– = Cd –0.403 2.0 volt are moderately electropositive Al, Zn, Fe, Ni, Co,
Co Co+++ 2e = Co –0.27
etc., belong to this group.
Ni Ni2++2e– = Ni –0.25
(c) Weakly electropositive : The metals which are
Sn Sn2++2e– = Sn –0.14
below hydrogen and possess positive values of reduction
Pb Pb+++ 2e = Pb –0.12
potentials are weakly electropositive metals. Cu, Hg, Ag,
H2 2H++2e– = H2 0.00
Cu Cu2++ 2e– = Cu +0.337
etc., belong to this group.
I2 I2+2e– = 2I– +0.535 (iii) Displacement reactions
Hg Hg2++2e– = Hg +0.885 (a) To predict whether a given metal will displace
Ag Ag++ e– = Ag +0.799 another, from its salt solution: A metal higher in the
Br2 Br2+2e– = 2Br– +1.08 series will displace the metal from its solution which is
Pt Pt+++ 2e = Pt +1.20 lower in the series, i.e., The metal having low standard
Cl2 Cl2+2e– = 2Cl– +1.36 reduction potential will displace the metal from its
Au Au 3++3e– = Au +1.50 salt's solution which has higher value of standard
F2 F2+2e–= 2F– +2.87 reduction potential. A metal higher in the series has
greater tendency to provide electrons to the cations of
(3) Application of Electrochemical series
the metal to be precipitated.
(i) Reactivity of metals: The activity of the metal
(b) Displacement of one nonmetal from its salt
depends on its tendency to lose electron or electrons,
solution by another nonmetal: A non-metal higher in the
i.e., tendency to form cation (M n ) . This tendency series (towards bottom side), i.e., having high value of
depends on the magnitude of standard reduction reduction potential will displace another non-metal
potential. The metal which has high negative value (or with lower reduction potential, i.e., occupying position
smaller positive value) of standard reduction potential above in the series. The non-metal's which possess high
readily loses the electron or electrons and is converted positive reduction potentials have the tendency to
into cation. Such a metal is said to be chemically active. accept electrons readily. These electrons are provided
The chemical reactivity of metals decreases from top to by the ions of the nonmetal having low value of
bottom in the series. The metal higher in the series is reduction potential,. Thus, Cl 2 can displace bromine
more active than the metal lower in the series. For
and iodine from bromides and iodides.
example,
Cl2  2 KI  2 KCl  I2
(a) Alkali metals and alkaline earth metals having
high negative values of standard reduction potentials 2 I   I2  2e  .....(Oxidation)
are chemically active. These react with cold water and Cl 2  2e   2Cl  .....(Reduction)
evolve hydrogen. These readily dissolve in acids
forming corresponding salts and combine with those [The activity or electronegative character or
substances which accept electrons. oxidising nature of the nonmetal increases as the value
of reduction potential increases.]
(b) Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a
(c) Displacement of hydrogen from dilute acids by
little down in the series do not react with cold water
but react with steam to evolve hydrogen. metals : The metal which can provide electrons to H 
ions present in dilute acids for reduction, evolve
(c) Metals like Cu, Ag and Au which lie below
hydrogen from dilute acids.
hydrogen are less reactive and do not evolve hydrogen
from water. Mn  Mn n  ne  .....(Oxidation)
 
(ii) Electropositive character of metals : The 2 H  2e  H 2
electropositive character also depends on the tendency .....(Reduction)
to lose electron or electrons. Like reactivity, the The metal having negative values of reduction
electropositive character of metals decreases from top
potential possess the property of losing electron or
to bottom in the electrochemical series. On the basis of
electrons.
standard reduction potential values, metals are divided
Thus, the metals occupying top positions in the
into three groups
electrochemical series readily liberate hydrogen from
(a) Strongly electropositive metals : Metals having
dilute acids and on descending in the series tendency to
standard reduction potential near about – 2.0 volt or more
liberate hydrogen gas from dilute acids decreases.
 506 Electrochemistry
The metals which are below hydrogen in decreases from top to bottom, the thermal stability of
electrochemical series like Cu, Hg, Au, Pt, etc., do not the oxide also decreases from top to bottom. The oxides
evolve hydrogen from dilute acids. of metals having high positive reduction potentials are
(d) Displacement of hydrogen from water : Iron not stable towards heat. The metals which come below
and the metals above iron are capable of liberating copper form unstable oxides, i.e., these are decomposed
hydrogen from water. The tendency decreases from top on heating.
to bottom in electrochemical series. Alkali and alkaline
 1
earth metals liberate hydrogen from cold water but Mg, Ag 2 O  2 Ag  O2
Zn and Fe liberate hydrogen from hot water or steam. 2

(iv) Reducing power of metals: Reducing nature BaO 

depends on the tendency of losing electron or electrons.

2 HgO  2 Hg  O2 ; Na2 O  

No decomposit ion

Al2 O3 
More the negative reduction potential, more is the
tendency to lose electron or electrons. Thus reducing (vii) Extraction of metals : A more
nature decreases from top to bottom in the electropositive metal can displace a less electropositive
electrochemical series. The power of the reducing agent metal from its salt's solution. This principle is applied
increases, as the standard reduction potential becomes for the extraction of Ag and Au by cyanide process.
more and more negative. Sodium is a stronger reducing silver from the solution containing sodium argento
agent than zinc and zinc is a stronger reducing agent cyanide, NaAg(CN )2 , can be obtained by the addition of
than iron. (decreasing order of reducing nature)
zinc as it is more electro-positive than Ag .
Element : Na  Zn  Fe
Reduction potential :  2 . 71  0 . 76  0 . 44 2 NaAg(CN )2  Zn  Na2 Zn(CN )4  2 Ag

Alkali and alkaline earth metals are strong Corrosion

reducing agents. (1) When metals are exposed to atmospheric
(v) Oxidising nature of non-metals : Oxidising conditions, they react with air or water in the
nature depends on the tendency to accept electron or environment to form undesirable compounds (usually
electrons. More the value of reduction potential, higher oxides). This process is called corrosion. Almost all
is the tendency to accept electron or electrons. Thus, metals except the least active metals such as gold,
oxidising nature increases from top to bottom in the platinum and palladium are attacked by environment
electrochemical series. The strength of an oxidising i.e., undergo corrosion. For example, silver tarnishes,
agent increases as the value of reduction potential copper develops a green coating, lead or stainless steel
becomes more and more positive. lose their lusture due to corrosion. Corrosion causes
F2 (Fluorine) is a stronger oxidant than Cl 2 , Br2 enormous damage to building, bridges, ships and many
other articles made of iron.
and I 2 , Cl 2 (Chlorine) is a stronger oxidant than
Thus corrosion is a process of deterioration of a
Br2 and I2
Element : metal as a result of its reaction with air or water
Reduction potential : (environment) surrounding it.
I2 Br2 Cl2 F2 In case of iron, corrosion is called rusting.
 0 . 53  1 . 06  1 . 36  2 . 85 Chemically, rust is hydrated form of ferric oxide,

Oxidising nature increases Fe 2 O 3 . xH 2 O . Rusting of iron is generally caused by
Thus, in electrochemical series moisture, carbon dioxide and oxygen present in air. It
has been observed that rusting takes place only when
(Strongest reducing agent)
Top iron is in contact with moist air. Iron does not rust in
Reducing
Oxidising

Highest negative reduction potential dry air and in vacuum.

nature
nature

or (2) Factors which affect corrosion : The main

factors which affect corrosion are
(Minimum reduction potential)
More the reactivity of metal, the more will be the
(Strongest oxidising agent) possibility of the metal getting corroded.
Botto The impurities help in setting up voltaic cells,
Highest positive value of reduction potential
m which increase the speed of corrosion
(vi) Thermal stability of metallic oxides : The Presence of electrolytes in water also increases
thermal stability of the metal oxide depends on its the rate of corrosion
electropositive nature. As the electropositivity

Presence of CO2 in natural water increase rusting
of iron.
(v) When the iron surface is coated with layers of
metals more active than iron, then the rate of corrosion
is retarded.
A rise in temperature (with in a reasonable limit)
increases the rate of corrosion.
(3) Classification of corrosion process :
Depending upon the nature of corrosion, and the
factors affecting it, the corrosion may be classified as
follows.
(i) Chemical corrosion : Such corrosion, generally
takes place when
(a) Reactive gases come in contact with metals at
high temperatures e.g., corrosion in chemical industry.
(b) Slow dissolution of metal takes place when
kept in contact with non conducting media containing
organic acids.
(ii) Bio-chemical corrosion or Bio-corrosion:
This is caused by the action of microorganisms. Soils of
definite composition, stagnant water and certain
organic products greatly favour the bio-corrosion.
(iii) Electrochemical corrosion : It occurs in a
gaseous atmosphere in the presence of moisture, in
soils and in solutions.
(4) Mechanism of rusting of
Electrochemical theory of rusting.
The overall rusting involves the following steps,
(i) Oxidation occurs at the anodes of each
electrochemical cell. Therefore, at each anode neutral
iron atoms are oxidised to ferrous ions.
At anode : Fe(s)  Fe 2  (aq)  2e  .
Thus, the metal atoms in the lattice pass into the
solution as ions, leaving electrons on the metal itself.
These electrons move towards the cathode region
through the metal.
Drop of
moisture
4H++O2+4e–2H2O
Rust (Cathode)
Fe2+
+ thin layer of zinc, nickel or chromium on it.
Fe 2e–
anode Flow of
electron
Iron s
Schematic representation of mechanism of rusting of
iron
Fig. 12.7
(ii) At the cathodes of each cell, the electrons are
taken up by hydrogen ions (reduction takes place). The
H  ions are obtained either from water or from acidic
substances (e.g. CO 2 ) in water
Electrochemistry 507
H 2 O  H   OH  or CO 2  H 2 O  H   HCO 3
At cathode : H   e   H
The hydrogen atoms on the iron surface reduce
dissolved oxygen. 4 H  O2  2 H 2 O
Therefore, the overall reaction at cathode of
different electrochemical cells may be written as,
4 H   O2  4 e   2 H 2 O
(iii) The overall redox reaction may be written by
multiplying reaction at anode by 2 and adding reaction
at cathode to equalise number of electrons lost and
gained i.e.
Oxi. half reaction : Fe(s)  Fe 2  (aq)  2e  ]  2
(E  0 .44 V )
Red. half reaction : 4 H   O2  4 e   2 H 2 O
(E  1 .23 V )
Overall cell reaction : 2 Fe (s)  4 H   O2  2 Fe 2  (aq )  2 H 2 O
( ECell  1 . 67 V )
The ferrous ions are oxidised further by
atmospheric oxygen to form rust.
4 Fe 2  (aq )  O2 (g)  4 H 2 O  2 Fe 2 O3  8 H  and
Fe2O3  xH 2O  Fe2O3 . xH 2O
iron : Rust
It may be noted that salt water accelerates
corrosion. This is mainly due to the fact that salt water
increases the electrical conduction of electrolyte
solution formed on the metal surface. Therefore,
rusting becomes more serious problem where salt
water is present.
(5) Corrosion protection : Corrosion of metals
can be prevented in many ways. Some commonly used
methods are
(i) By surface coating
(a) By applying, oil, grease, paint or varnish on
the surface.
(b) By coating/depositing a thin layer of any other
metal which does not corrode. For example, iron
surface can be protected from corrosion by depositing a
Copper/brass can be protected by coating it with a thin
layer of tin. Tinning of brass utensils is a very common
practice in our country.
(c) By Galvanization : Prevention of corrosion of
iron by Zn coating.
(ii) By connecting metal to a more
electropositive metal : As long as the more
electropositive metal is there, the given metal does not
get corroded. For example, iron can be protected from
corrosion by connecting it to a block/plate of zinc or
 508 Electrochemistry
magnesium. This method of corrosion protection is
called cathodic protection.
(iii) By forming insoluble phosphate or
chromate coating : Metal surfaces are treated with
phosphoric acid to form an insoluble phosphate.
Formation of a thin chromate layer also prevents the
corrosion of metals.
(iv) Using anti – rust solutions : Solutions of
alkaline phosphates and alkaline chromates are
generally used as anti – rust solutions. For example,
iron articles are dipped in boiling alkaline sodium
phosphate solutions, when a protective insoluble
sticking film of iron phosphate is formed.

 When two or more ions compete at the electrodes

then the ion with higher reduction potential gets
liberated at the cathode while the one with lower
reduction potential at the anode.
 Cell constant is determined with the help of
conductivity bridge, where a standard solution of
KCl is used.
 If the external EMF is slightly more than the
actual EMF, the current will flow into the cell
and reverse reaction takes place.
 Identification of cathode and anode is done by
the use of galvanometer.
 KCl / NaCl / NH4Cl etc., can not be used in the
salt bridge of a cell containing silver salt as one
of the electrodes as Cl– ions form a ppt. of AgCl
with silver ion.
 Weston cell is a common example of standard
cell. The emf of a standard cell does not change
with temperature.
 In Appolo moon flights, H2 – O2 fuel cell was the
source of energy and drinking water.
 Conductivity water is the highly purified water
whose on conductance is very small. It is
prepared by the demineralisation of ordinary
water by passing through cation and anion
exchange resins.
 506 Electrochemistry
9. On the electrolysis of aqueous solution of sodium
sulphate, on cathode we get [
(a) Na (b) H 2
(c) SO 2 (d) SO 3
10. Electrolysis involves oxidation and reduction
respectively at
Electrolytes and Electrolysis [CPMT 1973; AMU 1983; NCERT 1983, 84; MH CET 2001]
(a) Anode and cathode (b) Cathode and anode
1. Which of the following will not conduct electricity (c) At both the electrodes (d) None of the above
in aqueous solution [AMU 1982, 83] 11. Which of the following compounds will not
(a) Copper sulphate (b) Sugar undergo decomposition on passing electricity
(c) Common salt (d) None of these through aqueous solution [

2. Strong electrolytes are those which [MNR 1983] (a) Sugar (b) Sodium Chloride
(a) Dissolve readily in water (c) Sodium Bromide (d) Sodium Acetate
(b) Conduct electricity 12. During the electrolysis of an electrolyte, the
(c) Dissociate into ions at high dilution number of ions produced, is directly proportional to
the [AFMC 2002]
(d) Completely dissociate into ions at all dilutions
(a) Time consumed
3. In aqueous solution, strong electrolytes[AMU 1983, 84]
(a) Are partially ionized (b) Electro chemical equivalent of electrolysis
(b) Do not ionise (c) Quantity of electricity passed
(c) Ionise almost completely (d) Mass of electrons
(d) Form polymers 13. When the sample of copper with zinc impurity is
4. An electrolyte [KCET 1984; MP PET/PMT 1988]
to be purified by electrolysis, the appropriate
electrodes are
(a) Forms complex ions in solution
[AIEEE 2002]
(b) Gives ions only when electricity is passed
Cathode Anode
(c) Possesses ions even in solid state
(a) Pure zinc Pure copper
(d) Gives ions only when dissolved in water
(b) Impure sample Pure copper
5. Electrolytes when dissolved in water dissociates
into ions because [CPMT 1974, 78; MNR (c) Impure zinc Impure sample
1983] (d) Pure copper Impure sample
(a) They are unstable 14. In the electrolytic cell, flow of electrons is from
(b) The water dissolves it [IIT Screening 2003]
(c) The force of repulsion increases (a) Cathode to anode in solution
(d) The forces of electrostatic attraction are (b) Cathode to anode through external supply
broken down by water (c) Cathode to anode through internal supply
6. Electrolyte can conduct electricity because (d) Anode to cathode through internal supply
(a) Their molecules contain unpaired electrons, 15. An electric current is passed through an aqueous
which are mobile solution of the following. Which one shall
(b) Their molecules contain loosely held electrons decompose [NCERT 1972]
which get free under the influence of voltage
(a) Urea (b) Glucose
(c) The molecules break up into ions when a
(c) AgNO3 (d) Ethyl alcohol
voltage is applied
(d) The molecules are broken up into ions when 16. The electric conduction of a salt solution in water
the electrolyte is fused or is dissolved in the depends on the
solvent (a) Shape of its molecules
7. Which one of the following metals could not be (b) Size of its molecules
obtained on electrolysis of aqueous solution of its (c) Size of solvent molecules
salts [IIT 1990] (d) Extent of its ionization
(a) Ag (b) Mg 17. A solution of sodium sulphate in water is
(c) Cu (d) Cr electrolysed using inert electrodes. The products
8. Which of the following aqueous solution will at the cathode and anode are respectively[IIT 1987,96]
conduct an electric current quite well[MP PMT 1987] (a) H 2 , O2 (b) O2 , H 2
(a) Glycerol (b) HCl
(c) O2 , Na (d) O2 , SO 2
(c) Sugar (d) Pure water
 Electrochemistry 507
18. On electrolysing a solution of dilute H 2 SO 4 (d) Is readily decomposed
between platinum electrodes, the gas evolved at 27. Which is responsible for electrical conduction of
the anode is molten sodium chloride [MADT Bihar 1995]
[NCERT 1977, 79; MNR 1980; CBSE PMT 1992] (a) Free electrons
(a) SO 2 (b) SO 3 (b) Free ions
(c) O 2 (d) H 2 (c) Free molecules
(d) Atoms of sodium and chlorine
19. The addition of a polar solvent to a solid
electrolyte results in 28.[NCERT
In electrolysis
1973] of aqueous copper sulphate, the gas
at anode and cathode is [AFMC 1995]
(a) Polarization (b) Association
(a) O 2 and H 2 (b) SO 2 and H 2
(c) Ionization (d) Non-liberation of
heat (c) H 2 and O 2 (d) SO 3 and O 2
20. During the electrolysis of fused NaCl , which 29. Use of electrolysis is [AFMC 1995]
(a) Electroplating
reaction occurs at anode[NCERT 1973; AFMC 1992; MP PMT 2002] (b) Electrorefining
(a) Chloride ions are oxidized (c) (a) and (b) both (d) None of these
(b) Chloride ions are reduced 30. Sodium is made by the electrolysis of a molten
(c) Sodium ions are oxidised mixture of about 40% NaCl and 60% CaCl2
(d) Sodium ions are reduced because
21. The amount of ion discharged during electrolysis [CBSE PMT 1995]
is not directly proportional to [NCERT 1973] (a) CaCl2 helps in conduction of electricity
(a) Resistance (b) This mixture has a lower melting point than
(b) Time NaCl
(c) Current (c) Ca   can displace Na from NaCl
(d) Chemical equivalent of the ion
(d) Ca   can reduce NaCl to Na
22. Electrolysis of aqueous HCl solution produces
31. Electrolysis is a process in which the cations and
[CPMT 1987]
anions of the electrolyte are [
(a) H 2 gas at the anode
(a) Hydrated (b) Hydrolysed
(b) H 2 gas at the cathode (c) Charged (d) Discharged
(c) Cl2 gas at the cathode 32. Degree of ionisation of a solution depends upon
(d) Cl2 and O 2 gases both at the anode [BHU 1998]

23. During electrolysis of NaCl solution, part of the (a) Temperature (b) Nature of the
electrolyte
reaction is Na  e   Na. This is termed as[NCERT 1984]
(c) Nature of the solvent (d) None of these
(a) Oxidation (b) Reduction
33. Which of the following is non-electrolytes
(c) Deposition (d) Cathode reaction
[KCET (Med.) 1999]
24. When a solution of an electrolyte is heated the
conductance of the solution (a) 1991]
[KCET NaCl (b) CaCl 2
(a) Increases because of the electrolyte conducts (c) C12 H 22O11 (d) CH 3 COOH
better
34. When a molten ionic hydride is electrolysed
(b) Decreases because of the increased heat
[JIPMER 1999]
(c) Decreases because of the dissociation of the
(a) Hydrogen is liberated at the cathode
electrolyte is suppressed
(b) Hydrogen is liberated at the anode
(d) Increases because the electrolyte is
dissociated more (c) There is no reaction
25. The passage of current liberates H 2 at cathode (d) H  ions produced migrate to the cathode
and Cl 2 at anode. The solution is [EAMCET 1979,87] 35. During electrolysis, the species discharged at
cathode are
(a) Copper chloride in water (b) NaCl in water
[AFMC 2000]
(c) H 2 SO 4 (d) Water
(a) Ions (b) Cation
26. Pure water does not conduct electricity because it
(c) Anion (d) All of these
[Manipal MEE 1995]
36. Electrolysis of molten anhydrous calcium chloride
(a) Has a low boiling point
produces
(b) Is almost totally unionized [AIIMS 2000]
(c) Is neutral
 508 Electrochemistry
(a) Calcium (b) Phosphorus [EAMCET 1990; MP PET 1994, 97]
(c) Sulphur (d) Sodium (a) 9.89 g (b) 107.87 g
37. Which of the following properties of pure metal (c) 1.0787 g (d) 1.002 g
makes it more useful then the corresponding alloy 5. The atomic weight of Al is 27. When a current of
[RPET 2000] 5 Faradays is passed through a solution of
(a) It is harder than corresponding alloy Al    ions, the weight of Al deposited is
(b) It has high density (a) 27 gm (b) 36 gm
(c) It can be extracted easily (c) 45 gm (d) 39 gm
(d) It conducts heat and electricity easily 6. An apparatus used for the measurement of
38. Which of the following liberate hydrogen on quantity of electricity is known as a [BHU 1979]
reaction with dilute H 2 SO 4 (a) Calorimeter
[Roorkee 2000] (b) Cathetometer
(c) Coulometer (d) Colorimeter
(a) Fe (b) Cu
7. The unit of electrochemical equivalent is[EAMCET 1980]
(c) Al (d) Hg
(a) Gram (b) Gram/ampere
39. Which one of the following material conducts
electricity (c) Gram/coulomb (d) Coulomb/gram
[Kerala (Med.) 2003] 8. A certain current liberated 0.504 gm of hydrogen
in 2 hours. How many grams of copper can be
(a) Diamond
liberated by the same current flowing for the
(b) Crystalline sodium chloride same time in a copper sulphate solution[NCERT 1973, 77; C
(c) Barium sulphate (a) 12.7 gm (b) 15.9 gm
(d) Fused potassium chloride (c) 31.8 gm (d) 63.5 gm
(e) Molten sulphur 9. What weight of copper will be deposited by
40. Which of the following metals will give H 2 on passing 2 Faradays of electricity through a cupric
reaction with NaOH [RPET 2003] salt (Atomic weight of Cu = 63.5)[NCERT 1975; CPMT 1977,
(a) Mg (b) Ba (a) 2.0 gm (b) 3.175 gm
(c) Ca (d) Sr (c) 63.5 gm (d) 127.0 gm
41. Which of the following is not a non electrolyte[J & K 2005]
10. If the current is passed into the solution of an
(a) Acetic acid (b) Glucose electrolyte
(c) Ethanol (d) Urea [AIIMS 1979]
(a) Anions move towards anode, cations towards
Faraday's law of electrolysis cathode
(b) Anions and cations both move towards anode
1. Amount of electricity that can deposit 108 gm of (c) Anions move towards cathode, cations
towards
silver from AgNO3 solution is[AFMC 1993; MP PMT 2004] anode
(a) 1 ampere (b) 1 coulomb (d) No movement of ions takes place
(c) 1 faraday (d) None of the above 11. Unit of Faraday is
2. When 9.65 coulombs of electricity is passed (a) Ampere (b) Coulomb
through a solution of silver nitrate (atomic weight (c) Coulomb mole 1 (d) Coulomb Sec 1
of Ag  107 .87 taking as 108) the amount of silver 12. On passing 0.1 Faraday of electricity through
deposited is aluminium chloride, the amount of aluminium
[EAMCET 1992; KCET 2000] metal deposited on cathode is ( Al  27 ) [MP PMT 1991]
(a) 10.8 mg (b) 5.4 mg (a) 0.9 gm (b) 0.3 gm
(c) 16.2 mg (d) 21.2 mg (c) 0.27 gm (d) 2.7 gm
3. Three faradays electricity was passed through an 13. Which of the following represents the first law of
aqueous solution of iron (II) bromide. The weight Faraday
of iron metal (at. wt. = 56) deposited at the [MP PMT 1991]
cathode (in gm) is
(a) E  mc 2
(b) E  hv
[EAMCET 1991]
(c) m  ect (d) PV  nRT
(a) 56 (b) 84
14. 5 amperes is passed through a solution of zinc
(c) 112 (d) 168
sulphate for 40 minutes. Find the amount of zinc
4. A silver cup is plated with silver by passing 965 deposited at the cathode [CBSE PMT 1996]
coulombs of electricity, the amount of silver
(a) 40.65 gm (b) 4.065 gm
deposited is
(c) 0.4065 gm (d) 65.04 gm
 Electrochemistry 509
15. In an electroplating experiment m g of silver is 96500  m C  t  96500
(c) E  (d) E 
deposited, when 4 amperes of current flows for 2 Ct m
minutes. The amount (in gms ) of silver deposited 23. How many Faradays are required to generate one
by 6 amperes of current flowing for 40 seconds gram atom of magnesium from MgCl2 [MADT Bihar 1982]
will be [MNR 1991] (a) 1 (b) 2
(a) 4 m (b) m / 2 (c) 3 (d) 4
(c) m / 4 (d) 2m 24. To deposit 0.6354 gm of copper by electrolysis of
16. On passing 3 ampere of electricity for 50 minutes, aqueous cupric sulphate solution, the amount of
1.8 gram metal deposits. The equivalent mass of electricity required (in coulombs) is
metal is (a) 9650 (b) 4825
[MP PMT 1992] (c) 3860 (d) 1930
(a) 20.5 (b) 25.8 25. In electrolysis of a fused salt, the weight of the
(c) 19.3 (d) 30.7 deposit on an electrode will not depend on[CPMT 1973]
17. The desired amount of charge for obtaining one (a) Temperature of the bath
mole of Al from Al 3  (b) Current intensity
(a) 3  96500 C (b) 96500 C (c) Electrochemical equivalent of ions
96500 96500 (d) Time for electrolysis
(c) C (d) C
3 2 26. Faraday's laws of electrolysis will fail when[NCERT 1971]
18. On passing one faraday of electricity through the (a) Temperature is increased
 2 3 (b) Inert electrodes are used
electrolytic cells containing Ag , Ni and Cr ions
solution, the deposited (c) A mixture of electrolytes is used
Ag (At. wt.  108 ), Ni(At. wt.  59 ) and Cr ( At. wt.  52) is[AIIMS 1982]
(d) In none of these cases
Ag Ni Cr 27. According to the first law of Faraday, the weight
of a substance discharge at the electrode is
(a) 108 gm 29.5 gm 17.3 gm
(a) W  ZQ (b) W  eF
(b) 108 gm 59.0 gm 52.0 gm
Z
(c) 108.0 gm 108.0 gm 108.0 gm (c) W  It (d) W  ZI
F
(d) 108 gm 117.5 gm 166.0 gm
28. When 0.04 faraday of electricity is passed
19. One Faraday of electricity when passed through a through a solution of CaSO4 , then the weight of
solution of copper sulphate deposits [CPMT 1978]
Ca 2  metal deposited at the cathode is [BHU 1996]
(a) 1 mole of Cu (b) 1 gm atom of Cu
(a) 0.2 gm (b) 0.4 gm
(c) 1 molecule of Cu (d) 1 gm equivalent of (c) 0.6 gm (d) 0.8 gm
Cu 29. A current 2.0 A is passed for 5 hours through a
20. When 1 coulomb of charge is passed through molten metal salt deposits 22 g of metal (At. wt.
electrolyte solution, then the mass deposited is =177). The oxidation state of the metal in the
equal to metal salt is [KCET 1996]
(a) Equivalent weight (a) + 1 (b) + 2
(b) Atomic weight (c) + 3 (d) + 4
(c) Electrochemical equivalent 30. How many atoms of calcium will be deposited
(d) Chemical equivalent from a solution of CaCl2 by a current of 25
21. The platinum electrodes were immersed in a milliamperes flowing for 60 seconds
solution of cupric sulphate and electric current (a) 4.68  10 18 (b) 4.68  10 15
passed through the solution. After some time it
(c) 4 .68  10 12 (d) 4 .68  10 9
was found that colour of copper sulphate
31. On passing 0.5 faraday of electricity through
disappeared with evolution of gas at the
NaCl , the amount of Cl deposited on cathode is
electrode. The colourless solution contains [NCERT 1984]
[BHU 1997; RPET 1999]
(a) Platinum sulphate (b) Copper hydroxide
(a) 35.5 gm (b) 17.75 gm
(c) Copper sulphate (d) Sulphuric acid
(c) 71 gm (d) 142 gm
22. On passing C ampere of electricity through a
32. What is the amount of chlorine evolved when 2
electrolyte solution for t second, m gram metal
amperes of current is passed for 30 minutes in an
deposits on cathode. The equivalent weight E of
aqueous solution of NaCl [BHU 1998; AIIMS 1999]
the metal is [MP PMT 1990]
(a) 66 g (b) 1.32 g
Ct C m
(a) E  (b) E  (c) 33 g (d) 99 g
m  96500 t  96500
 510 Electrochemistry
33. On passing a current through KCl solution, 19 .5 g (a) 0.66 mole (b) 0.33 mole
of potassium is deposited. If the same quantity of (c) 0.66 gm (d) 0.33 gm
electricity is passed through a solution of 42. The number of electrons involved in redox
aluminium chloride, the amount of aluminium reactions when a Faraday of electricity is passed
deposited is [EAMCET 1997] through an electrolyte in solution is[NCERT 1982; Pb. PMT 2
(a) 4.5 g (b) 9.0 g (a) 6  10 23 (b) 6  10 23
(c) 13.5 g (d) 27 g (c) 96500 (d) 8  10 19
(e) None is correct 43. Coulomb is equal to [Orissa JEE 2002]
34. Electrolysis rules of Faraday’s states that mass (a) ampere  second (b) ampere  minute
deposited on electrode is proportional to [CBSE PMT 2000]
(c) watt  second (d) volt  second
(a) m  I 2 (b) m  Q 44. The energy required to release 1 electron from
(c) m  Q 2
(d) None of these He  is…….
[Orissa JEE 2002]
35. A current being passed for two hour through a
solution of an acid liberating 11.2 litre of oxygen (a) + 54.4 eV (b) – 13.6 eV
at NTP at anode. What will be the amount of (c) + 27.2 eV (d) Cannot be predicted
copper deposited at the cathode by the same 45. Faraday's laws of electrolysis are related to the[IIT 1983]
current when passed through a solution of copper (a) Atomic number of cation
sulphate for the same time [BVP 2003] (b) Atomic number of anion
(a) 16 g (b) 63 g (c) Equivalent weight of the electrolyte
(c) 31.5 g (d) 8 g (d) Speed of the cation
36. In a metal oxide, there is 20% oxygen by weight. 46. The electric charge for electrode decomposition of
Its equivalent weight is [Pb. PMT 2000] one gram equivalent of a substance is[IIT 1984; KCET 1992]
(a) 40 (b) 64 (a) One ampere per second
(c) 72 (d) 32 (b) 96500 coulombs per second
37. On the basis of the information available from the (c) One ampere for one hour
4 2
reaction Al  O2  Al2 O3 , G  827 kJmol 1 of (d) Charge on one mole of electrons
3 3 47. The number of electrons passing per second
O 2 , the minimum emf required to carry out an through a cross-section of copper wire carrying
1
electrolysis of Al2O3 is (F = 96500C mol )[CBSE PMT 2003] 10 6 amperes of current per second is found to be[EAMCET
(a) 8.56 V (b) 2.14 V (a) 1 . 6  10 19 (b) 6  10 35
(c) 4.28 V (d) 6.42 V (c) 6  10 16 (d) 6  10 12
38. Then during electrolysis of a solution of AgNO3, 48. The electrolytic cells, one containing acidified
9650 coulombs of charge pass through the ferrous chloride and another acidified ferric
electroplating bath, the mass of silver deposited chloride are connected in series. The ratio of iron
in the cathode will be deposited at cathodes in the two cells when
[AIEEE 2003] electricity is passed through the cells will be
(a) 1.08 g (b) 10.8 g [CPMT 1989]
(c) 21.6 g (d) 108 g (a) 3 : 1 (b) 2 : 1
39. Total charge on 1 mole of a monovalent metal ion is (c) 1 : 1 (d) 3 : 2
equal to 49. When 96500 coulomb of electricity is passed
[DPMT 2001] through a copper sulphate solution, the amount of
copper deposited will be [MP PMT 1996]
(a) 9 .65  10 4 Coulomb (b) 6 . 28  10 18 Coulomb
(a) 0.25 mol (b) 0.50 mol
(c) 1 . 6  10 19 Coulomb (d) None of these (c) 1.00 mol (d) 2.00 mol
40. When an electric current is passed through 50. During electrolysis of fused aluminium chloride
acidulated water 112 ml of hydrogen gas at N.T.P. 0.9 gm of aluminium was deposited on the
collect at the cathode in 965 seconds. The current
cathode. The volume of chlorine liberated at the
passed, in amperes is
anode will be
[MNR 1991; UPSEAT 2001]
(a) 2.24 litres (b) 11.2 litres
(a) 1.0 (b) 0.5
(c) 1.12 litres (d) 5.6 litres
(c) 0.1 (d) 2.0
41. How much chlorine will be liberated on passing 51. Faraday has the dimensions of [MP PET 1995]
one ampere current for 30 minutes through NaCl (a) Coulombs
solution [BVP 2003] (b) Coulomb equivalent
 Electrochemistry 511
(c) Coulomb per equivalent (c) Methanol (d) Potassium iodide
(d) Coulomb per degree Kelvin 60. The number of Faradays needed to reduce 4 gram
52. The required charge for one equivalent weight of equivalents of Cu   to Cu metal will be [BHU 1981]
silver deposite on cathode is [Roorkee
(a) 1 1995] (b) 2
(a) 9 .65  10 C
7
(b) 9 .65  10 C
4
(c) 1/2 (d) 4
(c) 9 .65  10 C
3
(d) 9 .65  10 C
5
61. When electricity is passed through the solution of
53. 96500 coulombs of electric current liberates from AlCl3 , 13 .5 gm of Al are deposited. The number of
CuSO 4 solution [MP PMT 1995] Faraday must be
(a) 63 .5 gm Cu (b) 31 .75 gm Cu [NCERT 1974; MP PET 1992; MP PMT 1994]

(c) 96500 gm Cu (d) 100 gm Cu (a) 0.50 (b) 1.00

(c) 1.50 (d) 2.00
54. A current of strength 2.5 amp was passed through
CuSO 4 solution for 6 minutes 26 seconds. The 62. The value of one Faraday is
[AMU 1983; AFMC 1989; MP PET 2001]
amount of copper deposited is
(Atomic weight of Cu  63 .5 ) (a) 95500 C mol 1 (b) 96550 C mol 1
(1 faraday = 96500 coulombs) (c) 96500 C mol 1 (d) 98500 C mol 1
[EAMCET 1989; MP PET 1994]
63. The quantity of electricity needed to liberate 0.5
(a) 0.3175 g (b) 3.175 g
gram equivalent of an element is[CPMT 1988; MP PMT 1997
(c) 0.635 g (d) 6.35 g
(a) 48250 Faradays (b) 48250 Coulombs
55. A certain quantity of electricity is passed through
an aqueous solution of AgNO3 and cupric salt (c) 193000 Faradays (d) 193000 Coulombs

solution connected in series. The amount of Ag 64. The number of coulombs required for the
deposition of 107.870 g of silver is[MP PET/PMT 1998]
deposited is 1.08 gm , the amount of copper
(a) 96,500 (b) 48,250
deposited is (atomic weight of Cu = 63.5; Ag =
108) [EAMCET 1986] (c) 1,93,000 (d) 10,000
(a) 0.6454 g (b) 6.354 g 65. When one of ampere current flows for
(c) 0.3177 g (d) 3.177 g 1 sec through a conductor, this quantity of
56. The number of electrons required to deposit 1gm electricity is known as
atom of aluminium (at. wt. = 27) from a solution [MP PMT 1993]
of aluminium chloride will be (where N is (a) Faraday (b) Coulomb
Avogadro's number)
(c) E.M.F. (d) Ohm
[AIIMS 1992]
66. The mass deposited at an electrode is directly
(a) 1 N (b) 2 N
proportional to
(c) 3 N (d) 4 N
[CPMT 1974; AFMC 1987; MP PET 2000]
57. Three faradays of electricity are passed through
molten Al 2 O3 , aqueous solution of CuSO 4 and (a) Atomic weight (b) Equivalent weight

molten NaCl taken in different electrolytic cells. (c) Molecular weight (d) Atomic number
The amount of Al, Cu and Na deposited at the 67. From the solution of which of the following one
cathodes will be in the ratio of faraday of electricity will liberate one gram atom
[BHU 1990]
of metal
(a) 1 mole : 2 mole : 3 mole [MHCET 1999; MP PET 1993,2000; AFMC 2000]

(b) 3 mole : 2 mole : 1mole (a) NaCl (b) BaCl2

(c) 1 mole : 1.5 mole : 3 mole (c) CuSO 4 (d) AlCl3
(d) 1.5 mole : 2 mole : 3 mole
68. On electrolysis, 1 mole of aluminium will be
58. An electrolytic cell contains a solution of Ag 2 SO 4
deposited from its molten salt by [MH CET 2000]
and have platinum electrodes. A current is passed
(a) 3 moles of electrons (b) 4 moles of electrons
until 1.6 gm of O 2 has been liberated at anode. The
(c) 2 moles of electrons (d) 1 mole of electrons
amount of silver deposited at cathode would be [CPMT 1971]
69. The atomic weight of Fe is 56. The weight of Fe
(a) 107.88 gm (b) 1.6 gm
deposited from FeCl3 solution by passing 0.6
(c) 0.8 gm (d) 21.60 gm
Faraday of electricity is
59. The aqueous solution of which of the following
[MH CET 2000]
decomposes on passing electric current[EAMCET 1973]
(a) 5.6 g (b) 11.2 g
(a) Canesugar (b) Urea
(c) 22.4 g (d) 33.6 g
 512 Electrochemistry
70. 2.5 F of electricity are passed through a CuSO4 heating gave 5 g of its oxide. The equivalent
solution. The number of gm equivalent of Cu weight of copper is [KCET 2004]
deposited on anode is (a) 23 (b) 32
[CPMT 1973; DPMT 1982; MP PMT 2001] (c) 12 (d) 20
(a) Zero (b) 1.25 81. The amount of silver deposited by passing 241.25
(c) 2.5 (d) 5.0 coulomb of current through silver nitrate solution
is [MHCET 2003]
71. The equivalent weight of a certain trivalent
element is 20. Molecular weight of its oxide is[KCET 2003] (a) 2.7 g (b) 2.7 mg
(a) 152 (b) 56 (c) 0.27 g (d) 0.54 g
(c) 168 (d) 68 82. When 1F of electricity is passed through
72. Silver is removed electrically from 200 ml of a 0.1 acidulated water, O 2 evolved is
N solution of AgNO3 by a current of 0.1 ampere. (a) 11 . 2 dm 3 (b) 5 . 6 dm 3
How long will it take to remove half of the silver
(c) 22 . 4 dm 3 (d) 1 . 0 dm 3
from the solution [AMU 1999]
(a) 16 sec (b) 96.5 sec 83. Charge required to liberate 11.5 g sodium is
(c) 100 sec (d) 10 sec [AIIMS 1992; DCE 2002]
73. In order to separate oxygen from one mole of (a) 0.5 F (b) 0.1 F
H 2 O the required quantity of coulomb would be [RPET 1999](c) 1.5 F (d) 96500 coulombs
(a) 1 .93  10 5 (b) 9 .6  10 4 84. In the electrolysis of water, one Faraday of
(c) 1.8 (d) 3.2 electrical energy would evolve
74. A current of 0.25A is passed through CuSO4 (a) One mole of oxygen (b) One g atom of
solution placed in voltameter for 45 minutes. The oxygen
amount of Cu deposited on cathode is (At weight (c) 8 g of oxygen (d) 22.4 litres of oxygen
of Cu  63 .6 ) 85. In a galvanic cell, the electrons flow from [KCET 2004]
[BHU 2001] (a) Anode to cathode through the solution
(a) 0.20 g (b) 0.22 g
(b) Cathode to anode through the solution
(c) 0.25 g (d) 0.30 g
(c) Anode to cathode through the external circuit
75. Faraday constant [KCET (Med.) 2001]
(d) Cathode to anode through the external circuit
(a) Is a numerical constant
86. An electric current is passed through silver
(b) Depends on equivalent
nitrate solution using silver electrodes. 10.79 g of
(c) Depends upon the current passed
silver was found to be deposited on the cathode if
(d) Depends on the number of electrons the same amount of electricity is passed through
76. If 0.5 amp current is passed through acidified copper sulphate solution using copper electrodes,
silver nitrate solution for 10 minutes. The mass of the weight of copper deposited on the cathode is
silver deposited on cathode, is (eq. wt. of silver [Kerala PMT 2004]
nitrate = 108) [AFMC 2001]
(a) 6.4 g (b) 2.3 g
(a) 0.235 g (b) 0.336 g
(c) 12.8 g (d) 1.6 g
(c) 0.536 g (d) 0.636 g
77. The unit for the electric current is[KCET (Med.) 2001] (e) 3.2 g
(a) Ohm (b) Volt 87. The law of electrolysis were proposed by
(c) Ampere (d) Coulomb [CPMT 1982;Pb.CET 2003]
78. The quantity of electricity required to liberate (a) Kohlraush (b) Faraday
112 cm 3 of hydrogen at STP from acidified water (c) Nernst (d) Berthelot
is 88. How many atoms of calcium will be deposited
[KCET (Med.) 2001] from a solution of CaCl2 by a current 0.25 mA
(a) 0.1 Faraday (b) 1 Faraday following for 60 seconds [BHU 2004]
(c) 965 Coulomb (d) 96500 Coulomb (a) 4.68  10 18 (b) 4.68  10 15
79. Which solution will show highest resistance
(c) 4 .68  10 12 (d) 4 .68  10 9
during the passage of current [BHU 2001]
(a) 0.05 N NaCl (b) 2 N NaCl 89. The number of coulombs required to reduce 12.3 g
of nitrobenzene to aniline [
(c) 0.1 N NaCl (d) 1 N NaCl
80. 4 g of copper was dissolved in concentrated nitric (a) 115800 C (b) 5790 C
acid. The copper nitrate solution on strong (c) 28950 C (d) 57900 C
 Electrochemistry 513
90. During the process of electrolytic refining of 3. The factor which is not affecting the conductivity
copper, some metals present as impurity settle as of any solution is
'anode mud'. These are (a) Dilution (b) Nature of electrolyte
[AIEEE 2005] (c) Temperature (d) None of these
(a) Sn and Ag (b) Pb and Zn 4. Specific conductance of 0.1 m nitric acid is
(c) Ag and Au (d) Fe and Ni 6 . 3  10 2 ohm 1 cm 1 . The molar conductance of
91. A galvanic cell is set up from a zinc bar weighing solution is
50g and 1.0litre, 1.0M, CuSO 4 solution. How long [Kerala (Med.) 2003]
would the cell run, assuming it delivers a steady 1
(a) 630 ohm cm mole 2 1
(b) 315 ohm 1cm 2 mole 1
current of 1.0 ampere
[Roorkee 2000]
(c) 100 ohm 1cm 2 mole 1 (d) 6300 ohm 1cm 2 mole 1

(a) 48 hrs (b) 41 hrs (e) 63.0 ohm 1cm 2 mole 1

(c) 21 hrs (d) 1 hr 5. The conductivity of strong electrolyte is[CPMT 2003]
92. On passing electric current through molten (a) Increase on dilution slightly
aluminium chloride, 11.2 litre of Cl2 is liberated (b) Decrease on dilution
at NTP at anode. The quantity of aluminium (c) Does not change with dilution
deposited at cathode is (at. wt. of Al = 27) [JIPMER
(d) Depend 2002]
upon density of electrolytes itself
(a) 9 g (b) 18 g 6. If X is the specific resistance of the solution and
(c) 27 g (d) 36 g M is the molarity of the solution, the molar
93. An electric current is passed through silver conductivity of the solution is given by[Kurukshetra CEE 20
voltameter connected to a water voltameter. The 1000 X 1000
(a) (b)
cathode of the silver voltameter weighed 0.108 g M MX
more at the end of the electrolysis. The volume of 1000 M MX
oxygen evolved at STP is (c) (d)
X 1000
[Kerala (Med.) 2003]
7. Conductivity (unit Siemen’s) is directly
3
(a) 56 cm (b) 550 cm 3 proportional to area of the vessel and the
(c) 5.6 cm 3 (d) 11.2 cm 3 concentration of the solution in it and is inversely
proportional to the length of the vessel then the
(e) 22.4 cm 3 unit of the constant of proportionality is [AIEEE 2002]
94. During electrolysis of aqueous NaOH, 4 g of O 2 (a) Sm mol 1 (b) Sm 2 mol 1
gas is liberated at NTP at anode, H 2 gas liberated
(c) S 2 m 2 mol (d) S 2 m 2 mol 2
at cathode is
8. If one end of a piece of a metal is heated, the
[CBSE PMT 1998]
other end becomes hot after some time. This is
(a) 2.8 litres (b) 5.6 litres due to
(c) 11.2 litres (d) 22.4 litres [CBSE PMT 1995]
(a) Energised electrons moving to the other part of
Conductor and conductance the metal
(b) Resistance of the metal
1. Which one of the following statements is correct (c) Mobility of atoms in the metal
[MP PET 1997] (d) Minor perturbation in the energy of atoms
(a) The oxidation number of oxygen in KO2 is 9. Conductivity of a solution is directly proportional
zero to
(b) The specific conductance of an electrolyte [KCET 1984]
solution decreases with increase in dilution (a) Dilution (b) Number of ions
(c) Sn 2  oxidises Fe 3  (c) Current density (d) Volume of the
solution
(d) Zn / ZnSO 4 is a reference electrode
10. The increase in equivalent conductance of an
2. In infinite dilutions, the equivalent conductances of electrolyte solution with dilution is due to the
Ba 2  and Cl  are 127 and 76 ohm 1cm 1 eqvt 1 . increase in
The equivalent conductivity of BaCl2 at indefinite [MP PMT 1996]
dilution is [CBSE 2000] (a) Ionic attraction
(a) 101.5 (b) 139.5 (b) Molecular attraction
(c) 203.5 (d) 279.5 (c) Degree of association of the electrolyte
 514 Electrochemistry
(d) Degree of ionisation of the electrolyte (c) Show a positive temperature coefficient for
11. Which of the following conducts electricity[AFMC 1995] conductance
(a) Fused NaCl (b) CO2 (d) A single stream of electrons flows from
cathode to anode
(c) Br2 (d) Si
19. Which one is not a conductor of electricity[RPET 1999]
12. Which of the following shows electrical (a) NaCl (aqueous) (b) NaCl (solid)
conduction
(c) NaCl (molten) (d) Ag metal
[CBSE PMT 1999; AIIMS 1999]
20. Solid sodium chloride is bad conductor of
(a) Potassium (b) Graphite
electricity because
(c) Diamond (d) Sodium
(a) It contains only molecules
13. The unit of equivalent conductivity is
(b) It does not possess ions
[CPMT 1999; BCECE 2005]
(c) The ions present in it are not free to move
(a) ohm cm
1
(d) It does not contain free molecules
(b) ohm cm 2 (gm equivalent ) 1
21. Which of the following is a poor conductor of
(c) ohm cm 2 (gm equivalent ) electricity
[EAMCET 1992]
(d) S cm 2
(a) CH 3 COONa (b) C 2 H 5 OH
14. It has been observed that gaseous hydrogen
(c) NaCl (d) KOH
chloride is a very poor conductor of electricity
but a solution of hydrogen chloride gas in water is 22. The molar conductivity is maximum for the
a good conductor of electricity. This is due to the solution of concentration [DCE 2002]
fact that [NCERT 1976] (a) 0.001 M (b) 0.005 M
(a) Water is good conductor of electricity (c) 0.002 M (d) 0.004 M
(b) Hydrogen chloride gas in water solution 23. The unit of molar conductivity is [DCE 2002]
ionizes (a) 1cm 2mol 1 (b)  cm 2mol 1
(c) A gas is non-conductor but a liquid conducts (c) 1cm 2mol 1 (d)  cm 2mol
electricity
24. The highest electrical conductivity of the
(d) Gas does not obey Ohm's law whereas solution following aqueous solutions is of
does
(a) 0.1 M acetic acid (b) 0.1 M chloroacetic
15. Electrolytic conduction differs from metallic acid
conduction in that in the case of electrolytic
(c) 0.1 M fluoroacetic acid (d) 0.1 M
conduction
difluoroacetic acid
[KCET 1987; Bihar CEE 1992]
25. Given l / a  0 .5 cm 1 , R  50 ohm , N  1 .0 . The
(a) The resistance increases with increasing
temperature equivalent conductance of the electrolytic cell is [Orissa JE
1
(b) The resistance decreases with increasing (a) 10 ohm cm 2 gm eq 1 (b) 20 ohm 1
cm 2 gm eq 1
temperature 1 1 1 1
(c) 300 ohm cm 2 gmeq (d) 100 ohm cm 2 gmeq
(c) The flow of current does not generate heat
26. If equivalent conductance of 1 M benzoic acid is
(d) The resistance is independent of the length of
the conductor 12 .8 ohm 1 cm 2 and if the conductance of benzoate
16. The electrolytic conductance is a direct measure ion and H  ion are 42 and 288 .42 ohm 1 cm 2
of respectively. its degree of dissociation is
[KCET 1990; CPMT 2003] (a) 39% (b) 3.9%
(a) Resistance (b) Potential (c) 0.35% (d) 0.039%
(c) Concentration (d) Dissociation 27. The unit ohm 1 is used for [
17. Conductivity of a strong electrolyte [KCET 1993] (a) Molar conductivity (b) Equivalent
(a) Increases on dilution conductivity
(b) Does not change considerably on dilution (c) Specific conductivity (d) Conductivity
(c) Decreases on dilution
(d) Depends on density Cell constant and Electrochemical Cells
18. Which of the following statements is not
applicable to electrolytic conductors [AIIMS 1991] 1. When electric current is passed through a cell
(a) New products show up at the electrodes having an electrolyte, the positive ions move
towards the cathode and the negative ions
(b) Ions are responsible for carrying the current
towards the anode. If the cathode is pulled out of
the solution [AIIMS 1980]
 Electrochemistry 515
(a) The positive and negative ions will move (b) H 2 SO 4 is regenerated
towards the anode
(c) PbSO4 is deposited on lead electrode
(b) The positive ions will start moving towards
the anode, the negative ions will stop moving (d) Lead is deposited on lead electrode
(c) The negative ions will continue to move 9. When lead storage battery is charged
towards the anode and the positive ions will [MP PET 1993; MP PMT 2000]
stop moving (a) Lead dioxide dissolves
(d) The positive and negative ions will start (b) Sulphuric acid is regenerated
moving randomly (c) The lead electrode becomes coated with lead
2. If the half cell reaction A  e   A  has a large sulphate
negative reduction potential, it follows that (d) The amount of sulphuric acid decreases
[MNR 1992; UPSEAT 2000, 02] 10. The electrolytic decomposition of dilute sulphonic
(a) A is readily reduced (b) A is readily oxidised acid with platinum electrode in cathodic reaction
(c) A  is readily reduced (d) A  is readily oxidised is
3. Mark the false statement [MP PET 1997] [MNR 1988; UPSEAT 1999, 2002]
(a) A salt bridge is used to eliminate liquid (a) Oxidation
junction potential (b) Reduction
(b) The Gibbs free energy change, G is related (c) Oxidation and reduction both
with electromotive force (E) , as G  nFE (d) Neutralisation
(c) Nernst equation for single electrode potential 11. Which colourless gas evolves, when NH 4 Cl reacts
RT
is E  E o  ln a M n  with zinc in a dry cell battery [Orissa JEE 2003]
nF
(a) NH 4 (b) N 2
(d) The efficiency of a hydrogen oxygen fuel cell
is 23% (c) H 2 (d) Cl2
4. The specific conductance of a 0.1 N KCl solution at 12. Which of the substances Na, Hg, S , Pt and
23 o C is 0 .012 ohm 1 cm 1 . The resistance of cell graphite can be used as electrodes in electrolytic
containing the solution at the same temperature cells having aqueous solutions
was found to be 55 ohm. The cell constant will be (a) Na, Pt and graphite (b) Na and Hg
[CBSE PMT 1999, 2000; KCET 2001]
1 (c) Pt and graphite only (d) Na and S only
(a) 0 . 142 cm (b) 0 .66 cm 1
13. In electrolysis of dilute H 2 SO 4 using platinum
(c) 0 .918 cm 1 (d) 1 . 12 cm 1 electrodes
5. Which of the following reactions occurs at the [DPMT 1983; IIT 1983; Kurukshetra CET 2002; AFMC 2005]
cathode of a common dry cell (a) H[NCERT 1978]at cathode
is evolved
2
(a) Mn  Mn 2   2e  (b) NH 3 is produced at anode
(b) 2 MnO 2  Zn 2   2e   ZnMn 2 O 4 (c) Cl2 is obtained at cathode
2 
(c) 2 ZnO 2  Mn  2e  MnZn 2 O 4 (d) O 2 is produced
2 
(d) Zn  Zn  2e 14. For cell reaction, Zn  Cu 2   Zn 2   Cu, cell
6. In Cu  Zn cell [BHU 1981] representation is [BCECE 2005]
(a) Reduction occurs at the copper cathode (a) Zn | Zn2+||Cu2+|Cu (b) Cu | Cu2+ ||Zn2+| Zn
(b) Oxidation occurs at the copper cathode (c) Cu | Zn2+ || Zn | Cu2+ (d) Cu2+ | Zn || Zn2+ | Cu
(c) Reduction occurs at the anode 15. Which one is not called a anode reaction from the
(d) Chemical energy is converted to light energy following
7. Which of the following reaction is used to make a 1
(a) Cl   Cl 2  e  (b) Cu  Cu    2e 
fuel cell 2
[AIIMS 2003]
(c) Hg   Hg    e  (d) Zn 2   2 e   Zn
(a) Cd(s)  2 Ni(OH )3 (s)  CdO(s)  2 Ni(OH )  H 2 O(l)
16. A cell from the following which converts electrical
(b) Pb(s)  PbO2 (s)  2H 2 SO 4 (aq)  2PbSO4 (s)  2H 2 O(l) energy into chemical energy
(c) 2 H 2 (g)  O2 (g)  2 H 2O(l) (a) Dry cell (b) Electrochemical cell
(d) 2 Fe (s)  O 2 (g)  4 H  (aq )  2 Fe 2  (aq )  2 H 2 O(l) (c) Electrolytic cell (d) None of these

8. When lead storage battery is charged[MP PET 2003] 17. In the cell Zn | Zn 2  || Cu 2  | Cu , the negative
(a) PbO2 is dissolved electrode is
 516 Electrochemistry
[MP PMT 1995] 25. The specific conductance of a solution is 0.2
(a) Cu (b) Cu 2 ohm 1cm 1 and conductivity is 0.04 ohm 1 . The cell
constant would be [RPET 1999]
(c) Zn (d) Zn 2 
(a) 1 cm 1 (b) 0 cm 1
18. Which of the following statements is correct ?
Galvanic cell converts [KCET 1991; MP PMT 1993] (c) 5 cm 1 (d) 0.2 cm 1
(a) Chemical energy into electrical energy 26. If the conductance and specific conductance of a
solution is one then its cell constant would be [RPET 1999]
(b) Electrical energy into chemical energy
(a) 1 (b) Zero
(c) Metal from its elemental state to the
(c) 0.5 (d) 4
combined state
27. Saturated solution of KNO3 is used to make ‘salt-
(d) Electrolyte into individual ions
bridge’ because [IIT Screening 2002]
19. Hydrogen–oxygen fuel cells are used in space–

craft to supply [MP PMT 1993; MP PET 1999] (a) Velocity of K is greater than that of NO 3
(a) Power for heat and light (b) Velocity of NO 3 is greater than that of K 
(b) Power for pressure (c) Velocities of both K  and NO 3 are nearly the
(c) Oxygen same
(d) Water (d) KNO3 is highly soluble in water
20. The standard cell potential of
28. In balancing the half reaction S 2 O32   S (s) the
Zn | Zn 2 (aq ) || Cu 2 (aq ) | Cu cell is 1.10 V. The
number of electrons that must be added is[DPMT 2000]
maximum work obtained by this cell will be [MP PET 2002]
(a) 4 on the left (b) 3 on the right
(a) 106.15 kJ (b) – 212.30 kJ
(c) 2 on the left (d) 2 on the right
(c) – 318.45 kJ (d) – 424.60 kJ 29. Which one of the following statement is true for a
21. The relationship between standard reduction electrochemical cell [Pb. PMT 1999; KCET 1999]
potential of cell and equilibrium constant is (a) H 2 is cathode and Cu is anode
shown by [MP PET 2002]
(b) H 2 is anode and Cu is cathode
n 0 .059
0
(a) E cell  log K c 0
(b) Ecell  log K c (c) Reduction occurs at H 2 electrode
0 . 059 n
(d) Oxidation occurs at Cu electrode
log K c
0
(c) Ecell  0 . 059 n log K c 0
(d) Ecell  30. In the reaction
n
Cu(s)  2 Ag  (aq)  Cu 2  (aq)  2 Ag(s)
22. Consider the Galvanic cell
The reduction half-cell reaction is [
Zn  | ZnSO 4 || CuSO 4 | Cu  the reaction at cathode
 2  2
(a) Cu  2e  Cu (b) Cu  2e  Cu
is [AMU 2000]
 
 (c) Ag  e  Ag (d) Ag  e   Ag 
(a) Zn 2  2e   Zn
31. Which of the following statements about galvanic
(b) Cu 2   2e   Cu cell is incorrect [JIPMER 1997]

(c) Cu 2   Zn  Cu  Zn 2  (a) Anode is positive

(b) Oxidation occurs at the electrode with lower
(d) Zn 2   Cu  Zn  Cu 2  reduction potential
23. The cell reaction Cu  2 Ag   Cu 2  Ag is best (c) Cathode is positive
represented by [AMU 2000] (d) Reduction occurs at cathode
32. The molar conductances of NaCl, HCl and
(a) Cu(s) | Cu 2(aq ) || Ag (aq ) | Ag(s)
CH 3 COONa at infinite dilution are 126.45, 426.16
(b) Pt | Cu 2 || Ag (aq ) | Ag(s) 1
and 91 ohm cm 2 mol 1 respectively. The molar
2
(c) Cu | Cu || Pt | Ag conductance of CH 3 COOH at infinite dilution is[CBSE PMT
1
(d) None of the above representations (a) 201 . 28 ohm cm 2 mol 1
24. Zn(s) | Zn 2  (aq ) | | Cu 2  (aq ) | Cu (s) is [Kerala (Engg.) 2002] (b) 390 .71 ohm 1 cm 2 mol 1
(anode) (cathode)
(c) 698 .28 ohm 1 cm 2 mol 1
(a) Weston cell (b) Daniel cell
(c) Calomel cell (d) Faraday cell (d) 540 .48 ohm 1 cm 2 mol 1
(e) Standard cell
 Electrochemistry 517
33. The electrodes of a conductivity cell are 3 cm 41. In electroplating, the article to be electroplated
2 serves as
apart and have a cross-sectional area of 4 cm .
[AMU 1982, 83]
The cell constant of the cell (in cm 1 ) is
(a) Cathode (b) Electrolyte
(a) 4  3 (b) 4 / 3
(c) Anode (d) Conductor
(c) 3 / 4 (d) 9 / 4
34. The anode half-reaction occurring during the 42. The position of some metals in the
discharge of a lead storage battery is electrochemical series in decreasing
electropositive character is given as
(a) Pb(s)  SO 2  O2  PbSO 4 (s)
Mg  Al  Zn  Cu  Ag . What will happen, if a
(b) Pb (s)  SO 42  (aq ) ⇌ PbSO 4 (s)  2 e  copper spoon is used to stir a solution of
aluminium nitrate
(c) PbO 2 (s)  4 H  (aq )  2e   SO 42  (aq ) ⇌
[NCERT 1977]
PbSO 4 (s)  2 H 2 O
(a) The spoon will get coated with Al
(d) Pb 2  (aq )  SO 42  (aq )  PbSO 4 (s) (b) An alloy of Cu and Al is formed
35. The unit of cell constant is [MP PET 1996] (c) The solution becomes blue
1 1 (d) There is no reaction
(a) ohm cm (b) ohm cm
43. In a electrochemical cell [AFMC 1989]
(c) cm (d) cm 1
(a) Potential energy changes into kinetic energy
36. In dry cell the reaction which takes place at the
(b) Kinetic energy changes into potential energy
zinc anode is
[MP PET 1996] (c) Chemical energy changes into electrical
energy
(a) Zn 2   2e   Zn(s)
(d) Electrical energy changes into chemical
(b) Zn(s)  Zn 2   2e  energy
44. In galvanic cell, the salt bridge is used to[MP PMT 2002]
(c) Mn2   2e   Mn(s)
(a) Complete the circuit
(d) Mn(s)  Mn  e   1.5 V (b) Reduce the electric resistance in the cell
37. The chemical reaction taking place at the anode of (c) Separate cathode from anode
a cell is (d) Carry salts for the chemical reaction
[MP PET 1996] 45. If a strip of Cu metal is placed in a solution of
(a) Ionisation (b) Reduction ferrous sulphate[NCERT 1974; CPMT 1977; MP PET 2000]
(a) Copper will precipitate out
(c) Oxidation (d) Hydrolysis
(b) Iron will precipitate out
38. Which of the following reactions occurs at the
(c) Copper will dissolve
cathode during the charging of a lead storage
battery (d) No reaction will take place
[Manipal MEE 1995; MP PET 2002] 46. Which of the following is not used to construct
2 
salt bridge
(a) Pb  2e  Pb [MP PET 2003]
2
(b) Pb  SO 42   PbSO 4
(a) CH 3 COOK (b) KCl
2  (c) NH 4 NO3 (d) KNO3
(c) Pb  Pb  2e
47. The reference electrode is made by using[MP PMT 2002]
(d) PbSO 4  2 H 2 O  2 PbO 2  4 SO 42   2 e 
(a) ZnCl2 (b) CuSO4
39. A depolarizer used in dry cell batteries is[NCERT 1981]
(c) HgCl2 (d) Hg 2 Cl2
(a) Ammonium chloride (b) Manganese dioxide
48. In a hydrogen – oxygen fuel cell, combustion of
(c) Potassium hydroxide (d) Sodium phosphate hydrogen occurs to [AIEEE 2004]
40. When a lead storage battery is discharged (a) Produce high purity water
[IIT 1987; MP PMT 2004] (b) Create potential difference between the two
(a) SO 2 is evolved electrodes
(c) Generate heat
(b) Lead sulphate is consumed
(d) Remove adsorbed oxygen from electrode
(c) Lead is formed
surfaces
(d) Sulphuric acid is consumed
49. ClCH 2COONa  224 ohm 1cm 2 gmeq 1 ,
 518 Electrochemistry
 NaCl  38 .2 ohm 1 cm 2 gmeq 1
, (a) Pt | H 2 (g),1bar | 1M KCl(aq)|AgCl(s)| Ag(s)

 HCl  203 ohm 1 cm 2 gmeq 1

, (b) Pt (s)| H 2 (g), 1bar | 1 M HCl (aq )|| 1 M Ag  (aq )| Ag (s)
What is the value of ClCH 2 COOH [JEE
(c)Orissa 2004]
Pt(s)| H 2 (g), 1bar | 1M HCl(aq)| AgCl(s)| Ag(s)
1 2 1
(a) 288 . 5 ohm cm gmeq (d) Pt(s)| H 2 (g), 1bar | 1M HCl(aq)| Ag(s)| AgCl(s)
1 2 1
(b) 289 . 5 ohm cm gmeq
58. If the Zn 2 / Zn electrode is diluted to 100 times
1 1
(c) 388 .5 ohm cm 2 gmeq then the change in e.m.f. [DPMT 2005]
(d) 59 . 5 ohm 1 cm 2 gmeq 1
(a) Increase of 59 mV
50. Which of the following statement is true for the (b) Decrease of 59 mV
electrochemical Daniel cell [AIIMS 2004]
(a) Electrons flow from copper electrode to zinc (c) Increase of 29 .5 mV
electrode
(d) Decrease of 29 .5 mV
(b) Current flows from zinc electrode to copper
electrode 59. If hydrogen electrode dipped in 2 solution of
(c) Cations move toward copper electrode which is pH  3 and pH  6 and salt bridge is connected
cathode the e.m.f. of resulting cell is [DPMT 2005]
(d) Cations move toward zinc electrode (a) 0.177 V (b) 0.3 V
51. Which of the following statement is true for an
(c) 0.052 V (d) 0.104 V
electrochemical cell [Pb.CET 2002]
(a) H 2 is cathode and Cu is anode 60. The tendency of an electrode to lose electrons is
known as
(b) H 2 is anode and Cu is cathode
[J & K 2005]
(c) Reduction occurs at H 2 electrode
(a) Electrode potential (b) Reduction potential
(d) Oxidation occurs at Cu electrode
(c) Oxidation potential (d) e.m.f.
52. Which of the following statements are true for an
fuel cells 61. When electric current is supplied through an ionic
[DPMT 2004] hydride of fused state, then [Kerala CET 2005]

(a) They run till the reactants are active (a) Hydrogen is obtained at anode
(b) They are free from pollution (b) Hydrogen is obtained at cathode
(c) They are more efficient (c) No change
(d) All of the above (d) Hydride ion moves towards cathode
53. For gold plating, the electrolyte used is[Pb.CET 2004] (e) hydride ion present in solution
(a) AuCl3 (b) HAuCl 4
Electrode potential, ECell, Nernt equation and ECS
(c) k[ Au(CN )2 ] (d) None of these

54. The acid used in lead storage battery is[Pb.CET 2003] 1. The hydrogen electrode is dipped in a solution of
pH  3 at 25 o C . The potential of the cell would
(a) H 2 SO 4 (b) H 3 PO4
be (the value of 2.303 RT / F is 0.059 V) [KCET 1993,2005]
(c) HCl (d) HNO3 (a) 0.177 V (b) – 0.177 V
55. At 25°C specific conductivity of a normal solution (c) 0.087 V (d) 0.059 V
of KCl is 0.002765 mho. The resistance of cell is 2. The standard electrode potentials of Zn 2 / Zn and
400 ohms. The cell constant is Ag  / [Pb.PMT
Ag are 2004]
 0.763 V and  0.799 V respectively.
(a) 0.815 (b) 1.016 The standard potential of the cell is [KCET 1993]
(c) 1.106 (d) 2.016 (a) 1.56 V (b) 0.036 V
56. Which of the following is used widely in the (c) – 1.562 V (d) 0.799 V
manufacture of lead storage battery [BHU 2004] 3. The standard reduction potentials at 298 K for the
(a) Arsenic (b) Lithium following half reactions are given against each

(c) Bismuth (d) Antimony Zn 2  (aq.)  2e ⇌ Zn(s) ; – 0.762

3
57. The chemical reaction, 2 AgCl(s)  H 2 (g)  Cr (aq)  3e ⇌ Cr (s) ; – 0.740

2 HCl (aq )  2 Ag (s) taking place in a galvanic cell is 2 H (aq)  2e ⇌ H 2 (g) ; 0.00
represented by the notation [AIIMS 2005]
 Electrochemistry 519
Fe 3  (aq)  e ⇌ Fe 2  (aq) ; 0.770 9. Beryllium is placed above magnesium in the
second group. Beryllium dust, therefore when
Which is the strongest reducing agent
added to MgCl2 solution will
[IIT 1981; MP PET/PMT 1988; MP PMT 1989;
MH CET 2001] [CPMT 1977]

(a) Zn(s) (b) Cr (s) (a) Have no effect

(b) Precipitate Mg metal
(c) H 2 (g) (d) Fe 2  (aq)
(c) Precipitate MgO
4. When Zn piece is kept in CuSO 4 solution, the
copper get precipitated due to standard potential (d) Lead to dissolution of Be metal
of zinc is 10. The name of equation showing relation between
[CPMT 1999] electrode potential (E) standard electrode
(a) > copper (b) < copper potential (E o ) and concentration of ions in
(c) > sulphate (d) < sulphate solution is
5. Which of the following metal does not react with (a) Kohlrausch's equation (b) Nernst's equation
the solution of copper sulphate [CPMT 1999] (c) Ohm's equation (d) Faraday's equation
(a) Mg (b) Fe 11. The correct representation of Nernst's equation is
(c) Zn (d) Ag 0 . 0591
(a) E M n  / M  E o M n  / M  log (M n  )
6. A solution containing one mole per litre of each n
Cu(NO3 )2 , AgNO3 , Hg 2 (NO3 )2 and Mg(NO3 )2 , is 0 . 0591
(b) E M n  / M  E o M n  / M  log (M n  )
being electrolysed by using inert electrodes. The n
values of standard electrode potentials in volts
n
(reduction potentials) are (c) E M n  / M  E o M n  / M  log (M n  )
0 . 0591
Ag / Ag   0 .80 , 2 Hg / Hg 22   0 .79 , Cu / Cu 2   0 .34 ,
(d) None of the above
Mg / Mg 2   2.37 with increasing voltage, the
12. Standard electrode potential of NHE at 298 K is
sequence of deposition of metals on the cathode
will be (a) 0.05 V (b) 0.1 V
[IIT 1984; AMU 1999; Kerala PMT 2004] (c) 0.00 V (d) 0.11 V
(a) Ag, Hg, Cu, Mg (b) Mg, Cu, Hg, Ag 13. When a copper wire is placed in a solution of
AgNO3 , the solution acquires blue colour. This is
(c) Ag, Hg, Cu (d) Cu, Hg, Ag
due to the formation of
7. The standard reduction electrode potentials of
[Roorkee 1989]
four elements are
2
A  0.250 V B  0.136 V (a) Cu ions

C  0.126 V D  0.402 V (b) Cu ions
(c) Soluble complex of copper with AgNO3
The element that displaces A from its compounds
is (d) Cu  ion by the reduction of Cu
(a) B (b) C 14. Consider the reaction M(naq )  ne   M(s) . The
(c) D (d) None of these
standard reduction potential values of the
8. The standard oxidation potential of zinc and elements M1 , M 2 and M 3 are 0.34 V,  3.05 V and
silver in water at 298 K are
1.66 V respectively. The order of their reducing
2 
Zn (s)  Zn  2e ; E  0 .76 V power will be [NCERT 1990]

Ag (s)  Ag 2 
 2e ; E  0 .80 V (a) M1  M 2  M 3 (b) M 3  M 2  M1

Which of the following reactions actually take (c) M1  M3  M 2 (d) M 2  M 3  M1

place RT
15. E0  In K eq . This is called
[NCERT 1983, 84; KCET 2003] nF
(a) Zn(s)  2 Ag  (aq )  Zn   (aq )  2 Ag (s) [CPMT 1988; MP PET 2000]
(a) Gibb's equation
(b) Zn   (aq )  2 Ag (s)  2 Ag  (aq )  Zn(s)
(b) Gibb's–Helmholtz equation
(c) Zn(s)  Ag (s)  Zn   (aq )  Ag  (aq ) (c) Nernst's equation
(d) Vander Waal's equation
(d) Zn   (aq )  Ag  (aq )  Zn(s)  Ag (s)
16. Four alkali metals A, B, C and D are having
respectively standard electrode potential as –
 520 Electrochemistry
3.05,–1.66,–0.40 and 0.80. Which one will be the (a) + 1.25 V (b)  1.75 V
most reactive
(c) + 1.75 V (d) + 4.0 V
[MP PMT/PET 1988 ; CPMT 1983;
25. Oxidation and reduction take place in a cell, then
MNR 1993; UPSEAT 2002]
its electromotive force will be [RPET 1999]
(a) A (b) B
(a) Positive (b) Negative
(c) C (d) D
(c) Zero (d) Stable
17. Which one of the following metals cannot evolve
H 2 from acids or H 2 O or from its compounds 26. For a spontaneous reaction the G, equilibrium
o
[MP PET/PMT 1988; CPMT 1996; constant (K) and E Cell will be respectively [
AFMC 1998, 99; Pb. PET 1999; BVP 2003] (a) ve,  1,  ve (b) ve,  1,  ve
(a) Hg (b) Al
(c) ve,  1,  ve (d) ve,  1,  ve
(c) Pb (d) Fe
27. The reference electrode is made from which of the
18. Which one of the following reaction is not
following
possible
[MP PET/PMT 1988]
[MP PMT 1991]
(a) ZnCl2 (b) CuSO 4
(a) Fe  H 2 SO 4  FeSO4  H 2
(c) Hg 2 Cl2 (d) HgCl2
(b) Cu  2 AgNO3  Cu (NO3 )2  2 Ag
(c) 2 KBr  I2  2 KI  Br2 28. The charge over anode in a galvanic cell is
(a) Negative
(d) CuO  H 2  Cu  H 2 O
(b) Positive
19. When a rod of metal A is dipped in an aqueous
(c) No charge
solution of metal B (concentration of B 2  ion
(d) Sometimes negative and sometimes positive
being 1M) at 25 o C , the standard electrode
29. The standard electrode potential for the two
potentials are A 2  / A =–0.76 volts, B 2  /B = + 0.34
electrode A  / A and B  / B are respectively 0.5 V
volts [KCET 1992]
and 0.75 V . The emf of the given cell
(a) A will gradually dissolve
A | A  (a  1) || B  (a  1) | B will be
(b) B will deposit on A
(c) No reaction will occur (a) 1.25 V (b) – 1.25 V
(d) Water will decompose into H 2 and O 2 (c) – 0.25 V (d) 0.25 V
30. The standard reduction potential for
20. The reaction Zn 2   2e   Zn has a standard
Li  / Li ; Zn 2  / Zn ; H  / H 2 and Ag  / Ag is
potential of 0.76 V . This means [KCET 1992]
3.05 ,  0.762 , 0.00 and 0.80 V. Which of the
(a) Zn can't replace hydrogen from acids
following has highest reducing capacity
(b) Zn is a reducing agent
(c) Zn is a oxidising agent (a) Ag (b) H 2

(d) Zn 2  is a reducing agent (c) Zn (d) Li

  31. If an iron rod is dipped in CuSO 4 solution
21. 2 H (aq )  2 e  H 2 (g). The standard electrode
potential for the above reaction is (in volts)[CPMT 1988] [MADT Bihar 1984]
(a) 0 (b) + 1 (a) Blue colour of the solution turns green
(c) – 1 (d) None of these (b) Brown layer is deposited on iron rod
22. K, Ca and Li metals may be arranged in the (c) No change occurs in the colour of the solution
decreasing order of their standard electrode (d) Blue colour of the solution vanishes
potentials as [CPMT 1990] (e) None of the above
(a) K, Ca, Li (b) Ca, K, Li
32. E o values of Mg 2  / Mg is 2.37 V , of Zn 2 / Zn is
(c) Li, Ca, K (d) Ca, Li, K
0.76 V and Fe 2  / Fe is 0.44 V . Which of the
23. The correct order of chemical reactivity with
following statements is correct [EAMCET 1989]
water according to electrochemical series[MP PMT 1991]
2
(a) K  Mg  Zn  Cu (b) Mg  Zn  Cu  K (a) Zn will reduce Fe
(c) K  Zn  Mg  Cu (d) Cu  Zn  Mg  K (b) Zn will reduce Mg 2 

24. EMF of cell Ni | Ni 2  (1 .0 M ) || Au 3  (1 .0 M ) | Au (c) Mg oxidises Fe

(Where E o for Ni 2  | Ni is  0 . 25 V; E o for (d) Zn oxidises Fe
Au 3 | Au is 1.50 V) is [MP PET 1993; MP PMT 2000] 33. The standard reduction potential for Fe 2  / Fe and
Sn 2 / Sn electrodes are 0 . 44 and 0 . 14 volt
 Electrochemistry 521
respectively. For the given cell reaction (a) P  Q  R  S (b) Q  P  R  S
Fe 2   Sn  Fe  Sn 2  , the standard EMF is[IIT Screening 1990;(c)  Q 2003]
MP RPMT S P (d) P  S  Q  R
(a) + 0.30 V (b) – 0.58 V 41. Which of the following metal can deposit copper
(c) + 0.58 V (d) – 0.30 V from copper sulphate solution[CPMT 1983; MP PMT 1989]
34. Electrode potential of Zn 2 / Zn is 0.76 V and that (a) Mercury (b) Iron
of Cu 2  / Cu is 0 . 34 V . The EMF of the cell (c) Gold (d) Platinum
constructed between these two electrodes is 42. Standard electrode potential of Ag  / Ag and

[EAMCET 1992; BHU 2001; CBSE PMT 2001; KCET 1990; Cu / Cu is 0 .80 V and 0 .34 V respectively. these
MHCET 1999, 2003; Pb. CET 2002; electrodes are joint together by salt bridge if[AMU 2002]
AFMC 2001; Pb. PMT 2004]
(a) Copper electrode is work like cathode, then
(a) 1.10 V (b) 0.42 V o
E cell is 0 . 45 V
(c) – 1.1V (d) – 0.42 V
o
35. EMF of a cell whose half cells are given below is (b) Silver electrode is work like anode then E cell
Mg 2 
 2e  Mg (s); E  2 .37 V is 0 . 34 V
o
Cu 2   2e   Cu (s); E  0 .33 V (c) Copper electrode is work like anode then E cell
[EAMCET 1987; MP PET 1994; Pb. PMT 2000] is 0 . 46 V
o
(a) – 2.03 V (b) 1.36 V (d) Silver electrode is work like cathode then E cell
(c) 2.7 V (d) 2.03 V is 0 . 34 V
36. A cell constructed by coupling a standard copper o
(e) Silver electrode is work like anode then E cell
electrode and a standard magnesium electrode
will be 1 . 14 V
has emf of 2.7 volts. If the standard reduction
43. The reaction is spontaneous if the cell potential is
potential of copper electrode is + 0.34 volt that of
magnesium electrode is [KCET 1989] [MP PET 1999]
(a) + 3.04 volts (b) – 3.04 volts (a) Positive (b) Negative
(c) + 2.36 volts (d) – 2.36 volts (c) Zero (d) Infinite
37. When E o   0.8 volt and E Zn
o
2  0 .76 volt, 44. Which substance eliminates bromine from KBr
Ag / Ag / Zn
solution
which of the following is correct [MP PMT 1994] [IIT 1981]
(a) Ag  can be reduced by H 2 (a) I2 (b) Cl2
(b) Ag can oxidise H 2 into H  (c) HI (d) SO 2
2
(c) Zn can be reduced by H 2 45. A standard hydrogen electrode has zero electrode
2 potential because [IIT 1997]
(d) Ag can reduce Zn ion
(a) Hydrogen is easiest to oxidise
38. Adding powdered lead and iron to a solution that
(b) The electrode potential is assumed to be zero
is 1.0 M in both Pb 2  and Fe 2  ions, would result a
reaction, in which (c) Hydrogen atom has only one electron
[CPMT 1987] (d) Hydrogen is the lightest element
2 46. In the electrochemical cell
(a) More iron and Pb ions are formed
(b) More lead and Fe 2
ions are formed H 2 (g)1 atm | H  (1 M )|| Cu 2  (1 M )| Cu (s)
(c) Concentration of both Pb 2  and Fe 2  ions Which one of the following statements is true
increases [EAMCET 1997]
(d) There is no net change (a) H 2 is cathode; Cu is anode
39. Given standard electrode potentials
(b) Oxidation occurs at Cu electrode
Fe    2e   Fe ; E o  0 .440 V (c) Reduction occurs at H 2 electrode
Fe     3 e   Fe ; E o  0 . 036 V (d) H 2 is anode; Cu is cathode
o
The standard electrode potential (E ) for 47. Expression representing the cell potential (E cell)
  
Fe  e  Fe is [AIIMS 1982] (a) Ecathode + Eanode (b) Eanode – Ecathode
(a) – 0.476 V (b) – 0.404 V (c) Ecathode – Eanode (d) Eleft – Eright
(c) + 0.404 V (d) + 0.771 V 48. Iron displaces copper from its salt solution,
40. Reduction potential of four elements P, Q, R, S is because
[MP PMT 1996]
 2.90 ,  0.34 ,  1.20 and  0.76 . Reactivity decreases
(a) Atomic number of iron is less than that of
in the order [MP PET 1989; UPSEAT 2001]
copper
 522 Electrochemistry
(b) The standard reduction potential of iron is (c) 96500 J (d) – 49215 J
less than that of copper 54. In which cell the free energy of a chemical
(c) The standard reduction potential of iron is reaction is directly converted into electricity ?[MP PET/PM
more than that of copper (a) Leclanche cell (b) Concentration cell
(d) The iron salt is more soluble in water than the (c) Fuel cell (d) Lead storage battery
copper salt
55. Nernst equation is related with
49. (i) Copper metal dissolves in 1M silver nitrate
(a) The electrode potential and concentration of
solution and crystals of silver metal get deposited.
ions in the solution
(ii) Silver metal does not
(b) Equilibrium constant and concentration of
react with 1 M zinc nitrate solution
ions
(iii) Zinc metal dissolves in
(c) Free energy change and E.M.F. of the cell
1M copper sulphate solution and copper metal
gets deposited (d) None of these
Hence the order of decreasing strength of the 56. The standard reduction potentials of 4 elements
three metals as reducing agents will be are given below. Which of the following will be
the most suitable reducing agent
(a) Cu  Ag  Zn (b) Ag  Cu  Zn
I = – 3.04 V, II = – 1.90 V, III = 0 V, IV = 1.90 V
(c) Zn  Cu  Ag (d) Cu  Zn  Ag [CPMT 1999]
50. Standard electrode potentials of Zn and Fe are (a) I (b) II
known to be (i) 0.76 V and (ii) 0.44 V (c) III (d) IV
respectively. How does it explain that 57. Electrode potential data are given below :
galvanization prevents rusting of iron while zinc
Fe 3  (aq )  e   Fe 1 (aq ); E o  0 . 77 V
slowly dissolves away
(a) Since (i) is less than (ii), zinc becomes the Al 3  (aq )  3 e   Al (s); E o  1 . 66 V
cathode and iron the anode Br 2 (aq )  2e   2 Br  (aq ); E o  1 .08 V
(b) Since (i) is less than (ii), zinc becomes the
Based on the data given above, reducing power of
anode and iron the cathode
Fe 2 , Al and Br  will increase in the order[Pb. PMT 1998]
(c) Since (i) is more than (ii), zinc becomes the
anode and iron the cathode (a) Br   Fe 2   Al (b) Fe 2   Al  Br 
(d) Since (i) is more than (ii), zinc becomes the (c) Al  Br   Fe 2  (d) Al  Fe 2   Br 
cathode and iron the anode
58. The standardelectrode potential (E o ) for
51. Amongst the following electrodes the one with
1
zero electrode potential is OCl
[MP

PMT/ Cl

1997]and Cl  / Cl 2 respectively are 0.94 V
2
(a) Calomel electrode
1
(b) Standard hydrogen electrode and 1.36 V . The E value for OCl  / Cl 2 will be[KCET 19
o
2
(c) Glass electrode (a) 0.42 V (b)  2.20 V
(d) Gas electrode
(c) 0.52 V (d) 1.04 V
52. Which of the following is correct expression for
electrode potential of a cell 59.[MP
If PMT
the reduction
1997] potential is more, then [CPMT 1996]
RT [product] (a) It is easily oxidised
(a) E  E o  ln (b) It is easily reduced
nF [reactant]
(c) It acts as oxidising agent
RT [product]
(b) E  E o  ln (d) It has redox nature
F [reactant] 60. One of the following is false for Hg [BHU 1998]
RT [reactant] (a) It can evolve hydrogen from H 2 S
(c) E  E o  ln
nF [product]
(b) It is a metal
RT [product] (c) It has high specific heat
(d) E   ln
F [reactant] (d) It is less reactive than hydrogen
53. Calculate standard free energy change for the 61. E o for the cell Zn | Zn 2  (aq )|| Cu 2  (aq )| Cu is 1.10 V
1 1 1
reaction Cu(s)  Cl 2 (g) ⇌ Cu 2   Cl  taking at 25 o C , the equilibrium constant for the reaction
2 2 2
Zn  Cu 2  (aq) ⇌ Cu  Zn 2  (aq) is of the order of
place at 25 o C in a cell whose standard e.m.f. is [CBSE PMT 1997]
1.02 volts [MP PMT 1997]
(a) 10 28 (b) 10 37
(a) – 98430 J (b) 98430 J
(c) 10 18 (d) 10 17
 Electrochemistry 523
62. Standard reduction potentials at 25 o C of (a) – 1.20 V (b) + 0.32 V
 2  2 (c) – 0.32 V (d) + 1.20 V
Li | Li, Ba | Ba , Na | Na and Mg | Mg are
3.05 ,  2.90 ,  2.71 and 2.37 volt respectively. 69. The E o for half cells Fe / Fe 2  and Cu / Cu 2  are –
Which one of the following is the strongest 0.44 V and + 0.32 V respectively. Then[MP PMT 2003]
oxidising agent (a) Cu 2  oxidises Fe (b) Cu 2  oxidises Fe 2 
[CBSE PMT 1994; JIPMER 2002] 2
(c) Cu oxidises Fe (d) Cu reduces Fe 2 
 
(a) Na (b) Li
70. What is E o for electrode represented by
(c) Ba 2  (d) Mg 2 
Pt , O 2 (1 atm ) / 2 H  (Im) [JIPMER 1997]
63. Which of the following displaces Br2 from an
(a) Unpredictable (b) Zero
aqueous solution containing bromide ions
(c) 0.018 V (d) 0.118 V
[CBSE PMT 1994; JIPMER (Med.) 2002]
71. The cell potential of a cell in operation is
(a) Cl2 (b) Cl 
(a) Zero (b) Positive
(c) I2 (d) I 3 (c) Negative (d) None of the above
64. For the cell reaction 72. Which of the following is displaced by Fe [Roorkee 1995]
2 2
Cu (C1 aq )  Zn(s)  Zn (C 2 aq )  Cu (s) (a) Ag (b) Hg
of an electrochemical cell, the change in free (c) Zn (d) Na
energy at a given temperature is a function of 73.[CBSE
ThePMT standard
1998] electrode potential of the half cells
(a) ln (C1 ) (b) ln (C 2 ) are given below
Zn 2   2 e   Zn; E  7 .62 V ,
(c) ln (C1  C 2 ) (d) ln (C2 / C1 )
Fe 2   2e   Fe ; E  7 .81 V
65. The e.m.f. of the cell in which the following
reaction Zn(s)  Ni2  (a  1.0) ⇌ Zn 2  (a  10 )  Ni(s) The emf of the cell Fe 2  Zn  Zn 2  Fe is
occurs, is found to be 0.5105 V at 298 K . The [CPMT 2003]
standard e.m.f. of the cell is (a) 1.54 V (b) – 1.54 V
[Roorkee Qualifying 1998] (c) – 0.19 V (d) + 0.19 V
(a) 0.5400 (b) 0.4810 V 74. Zn 2   2e   Zn(s); E o   0 .76 ,
(c) 0.5696 V (d) – 0.5105 V Fe 3   e   Fe 2  ; E o   0 .77 ,
66. For the redox reaction Cr 3   3 e   Cr ; E o   0 .79 ,
Zn(s)  Cu 2  (0.1M )  Zn 2  (1M )  Cu(s) taking place in
o
H   2e   1 / 2 H 2 ; E o  0 .00
a cell, E cell is 1.10 volt. Ecell for the cell will be
Strongest reducing agent is [
 RT 
 2 . 303  0 . 0591  [AIEEE 2003] (a) Fe 2
(b) Zn
 F 
(c) Cr (d) H 2
(a) 2.14 volt (b) 1.80 volt
75. Standard reduction electrode potentials of three
(c) 1.07 volt (d) 0.82 volt
metals A, B and C are respectively + 0.5V, – 3.0V
67. The emf of a Daniel cell at 298K is E1 and – 1.2 V. The reducing powers of these metals
Zn | ZnSO 4 || CuSO 4 | Cu when the concentration of are [IIT 1998; AIEEE 2003]
(0 . 01 M ) (1 . 0 M )
(a) B > C > A (b) A > B > C
ZnSO 4 is 1.0 M and that of CuSO4 is 0.01 M, the
(c) C > B > A (d) A > C > B
emf changed to E 2 . What is the relationship 76. For a cell reaction involving a two-electron
between E1 and E2 change, the standard emf of the cell is found to be
[CBSE PMT 2003] 0.295 V at 25 o C . The equilibrium constant of the
o
(a) E2  0  E1 (b) E1  E2 reaction at 25 C will be
(c) E1  E2 (d) E1  E2 [Roorkee 1999; AIEEE 2003; CBSE PMT 2004]
(a) 1  10 10 (b) 29 .5  10 2
68. The oxidation potentials of following half-cell
reactions are given (c) 10 (d) 1  10 10
Zn  Zn 2   2e  ; E o  0 .76 V , 77. For the electrochemical cell,
Fe  Fe 2   2e  ; E o  0 .44 V what will be the emf of M | M  || X  | X , E o (M  / M ) = 0.44 V and
o 
cell, whose cell-reaction is E ( X / X ) = 0.33 V. From this data one can deduce
Fe 2  (aq)  Zn  Zn 2  (aq)  Fe that
[MP PMT 2003] [IIT-JEE (Screening) 2000]
 524 Electrochemistry
(a) M  X  M   X  is the spontaneous reaction with 10 8 M H  and positive one in contact with
(b) M   X   M  X is the spontaneous reaction 0.025 M H 
[MP PMT 2000]
(c) Ecell = 0.77 V
(a) 0.18 V (b) 0.28 V
(d) Ecell = – 0.77 V
(c) 0.38 V (d) 0.48 V
78. The standard potential at 25 o C for the following
85. Will Fe(s) be oxidised to Fe 2  by the reaction with
half reactions are given against them
Zn 2   2e  Zn, E o  0.762 V 1 M HCl (E o for Fe / Fe 2  = + 0.44 V)[Pb. PMT 2000]
Mg 2   2e  Mg, E o  2.37 V (a) Yes (b) No
When zinc dust is added to the solution of MgCl2 (c) May be (d) Can’t say
[UPSEAT 2001] 86. EMF of a cell in terms of reduction potential of its
(a) ZnCl2 is formed left and right electrodes is [
(a) E  Eleft  Eright (b) E  Eleft  Eright
(b) Zinc dissolves in the solution
(c) No reaction takes place (c) E  Eright  Eleft (d) E  (Eright  Eleft )
(d) Mg is precipitated 87. Arrange the following in the order of their
79. KMnO4 acts as an oxidising agent in the neutral decreasing electrode potential Mg, K, Ba, Ca[JIPMER 2002]
medium and gets reduced to MnO2 . The equivalent (a) K , Ba , Ca , Mg (b) Ca , Mg , K , Ba
weight of KMnO4 in neutral medium [AMU 2001] (c) Ba , Ca , K , Mg (d) Mg , Ca , Ba , K
(a) mol. wt/2 (b) mol.wt/3 88. Which of the following has highest electrode
(c) mol. wt/4 (d) mol .wt/7 potential
80. Which of the following condition will increase the [Pb. PMT 2000]
voltage of the cell, represented by the equation (a) Li (b) Cu
Cu(s)  2 Ag (aq )  Cu 2 (aq )  2 Ag(s) [CBSE PMT 2001] (c) Au (d) Al
 89. The cell reaction of a cell is
(a) Increase in the concentration of Ag ion
(b) Increase in the concentration of Cu  ion Mg(s)  Cu 2 (aq)  Cu(s)  Mg 2 (aq)
(c) Increase in the dimension of silver electrode If the standard reduction potentials of Mg and
(d) Increase in the dimension of copper electrode Cu are  2.37 and  0.34 V respectively. The emf
81. Which will increase the voltage of the cell of the cell is
Sn(s)  2 Ag (aq )  Sn 2 (aq )  2 Ag(s) [DPMT 2001] [EAMCET 1995; JIPMER (Med.) 2001;
AFMC 2002; CBSE PMT 2002]
(a) Increase in the concentration of Ag  ions
(a) 2.03 V (b) – 2.03 V
(b) Increase in the concentration of Sn 2  ions
(c) + 2.71 V (d) – 2.71 V
(c) Increase in size of the silver rod
90. The element which can displace three other
(d) None of these
halogens from their compound is [EAMCET 1998]
82. The mass of the proton is 1840 times that of
(a) Cl (b) F
electron, its potential difference is V. The kinetic
energy of proton is (c) Br (d) I
[DCE 2001] 91. Which of the following has been universally
(a) 1840 KeV (b) 1 KeV accepted as a reference electrode at all
temperatures and has been assigned a value of
1
(c) KeV (d) 920 KeV zero volt [AIIMS 1998]
1840
(a) Graphite electrode
83. What will be the emf for the given cell
(b) Copper electrode
Pt | H 2 (P1 )| H  (aq ) || H 2 (P2 )| Pt [AIEEE 2002]
(c) Platinum electrode
RT P RT P (d) Standard hydrogen electrode
(a) log 1 (b) log 1
f P2 2f P2
92. Aluminium is more reactive than Fe . But Al is
RT P less easily corroded than iron because [DCE 1999]
(c) log 2 (d) None of these
f P1 (a) Al is noble metal
84. What is the potential of a cell containing two (b) Iron forms both mono and divalent ions
hydrogen electrodes the negative one in contact (c) Oxygen forms a protective oxide layer
 Electrochemistry 525
(d) Fe undergoes reaction easily with H 2 O 99. What is wrongly stated about electrochemical
series
93. Zinc displaces copper from the solution of its salt
[DCE 1999]
because
[MP PET 1995] (a) It is the representation of element in order of
increasing or decreasing standard electrode
(a) Atomic number of zinc is more than that of reductional potential
copper
(b) It does not compare the relative reactivity of
(b) Zinc salt is more soluble in water than the metals
copper salt
(c) It compares relative strengths of oxidising
(c) Gibbs free energy of zinc is less than that of agents
copper
(d) H 2 is centrally placed element
(d) Zinc is placed higher than copper in electro-
chemical series 100. Which of the following statements is true for fuel
cells
94. An electrochemical cell is set up as follows
[KCET (Med.) 1999; AFMC 2000]
Pt(H 2 , 1 atm) / 0.1 M HCl
(a) They are more efficient
|| 0.1 M acetic acid /( H 2 , 1 atm ) Pt (b) They are free from pollution
E.M.F. of this cell will not be zero because (c) They run till reactants are active
[CBSE PMT 1995] (d) All of these
(a) The pH of 0.1 M HCl and 0.1 M acetic acid is 101. What is the potential of a half-cell consisting of
not the same zinc electrode in 0.01m ZnSO 4 solution at 258 o C
(b) Acids used in two compartments are different ( E o  0 . 763 V )
(c) E.M.F. of a cell depends on the molarities of [AIIMS 2000; BHU 2000]
acids used
(a) 0.8221 V (b) 8.221 V
(d) The temperature is constant
(c) 0.5282 V (d) 9.232 V
95. Cu  ion is not stable in aqueous solution because 102. The emf of a galvanic cell, with electrode potentials
of disproportionation reaction. E o value for of silver = +0.80V and that of copper = + 0.34 V, is[AIIMS 19
disproportionation of Cu  is (a) – 1.1 V (b) + 1.1 V
o
(Given ECu 2
/ Cu 
 0 .15 , ECu
o
2
/ Cu
 0 .34 V ) [IIT 1995] (c) + 0.46 V (d) + 0.76 V
103. Copper cannot replace….. from solution[DPMT 2002]
(a) – 0.49 V (b) 0.49 V
(a) Fe (b) Au
(c) – 0.38 V (d) 0.38 V
(c) Hg (d) Ag
96. E o of a cell aA  bB  cC  dD is [CPMT 1997]
104. The strongest reducing agent of the alkali metal is
c d
RT [C ] [ D] [a] A [b ] B [CBSE PMT 2000]
(a)  log (b)  RT log
nF [ A ] a [ B ]b [a]C [d ] D (a) Li (b) Na
RT [C ]c [d ] D RT [C ]c [d ] D (c) K (d) Cs
(c)  log (d)  log
nF [ A ] a [ B ]b nF [a] A [B]b 105. Which of the following is the most electropositive
97. In the experiment set up for the measurement of element
EMF of a half cell using a reference electrode and [Pb. PMT 2000]
a salt bridge, when the salt bridge is removed, the (a) Carbon (b) Calcium
voltage (c) Chlorine (d) Potassium
[NCERT 1984; CPMT 1985]
106. The metal that forms a self protecting film of
(a) Does not change oxide to prevent corrosion, is [BHU 1999]
(b) Decreases to half the value
(a) Cu (b) Al
(c) Increase to maximum
(c) Na (d) Au
(d) Drops to zero
98. Electrode potentials of five elements A, B, C, D and 107. In a cell that utilises the reaction Zn(s)  2 H  (aq) 
E are respectively – 1.36 , – 0.32, 0, – 1.26 and – Zn 2  (aq)  H 2(g) addition of H 2 SO4 to cathode
0.42. The reactivity order of these elements are in compartment, will [AIEEE 2004]
the order of
(a) Increase the E and shift equilibrium to the
[MP PMT 1995]
right
(a) A, D, E, B and C (b) C, B, E, D and A
(b) Lower the E and shift equilibrium to the right
(c) B, D, E, A and C (d) C, A, E, D and B
 526 Electrochemistry
(c) Lower the E and shift equilibrium to the left 0.2905 then the value of equilibrium for the cell
(d) Increase the E and shift equilibrium to the left reaction is [IIT-JEE Screening 2004]
0 .32 0 . 32
108. For the electrochemical cell, M | M  || X  | X , (a) (b)
e 0 .0295 10 0 .0295
E(M  | M )  0.44 V E( X | X  )  0 .33 V From this
0 . 26 0 . 32
data, one can deduce that (c) 2004]
[Pb.CET 0 . 0295
(d)
10 10 0 .0591
(a) Ecell  0.77 V
117. Aluminium displaces hydrogen from dilute HCl
(b) M   X   M  X is the spontaneous reaction whereas silver does not. The e.m.f. of a cell
(c) M  X  M   X  is the spontaneous reaction prepared by combining Al / Al 3  and Ag / Ag  is
2.46 V. The reduction potential of silver electrode
(d) Ecell  .77 V is 0.80 V . The reduction potential of aluminium
109. The standard e.m.f. of a call, involving one electrode is [KCET 2004]
electron change is found to be 0.591 V at 25°C.
(a) 1.66 V (b) 3.26 V
The equilibrium constant of the reaction is
( F  96 ,500 C mol 1 ; R  8 . 314 JK 1mol 1 ) [AIEEE (c) 3.26 V (d) 1.66 V
2004] 118. Consider the following E 0 values :
(a) 1 .0  10 10 (b) 1 .0  10 5 E 0 Fe 3  / Fe 2 = 0.77 V
(c) 1.0  10 1 (d) 1 .0  10 30
E 0 Sn 2  / Sn  0 .14 V
110. Standard electrode potential of cell
H 2 | H  || Ag  | Ag is Under standard conditions the potential for the
reaction Sn(s)  2 Fe 3  (aq)  2 Fe 2  (sq)  Sn 2  (aq) is[AIEEE 2004
[AIEEE 2004]
(a) 0.8 V (b) – 0.8 V (a) 0.91 V (b) 1.40 V
(c) – 1.2 V (d) 1.2 V (c) 1.68 V (d) 0.63 V
111. A galvanic cell with electrode potential of 119. Cr2 O72   I   I2  Cr 3 
' A'  2.23 V and ' B'  1.43 V . The value of Ecell is[Pb.CET 2003]
E 0 cell  0 .79 V
(a) 3.66 V (b) 0.80 V
(c) – 0.80 V (d) – 3.66 V 0
ECr 2  1.33 V , E 0 I2 is [BVP 2004]
2 O7
112. The e.m.f. of a cell whose half cells are given
below is (a) 0.10 V (b) 0.18 V
2 
Mg  2e  Mg (s) E  2 .37 V (c) 0.54 V (d) 0.54 V
2 
Cu  2e  Cu (s) E  0 .34 V [Pb.CET 2001]
120. Zn(s)  Cl 2 (1 atm)  Zn2   2Cl  . E0 cell of the cell is
(a) + 1.36 V (b) + 2.71 V 2.12 V. To increase E [BVP 2004]
(c) + 2.17 V (d) – 3.01 V 2
(a) [ Zn ] should be increased
113. For the cell reaction, 2Ce 4   Co  2Ce 3   Co 2 
Ecell is 1.89 V. If ECe 4  / Ce 3  [Pb.CET 2000] (b) [ Zn 2  ] should be decreased

(a) – 1.64 V (b) + 1.64 V (c) [Cl  ] should be decreased

(c) – 2.08 V (d) + 2.17 V (d) PCl 2 should be decreased
114. If the G of a cell reaction AgCl  e   Ag  Cl  is
121. The E 0 M 3  / M 2 values for Cr, Mn, Fe and Co are
21 .20 KJ ; the standard e.m.f., of cell is [MP PMT 2004]
0.41,  1.57 ,  0.77 and 1.97 V respectively. For
(a) 0.229 V (b) 0.220 V which one of these metals the change in oxidation
(c) – 0.220 V (d) – 0.110 V state from  2 to  3 is easiest
115. The e.m.f. of the cell Ag | Ag  (0 . 1 M )|| Ag  (1 M )| Ag (a) Fe (b) Mn
at 298 K is [DCE 2003] (c) Cr (d) Co
(a) 0.0059 V (b) 0.059 V 122. The rusting of iron takes place as follows
(c) 5.9 V (d) 0.59 V 2H+ + 2e + ½O2  H2O(l) ;
116. The e.m.f. of the cell E° = +1.23 V
Zn | Zn 2  (0 .01 M )|| Fe 2  (0 . 001 M )| Fe at 298 K is Fe2+ + 2e  Fe(s) ; E° = 0.44 V
 Electrochemistry 527
Calculate G° for the net process [IIT 2005] (a) FeCl2 (b) PbCl2
(a) 322 kJ mol1 (b) 161 kJ mol1 (c) Hg 2 Cl2 (d) HgCl2
(c) 152 kJ mol1 (d) 76 kJ mol1
4. Corrosion of iron is essentially an electrochemical
123. When an acid cell is charged, then [AFMC 2005]
phenomenon where the cell reactions are [KCET 2005]
(a) Voltage of cell increases
(b) Electrolyte of cell dilutes (a) Fe is oxidised to Fe 2  and dissolved oxygen

(c) Resistance of cell increases in water is reduced to OH
(d) None of these
(b) Fe is oxidised to Fe 3  and H 2 O is reduced to
124. The standard electrode potential is measured by
[KCET 2005] O 22 
(a) Electrometer (b) Voltmeter
(c) Fe is oxidised to Fe 2  and H 2 O is reduced to
(c) Pyrometer (d) Galvanometer
125. Aluminium displaces hydrogen from acids but O 2
copper does not. A galvanic cell prepared by (d) Fe is oxidised to Fe 2  and H 2 O is reduced to
combining Cu / Cu 2  and Al / Al 3  has an e.m.f. of O2
2.0 V at 298 K. If the potential of copper electrode
is + 0.34 V, that of aluminium is
[CPMT 2001; KCET 2001]
(a) + 1.66 V (b) – 1.66 V
(c) + 2.34 V (d) – 2.3 V
126. If the standard electrode potential of Cu 2 / Cu
electrode is 0.34V, what is the electrode potential
of 0.01M concentration of Cu 2  (T  298 K) [EAMCET 2003]
1. The limiting molar conductivities  0 for NaCl, KBr
(a) 0.399 V (b) 0.281 V and KCl are 126, 152 and 150 S cm 2 mol 1
(c) 0.222 V (d) 0.176 V respectively. The  0 for NaBr is
127. Calculate the electrode potential at 298 o K for
(a) 278 S cm 2 mol 1 (b) 176 S cm 2 mol 1
Zn | Zn   electrode in which the activity of zinc
(c) 128 S cm 2 mol 1 (d) 302 S cm 2 mol 1
ions is 0.001 M and E o Zn / Zn   is –0.74 volts [AMU 2002]
(a) 0. 38 volts (b) 0.83 volts 2. On the basis of the electrochemical theory of
aqueous corrosion, the reaction occurring at the
(c) 0.40 volts (d) 0.45 volts
cathode is
128. Which of the following expression is correct
[MP PET 1994; UPSEAT 2001]
[Orissa JEE 2005]
(a) G  o
nFE cell
o
(b) G  o
nFE cell
o (a) O2 (g)  4 H(aq )  4 e   2 H 2 O(l)

(c) G o  2 . 303 RT nFE cell

o
(d) G o  nF log K C (b) Fe(s)  Fe(2aq )  2e 
129. For the feasibility of a redox reaction in a cell, the (c) Fe(2aq )  Fe(3aq )  e 
e.m.f. should be [J & K 2002]
(a) Positive (b) Fixed (d) H 2(g)  2OH (aq )  2 H 2 O(l)  2e 
(c) Zero (d) Negative 3. The reaction
1
2
H 2 (g)  AgCl(s)  H  (aq)  Cl  (aq)  Ag(s)
Corrosion
occurs in the galvanic cell
1. Corrosion is basically a [Kerala (Med.) 2002] [IIT 1985; AMU 2002; KCET 2003]
(a) Altered reaction in presence of H 2 O (a) Ag / AgCl(s) KCl (soln) || AgNO3 (soln) / Ag

(b) Electrochemical phenomenon (b) Pt / H 2 (g) HCl (soln) || AgNO3 (soln) / Ag

(c) Interaction (c) Pt / H 2 (g) HCl (soln) || AgCl (s) / Ag
(d) Union between light metal and heavy metal (d) Pt / H 2 (g) KCl (soln) || AgCl (s) / Ag
2. Rusting of iron is catalysed by which of the
following 4. The standard reduction potential E o for the half
[MNR 1990; UPSEAT 2001]
reactions are as
(a) Fe (b) O 2 Zn  Zn 2   2 e  ; E o  0 . 76 V

(c) Zn (d) H  Fe  Fe 2   2e  ; E o  0 .41 V

3. Which of the following is a highly corrosive salt The EMF for cell reaction Fe 2   Zn  Zn 2   Fe is
[AFMC 2005]
 528 Electrochemistry
[IIT 1988; CBSE PMT 1993, 96; BHU 1995, 2000; Calculate HOAc using appropriate molar
CPMT 2000; KCET 2000; AIIMS 2001; Orissa JEE 2002]
conductances of the electrolytes listed above at
(a)  0.35 V (b)  0.35 V infinite dilution in H 2O at 25°C [AIEEE 2005]
(c)  1.17 V (d)  1.17 V (a) 517.2 (b) 552.7
5. The number of electrons to balance the following (c) 390.7 (d) 217.5
equation NO 3  4 H   e   2 H 2 O  NO is[IIT Screening 1991]
12. The mass of carbon anode consumed (giving only
carbondioxide) in the production of 270kg of
(a) 5 (b) 4
aluminium metal from bauxite by the Hall process
(c) 3 (d) 2 is [CBSE PMT 2005]
6. The standard EMF for the given cell reaction (a) 180kg (b) 270kg
Zn  Cu 2   Cu  Zn 2  is 1 . 10 V at 25 o C . The EMF (c) 540kg (d) 90kg
for the cell reaction, when 0 . 1 M Cu 2  and 13. 4.5g of aluminium (at mass 27amu) is deposited
0 . 1 M Zn 2  solutions are used, at 25 o C is at cathode from Al 3  solution by a certain
quantity of electric charge. The volume of
[MNR 1994; AMU 1999; UPSEAT 2002]
hydrogen produced at STP from H  ions in
(a) 1.10 V (b) 0.110 V
solution by the same quantity of electric charge
(c) 1.10 V (d)  0.110 V will be
[CBSE PMT 2005]
7. A gas X at 1 atm is bubbled through a solution (a) 22.4 L (b) 44.8 L
containing a mixture of 1 M Y  and 1 M Z  at (c) 5.6 L (d) 11.2 L
14. What amount of Cl2 gas liberated at anode, if 1
25 C . If the reduction potential of Z  Y  X , then[IIT 1999]
o
amp. current is passed for 30 min. from NaCl
(a) Y will oxidize X and not Z solution.
(b) Y will oxidize Z and not X [BHU 2005]
(a) 0.66 moles (b) 0.33 moles
(c) Y will oxidize both X and Z
(c) 0.66 g (d) 0.33 g
(d) Y will reduce both X and Z
8. The oxidation potential of a hydrogen electrode at
pH = 10 and pH 1  1 [JIPMER 2000]

(a) 0.059 V (b) 0.59 V

(c) 0.00 V (d) 0.51 V
9. The decomposition of hydrogen peroxide is an
example of Read the assertion and reason carefully to mark the
[Roorkee 2000] correct option out of the options given below :
(a) Exothermic reaction (b) Endothermic (a) If both assertion and reason are true and the
reaction reason is the correct explanation of the assertion.
(c) Negative catalysis (d) Auto-oxidation (b) If both assertion and reason are true but reason is
10. Aluminium oxide may be electrolysed at 1000°C not the correct explanation of the assertion.
to furnish aluminium metal (At. Mass = 27 amu; 1 (c) If assertion is true but reason is false.
Faraday = 96,500 Coulombs). The cathode (d) If the assertion and reason both are false.
reaction is (e) If assertion is false but reason is true.
Al 3  3e   Al
1. Assertion : Sodium ions are discharged in
To prepare 5.12kg of aluminium metal by this preference to hydrogen ions at a
method would require [AIEEE 2005] mercury cathode.
(a) 5 . 49  10 7 C of electricity Reason : The nature of the cathode can effect
the order of discharge of ions.
(b) 1 .83  10 C of electricity
7
2. Assertion : In electrolysis, the quantity of
(c) 5 .49  10 4 C of electricity electricity needed for depositing 1
mole of silver is different from that
(d) 5 .49  10 1 C of electricity
required for 1 mole of copper.
11. Electrolyte : KCl KNO3 HCl NaOAc NaCl Reason : The molecular weights of silver and
 (Scm mol
 2 –
149. 145. 426. 91.0 126. copper are different
1
): 9 0 2 5 3. Assertion : Equivalent conductance of all
electrolytes decreases with the
increases in concentration.
 Electrochemistry 529
Reason : Lesser number of ions are available sodium chloride is given by the
per gram equivalent at higher equation:  0NaCl  0Na   0Cl  .
concentration.
4. Assertion : Copper reacts with hydrochloric Reason : This is according to Kohlrausch law
acid and liberates hydrogen from of independent migration of ions.
15. Assertion : One coulomb of electric charge
the solution of dilute hydrochloric
deposits weight equal to the
acid.
Reason : Hydrogen is below copper in the electrochemical equivalent of the
electrochemical series. substance.
Reason : One Faraday deposits one mole of
5. Assertion : Copper liberates hydrogen from a
the substance.
solution of dil. HCl.
Reason : Hydrogen is below copper in the 16. Assertion : Auric chloride ( AuCl3 ) solution
reactivity series. cannot be stored in a vessel made of
6. Assertion : Zn metal is formed when a Cu plate copper, iron, nickel, chromium, zinc
in dipped in ZnSO 4 solution. or tin.
Reason : Gold is a very precious metal.
Reason : Cu being placed above Zn in
electrochemical series. 17. Assertion : For a cell reaction Zn(s)  Cu 2  (aq) 
7. Assertion : Electrical conductivity of copper Zn 2  (aq)  Cu(s) ; at the equilibrium,
increases with increase in voltmeter gives zero reading.
temperature. Reason : At the equilibrium, there is no
Reason : The electrical conductivity of change in the concentration of
metals is due to the motion of Cu 2  and Zn 2  ions.
electrons. 18. Assertion : A negative value of standard
8. Assertion : A small amount of acid or alkali is reduction potential means that
added before electrolysis of water. reduction take place on this
Reason : Pure water is weak electrolyte. electrode with reference to
9. Assertion : Copper reacts with HCl and standard hydrogen electrode.
liberates hydrogen. Reason : The standard electrode potential of
Reason : Hydrogen is present above Cu in the a half cell has a fixed value.
reactivity series. 19. Assertion : Weston is a standard cell.
10. Assertion : K and Cs are used in photoelectric Reason : Its e.m.f. does not change with
cells. temperature.
Reason : K and Cs emit electrons on exposure 20. Assertion : Galvanic cells containing hydrogen,
to light. methane, methanol etc. as fuels are
11. Assertion : A large dry cell has high e.m.f. called fuel cells.
Reason : The e.m.f. of a dry cell is Reason : They are designed to convert the
proportional to its size. energy of combustion of fuels
12. Assertion : The resistivity for a substance is its directly into electrical energy.
resistance when its is one meter long 21. Assertion : Zinc displaces copper from copper
and its area of cross section is one sulphate solution.
square meter.
Reason : The SI uints of resistivity are ohm Reason : The E 0 of zinc is 0.76 V and that of
metre ( m ) and ohm centimeter copper is 0.34 V .
( cm) . 22. Assertion : Identification of cathode and anode
13. Assertion : When acidified zinc sulphate is done by the use of a
solution is electrolysed between thermometer.
zinc electrodes, it is zinc that is Reason : Higher is the value of reduction
deposited at the cathode and potential, greater would be its
hydrogen evolution does not take reducing power.
place. 23. Assertion : An electrochemical cell can be set
Reason : The electrode potential of zinc is up only if the redox reaction is
more negative than hydrogen as the spontaneous.
overvoltage for the hydrogen as the Reason : A reaction is spontaneous if free
evolution on zinc is quite large. energy change is negative.
14. Assertion : If 0Na   0Cl  are molar limiting 24. Assertion : Galvanised iron does not rust.
Reason : Zinc has a more negative electrode
conductivity of the sodium and
potential than iron. [AIIMS 2005]
chloride ions respectively, then the
limiting molar conducting for
 530 Electrochemistry
25. Assertion : In an electrochemical cell anode 41 c 42 a 43 a 44 b 45 c
and cathode are respectively
46 b 47 d 48 d 49 b 50 a
negative and positive electrodes.
Reason : At anode oxidation takes place and 51 c 52 b 53 b 54 a 55 c
at cathode reduction takes place. 56 c 57 c 58 d 59 d 60 d
26. Assertion : Ni / Ni 2  (1 .0 M )|| Au 3  (1 .0 M )| Au , for 61 c 62 c 63 b 64 a 65 b
this cell emf is 1.75 V if 66 b 67 a 68 a 69 b 70 c
E oAu 3  / Au  1 .50 and E Ni
o
2  0 .25 V .
/ Ni 71 c 72 b 73 a 74 b 75 c
Reason : Emf of the cell  E cathode
o
 E anode
o
. 76 b 77 c 78 c 79 b 80 b
27. Assertion : Salts like KCl, KNO3 i.e., inert 81 c 82 b 83 a 84 c 85 c
electrolytes are used in salt bridge.
86 e 87 b 88 a 89 d 90 c
Reason : An inert electrolyte can easily be
filled in the U-tube. 91 c 92 a 93 c 94 b
28. Assertion : Emf and potential difference are
same for cell. Conductor and Conductance
Reason : Both gives the difference in
electrode potential under any 1 b 2 b 3 d 4 d 5 a
condition. 6 b 7 b 8 a 9 b 10 d
11 a 12 b 13 b 14 b 15 b
16 d 17 b 18 d 19 b 20 c
21 b 22 a 23 c 24 d 25 a
26 b 27 d

Cell constant and Electrochemical cells

Electrolytes and Electrolysis 1 d 2 d 3 d 4 b 5 b

6 a 7 c 8 c 9 b 10 b
1 b 2 d 3 c 4 c 5 d 11 c 12 c 13 a 14 a 15 d
6 d 7 b 8 b 9 b 10 a 16 c 17 c 18 a 19 b 20 b

11 a 12 c 13 d 14 d 15 c 21 b 22 b 23 a 24 b 25 c

16 d 17 a 18 c 19 c 20 a 26 a 27 c 28 a 29 b 30 c
31 a 32 b 33 c 34 b 35 d
21 a 22 b 23 b 24 d 25 b
36 b 37 c 38 d 39 b 40 d
26 b 27 b 28 a 29 c 30 b
41 a 42 d 43 c 44 a 45 d
31 d 32 d 33 c 34 b 35 b
46 a 47 d 48 b 49 c 50 c
36 a 37 d 38 c 39 d 40 a
51 b 52 d 53 c 54 a 55 c
41 a 56 d 57 b 58 a 59 a 60 c
61 a
Faraday’s law of electrolysis
Electrode potential, ECell, Nernst equation and ECS
1 c 2 a 3 b 4 c 5 c
1 b 2 a 3 a 4 b 5 d
6 c 7 c 8 b 9 c 10 a
6 c 7 c 8 a 9 a 10 b
11 c 12 a 13 c 14 b 15 b
11 a 12 c 13 a 14 d 15 c
16 c 17 a 18 a 19 d 20 c
16 a 17 a 18 c 19 b 20 b
21 d 22 c 23 b 24 d 25 a
21 a 22 b 23 a 24 c 25 a
26 d 27 a 28 d 29 c 30 a
26 a 27 c 28 a 29 d 30 d
31 b 32 b 33 a 34 b 35 b
31 b 32 a 33 d 34 a 35 c
36 b 37 b 38 b 39 a 40 a
36 d 37 a 38 b 39 d 40 d
 Electrochemistry 531
41 b 42 c 43 a 44 b 45 b
46 d 47 c 48 b 49 c 50 b
51 b 52 a 53 a 54 c 55 a
56 a 57 a 58 a 59 c 60 a
61 b 62 d 63 a 64 d 65 b
66 c 67 b 68 b 69 a 70 b
71 b 72 ab 73 c 74 c 75 a
76 d 77 b 78 c 79 b 80 a
81 a 82 b 83 b 84 c 85 a
86 c 87 a 88 c 89 c 90 b
91 d 92 c 93 d 94 a 95 d
96 a 97 d 98 a 99 b 100 d
101 a 102 c 103 a 104 a 105 d
106 b 107 a 108 b 109 a 110 a
111 a 112 b 113 b 114 b 115 b
116 b 117 d 118 a 119 d 120 b
121 c 122 a 123 a 124 b 125 b
126 b 127 b 128 a 129 a

Corrosion

1 b 2 d 3 d 4 a

Critical Thinking Questions

1 c 2 a 3 c 4 b 5 c
6 a 7 a 8 b 9 acd 10 a
11 c 12 d 13 c 14 c

Assertion & Reason

1 a 2 b 3 a 4 d 5 d
6 d 7 e 8 a 9 e 10 a
11 d 12 b 13 a 14 a 15 c
16 b 17 a 18 e 19 a 20 a
21 a 22 d 23 b 24 a 25 a
26 a 27 c 28 d
 Electrochemistry 529
26. (b) Because it does not have ions.
27. (b) NaCl ⇌ Na   Cl  .
28. (a) Cathode: 2 H 2 O  2 e   H 2  2OH 
1
Anode : H 2 O  2 H   O 2  2e  .
2
29. (c) Electrolysis use for electroplating
and
Electrolytes and Electrolysis electrorefining.
32. (d) The degree of ionization depend upon the
1. (b) Sugar solution does not form ion; hence does nature of the solute the size of the solute
not conduct electricity in solution. molecules and the concentration of the
3. (c) Strong electrolytes are almost completely solution.
ionised in polar solvent. 33. (c) C12 H 22O11 is an non-electrolyte.
7. (b) The reduction potential of Mg is less than that 34. (b) On electrolysis molten ionic hydride liberate
of water (E  0.83 V ) . Hence their ions in the
o H 2 at the anode.
aqueous solution cannot be reduced instead 35. (b) During electrolysis cation discharged at
water will be reduced cathode and anion discharged at anode.
2 H 2 O  2 e   H 2  2 OH  . 36. (a) Calcium is produces when molten anhydrous
calcium chloride is electrolysed.
8. (b) HCl is an electrolyte.
37. (d) All metals conducts heat and electricity.
9. (b) Water is reduced at the cathode and oxidized
38. (c) 2 Al  dil. H 2 SO 4  Al 2 SO 4  H 2  .
at the anode instead of Na  and SO 42  .
39. (d) Generally fussed potassium chloride flow the
Cathode: 2 H 2 O  2e   H 2  2OH  electric conductivity.
1 41. (a) The substances whose aqueous solutions allow
Anode : H 2 O  2 H   O2  2 e  .
2 the passage of electric current and are
10. (a) In electrolysis process oxidation occurs at chemically decomposed, are termed
anode and reduction occurs at cathode. electrolytes. Electrolytic substances are
11. (a) Because in it covalent bonding is present. classified as strong or weak according to how
12. (c) According to Faraday’s law. readily they dissociate into conducting ions.
13. (d) Impure metal made anode while pure metal Acetic acid is a weak electrolyte. Glucose,
made cathode. ethanol and urea are non-electrolytes.
14. (d) In electrolytic cell, cathode acts as source of
electrons. Faraday's law of electrolysis
15. (c) AgNO3 is an electrolyte.
Atomic Mass
17. (a) At cathode: 2 H   2e  H 2 , 1. (c) Ag   e   Ag; E Ag   108
1
1
At anode : 2OH   H 2 O  O 2  2e W Ag 108
2 Number of faraday   1.
E Ag 108
18. (c) In between dilute H 2 SO 4 and platinum
E Ag  Q 108  9 . 65
electrode O 2 gas evolve at anode. 2. (a) W Ag  
96500 96500
19. (c) When polar solvent added in to solid
electrolyte than it is ionised.  1 . 08  10 2 gm  10 . 8 mg
20. (a) In fused NaCl chloride ions are oxidized at 56
anode and it is called oxidation. 3. (b) Fe 2   2e   Fe; E Fe   28
2
21. (a) w  zit, Q  it .
WFe  EFe × Number of faraday
22. (b) 2 H   2e   H 2(g) at cathode.  28  3  84 gm .
23. (b) Na   e   Na , means oxidation number is E Ag  Q 107 . 87  965
1 0 4. (c) W Ag    1 .0787 gm .
decreased so the reaction is reduction. 96500 96500
24. (d) Degree of dissociation of weak electrolyte 5. (c) Al 3  3e   Al
increases on increasing temperature. 27
25. (b) Since discharge potential of water is greater E Al  9
3
than that of sodium so water is reduced at
WAl  E Al  No. of faradays  9  5  45 gm .
cathode instead of Na 
1 6. (c) Cu voltameter or Cu or Ag coulometer are
Cathode: H 2 O  e   H 2  OH  used to detect the amount deposited on an
2
electrode during passage of know charge
1
Anode: Cl  Cl2  e  .

through solution.
2
 530 Electrochemistry
Weight of Cu Eq. weight of Cu Weight of metal  96500
8. (b)  29. (c) E metal 
Weight of H 2 Eq. weight. of H Number of coulombs
Weight of Cu 63 .6 / 2 22 .2  96500
   59 .5
0 .50 1 2  5  60  60
Weight of Cu  15 .9 gm. Oxidation number of the metal 
177
 3
59 .5
9. (c) Cu 2  2e   Cu
25
2 Faradays will deposit 30. (a) Quantity of electricity passed =  60  1 .5
1000
 1 g atom of Cu  63 .5 g .
2 F  2  96500 C deposit Ca  1mole
12. (a) At cathode; Al 3  3e   Al
1
27  1.5 C will deposit Ca   1 .5 mole
E Al  9 2  96500
3
1
WAl  E Al  No. of faradays  9  0.1  0.9 gm .   1 .5  6 .023  10 23 atom  4.68  10 18 .
2  96500
32 .69  5  60  40
14. (b) W  zit ; W   4 .065 gm . 31. (b) Equivalent of Cl deposited
96500 = No. of Faraday passed = 0.5
15. (b) m  Z  4  120 ; M  Z  6  40 Wt. of Cl  0.5  Eq. wt.  0.5  35 .5  17 .75 gm .
M 6  40 1
  ; M m/2 . 1
m 4  120 2 32. (b) At Andoe At Anode Cl   Cl2  e 
2
E  I  t E  3  50  60
16. (c) Wmetal   35 .5  2
96500 96500 E Cl 2   35 .5
2
96500  w 96500  1 .8
E   19 .3 . ECl 2  I  t 35 .5  2  30  60
3  50  60 3  50  60 WCl 2    1 .32 gm .
96500 96500
17. (a) Al  Al 3  3e  .
34. (b) It is Faraday’s law.
The charged obtained is 3  96500 C .
35. (b) Equivalent wt. of O 2 = Equivalent wt. of Cu
18. (a) Wt.of Ag deposited  Eq. wt of Ag  108 gm
36. (d) O2 %  20 %
Wt.of Ni deposited  Eq. wt. of Ni  29 .5 gm
80
Wt. of Cr deposited  Eq. wt. of Cr  17 .3 gm . Metal%  80 %   8  32 g of metal .
20
19. (d) One Faraday  1 gm of equivalent of Cu .
827  10 3
E 37. (b) V   2.14 V .
20. (c) W  Zit ; Z  . 4  96500
96500 e 
38. (b) Ag    Ag, 96500 C will liberate silver
21. (d) During electrolysis of CuSO 4 . Cu 2  gets
=108 gm. 9650C will liberate silver = 10.8 gm.
discharged at cathode and OH  at anode. Thus 39. (a) One mole of monovalent metal ion means
solution becomes acidic due to excess of H  charge of N electron i.e. 96500 C or 1
and SO 42  or H 2 SO 4 . Faraday.
42. (a) 1 Faraday involves charge of 1 mole electrons.
23. (b) 1 mole of electrons  1 faraday
43. (a) Coulomb = ampere (A) × second (S).
Mg   2e   Mg ; 2 moles of electrons  2 faraday . 13 .6
44. (b) E   2 for He  n  1
24. (d) Cu   2e   Cu n
63 .54 13 .6
ECu   31 .77 E   2  13 .6 eV .
2 1
Amount of electricity required to deposit 45. (c) w  E if i and t are constant.
.6354 gm of Cu 47. (d) Charge (Coulombs) pass per second  10 6
96500  0 .6354 number of electrons passed per second
  1930 Coulombs .
31 .77 10 6
  6 .24  10 12 .
25. (a) The amount deposited is directly proportional 1.602  10 19
to current intensity, electrochemical 48. (d) At cathode;
equivalent of ions and the time for electrolysis Fe 2  2e   Fe ; Fe 3  3e   Fe
and is independent of the temperature.
Atomic.weight Atomic.weight
27. (a) W  ZQ ; W  Zit . (E Fe )1  ; (E Fe )2 
2 3
28. (d) Ca   2e   Ca Ratio of weight of Fe liberated
40 Atomic weight Atomic weight
ECa   20  : 3 : 2 .
2 3 2
WCa  ECa × No. of faradays  20  0.04  0.8 gm . 49. (b) 31.75 g copper gets deposited at cathode on
passing 96500 coulomb charge. We know that
 Electrochemistry 531
31.75 gm of Cu is equal to 0.5 mole of Cu  2.5 F obtained from 2.5 g equivalent.
deposited at cathode on passing 1F of current. 75. (c) Faraday constant depends upon the current
52. (b) For deposition of one equivalent silver passed.
required charged is 96500 C.
80. (b) In 5 gm CuO, 4 gm Cu and 1 gm O be present.
63 .55
53. (b) Cu   2e   Cu ; ECu   31 .75 gm Cu .
2 Eleme Wt. At Wt . / At .Wt .  x Ratio
54. (a) Q  2.5  386  96500 C nt Wt.
Cu 4 63.5 4/63.5=.0625 . 0625
2 F(2  96500 C) deposited Cu  63 .5 g gm
1
. 0625
Hence 965 C will deposited; Cu  0.3175 gm . O 1 gm 16 1/16 =.0625 . 0625
1
Wt.of Cu Eq. wt. of Cu Wt. of Cu 63 .5 / 2 . 0625
55. (c)  ; 
Wt.of Ag Eq. wt. of Ag 1 .08 108
Emperical formula = CuO of oxide
Wt. of Cu  0.3177 gm .
In this oxide, oxidation no. of Cu  2
56. (c) 1 g atom of Al = 3 equivalent of Al  3 faraday
Equivalent weight
charge
Molecular weight 63 .5
3 mole electrons = 3 N electron.    31 .75 but Equivalent
Oxidation no. 2
57. (c) At cathode : Al 3  3e   Al
weight should be an integeral no. = 32
Atomic mass
E Al  81. (c) Given, Current = 241.25 columb
3
1 coulomb current will deposite
At cathode : Cu 2  2e   Cu
 1 . 118  10 3 gm Ag .
Atomic mass
E Cu   241.25 current will deposite
2
At cathode : Na   e   Na = 1.118  10 3  241 .25
Atomic mass  0.27 gm silver.
E Na 
1 82. (b) Reaction for electrolysis of water is
For the passage of 3 faraday; 2 H 2 O ⇌ 4 H   2O 2 
mole atoms of Al deposited = 1
1 3 2O 2   O 2  4 e 
mole atoms of Cu deposited   1.5
2 4e   4 H   2H 2
mole atoms of Na deposited  1  3  3 .
 n  4 so 4 Faraday charge will liberate
58. (d) At cathode: Ag   e   Ag
1 mole  22 . 4 dm 3 oxygen
1
At Anode: 2OH   H 2 O  O 2  2e   1 Faraday charge will liberate
2
22 .4
1  5 .6 dm O 2 .
3
 32 4
108
E Ag   108 ; E O 2  2 8
1 2 83. (a) Na   e   Na
W Ag WO 2 1 .6  108 Charge (in F) = moles of e– used = moles of
 ; W Ag   21 .6 gm . Na deposited
E Ag E O2 8
11 .5
59. (d) KI is an electrolyte.  gm  0 .5 Faraday.
60. (d) Number of gm equivalent = Number of 23
faraday pass 84. (c) Hydrolysis of water : 2 H 2 O ⇌ 4 H   4 e   O 2
4 gm = 4 faraday.
4 F charge will produce = 1 mole
13 .5
61. (c) Eq. of Al =  1 .5 . O2  32 gm O2
27 /3
32
Thus 1.5 Faraday is needed. 1 F charge will produce   8 gm O 2 .
4
63. (b) Electricity required
85. (c) In a galvanic cell, the electrons flow from
= No. of gm equivalent  96500 coulombs
anode to cathode through the external circuit.
= 0.5  96500 = 48250 C.
At anode (–ve pole) oxidation and at cathode
64. (a) Equivalent weight of silver = 107.870 g. (+ pole) reduction takes place.
1 Faraday = 96500 coulomb. 86. (e) Number of equivalents of silver formed =
67. (a) Equivalent weight and atomic weight of Na Number of equivalents of copper formed.
metal are the same, so 1g atom of Na is
In AgNO3 , Ag is in +1 oxidation state.
deposited by one Faraday of current.
In CuSO 4 , Cu is in +2 oxidation state.
68. (a) Al  Al 3  3e  .
70. (c)  1F obtained from 1 g equivalent
 532 Electrochemistry
108 16. (d) Because conductance is increase when the
Equivalent weight of Ag =  108
1 dissociation is more.
63 .6 17. (b) Strong electrolyte ionize completely at all
Equivalent weight of Cu   31 .8 dilutions and the number of ions does not
2
increase on dilution. A small increase in m
M1 E 10 .79 108
 1 ;  volume with dilution is due to the weakening
M 2 E2 M Cu 31 .8
of electrostatic attraction between the ions on
10 .79  31 .8 dilution.
M Cu   3 .2 gm .
108 18. (d) In electrolytic conductors, a single stream of
87. (b) Laws of electrolysis were proposed by electrons flow from cathode to anode.
Faraday. 19. (b) In solid state NaCl does not dissociate into
88. (a) Given, Current (i) = 25 mA = 0.025 A ions so it does not conduct electricity.
Time (t) = 60 sec 20. (c) The ions are not free to move in solid state
Q = i t  60  0 .025  1 .5 coulombs and held up in lattice due to strong coulombic
forces of attraction.
1.5  6.023  10 23
No. of electrons  21. (b) C2 H 5 OH being non electrolyte so does not
96500
ionize.
e   9 .36  10 18
1
Ca  Ca 2  2e  22. (a) Since molar conductance  .
Molarity
2e  are required to deposite one Ca atom 1
23. (c) Molar condcutivity 
9 .36  10 18 e  will be used to deposite M
9 .36  10 18 So its unit will be  1 cm 2 mol 1 .
  4 .68  10 18 .
2 25. (a) l / a  0 . 5 cm 1 , R  50 ohm
 
89. (d) C 6 H 5 NO 2  6 H  6 e  C6 H 5 NH 2  2 H 2 O Ra 50
p   100
1 mole = 123 gm nitrogen requires 6 mole l 0.5
electron e 1000 1 1000 1 1000
 6  96500 coulomb charge k    
N p N 100 1
 12.3 gm nitrobenzene will require 1
10 ohm cm 2 gm eq 1
6  96500  12 .3
  6  9650  57900 C.
123 26. (b) om (C6 H 5 COOH)  o   o(H  )
(C 6 H 5 COO )
90. (c) Au and Ag settle down below the anode as  42  288 . 42  330 . 42
anode mud during the process of electrolytic
cm 12 .8
refining of copper.    3 .9 %
om 330 .42
Conductor and Conductance 1 1
27. (d) Conductance    ohm 1
resistance ohm
1  2 or mho
2. (b)   BaCl2   Ba    Cl 
2
127 Cell constant and Electrochemical cells
  76  139 .5 ohm 1 cm 1 eq 1 .
2
3. (d) Dilution, temperature and nature of 1. (d) In the absence of electric field the ions in the
electrolyte affect the conductivity of solution. solution move randomly due to thermal
energy.
5. (a) Generally strong electrolyte on dilution shows
conductivity characters. 2. (d) Since E oA / A  has large negative value, the

6. (b) Molar conductivity =

1000
. tendency of A to be reduced to A  is very
MX small. In other words tendency of A  to be
K [ A] A C l Sm oxidized to A is very large.
7. (b) C ,K   Sm 2 mol 1 .
l [ A] A mol m 3 m 2 3. (d) Practically only 60-70% efficiency has been
9. (b) Conductivity of a solution is directly attained.
proportional to the number of ions. 1
4. (b) K   Cell constant
R
11. (a) NaCl ⇌ Na   Cl  . So it conduct electricity.
Cell constant  K  R ; 0 .012  55  0 .66 cm 1 .
12. (b) Graphite is a good conductor of electricity.
15. (b) Electrolytic conduction resistance decreases 5. (b) In common dry cell.
with increasing temperature. Anode : Zn  Zn   2e 
 Electrochemistry 533
Cathode: 2 MnO 2  Zn    2e   ZnMn 2 O 4 . 36. (b) At anode: Zn(s)  Zn 2  2e  .
6. (a) Because the reduction potential of Cu is 38. (d) PbSO 4  2 H 2 O  2 PbO 2  4 SO 4   2e  .
highest. 39. (b) MnO2 is used in dry batteries cell.
7. (c) Overall reaction - 2 H 2(g)  O 2(g)  2 H 2 O(l) .
40. (d) Pb  PbO2  2H 2 SO 4 Discharge
2 PbSO 4  2 H 2 O .
9. (b) During charging of a lead storage battery, the Recharge

reaction at the anode and cathode are Sulphuric acid is consumed on discharging.
 2 42. (d) The metal placed below in electrochemical
Anode: PbSO 4  2 e  Pb  SO 4
series does not react with that metal salt
Cathode: solution which metal is placed above in series.
PbSO 4  2 H 2 O  PbO 2  4 H   SO 42   2 e  43. (c) In the electrochemical cell chemical energy
In both the reactions H 2 SO 4 is regenerated. changes into electrical energy.
44. (a) In galvanic cell, the salt bridge used to
11. (c) 2 NH 4 Cl  Zn  2 NH 3  ZnCl 2  H 2  . complete the circuit.
13. (a) When platinum electrodes are dipped in dilute 45. (d) Cu  FeSO 4  No reaction Because Cu has
solution H 2 SO 4 than H 2 is evolved at
E o  0 .34 volt and Fe has E o   0 . 44 volt.
cathode.
47. (d) Calomel electrode as reference electrode is
14. (a) Electrode on which oxidation occurs is written
made by using Hg 2 Cl2 .
on L. H .S . and the other on the R . H .S . as
represented by 48. (b) In hydrogen–oxygen fuel cell following
2 2 reactions take place to create potential
Zn | Zn || Cu | Cu .
difference between two electrodes.
Reduction
2 H 2 (g)  4 OH  (aq )  4 H 2 O(l)  4 e 
15. (d) Zn 2  2e   Zn . It shows reduction reaction.
O 2 (g)  2 H 2 O(l)  4 e   4 OH  (aq )
16. (c) In the electrolytic cell electrical energy
Overall reaction = 2 H 2 (g)  O 2(g)  2 H 2 O(l)
change into chemical energy.
17. (c) In the cell Zn | Zn 2  || Cu 2  | Cu the negative the net reaction is the same as burning
(Combustion) of hydrogen to form water.
electrode (anode) is Zn. In electrochemical
49. (c) Cl CH 2 COONa  HCl  ClCH 2 COOH  NaCl
cell representation anode is always written on ClCH 2 COONa   HCl   ClCH COOH  NaCl
left side while cathode on right side. 2

18. (a) Galvanic cell converts the chemical energy 224  203  ClCH 2COOH  38 .2
into electrical energy. ClCH 2COOH  427  38 .2  388 .8 ohm 1 cm 2 gmeq 1 .
19. (b) Fuel-cells are used to provide power and
50. (c) In daniel cell copper rod acts as cathode so
drinking water to astronauts in space
there cations move towards copper electrode
programme.
and reduction take place on copper rod.
2.303 RT 0 .0591
21. o
(b) E cell  log K  log K c at 298 K . 51. (b) Elements with lower reduction potential act
nF n
as anode. His placed above Cu in
22. (b) Cu 2  2e   Cu electrochemical series so it has lesser
reduction potential and thus act as anode and
Reductio
Cu act as cathode.
24. (b) The celln in which Cu and Zn roads are dipped 52. (d) Fuel cells are more efficient as they are free
in its solutions called Daniel cell. from pollution and hence they run till the
K 0 .2
25. (c) K  C  Cell constant    5 cm 1 . reactants are active. They have longer life
C 0 .04 than lead storage cells.
K 53. (c) For gold plating, the used electrolyte is
 Cell Constant .
KAu(CN )2  .
26. (a)
C
27. (c) Velocities of both K  and NO 3 are nearly the 54. (a) Dil. H 2 SO 4 is used in lead in lead storage
same in KNO3 so it is used to make salt- battery as electrolyte.
Specific conductivity
bridge. 55. (c) Cell constant 
28. (a) In this reaction 4 electrons are needed for the Observed conductance
reaction volume. 0 .002765
 =0 .002765  400  1.106 .
29. (b) In electrochemical cell H 2 release at anode 1/R
and Cu is deposit at the cathode. 57. (b) 2AgCl(s) + H2(g)  2HCl(aq.) + 2Ag(s)
31. (a) Anode has negative polarity. The activities of solids and liquids are takes as
32. (b)  mo (CH 3 COOH )  unity and at low concentrations, the activity
of a solute is approximated to its molarity.
 o (CH 3 COONa )   o (HCl )   o ( NaCl ) Th cell reaction will be
 91  426 .16  126 . 45  390 .71 ohm 1 cm 2 mol 1 .
 534 Electrochemistry
Pt(s) | H2(g), 1 bar | H+(aq) 1 M | AgCl(aq) 1 M | 2 .303 RT
E  Eo  log[M n  ]
Ag(s) nF
0 .059 1 0 .059 1 Substituting the value of R, T (298K) and F we
58. (a) E cell  log   log
n C 2 100 get
0 .059 0 .0591
 (2)  0 .059 V  59 mV . (increase) E  Eo  log(M n  ) .
2 n
10 6 12. (c) At 298 K standard electrode potential of NHE
59. (a) E cell  0 .059 log 3
 0 .059 log 10  3 electrode is 0.00 V.
10
 0.059  (3)  0 .177 V . 13. (a) Since, Ag  ions are reduced to Ag and
60. (c) The magnitude of the electrode potential of a E oAg / Ag  ECu
o
 Cu is oxidized to Cu   .
/ Cu
metal is a measure of its relative tendency to 14. (d) The reducing power decreases as the
lose or gain electrons. i.e., it is a measure of reduction potential increase (becomes less
the relative tendency to undergo oxidation negative).
(loss of electrons) or reduction (gain of 15. (c) Actually the equation is derived from Nerst
electrons). equation assuming equilibrium condition in a
M  M n  ne  (oxidation potential) cell reaction, when E  0 .
M n  ne   M (reduction potential) 16. (a) More negative is the standard reduction
61. (a) On electrolysis of fused ionic hydride (LiH ) , potential, greater is the tendency to lose
hydrogen obtained at anode. electrons and hence greater reactivity.
MH  H 2 O  MOH  H 2  17. (a) Hg has greater reduction potential than that
of H  and hence cannot displace hydrogen
Electrode potential, Ecell, Nernst equation and ECS from acid.
18. (c) Brown layer is deposited on iron rod because
1. (b) Reduction potential of hydrogen electrode, Cu has greater reduction potential than that
2.303 RT 1 of Fe 2  .
EH  log 
F [H ] 19. (b) Since E oA 2  / A  E Bo 2  / B . A has greater tendency
 0.059 pH  0.059  3  0.177 V . to be oxidized.
2. (a) o
E cell  o
E cathode  o
E anode = 0.799  (0.763 )  1.562 V A  B 2  A 2  B .
o
3. (a) More negative is the reduction potential, 20. (b) Since E Zn 
/ Zn
is negative, so Zn has greater
higher will be the reducing property, i.e. the tendency to be oxidized than hydrogen. Hence
power to give up electrons. it can act as reducing agent.
4. (b) Standard potential of Zinc < Copper. 21. (a) Standard electrode potential of Hydrogen is
6. (c) A cation having highest reduction potential zero.
will be reduced first and so on. However, 22. (b) According to electrochemical series.
Mg 2  in aqueous solution will not be reduced 23. (a) The standard reduction potential of K  ,
  Mg 2  , Zn 2 Cu 2  increase in this order.
 E 0 2  E  . Instead water would
 Mg / Mg H 2 O / H 2  OH 
1 
(c) E cell  E oAu 3  / Au  E Ni
o
 1.50  (0.25 )  1.75 V.
 2  24. 2
/ Ni
be reduced in preference. 25. (a) Electromotive force is +ve if oxidation and
7. (c) A is displace from D because D have a reduction both takes place in a cell.
E o  0 . 402 V . 28. (a) In galvanic cell anode always made up of
Reductio
n negative electrode.
Anode Cathode
(d) A | A  (a  1)|| B  (a  1)| B
o o
8. (a) Zn(s)  2 Ag (aq )  Zn(2aq )  2 Ag (s) 29.
Oxidation EMF  Ecathode  Eanode  0 .75  (0 .5) ; EMF  0.25 V .

In this reaction zinc act as a anode and Ag act 30. (d) E o  3 .05 Li  / Li is most negative (minimum)
as a cathode. and hence Li has maximum tendency to lose
9. (a) No doubt Be is placed above Mg in the electrons or it is the strongest reducing agent.
31. (b) Brown layer is deposited on iron rod because
second group of periodic table but it is below
Cu has greater than reduction potential than
Mg in electrochemical series.
that of Fe 2  .
10. (b) Nernst’s equation shows relation between
E and E o . 32. o
(a) E Zn 
/ Zn
 E Fe
o

/ Fe
, so Zn will reduce Fe   . Zn
RT 1 RT cannot reduce Mg 2  because E Zn
o
 E Mg
o
11. (a) E  E o  ln ; E  Eo  ln[M n  ] 
/ Zn 
/ Mg
nF [M n  ] nF
 Electrochemistry 535
On similar reason Mg and Zn cannot oxidize (c) Anode is made of Zinc
Fe . EMF = 0.34 –(– 0.76) = 1.1 volt.
33. (d) For the cell reaction, Fe acts as cathode and Sn 46. (d) H 2 is anode because oxidation takes place.
as anode. Hence, Cu is cathode because reduction is takes place.
o
E cell  o
E cathode  o
E anode = – 0.44 – (– 0.14)= – 47. o
(c) E cell  E cathode  E anode .
0.30V 51. (b) Standard hydrogen electrode have zero electrode
The negative EMF suggests that the reaction potential.
goes spontaneously in reversed direction. 53. (a) G  nFE o
G  1  96500  1 .02 ; G  98430 .
34. (a) o
E cell  o
E cathode  o
E anode  0.34  ( 0.76 )  1.10 V .
54. (c) Fuel cell converts the chemical energy into
35. (c) o
E cell  o
E cathode  E anode ; o
E cell  0 . 34  ( 2 . 37 ) electrical energy.
2.303 RT [M ]
o
E cell  2 .71 V . 55. (a) E  E o  log .
nF [M n  ]
36. (d) Mg lies above Cu in electrochemical series and 56. (a) Less is the reduction potential stronger is the
hence Cu electrode acts as cathode reducing agent.
57. (a) Reducing power, i.e. the tendency to lose
o
Ecell  ECu
o
  EMg
o

/ Cu / Mg electrons increases as the reduction potential
2.70 V  0.34  EMg
o

/ Mg
; E o 
Mg / Mg
 2.36 V . decreases.
58. (a) OCl   C  , E o  0 . 94 V
37. (a) Because H 2 has greater reduction potential so
1
it reduced the Ag  . Cl   Cl 2  e  E o  1 .36 V
2
39. (d) G o  nE o F adding the two equations, we get
1
Fe 2  2e   Fe …..(i) OCl   Cl 2 , E o  0 .94  1 .36  0 .42 V .
2
G  2  F  (0 . 440 V )  0 . 880 F
o
60. (a) It cannot evolved H 2 from H 2S
3 
Fe  3e  Fe …..(ii) Hg  H 2 S  No reaction .
G  3  F  (0.036 )  0.108 F
o
61. o
(b) E cell 
0 .059
log K
On subtracting equation (i) from (ii) n
1 .10  2
Fe 3  e   Fe 2 log K   37 .2881 or K  10 37 .
0.059
G o  0.108 F  0.880 F  0.772 F 62. (d) The oxidizing character i.e. acceptance of
G o electrons increases with the reduction
E o
for the reaction  potential.
nF
( 0.772 F) 63. (a) According to electrochemical series.
   0 .772 V . RT C 2
1 F 64. (d) Ecell  Ecell
o
 ln and G  nF Ecell
nF C1
40. (d) Reducing power i.e. the tendency to lose
electrons increases as the reduction potential C 
hence G is the function of ln  2 .

decreases.  C1 
41. (b) Cu   will be reduced and Fe will be oxidized. 0 . 059 [ Zn   ] 0 .059 1
  66. (c) E  E o  log  1 .10  log
Cu  Fe  Cu  Fe . n [Cu   ] 2 0.1
42. (c) Cell reaction is  1.10  0.0295 log 10  1.07 volt .
Cu (s)  2 Ag   Cu 2   2 Ag 0.0591 0 .01 0.0591
67. (b) E1  Eo  log  Eo  2
Two half cell reaction is 2 1 2
Cu  Cu 2  2e  Oxidation (anode) E 2  Eo 
0.0591
log
100
 Eo 
0.0591
4
Ag   e   Ag Reduction (cathode) 2 0.01 2
 E1  E2 .
ECell  Eox  ERe d  0.80  0.34  0.46 V
43. (a) EMF = [s.r.p. of cathode–s.r.p of anode] Oxidation

Where s.r.p. = Standard reduction potential 68. (b) Fe 2  Zn  Zn 2  Fe

If EMF is positive then the reaction is Reduction
spontaneous
EMF  Ecathode  Eanode  0.44  (0.76 )  0.32 V .
For e.g. in Galvanic cell
(a) EMF = 1.1 volt 69. (a) Fe is more electropositive than copper. Hence
(b) Cathode is made of copper Cu 2  can oxidise Fe.
 536 Electrochemistry
70. (b) E o  0 because hydrogen have zero potential. Einf  Eanode  Ecathode
71. (b) Cell potential of the cell is positive. RT (H  ) 2 RT P2
72. (a,b) Because these comes after the Fe in  ln  ln
2F P1 2 F (H  ) 2
electrochemical series.
RT P2 RT P1
Oxidation  ln  ln .
2 F P1 2 F P2
73. (c) Fe2   Zn  Zn2   Fe 1
84. (c) H 2  H  (10 8 M )  e  (oxidation )
Reduction 2
1
EMF  Ecathode  Eanode  7 .81  (7 .62 ) H  (0 .025 M )  e   H 2 (reduction)
2
EMF  0.19 V . Cell reaction is :
74. (c) Cr 3   Zn 2   H  Fe 3  . H  (0 .025 M )  H  (10 8 M ) ; Ecell  0.38 V .
Reducing nature decreasing order.
85. (a) E o for Fe / Fe 2   0 .44 V .
75. (a) More is reduction potential, more is the power
to get itself reduced or lesser is reducing 86. (c) (Reduction potential of cathode) – (reduction
power or greater is oxidising power. potential of anode).
76. (d) G  nFE o 87. (a) The correct decreasing electrode potential
order is : K, Ba, Ca, Mg .
G  2.303 RT log K ; nFE o  2 .303 RT log K
89. o
(c) E cell  E cathode
o
 E anode
o
nFEo 2  96500  0.295
log K    0.34  ( 2.37 )   2.71 V .
2.303 RT 2.303  8.314  298
90. (b) Because flourine is most powerful reducing
log K  9.97  K  1  10 10 .
agent than other halogens.
77. (b) For the given cell M | M  || X  | X , the cell 92. (c) Aluminium forms a protective oxide layer but
reaction is derived as follows: iron does not.
RHS: reduction X  e   X  …..(i) 93. (d) The reduction potential of Zn is very higher
  than Cu.
LHS: Oxidation M  M  e …..(ii)
94. (a) The pH of 0.1 M HCl and 0.1 M acetic acid is
Add (i) and (ii) M  X  M   X  not the same, because HCl is a strong acid so
The cell potential = 0.11 V its pH is less and CH 3 COOH is a weak acid, so
Since Ecell  – ve, the cell reaction derived its pH is more.
above is not spontaneous. In fact, the reverse 95. (d) The required reaction (Cu    Cu  2Cu  ) can
reaction will occur spontaneously. be obtained by using the following reactions.
0 2 2
78. (c) Zn  MgCl 2  ZnCl 2  Mg No reaction Cu   e   Cu  ; ECu
o

/ Cu 
 0 .15 V …..(i)
Oxidation
Cu    2e   Cu; ECu
o

/ Cu
 0 . 34 V …..(ii)
Reduction
This type of reaction does not occur because Multiplying eq. (i) by 2 we get
2 2 2Cu   2e   2Cu  …..(iii)
Mg E  2.37 V while Zn E  0.76 V .
o o
G1  nFE  2  F  0.15
79. (b) In neutral medium Mn 7 oxidation state
Cu    2 e   Cu …..(iv)
change into +4 oxidation state, hence
M G2  nFE  2  F  0.34
equivalent weight of KMnO4  .
3 Subtract the eq. (iv) from (iii)
80. (a) Increase in the concentration of Ag  ion Cu   Cu  2Cu 
increase the voltage of the cell. G 3   nFE  1  F  E o
0 . 059 ( Ag  ) Also G3  G1  G2
81. (a) E cell  E cell
o
 log .
2 (Sn 2  )  1 FE o  ( 2 F  0 .15 )  ( 2 F  0 .34 )
82. (b) The K.E. of proton is 1 KeV.
E o   0 . 38
83. (b) Anodic reaction : H 2 (P1 )  2 H 
This is the value for the reaction
Cathodic reaction : 2 H   H 2 (P2 ) Cu   Cu  2Cu 
RT P2 RT [H  ]2 But the given reaction is just reverse of it
Ecathode   ln ; E   ln
2 F [H  ]2
anode
2F P1  Ecell for given reaction = + 0.38V.
97. (d) It connect two solutions and complete the
circuit.
98. (a) Greater the oxidation potential, greater is the
reactivity.
 Electrochemistry 537
99. (b) Electrochemical series compare the relative 21200
E  0 .2196 V  0 .22 V .
reactivity of metals. 1  96500
100. (d) Fuel cells are more efficient, free from
115. (b) Ag | Ag  (. 1m )|| Ag  1 M | Ag |
pollution and they run till reactants are
active. 2.303 RT c 0.059 1
E Cell  log 1  log
102. (c) E o  E oAg 2  / Ag  E Cu
o
/ Cu 2 
 0.34  0.80  0.46 V . nF c2 1 0.1
103. (a) Fe is placed above Cu in electrochemical  0.059 log 10  0.059 Volt .
series. 116. (b) For this cell, reaction is: Zn  Fe 2  Zn 2  Fe
104. (a) Lithium is the strongest reducing agent of the c c
0.0591 0.0591
alkali metals. E  E0  log 1 ; E 0  E  log 1
n c2 n c2
105. (d) Potassium is more electropositive element,
because it is the only alkali metal among the 0 .0591 10 2
 0.2905  log 3  0 .32 V .
given elements. 2 10
106. (b) Aluminium forms a self protecting film of 0 . 0591 0.32  2 0 .32
oxide to prevent corrosion. E0  log K c ; log K c  
2 0.0591 0 .0295
107. (a) Zn(s)  2 H  (aq ) ⇌ Zn(2aq )  H 2(g)
0 .32
 Kc  .
. 059 [ Zn 2  ] 10 0295
E Cell  E Cell
0
 log
2 [H  ] 2 117. (d) Al displaces H from HCl but silver cannot it
When H 2 SO 4 is added then [H  ] will increase means Al is situated above the Ag in ECS,
hence Al will acts as anode and Ag will act as
therefore ECell will also increases and cathode.
equilibrium will shift towards right.  E Cathode  E 0Anode  E 0 
0
E Cell 0
 E 0Al3  / Al
108. (b) For M   X   M  X
Ag / Ag

0
E Cell  E Cathode
0
 E 0Anode  0.44  0.33  0.11 V 2 .46  0 .8  E 0Al 3  / Al ; E 0Al  0 . 8  2 . 46  1 . 66 V .
0
Since E Cell  () 0 .11 V is positive hence this 118. (a) For Sn (s)  2 Fe(3aq )  2 Fe(2aq )  Sn (2aq )
reaction should be spontaneous. 0
ECell  E Sn
0
/ Sn 2 
 E Fe
0
3
/ Fe 2 
 (0 .14 )  (0 .77 )
0 .0591
109. (a) E Cell  E Cell
0
 log K c E Cell  0 .91 Volts .
n
0 .0591 119. (d) I  get oxidised to I2 hence will form anode
At 298 K ECell  0 O  0 .591  log K c
n and Cr 2 O 72  get reduced to Cr 3  hence will form
0 .591  1
log K c   10 ; K c  Anti log 10  1  10 10 . cathode.
0 .0591 0
E Cell  E Cathode
0
 E 0Anode ; ECell
0
E  E I02
Cr2 O7 2
1
110. (a) H 2 | H  | | Ag  | Ag |
2 0.79  1.33  E I02 ; E I02  1.33  0.79 ; E I02  0.54 V .
0
E Cell  0
E Cathode  E 0Anode  E 0Ag  / Ag E 0
1 120. (b) According to nernst's equation
H  / H2
2
nRT c
(0.80 )  (0.0)  0.80 V. E Cell  E Cell
0
 log 1
F c2
111. (a) E A  2.23 V  EB  1.43 V
For Zn(s)  Cl 2(1 atm )  Zn 2  2Cl 
So A will act as cathode in galvanic cell. Hence
c1  [ Zn 2  ] and c 2  [Cl  ]
0
E Cell  E Cathode  E Anode  E A  EB
Hence to increase E, c1 should be decreased
 (2 .23 )  (1 .43 )  3.66 V .
and c 2 should be increased is [ Zn 2 ] should be
0
112. (b) ECu  E Mg
0
hence Cu acts as cathode and Mg
decreased and Cl should be increased.
acts as anode. 121. (c)
0
ECell  ECu
0
 E Mg
0
 (0.34 )  (2.37 )  2.71 V . Reduction E0 M 2  / M 3 
Cell reaction
113. (b) In this cell Co is oxidised and it acts as anode E0 M 3  / M 2  (Oxidation)
and Ce acts as cathode. – .41 V Cr 2  Cr 3  + . 41 V
0
E Cell  E Cathode
0
 E 0Anode  1 .89  E Cell
0
 (0 .28 ) + 1.57 V Mn 2  Mn 3  – 1.57 V
0
E Cell  1 . 89  0 . 28  1 . 61 Volts. + 0.77 V Fe 2
Fe 3 – 0.77 V
+ 1.97 V 2 3 – 1.97 V
114. (b) Given: G  21 .20 kJ  21200 J Co Co

 G  nFE As Cr has maximum oxidation potential

value, therefore its oxidation should be
easiest.
 538 Electrochemistry

122. (a) Fe(s) 

 Fe2+ + 2e ; G1o
EMF  Ecathode  Eanode  0.41  (0.76 )
2H+ + 2e + ½O2 
 H2O(l) ; G 2o
EMF  0 .35 V.
Fe(s) + 2H+ + ½O2 
 Fe2+ + H2O ; G 3o 5. (c) NO 3  4 H   4 e   2 H 2 O  NO . In this equation

Applying, G1o  G 2o  G 3o all the atoms are balanced. For balancing

added 3e  to L. H . S . we have,
G 3o = (2F  0.44) + (2F  1.23)
NO 3  4 H  3 e   2 H 2 O  NO .
 

G 3o = (2  96500  0.44+ 2  96500  1.23)

0 . 059 (Zn   )
6. (a) E cell  E cell
o
 log
G 3o = 322310 J 2 (Cu   )
 G 3o = 322 kJ 0 .059 0.1
 1 .10  log  1 .10 V .
128. (a) G o  2.303 RT log K eq or G o  nFE cell
o 2 0.1
7. (a) The tendency to gain electron is in the order
129. (a) Any redox reaction would occur spontaneously
Z>Y>X
if the free energy change (G) is negative. 
Thus Y  e  Y ; X  X e .
G o  nFE o
Where n is the number of electrons involved, 0 .059 [H  ]
8. (b) E OP  E OP
o
 log
F is the value of Faraday and E o is the cell 1 PH 2
emf. G o can be negative if E o is positive.  [H  ]  10 10 ; PH 2  1 atm ; EOP  0.59 V .

Corrosion 9. (a.c,d)Decomposition of H 2 O2 is an example of

exothermic reaction, negative catalysis and
2. (d) Rusting of iron is catalysed by [H  ] . auto-oxidation.
3. (d) HgCl 2 has corrosive action. It is highly 10. (a) 27 gm of Al is obtained by passing a current of
poisonous. It sublimes on heating. It is, 3 × 96500 C.
therefore, known as corrosive sublimate.  1 gm of Al is obtained by passing a current
96500
4. (a) Fe  Fe 2  2e (anode reaction) of 3  C.
27
O 2  2 H 2 O  4 e  4 OH  (cathode reaction)
 5.12 × 103 gm of Al is obtained by passing a
The overall reaction is 96500
current of 3   5 .12  1000
2Fe  O2  2 H 2 O  2 Fe(OH )2 27
Fe(OH )2 may be dehydrated to iron oxide = 1.83 × 107 C × 3 = 5.49 × 107C.
FeO , or further oxidised to Fe(OH )3 and then 11. (c) HOAC  NaOAC  HCl  NaCl
dehydrated to iron rust, Fe 2 O 3 .  91 .0  426 .2  126 .5  390 .7
1 2
 270
Critical Thinking Questions 12. (d)  ; 1  ; 1  90 kg .
E1 E2 3 93

1. (c) (126 scm 2 )  0NaCl   0Na    0Cl  .....(1) 13. (c) Eq of Al = eq of H 2

4 .5 4 .5
(152 scm 2 )  0KBr   0K    0Br  .....(2)  eq of H 2 ;  eq of H 2
27 9
(150 scm 2 )  0KCl   0K    0Cl  .....(3) 3

By equation (1)+(2) – (3) 2 H   2e   H 2

  NaBr  
0 0
  0Br  eq. of H 2 = Number of moles × n factor
Na 
0 .5  n H 2  2
 126  152  150  128 Scm 2 mol 1
0.5
2. (a) At cathode : 2 H  (aq )  2e   2 H VH 2   22 .4 ; VH 2  5 .6 L
2
1 14. (c) The reaction taking place at anode is
2H  O2  H 2 O
2 2Cl–  Cl2 + 2e–
1 1 mole 2  96500 coulomb
2H   O 2  2e   H 2 O
2 Q = i . t = 1  30  60 = 1800 coulomb.
3. (c) H 2 undergoes oxidation and AgCl ( Ag  ) The amount of chlorine liberated by passing
1800 coulomb of electric charge
undergoes reduction.
Oxidation 1  1800  71
  0 .66 g .
0 2 0 2  96500
4. (b) In this reaction Fe 2   Zn  Zn  Fe
Reduction

Assertion & Reason
1. (a) The nature of the cathode can affect the order
of discharge of ions.
2. (b) 1 mole of silver = 1g equivalent of silver
1 mole of copper = 2g equivalent of copper
We know from Faraday's law of electrolysis
that “The weight of ion deposited on an
electrode is directly proportional to the
quantity of electricity passed”.
4. (d) Copper is present below hydrogen therefore
hydrogen from HCl cannot be liberated by
treating with copper. Hence assertion is false
while reason is true.
5. (d) Copper cannot liberate hydrogen from a dil.
HCl solutions because it is situated below
hydrogen in the reactivity series. Here both
assertion and reason are false.
6. (d) The formation of Zn is not possible by placing
Cu plate in ZnSO 4 solution because Zn is
placed above Cu in electrochemical series.
Therefore, both assertion and reason are
false.
7. (e) Electrical conductivity of copper decreases
with increase in temperature because the
metallic conductivity is due to the motion of
electrons. On increasing temperature the
motion of electron increases which hinder in
conductance of current. Hence, here assertion
is false but the reason is true.
8. (a) Dry air is heavier than wet air because the
density of dry air is more than water.
9. (e) Copper is present below hydrogen therefore
hydrogen from HCl cannot be liberated by
treating with copper. Hence, assertion is false
while reason is true.
10. (a) K and Cs emit electrons on exposure to light
hence, both are used in photoelectric cells .
Here, assertion and reason are true and
reason is a correct explanation.
l  l 
12. (b) We know, R or R    , where
A  A
proportionality constant  is called
resistivity. If l  1m and A  1m 2 , then R  
i.e. Resistance = Resistivity.
14. (a) According to Kohlrausch law, “Limiting molar
conductivity of an electrolyte can be
represented as the sum of the individual
contributions of the anion and cation of the
electrolyte”.
15. (c) One Faraday deposite one gram equivalent of
the substance.
16. (b) Gold has higher reduction potential than the
given metals. Hence AuCl3 will react with
these metals.
17. (a) Zn(s)  Cu 2  (aq)  Zn 2  (aq)  Cu(s)
Electrochemistry 539
As the time passes, the concentration of Zn 2 
keeps on increasing while the concentration of
Cu 2  keeps on decreasing. At the same time
voltage of the cell keeps on decreasing. When
there is no change in concentration of Cu 2 
and Zn 2  ions, voltmeter gives zero reading
and this state is known as equilibrium.
18. (e) A negative value of standard reduction
potential means that oxidation takes place on
this electrode with reference to SHE.
19. (a) A standard cell is one whose e.m.f. almost
does not change with temperature.
22. (d) Identification of cathode and anode is done by
the use of ammeter/voltmeter. Higher is the
value of reduction potentials greater would be
its oxidising power.
23. (b) If redox reaction is spontaneous, G is –ve
and hence E 0 is positive.  G 0  nFE 0 cell
24. (a) Zinc metal which has a more negative
electrode potential than iron will provide
electrons in preference of the iron, and
therefore corrode first. Only when all the zinc
has been oxidised does the iron start to rust.
25. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
Anode (oxidation) for eq. Zn  Zn2   2e  , so
Excess of electrons and hence negatively
charged while cathode is positively charged.
26. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
E 0Au 3  / Au  E Ni
0
 1.50  (0.25 )  1.75 V
/ Ni 2 
27. (c) Assertion is true but reason is false. Ions of
inert electrolytes are not involved in any
electrochemical change until they react
chemically with the electrolytes in the two
half-cells.
28. (d) Both assertion and reason are false. Potential
difference is the difference between the
electrode potential of the two electrodes of
the cell when cell is under operation while
emf is the potential difference generated by a
cell when there is zero electron flow.
 Electrochemistry 539

1. The mass of copper deposited from a solution of (c) 0.34  (0.76 )  1.10 V
CuSO4 by passage of 5 A current for 965 second is
(d) 0.76  (0.34 )  1.10 V
(Mol. wt. of Copper = 63.5) [AIIMS 2001]
7. Normal aluminium electrode coupled with normal
(a) 15.875 g (b) 1.5875 g
hydrogen electrode gives an emf of 1.66 volts . So
(c) 4825 g (d) 96500 g
the standard electrode potential of aluminium is[KCET 198
2. The current in a given wire is 1.8 A. The number
(a) – 1.66 V (b) + 1.66 V
of coulombs that flow in 1.36 minutes will be [AIIMS 2001]
(c) – 0.83 V (d) + 0.83 V
(a) 100 C (b) 147 C
8. Which one among the following is the strongest
(c) 247 C (d) 347 C
reducing agent
3. A solution of a salt of a metal was electrolysed
for 150 minutes with a current of 0.15 amperes. Fe 2   2e   Fe (0 .44 V )
The weight of metal deposited was 0.783 gm.
Ni 2   2e   Ni(0 .25 V )
The equivalent weight of the metal is [AFMC 2001]
(a) 55.97 gm (b) 65.97 gm Sn 2   2e   Sn (0.14 V )

(c) 75.97 gm (d) 85.97 gm Fe 3   e   Fe 2  (0 . 77 V ) [BHU 1998]

4. The resistance of 0.01N NaCl solution at 25 o C is

(a) Fe (b) Fe 2 
200 . Cell constant of conductivity cell is 1 cm–1.
The equivalent conductance is (c) Ni[CBSE PMT 1999] (d) Sn

9. The cell reaction of the galvanic cell

(a) 5  10 2 1cm 2 eq 1 (b) 6  10 3 1cm 2 eq 1
2 2
Cu(s) | Cu (aq ) || Hg (aq ) | Hg(l) is [EAMCET 2003]
(c) 7  10 4 1cm 2 eq 1 (d) 8  10 5 1cm 2 eq 1
(a) Hg  Cu 2   Hg 2   Cu
5. Which of the following reaction is possible at
anode (b) Hg  Cu 2   Cu   Hg 
[AIEEE 2002]
(c) Cu  Hg  CuHg
3 2 
(a) 2Cr  7 H 2 O  Cr2 O7  14 H
(d) Cu  Hg 2   Cu 2   Hg

(b) F2  2 F
10. The specific conductivity of N/10 KCl solution at
1
(c) O2  2 H   H 2 O 20 o C is 0 .0212 ohm 1 cm 1 and the resistance of
2
cell containing this solution at 20 o C is 55 ohm.
(d) None of these
The cell constant is
6. What is the standard cell potential for the cell
[AIIMS 1999]
Zn / Zn 2  (1 M )|| Cu 2  (1 M ) / Cu
(a) 1.166 cm 1
E o for Zn / Zn 2  (1 M )  0 . 76 V & Cu 2  / Cu  0 . 34 V
(b) 2.173 cm 1
[AIIMS 1980]
(a) 0.76  (0.34 )  0.42 V (c) 3.324 cm 1

(b) 0.34  0.76  0.42 V (d) 4.616 cm 1

11. The oxide which is not reduced by hydrogen is
 538 Electrochemistry
[JIPMER 1999] (c) Fe2O3 (d) P4 O10
(a) Ag2O (b) K2O

(SET -12)

1. (b) Current (I) = 5A and time (t) = 965 sec. 6. (c) E o  E cathode  E anode
We know that equivalent weight of copper
E o  0.34  (0.76 ) ; E o  1 . 10 volt .
Molecular weight 63 . 5
  and quantity of
Valancy 2 7. o
(a) E cell  1 . 66  E Ho  / H  E oAl 3  / Al
2
electricity passed in coulomb = current × time
= 5 × 965 = 4825C. Since 96500 coulombs will O E oAl 3 / Al or E  1 . 66 V .
Al 3  / Al
63 . 5
deposit g of copper therefore 4825 8. (a) The reduction potential of Fe is very high, so
2
coulombs will deposit it is a strongest reducing agent.
 2
63 .5  4825 9. (b) Cu ( s ) | Cu (2Ag ) | | Hg ( Ag ) | Hg (l )
=  1 .5875 g .
96500  2 anode oxidation cathode reduction

2. (b) Q  I  t ; 1.8  1.36  60  147 C .

Reduction
3. (a) Time (t) = 150 min = 9000 sec
Cu  Hg 2   Cu 2   Hg .
Current (I) = 0.15 A
Oxidation
Weight of metal (w) = 0.783 g.
We know Q  I  t = 0.15  9000  1350 C . Since 10. (a) K 
1
 cell constant
R
1350 C of electricity will deposited 0.783 g of
metal, so, 96500 C of electricity will  K  R  0 . 0212  55  1 . 166 cm 1 .
0 .783  96500
deposited  55 .97 g . 11. (b) On the basis of electrochemical series K 2 O is
1350
not reduced by hydrogen.
1 l 1
4. (a)   k  V   V   1  10 ,000
R a 200

 5  10 2  1 cm 2 eq. 1

5. (a) Oxidation always occurs at anode.

***
 Redox Reactions 541

Chapter

13
Redox Reactions

Chemical reactions involve transfer of electrons Zn  2 H   2Cl   Zn 2   H 2  2Cl  (Ionic

from one chemical substance to another. These electron – equation)
transfer reactions are termed as oxidation-reduction or
redox-reactions. Zn  2 H   Zn 2   H 2 (Final ionic
equation)
Molecular and Ionic equations
In above example, the Cl  ions are the spectator
(1) Molecular equations : When the reactants
ions and hence are not included in the final ionic
and products involved in a chemical change are written
balanced equation.
in molecular forms in the chemical equation, it is
termed as molecular equation. Oxidation-reduction and Redox reactions
Example : MnO2  4 HCl  MnCl2  2 H 2 O  Cl2 (1) Oxidation : Oxidation is a process which
In above example the reactants and products have involves; addition of oxygen, removal of hydrogen,
been written in molecular forms, thus the equation is addition of non-metal, removal of metal, Increase in
termed as molecular equation. +ve valency, loss of electrons and increase in oxidation
number.
(2) Ionic equations : When the reactants and
products involved in a chemical change are ionic (i) Addition of oxygen : 2Mg + O2  2MgO
compounds, these will be present in the form of ions in
(ii) Removal of hydrogen : H2S+Cl2  2HCl + S
the solution. The chemical change is written in ionic
forms in chemical equation, it is termed as ionic (iii) Addition of Non-metal : Fe + S  FeS
equation. Example,
(iv) Removal of metal : 2KI+H2O2  2KOH+I2
MnO 2  4 H   4 Cl   Mn 2   2Cl   2 H 2 O  Cl 2
2 3 
(v) Increase in +ve valency : Fe  Fe  e
In above example the reactants and products have
been written in ionic forms, thus the equation is
termed as ionic equation. (vi) Loss of electrons (also known as de-
(3) Spectator ions : In ionic equations, the ions electronation)
which do not undergo any change and equal in number 4 3 2 1 0 1 2 3 4
M M M M M M M M M
in both reactants and products are termed as spectator
ions and are not included in the final balanced
–e– –e– –e– –e– –e– –e– –e– –
equations. Example,
e–
 542 Redox Reactions
Loss of electrons (ii) Types of redox reaction
(a) Direct redox reaction : The reactions in which
(a) H 0  H   e  (Formation of proton)
oxidation and reduction takes place in the same vessel
(b) MnO 42   MnO 4  e  (De-electronation of MnO 42  )are called direct redox reactions.
(b) Indirect redox reaction : The reactions in
3 
(c) 2 Fe  2 Fe  6 e
0
(De-electronation of iron) which oxidation and reduction takes place in different
vessels are called indirect redox reactions. Indirect
(vii) Increase in oxidation number redox reactions are the basis of electro-chemical cells.
(c) Intermolecular redox reactions : In which one
(a) Mg 0  Mg 2  (From 0 to +2) substance is oxidised while the other is reduced.


(b) Fe 2 (CN )6
4

 Fe 3 (CN )6 
3

(From +2 to +3)
For example, 2 Al  Fe2O3  Al2O3  2 Fe
Here, Al is oxidised to Al2 O3 while Fe2O3 is
(c) 2 Cl   Cl 20 (From –1 to 0) reduced to Fe.
(d) Intramolecular redox reactions : In which one
(2) Reduction : Reduction is just reverse of
element of a compound is oxidised while the other is
oxidation. Reduction is a process which involves;
reduced.
removal of oxygen, addition of hydrogen, removal of 
non-metal, addition of metal, decrease in +ve valency, For example, 2 KClO 3  2 KCl  3 O 2
gain of electrons and decrease in oxidation number. Here, Cl 5 in KClO3 is reduced to Cl 1 in KCl
(i) Removal of oxygen : CuO  C  Cu  CO while O 2  in KClO3 is oxidised to O 20 .
(ii) Addition of hydrogen : Cl 2  H 2  2 HCl
Oxidising and Reducing agents
(iii) Removal of non-metal
2HgCl2  SnCl 2  Hg 2 Cl 2  SnCl 4 (1) Definition : The substance (atom, ion or
molecule) that gains electrons and is thereby reduced
(iv) Addition of metal : HgCl2  Hg  Hg 2 Cl2
to a low valency state is called an oxidising agent,
(v) Decrease in +ve valency
while the substance that loses electrons and is thereby
(a) Fe 3   Fe 2  (+ve valency decreases) oxidised to a higher valency state is called a reducing
3 4
(b) [Fe (CN )6 ]  [Fe (CN )6 ] (–ve valency increases) agent.
(vi) Gain of electrons (also known as Or
electronation) An oxidising agent is a substance, the oxidation
4 3 2 1 0 1 2 3 4 number of whose atom or atoms decreases while a
M M M M M M M M M
reducing agent is a substance the oxidation number of
whose atom increases.
+e– +e– +e– +e– +e– +e– +e– +e–
Gain of electrons (2) Important oxidising agents
2  2
(a) Zn (aq)  2e  Zn(S ) (Electronation of Zn ) (i) Molecules made up of electronegative
elements.
(b) Pb 2   2e   Pb0 (Electronation of Pb 2  )
Example : O2, O3 and X2 (halogens).
(c) [Fe (CN )6 ]3   e   [Fe (CN )6 ]4 
(ii) Compounds containing an element which is in
(Electronation of [Fe (CN )6 ]3  )
the highest oxidation state.
(vii) Decrease in oxidation number
Example : KMnO4 , K2Cr2O7 , Na2 Cr2 O7 , CrO3, H 2 SO 4 ,
(a) Mg 2  Mg 0 (From +2 to 0)
HNO3 , NaNO3 , FeCl3 , HgCl2 , KClO4 , SO 3 , CO2 , H 2O2 etc.
(b) Fe(CN )6 3   Fe(CN )6 4  (From +3 to +2)
(iii) Oxides of elements, MgO, CuO, CrO3 , CO2 , P4 O10 ,
(c) Cl 20  2 Cl  (From 0 to –1)
etc.
(3) Redox-reactions
(i) An overall reaction in which oxidation and (iv) Fluorine is the strongest oxidising agent.
reduction takes place simultaneously is called redox or (3) Important reducing agents
oxidation-reduction reaction. These reactions involve (i) All metals e.g. Na, Zn, Fe, Al, etc.
transfer of electrons from one atom to another. Thus
(ii) A few non-metals e.g. C, H2, S etc.
every redox reaction is made up of two half reactions;
(iii) Hydracids : HCl, HBr, HI, H2S etc.
One half reaction represents the oxidation and the
other half reaction represents the reduction. (iv) A few compounds containing anelement in the
lower oxidation state (ous).

Example : FeCl2 , FeSO4 , SnCl 2 , Hg 2Cl2 , Cu2O etc.
(v) Metallic hydrides e.g. NaH, LiH etc.
(vi) Organic compounds like HCOOH and (COOH)2
and their salts, aldehydes, alkanes etc.
(vii) Lithium is the strongest reducing agent in
solution.
(viii) Cesium is the strongest reducing agent in
absence of water. Other reducing agents are Na2 S 2 O3
and KI.
(ix) Hypo prefix indicates that central atom of
compound has the minimum oxidation state so it will
act as a reducing agent.
Example : H 3 PO2 (hypophosphorous acid).
(4) Substances which act as oxidising as well as
reducing agents
Examples :
H2O2,SO2,H2SO3,HNO2,NaNO2,Na2SO3,O3 etc.
(5) Tips for the identification of oxidising and
reducing agents
(i) If an element is in its highest possible
oxidation state in a compound, the compound can
function as an oxidising agent.
Example : KMnO4 , K2Cr2O7 , HNO3 , H 2 SO 4 , HClO4 etc.
(ii) If an element is in its lowest possible
oxidation state in a compound, the compound can
function only as a reducing agent.
Example : H 2 S , H 2C2O4 , FeSO4 , Na2 S 2O3 , SnCl 2 etc.
Redox Reactions 543
(iii) If an element is in its intermediate oxidation
state in a compound, the compound can function both
as an oxidising agent as well as reducing agent.
Example : H 2O2 , H 2 SO 3 , HNO 2 , SO 2 etc.
(iv) If a highly electronegative element is in its
highest oxidation state in a compound, that compound
can function as a powerful oxidising agent.
Example : KClO4 , KClO3 , KBrO3 , KIO3 etc.
(v) If an electronegative element is in its lowest
possible oxidation state in a compound or in free state,
it can function as a powerful reducing agent.
Example : I  , Br  , N 3  etc.
(6) Equivalent weight of oxidising and reducing
agents
Equivalent weight of a substance (oxidant or
reductant) is equal to molecular weight divided by
number of electrons lost or gained by one molecule of
the substance in a redox reaction.
Eq. wt. of O. A. =
Molecular weight
No. of electrons gained by one molecule
Molecular weight
=
Change in O. N. per mole
Molecular weight
Eq. wt. of R. A. =
No. of electrons lost by one molecule
Molecular weight
=
Change in O. N. per mole

Table : 13.1 Equivalent weight of few oxidising/reducing agents

Change in Total
Agents O. N. Product O. N. O. N. per Change in Eq. wt.
atom O. N. per mole
2
Cr2 O7 +6 Cr 3  +3 3 3×2=6 Mol. wt./6
2 CO2
C2O4 +3 +4 1 1×2=2 Mol. wt./2
2 2
S 2O3 +2 S 4 O6 + 2.5 0.5 0.5 × 2 = 1 Mol. wt./1
H 2O2 –1 H 2O –2 1 1×2=2 Mol. wt./2
H 2O2 –1 O2 0 1 1×2=2 Mol. wt./2
MnO 4
+7 Mn 2  +2 5 5×1=5 Mol. wt./5
(Acidic medium)
MnO 4
+7 MnO2 +4 3 3×1=3 Mol. wt./3
(Neutral medium)
MnO 4
+7 MnO 42  +6 1 1×1=1 Mol. wt./1
(Alkaline medium)

Oxidation number or Oxidation state number or oxidation state. It is the number of

effective charges on an atom.
(1) Definition : Charge on an atom produced by
(2) Valency and oxidation number : Valency and
donating or accepting electrons is called oxidation
oxidation number concepts are different. In some cases
 544 Redox Reactions
(mainly in the case of electrovalent compounds), For example, Oxidation number of Cl in Cl2, O in
valency and oxidation number are the same but in O2 and N in N2 is zero.
other cases they may have different values. Points of (ii) If covalent bond is between two different
difference between the two have been tabulated below atoms then electrons are counted towards more
Oxidation number Valency electronegative atom. Thus oxidation number of more
O.N. is the charge (real or It is the combining capacity electronegative atom is negative and oxidation number
imaginary) present on the of the element. No plus or of less electronegative atom is positive. Total number
atom of the element when minus sign is attached to it.
of charges on any element depends on number of
it is in combination. It may
have plus or minus sign. bonds.
O.N. of an element may Valency of an element is A – B  A+ + B– :
have different values. It usually fixed.
depends on the nature of A – B  A+2 + : B–2 :
compound in which it is
present. The oxidation number of less electronegative
O.N. of the element may be Valency is always a whole element (A) is + 1 and + 2 respectively.
a whole number or number.
fractional.
(iii) If there is a coordinate bond between two
O.N. of the element may be Valency of the element is
atoms then oxidation number of donor atom will be + 2
zero. never zero except of noble and of acceptor atom will be – 2.
gases.
A  B  A2+ + :B-2 :
(3) Oxidation number and Nomenclature
(iv) The oxidation number of all the atoms of
(i) When an element forms two monoatomic different elements in their respective elementary states
cations (representing different oxidation states), the is taken to be zero. For example, in
two ions are distinguished by using the ending-ous and N 2 , Cl2 , H2 , P4 , S 8 , O2 , Br2 , Na, Fe, Ag etc. the oxidation
ic. The suffix – ous is used for the cation with lower
number of each atom is zero.
oxidation state and the suffix – ic is used for the cation
with higher oxidation state. (v) The oxidation number of a monoatomic ion is
the same as the charge on it. For example, oxidation
For example : Cu+ (oxidation number +1) cuprous
numbers of Na  , Mg 2  and Al 3  ions are + 1, + 2 and + 3
Cu2+ (oxidation number +2) cupric
respectively while those of Cl  , S 2  and N 3  ions are –1,
(ii) Albert Stock proposed a new system known as
–2 and –3 respectively.
Stock system. In this system, Roman numeral written in
parentheses immediately after the name of the element (vi) The oxidation number of hydrogen is + 1
indicates the oxidation states. For example, when combined with non-metals and is –1 when
combined with active metals called metal hydrides such
Cu2O Copper (I) oxide SnO Tin (II) oxide as LiH, KH, MgH2, CaH2 etc.
FeCl2 Iron (II) Mn2O7 Manganess (VII) (vii) The oxidation number of oxygen is – 2 in
chloride oxide
most of its compounds, except in peroxides like
K2Cr2O7 Potassium Na2CrO4 Sodium chromate H 2O2 , BaO2 etc. where it is –1. Another interesting
dichromate (VI) (VI) exception is found in the compound OF2 (oxygen
V2O5 Vanadium (V) CuO Copper (II) oxide difluoride) where the oxidation number of oxygen is +
oxide 2. This is due to the fact that fluorine being the most
SnO2 Tin (IV) oxide FeCl3 Iron (III) chloride electronegative element known has always an oxidation
number of –1.
(4) Rules for the determination of oxidation
(viii) In compounds formed by union of metals
number of an atom : The following rules are followed
in ascertaining the oxidation number of an atom, with non-metals, the metal atoms will have positive
oxidation numbers and the non-metals will have
(i) If there is a covalent bond between two same negative oxidation numbers.
atoms then oxidation numbers of these two atoms will
For example,
be zero. Bonded electrons are symmetrically
distributed between two atoms. Bonded atoms do not (a) The oxidation number of alkali metals (Li, Na,
acquire any charge. So oxidation numbers of these two K etc.) is always +1 and those of alkaline earth metals
atoms are zero. (Be, Mg, Ca etc) is + 2.
A : A or A – A  A* + A*
 Redox Reactions 545
(b) The oxidation number of halogens (F, Cl, Br, I) VA ns2np3 +5,+3,+1, –1, –3
is always –1 in metal halides such as KF, AlCl3, MgBr2,
VI A ns2np4 +6,+4,+2,–2
CdI2. etc.
2 5
VII A ns np +7,+5,+3, +1, –1
(ix) In compounds formed by the union of different
elements, the more electronegative atom will have (xiii) Transition metals exhibit a large number
negative oxidation number whereas the less of oxidation states due to involvement of (n –1) d
electronegative atom will have positive oxidation electron besides ns electron.
number. (xiv) Oxidation number of a metal in carbonyl
For example, complex is always zero.

(a) N is given an oxidation number of –3 when it Example : Ni has zero oxidation state in NiCO4  .
is bonded to less electronegative atom as in NH3 and (xv) Those compounds which have only C, H and
NI3, but is given an oxidation number of + 3 when it is O the oxidation number of carbon can be calculated by
bonded to more electronegative atoms as in NCl3. following formula,
(b) Since fluorine is the most electronegative (nO  2 - nH )
Oxidation number of ' C' 
element known so its oxidation number is always –1 in nC
its compounds i.e. oxides, interhalogen compounds etc. Where, nO is the number of oxygen atom, n H is the
(c) In interhalogen compounds of Cl, Br, and I; the number of hydrogen atom, nC is the number of carbon
more electronegative of the two halogens gets the atom.
oxidation number of –1. For example, in BrCl3, the *
oxidation number of Cl is –1 while that of Br is +3. For example, (a) CH 3 OH ; nH  4, nC  1, nO  1
(x) For neutral molecule, the sum of the oxidation (1  2  4 )
Oxidation number of ‘C’ =  2
numbers of all the atoms is equal to zero. For example, 1
in NH3 the sum of the oxidation numbers of nitrogen *
(b) HCOOH ; nH  2, nO  2, nc  1
atom and 3 hydrogen atoms is equal to zero. For a
complex ion, the sum of the oxidation numbers of all (2  2  2)
Oxidation number of carbon =  2
the atoms is equal to charge on the ion. For example, in 1
SO 42  ion, the sum of the oxidation numbers of sulphur (5) Procedure for calculation of oxidation
atom and 4 oxygen atoms must be equal to –2. number : By applying the above rules, we can calculate
the oxidation numbers of elements in the
(xi) It may be noted that oxidation number is also
molecules/ions by the following steps.
frequently called as oxidation state. For example, in
H2O, the oxidation state of hydrogen is +1 and the (i) Write down the formula of the given
oxidation state of oxygen is – 2. This means that molecule/ion leaving some space between the atoms.
oxidation number gives the oxidation state of an (ii) Write oxidation number on the top of each
element in a compound. atom. In case of the atom whose oxidation number has
(xii) In the case of representative elements, the to be calculated write x.
highest oxidation number of an element is the same as (iii) Beneath the formula, write down the total
its group number while highest negative oxidation oxidation numbers of each element. For this purpose,
number is equal to (8 – Group number) with negative multiply the oxidation numbers of each atom with the
sign with a few exceptions. The most common number of atoms of that kind in the molecule/ion.
oxidation states of the representative elements are Write the product in a bracket.
shown in the following table,
(iv) Equate the sum of the oxidation numbers to
Group Outer shell Common oxidation numbers zero for neutral molecule and equal to charge on the
configuration (states)
ion.
except zero in free state
(v) Solve for the value of x.
IA ns1 +1

II A ns2 +2

III A ns2np1 +3, +1

2 2
IV A ns np +4,+3,+2,+1, –1, –2, –3, –4

Table : 13.2 Oxidation number of some elements in compounds, ions or chemical species
 546 Redox Reactions

Element Oxidation Compounds, ions or chemical species

Number

Sulphur (S) –2 H2S, ZnS, NaHS, (SnS3)2–, BaS, CS2

0 S, S4, S8, SCN–
+1 S2F2, S2Cl2
+4 SO2, H2SO3, (SO3)2–, SOCl2, NaHSO3, Ca[HSO3]2, [HSO3]–, SF4
+6 H2SO4, (SO4)2-, [HSO4]–, BaSO4, KHSO4, SO3, SF6, H2S2O7, (S2O7)2–

Nitrogen (N) –3 NH3, (NH4)+, AlN, Mg3N2, (N)3–, Ca3N2, CN–

–2 N2H4, (N2H5)+
–1 NH2OH
–1/3 NaN3, N3H
0 N2
+1 N2 O
+2 NO
+3 HNO2, (NO2)–, NaNO2, N2O3, NF3
+4 NO2
+5 HNO3, (NO3)–, KNO3, N2O5

Chlorine (Cl) –1 HCl, NaCl, CaCl2, AlCl3, ICl, ICl5, SOCl2, CrO2Cl2, KCl, K2PtCl6, HAuCl4, CCl4
0 Cl, Cl2
+1 HOCl, NaOCl, (OCl)–, Cl2O
+3 KClO2, (ClO2)–, HClO2
+4 ClO2
+5 (ClO3)–, KClO3, NaClO3, HClO3
+7 HClO4, Cl2O7, KClO4, (ClO4)–

Hydrogen (H) –1 NaH, CaH2, LiAlH4, LiH

+1 NH3, PH3, HF

Phosphorus –3 PH3, (PH4)+, Ca3P2

(P)

0 P4

+1 H3PO2, KH2PO2, BaH4P2O4

+3 PI3, PBr3, PCl3, P2O3, H3PO3

+5 (PO4)3–, H3PO4, Ca3(PO4)2, H4P2O7, P4O10, PCl5, (P2O7)4–, Mg2P2O7, ATP

Oxygen (O) –2 H2O, PbO2, (CO3)2–, (PO4)2–, SO2, (C2O4)2–, HOCl, (OH)–, (O)2–

–1 Na2O2, BaO2, H2O2, (O2)2–, Peroxides

– 1/2 KO2

0 O, O2, O3

+1 O2F2
 Redox Reactions 547

+2 OF2

Carbon (C) –4 CH4

–3 C2H6

–2 CH3Cl, C2H4

–1 CaC2, C2H2

0 Diamond, Graphite, C6H12O6, C2H4O2, HCHO, CH2Cl2

+2 CO, CHCl3, HCN

+3 H2C2O4, (C2O4)2–

+4 CO2, H2CO3, (HCO3)–, CCl4, Na2CO3, Ca2CO3, CS2, CF4, (CO3)–2

Chromium (Cr) +3 Cr2(SO4)3, CrCl3, Cr2O3, [Cr(H2O)4Cl3]

+6 K2CrO4, (CrO4)2–, K2Cr2O7, (Cr2O7)2–, KCrO3Cl, CrO2Cl2, Na2Cr3O10, CrO3

Manganese +2 MnO, MnSO4, MnCl2, Mn(OH)2

(Mn)

+ 8/3 Mn3O4

+3 Mn(OH)3

+4 MnO2, K2MnO3

+6 K2MnO4, (MnO4)2–

+7 KMnO4, (MnO4)–, HMnO4

Silicon (Si) –4 SiH4, Mg2Si

+4 SiO2, K2SiO3, SiCl4

Iron (Fe) 8 Fe3O4


3

+2 FeSO4. (NH4)2SO4 (Ferrous ammonium sulphate), K4Fe(CN)6, FeCl2

+3 K3[Fe(CN)6], FeCl3

Iodine (I) +7 H 4 IO 6 , KIO4

Osmium (Os) +8 OsO4

Xenon(Xe) +6 XeO3, XeF6

(6) Exceptional cases of evaluation of oxidation 2  1  x  5  (2)  0 or x  8
numbers : The rules described earlier are usually
But this cannot be true as maximum oxidation
helpful in determination of the oxidation number of a
number for S cannot exceed + 6. Since S has only 6
specific atom in simple molecules but these rules fail in
electrons in its valence shell. This exceptional value is
following cases. In these cases, the oxidation numbers
due to the fact that two oxygen atoms in H 2 SO5 shows
are evaluated using the concepts of chemical bonding
peroxide linkage as shown below,
Peroxide
involved.
linkage
O
Type I. In molecules containing peroxide linkage
in addition to element-oxygen bonds. For example, H O S O O H
(i) Oxidation number of S in H2SO5 O

(Permonosulphuric acid or Caro's acid) Therefore the evaluation of o.n. of sulphur here
By usual method; H 2 SO5 should be made as follows,
2 × (+1) + x + 3 × (–2) + 2 × (–1)
 548 Redox Reactions
(for H) (for S) (for O) (for O–O) electronegative element is assigned the oxidation
or 2 + x – 6 – 2 = 0 or x = + 6. number of –1.
(ii) Oxidation number of S in H2S2O8 (ii) In case of a coordinate-covalent bond between
(Peroxidisulphuric acid or Marshall's acid) similar or dissimilar atoms but the donor atom is less
By usual method ; H 2 S 2O8 electronegative than the acceptor atom, an oxidation
number of +2 is assigned to the donor atom and an
1 × 2 + 2x + 8 (–2) = 0 oxidation number of –2 is assigned to the acceptor
2x = + 16 – 2 = 14 or x=+7 atom.
Similarly Caro's acid, Marshall's acid also has a Conversely, if the donor atom is more
peroxide linkage so that in which S shows +6 oxidation electronegative than the acceptor atom, the
state. contribution of the coordinate bond is neglected.
Peroxide Examples,
O O linkage 
(a) Oxidation number of C in HC  N and HN  C
H O S O O S O H
O O The evaluation of oxidation number of C cannot
be made directly by usual rules since no standard rule
Therefore the evaluation of oxidation state of exists for oxidation numbers of N and C.
sulphur should be made as follow,
In such cases, evaluation of oxidation number
2 × (+1) + 2 × (x) + 6 × (–2) + 2 × (–1) should be made using indirect concept or by the
=0 original concepts of chemical bonding.
(for H) (for S) (for O) 
(b) Oxidation number of carbon in H – N  C
(for O–O)
The contribution of coordinate bond is neglected
or 2 + 2x – 12 – 2 = 0 or x = + 6.
since the bond is directed from a more electronegative
(iii) Oxidation number of Cr in CrO5 N atom (donor) to a less electronegative carbon atom
(acceptor).
(Blue perchromate)

By usual method CrO5 ; x – 10 = 0 or x = + 10 Therefore the oxidation number of N in HN  C
remains – 3 as it has three covalent bonds.
This cannot be true as maximum O. N. of Cr
1 × (+ 1) + 1 × (– 3) +x = 0
cannot be more than + 6. Since Cr has only five
electrons in 3d orbitals and one electron in 4s orbital. (for H) (for N) (for C)
This exceptional value is due to the fact that four or 1+x–3=0 or x = + 2.
oxygen atoms in CrO5 are in peroxide linkage. (c) Oxidation number of carbon in HC  N
The chemical structure of CrO5 is In HC  N , N is more electronegative than
O O carbon, each bond gives an oxidation number of –1
Peroxide Peroxide linkage to N. There are three covalent bonds, the oxidation
Cr
linkage number of N in HC  N is taken as – 3
O O
O Now HC  N  +1 + x – 3 = 0  x = + 2

Therefore, the evaluation of o.n. of Cr should be
made as follows
x + 1 × (– 2) + 4 (–1) = 0
(for Cr) (for O) (for O–O)
or x – 2 – 4 = 0 or x = + 6.
Type II. In molecules containing covalent and
coordinate bonds, following rules are used for
evaluating the oxidation numbers of atoms.
(i) For each covalent bond between dissimilar
atoms the less electronegative element is assigned the
oxidation number of + 1 while the atom of the more
Type III. In a molecule containing two or more
atoms of same or different elements in different
oxidation states.
(i) Oxidation number of S in Na2S2O3
By usual method Na2 S 2 O3
 2 × (+1) + 2 × x + 3 (–2) = 0 or 2 + 2x – 6 = 0
or x = 2.
But this is unacceptable as the two sulphur atoms
in Na2S2O3 cannot have the same oxidation number
because on treatment with dil. H2SO4, one sulphur atom
is precipitated while the other is oxidised to SO2.

Na2 S 2 O3  H 2 SO 4  Na2 SO 4  SO 2  S  H 2 O
In this case, the oxidation number of sulphur is
evaluated from concepts of chemical bonding. The
chemical structure of Na2S2O3 is
S have oxidation number zero. The oxidation number of
Na  O S O Na 
O Let oxidation number of S = x.
Due to the presence of a co-ordinate bond
between two sulphur atoms, the acceptor sulphur atom
has oxidation number of – 2 whereas the other S atom
gets oxidation number of + 2.
2 × (+1) + 3 × (–2) + x × 1 + 1 × (– 2) =
0 Though there are a number of methods for
(for Na) (for O) (for S)
coordinated S)
or + 2 – 6 + x–2=0 or x = + 6
Thus two sulphur atoms in Na2S2O3 have
oxidation number of – 2 and +6.
(ii) Oxidation number of chlorine in CaOCl2
(bleaching powder)
In bleaching powder, Ca(OCl)Cl, the two Cl
atoms are in different oxidation states i.e., one
Cl – having oxidation number of –1 and the other as
OCl – having oxidation number of +1.
(iii) Oxidation number of N in NH4NO3
By usual method N2H4O3 ; 2x + 4 × (+1) + 3 × (–1)
=0
2x + 4 – 3 = 0 or 2x = + 1 (wrong)
No doubt NH4NO3 has two nitrogen atoms but one
N has negative oxidation number (attached to H) and
the other has positive oxidation number (attached to
O). Hence the evaluation should be made separately for
NH 4 and NO 3
NH 4 x + 4 × (+1) = +1 or x = – 3
NO 3 x + 3 (– 2) = –1 or x = + 5.
(iv) Oxidation number of Fe in Fe3O4
In Fe3O4, Fe atoms are in two different oxidation
states. Fe3O4 can be considered as an equimolar
mixture of FeO [iron (II) oxide] and Fe2O3 [iron (III)
oxide]. Thus in one molecule of Fe3O4, two Fe atoms are
in + 3 oxidation state and one Fe atom is in + 2
oxidation state.
(v) Oxidation number of S in
tetrathionate (Na2S4O6)
Its structure can be represented as follows,
Redox Reactions 549
O O
Na  O S S S S O Na 
O O
The two S-atoms which are linked to each other
other S-atoms can be calculated as follows
 2×x + 2 × 0 + 6 × ( – 2) = – 2
(for S) (for S–S) (for O)
x = + 5.
Balancing of oxidation-reduction reactions
balancing oxidation – reduction reactions, two methods
(for
are very important. These are,
(1) Oxidation number method
(2) Ion – electron method
(1) Oxidation number method : The method for
balancing redox reactions by oxidation number change
method was developed by Johnson. In a balanced redox
reaction, total increase in oxidation number must be
equal to the total decrease in oxidation number. This
equivalence provides the basis for balancing redox
reactions. This method is applicable to both molecular
and ionic equations. The general procedure involves the
following steps,
(i) Write the skeleton equation (if not given,
frame it) representing the chemical change.
(ii) Assign oxidation numbers to the atoms in the
equation and find out which atoms are undergoing
oxidation and reduction. Write separate equations for
the atoms undergoing oxidation and reduction.
(iii) Find the change in oxidation number in each
equation. Make the change equal in both the equations
by multiplying with suitable integers. Add both the
equations.
(iv) Complete the balancing by inspection. First
balance those substances which have undergone change
in oxidation number and then other atoms except
hydrogen and oxygen. Finally balance hydrogen and
oxygen by putting H2O molecules wherever needed.
The final balanced equation should be checked to
ensure that there are as many atoms of each element
on the right as there are on the left.
sodium (v) In ionic equations the net charges on both
sides of the equation must be exactly the same. Use H+
ion/ions in acidic reactions and OH– ion/ions in basic
 550 Redox Reactions
reactions to balance the charge and number of
hydrogen and oxygen atoms.
The following example illustrate the above rules,
Step : I Cu  HNO3  Cu(NO3 )2  NO2  H 2O
(Skeleton equation)
Step: II Writing the oxidation number of all the
atoms.
0 1 5  2 2 5 2 4 2 1 2
Cu  H N O 3  Cu ( N O 3 )2  N O 2  H 2 O
Step: III Change in oxidation number
occurred in copper and nitrogen.
0 2
Cu  Cu (NO3 )2 ......(i)
5 4
H N O3  N O 2 ......(ii)
Increase in oxidation number of copper
units per molecule Cu
Decrease in oxidation number of nitrogen = 1
unit per molecule HNO3
Step: IV To make increase and decrease equal,
equation (ii) is multiplied by 2.
Cu  2 HNO3  Cu (NO3 )2  2 NO2  H 2O
Step: V Balancing nitrate ions, hydrogen and
oxygen, the following equation is obtained.
Cu  4 HNO3  Cu (NO3 )2  2 NO2  2 H 2O
This is the balanced equation.
(2) Ion-electron method (half reaction method)
Jette and LaMev developed the method for
balancing redox-reactions by ion electron method in
1927. It involves the following steps
(i) Write down the redox reaction in ionic form.
(ii) Split the redox reaction into two half
reactions, one for oxidation and other for reduction.
(iii) Balance each half reaction for the number of
atoms of each element. For this purpose,
(a) Balance the atoms other than H and O for each
half reaction using simple multiples.
(b) Add water molecules to the side deficient in
oxygen and H+ to the side deficient in hydrogen. This is
done in acidic or neutral solutions.
(c) In alkaline solution, for each excess of oxygen,
add one water molecule to the same side and 2OH– ions to
the other side. If hydrogen is still unbalanced, add one
OH– ion for each excess hydrogen on the same side and
one water molecule to the other side.
(iv) Add electrons to the side deficient in
electrons as to equalise the charge on both sides.
(v) Multiply one or both the half reactions by a
suitable number so that number of electrons become
equal in both the equations.
(vi) Add the two balanced half reactions and
cancel any term common to both sides.
The following example illustrate the above rules
Step: I I2  OH   IO3  I   H 2 O (Ionic equation)
Step: II Splitting into two half reactions,
I2  OH   IO3  H 2 O ; I2  I 
(Oxidation half reaction) (Reduction half
has reaction)
Step: III Adding OH  ions,
I2  12 OH   2 IO3  6 H 2 O
Step: IV Adding electrons to the sides deficient in
electrons, (Si)
I2  12 OH   2 IO3  6 H 2 O  10 e  ; I2  2 e   2 I 
= 2
Step: V Balancing electrons in both the half
reactions.
I2  12 OH   2 IO3  6 H 2 O  10 e  ; 5 [I2  2 e   2 I  ]
Step: VI Adding both the half reactions.
6 I2  12 OH   2 IO3  6 H 2 O  10 I  ;
Dividing by 2, 3 I2  6 OH   IO3  5 I   3 H 2 O
Autoxidation
(1) Turpentine and numerous other olefinic
compounds, phosphorus and certain metals like Zn and
Pb can absorb oxygen from the air in presence of water.
The water is oxidised to hydrogen peroxide. This
phenomenon of formation of H2O2 by the oxidation of
H2O is known as autoxidation. The substance such as
turpentine or phosphorus or lead which can activate
the oxygen is called activator. The activator is
supposed to first combine with oxygen to form an
addition compound, which acts as an autoxidator and
reacts with water or some other acceptor so as to
oxidise the latter. For example;
Pb  O 2  PbO 2 ; PbO 2  H 2 O  PbO  H 2 O 2
(activator ) (autoxidat or) (acceptor )
(2) The turpentine or other unsaturated
compounds which act as activators are supposed to
take up oxygen molecule at the double bond position to
form unstable peroxide called moloxide, which then
gives up the oxygen to water molecule or any other
acceptor.
RCH  CHR  O2  RHC CHR
O O
RHC CHR  2 H 2 O  RCH  CHR  2 H 2 O2
O O

2 KI  H 2O2  2 KOH  I2
The evolution of iodine from KI solution in
presence of turpentine can be confirmed with starch
solution which turns blue.
(3) The concept of autoxidation help to explain
the phenomenon of induced oxidation. Na2 SO 3 solution
is oxidised by air but Na3 AsO3 solution is not oxidised
by air. If a mixture of both is taken, it is observed both
are oxidised. This is induced oxidation.
Na2 SO 3  O2  Na2 SO5
Moloxide
Na2 SO5  Na3 AsO3  Na3 AsO4  Na2 SO 4
Na2 SO 3  Na3 AsO3  O2  Na2 SO 4  Na3 AsO4
Disproportionation
One and the same substance may act
simultaneously as an oxidising agent and as a reducing
agent with the result that a part of it gets oxidised to a
higher state and rest of it is reduced to lower state of
oxidation. Such a reaction, in which a substance
undergoes simultaneous oxidation and reduction is
called disproportionation and the substance is said to
disproportionate.
Following are the some
disproportionation,
Redox Reactions 551
 If an element is in its highest possible oxidation
state in a compound, it can act as an oxidising
agent. for example, KMnO4, K2Cr2O7, HNO3,
H2SO4, HClO4 etc.
 If an element is in its lowest oxidation state in a
compound, it can act as a reducing agent. For
example, H2S, H2C2O4, FeSO4, Na2S2O3, SO2, SnCl2,
many metals etc.
 The strength of oxyacids of chlorine decrease in
the order. HClO4 > HClO3 > HClO2 >HClO
 If highly electronegative element is in its highest
oxidation state in a compound that compound can
act as powerful oxidant. For example, KClO4,
KClO3, KBrO3, KIO3 etc.
 If an element is in intermediate oxidation state
in a compound, it can act as both oxidising &
reducing agent. For example, H2O2, H2SO3, HNO3,
SO2 etc.
examples of

increase

1 0
(1) H 2 O2  H 2 O 2  H 2 O  O 2
Oxidation, Reduction
–1 –2 
1. H 2 O2 reduces MnO4 ion to [KCET (Med.) 2000]

decrease (a) Mn (b) Mn 2 
decrease (c) Mn 3  (d) Mn 
5 7 1
2. When a sulphur atom becomes a sulphide ion
(2) 4 K Cl O3  3 K Cl O4  KCl [AMU 1999]
(a) There is no change in the composition of atom
increase
(b) It gains two electrons
decrease (c) The mass number changes
0 1 3 (d) None of these
(3) 4 P  3 NaOH  3 H 2 O  3 NaH 2 PO 2  PH 3 3. The ultimate products of oxidation of most of
hydrogen and carbon in food stuffs are [DCE 2001]
increase
(a) H 2 O alone (b) CO2 alone
decrease (c) H 2 O and CO2 (d) None of these
0 1 5 4. When P reacts with caustic soda, the products
(4) 3 Cl 2  6 NaOH  5 Na Cl  Na ClO 3  3 H 2 O
hot
(conc .) are PH3 and NaH2 PO2 . This reaction is an
increase example of
[IIT 1980; Kurukshetra CEE 1993; CPMT 1997]
(a) Oxidation
(b) Reduction
(c) Oxidation and reduction (Redox)
(d) Neutralization
 552 Redox Reactions
5. Which one of the following does not get oxidised
by bromine water [MP PET/PMT 1988]
(a) Fe 2 to Fe 3 (b) Cu  to Cu 2
(c) Mn 2 to MnO 4 (d) Sn 2 to Sn 4
6. In the reaction H 2 S  NO2  H 2 O  NO  S . H 2 S is
(a) Oxidised (b) Reduced
(c) Precipitated (d) None of these
7. The conversion of PbO2 to Pb(NO3 )2 is
(a) Oxidation
(b) Reduction
(c) Neither oxidation nor reduction
(d) Both oxidation and reduction
8. In the course of a chemical reaction an oxidant
[MP PMT 1986]
(a) Loses electrons
(b) Gains electrons
(c) Both loses and gains electron
(d) Electron change takes place
9. 2CuI  Cu  CuI2 , the reaction is [RPMT 1997]

(a) Redox (b) Neutralisation

(c) Oxidation (d) Reduction
 Redox Reactions 551
10. H 2 S reacts with halogens, the halogens[JIPMER 2000] (c) Is oxidised to Cu 2 
(a) Form sulphur halides (b) Are oxidised (d) Is reduced to Cu 2 
(c) Are reduced (d) None of these 20. Solution of sodium metal in liquid ammonia is
11. H 2 O2 reduces K4 Fe(CN )6 [MP PMT 1985] strongly reducing due to the presence of the
following in the solution
(a) In neutral solution (b) In acidic solution
[NCERT 1977; KCET (Med.) 2000]
(c) In non-polar solvent (d) In alkaline solution
(a) Sodium atoms (b) Solvated electrons
12. Max. number of moles of electrons taken up by
(c) Sodium hydride (d) Sodium amide
one mole of NO 3 when it is reduced to[DPMT 2002]
21. When Sn 2  changes to Sn 4  in a reaction[CPMT 1981]
(a) NH 3 (b) NH 2 OH (a) It loses two electrons(b) It gains two
(c) NO (d) NO2 electrons
13. In the reaction 3 Mg  N 2  Mg3 N 2 [MP PMT 1999] (c) It loses two protons (d) It gains two protons

(a) Magnesium is reduced (b)Magnesium is oxidized22. Oxidation of thiosulphate (S 2 O 32  ) ion by iodine

(c) Nitrogen is oxidized (d) None of these gives
14. When sodium metal is dissolved in liquid [NCERT 1976]
ammonia, blue colour solution is formed. The blue (a) SO 32  (b) SO 42 
colour is due to
(c) S 4 O 62  (d) S 2 O 62 
[NCERT 1981]
(a) Solvated Na  ions (b) Solvated electrons 23. Zn 2  (aq )  2 e  Zn(s). This is [CPMT 1985]

(c) Solvated NH 2 ions (d) Solvated protons (a) Oxidation (b) Reduction
(c) Redox reaction (d) None of these
15. Following reaction describes the rusting of iron
24. One gas bleaches the colour of flowers by
4 Fe  3 O 2  4 Fe 3   6 O 2 
reduction while the other by oxidation[EAMCET 1980]
Which one of the following statement is incorrect (a) CO and Cl2 (b) SO 2 and Cl2
[NCERT 1981; MNR 1991; AIIMS 1998]
(c) H 2 S and Br2 (d) NH 3 and SO 2
(a) This is an example of a redox reaction
25. Reduction involves NCERT 1972]
(b) Metallic iron is reduced to Fe 3 
3 (a) Loss of electrons
(c) Fe is an oxidising agent
(b) Gain of electrons
(d) Metallic iron is a reducing agent
(c) Increase in the valency of positive part
16. SnCl 2 gives a precipitate with a solution of
(d) Decrease in the valency of negative part
HgCl2 . In this process HgCl2 is [CPMT 1983]
26. In a reaction between zinc and iodine, in which
(a) Reduced zinc iodide is formed, what is being oxidised[NCERT 1975]
(b) Oxidised (a) Zinc ions (b) Iodide ions
(c) Converted into a complex compound (c) Zinc atom (d) Iodine
containing both Sn and Hg
27. Which one of the following reactions does not
(d) Converted into a chloro complex of Hg involve either oxidation or reduction [EAMCET 1982]
17. Oxidation involves [NCERT 1971, 81; CPMT 1980, 82, 83; (a) VO 2  V2 O 3 (b) Na  Na 
MP PMT 1983]
(a) Loss of electrons (c) CrO 42   Cr2 O72  (d) Zn 2   Zn
(b) Gain of electrons 28. In the following reaction,
(c) Increase in the valency of negative part 3 Br2  6 CO 32   3 H 2 O  5 Br   BrO 3  6 HCO 3
(d) Decrease in the valency of positive part
[MP PMT 1994, 95]
18. Incorrect statement regarding rusting is [MP PET 2000]
(a) Bromine is oxidised and carbonate is reduced
(a) Metallic iron is oxidised to Fe 3  ions (b) Bromine is reduced and water is oxidised
(b) Metallic iron is reduced to Fe 2  ions (c) Bromine is neither reduced nor oxidised
(c) Oxygen gas is reduced to oxide ion (d) Bromine is both reduced and oxidised
(d) Yellowish – brown product is formed 29. In the following reaction,
19. When copper turnings are added to silver nitrate 4 P  3 KOH  3 H 2O  3 KH2 PO2  PH3 [Pb. PMT 2002]
solution, a blue coloured solution is formed after
(a) P is oxidized as well as reduced
some time. It is because, copper[CPMT 1974, 79; DPMT 2000]
(b) P is reduced only
(a) Displaces silver from the solution
(b) Forms a blue coloured complex with AgNO3 (c) P is oxidised only
(d) None of these
 552 Redox Reactions
30. In the following reaction (d) Reducing nature of H 2 O2
Cr2 O7  
 14 H  6 I  2 Cr 3
 3 H 2 O  3 I2 2. In the reaction
Which element is reduced [CPMT 1976] C 2 O 42   MnO 4  H   Mn 2   CO 2  H 2 O
(a) Cr (b) H the reductant is [EAMCET 1991]
(c) O (d) I (a) C 2 O 42  (b) MnO 4
31. The conversion of sugar C12 H 22O11  CO2 is 2
(c) Mn (d) H 
(a) Oxidation 3. A reducing agent is a substance which can
(b) Reduction [CPMT 1971, 74, 76, 78, 80; NCERT 1976]
(c) Neither oxidation nor reduction (a) Accept electron (b) Donate electrons
(d) Both oxidation and reduction (c) Accept protons (d) Donate protons
32. Which halide is not oxidised by MnO2 4. Which of the following is the most powerful
[MNR 1985; JIPMER 2000] oxidizing agent
[MNR 1990; CPMT 2003]
(a) F (b) Cl
(a) F2 (b) Cl2
(c) Br (d) I
(c) Br2 (d) I2
33. When Fe 2  changes to Fe 3  in a reaction
(a) It loses an electron (b) It gains an electron 5. Of the four oxyacids of chlorine the strongest
oxidising agent in dilute aqueous solution is [MP PET 2000
(c) It loses a proton (d) It gains a proton
(a) HClO4 (b) HClO3
34. In acid solution, the reaction MnO 4  Mn 2 
(c) HClO2 (d) HOCl
involves
[MP PMT 1989] 6. Identify the correct statement about H 2 O2 [AIIMS 1996]
(a) Oxidation by 3 electrons (a) It acts as reducing agent only
(b) Reduction by 3 electrons (b) It acts as both oxidising and reducing agent
(c) Oxidation by 5 electrons (c) It is neither an oxidiser nor reducer
(d) Reduction by 5 electrons (d) It acts as oxidising agent only
35. When iron or zinc is added to CuSO 4 solution, 7. Several blocks of magnesium are fixed to the
bottom of a ship to [AIEEE 2003]
copper is precipitated. It is due to [CPMT 1974, 79]
(a) Keep away the sharks
(a) Oxidation of Cu 2 (b) Reduction of Cu 2
(b) Make the ship lighter
(c) Hydrolysis of CuSO 4 (d) Ionization of CuSO 4
(c) Prevent action of water and salt
36. In the reaction, 4 Fe  3 O 2  4 Fe 3   6 O 2  which of (d) Prevent puncturing by under-sea rocks
the following statement is incorrect[UPSEAT 2001, 02] 8. Which of the following behaves as both oxidising
(a) A Redox reaction and reducing agents [AFMC 1995]

(b) Metallic iron is a reducing agent (a) H 2 SO 4 (b) SO 2

(c) Fe 3  is an oxidising agent (c) H 2 S (d) HNO 3

(d) Metallic iron is reduced to Fe 3 9. The reaction H 2 S  H 2O2  2 H 2O  S shows

37. Which of the following is redox reaction[CBSE PMT 1997] [JIPMER 2001]
(a) H 2 SO 4 with NaOH (a) Oxidizing action of H 2 O2

(b) In atmosphere, O 3 from O 2 by lightning (b) Reducing action of H 2 O2

(c) Evaporation of H 2 O (c) Alkaline nature of H 2 O2

(d)Nitrogen oxides form nitrogen and oxygen by lightning (d) Acidic nature of H 2 O2
10. Which of the following is not a reducing agent
Oxidizing and Reducing agent [EAMCET 1987]
(a) NaNO2 (b) NaNO3
1. Equation H 2 S  H 2O2  S  2 H 2O represents (c) HI (d) SnCl 2
[UPSEAT 2001]
11. Which of the following cannot work as oxidising
(a) Acidic nature of H 2 O2 agent
(b) Basic nature of H 2 O2 [CPMT 1996]

(c) Oxidising nature of H 2 O2 (a) O 2 (b) KMnO4

 Redox Reactions 553
(c) I2 (d) None of these 22. Which substance is serving as a reducing agent in
the following reaction
12. H 2 O2 is used as [CPMT 1994]
14 H   Cr 2 O 72   3 Ni  2Cr 3   7 H 2 O  3 Ni 2 
(a) An oxidant only
[CBSE PMT 1994; AFMC 2000; DPMT 2001]
(b) A reductant only
(a) H 2 O (b) Ni
(c) An acid only
(d) An oxidant, a reductant and an acid (c) H  (d) Cr 2 O 72 
13. In C  H 2 O  CO  H 2 , H 2 O acts as [AFMC 1988] 23. Which of the following acid possesses oxidising,
reducing and complex forming properties[MNR 1985]
(a) Oxidising agent (b) Reducing agent
(a) HNO 3 (b) H 2 SO 4
(c) (a) and (b) both (d) None of these
14. Strongest reducing agent is [CPMT 1977;
(c) HCl (d) HNO 2
BHU 1984, 96; MP PET 1990; AMU 1999] 24. Which one is oxidising substance [CPMT 1997]
 
(a) F (b) Cl (a) C 2 H 2 O 2 (b) CO
 
(c) Br (d) I (c) H 2 S (d) CO2
15. A solution of sulphur dioxide in water reacts with 25. The compound that can work both as oxidising
H 2 S precipitating sulphur. Here sulphur dioxide and reducing agent is [CPMT 1986; MP PET 2000]
acts as (a) KMnO4 (b) H 2 O2
[NCERT 1980]
(c) BaO2 (d) K2 Cr2 O7
(a) As oxidising agent (b) A reducing agent
(c) An acid (d) A catalyst 26. Which one is oxidising agent in the reaction
16. Which of these substances is a good reducing below
agent 2CrO 42   2 H   Cr 2 O 72   H 2 O [CPMT 1997]
[NCERT 1979; CPMT 1988]
(a) H  (b) Cr 2 O 4
(a) NaOCl (b) HI
(c) FeCl3 (d) KBr (c) Cr   (d) None of these
17. The strongest reducing agent is [MNR 1982] 27. Which is the best description of the behaviour of
bromine in the reaction given below
(a) HNO 2 (b) H 2 S
H 2 O  Br2  HOBr  HBr [CBSE PMT 2004]
(c) H 2 SO 3 (d) SnCl 2
(a) Oxidised only
18. Which one is an oxidising agent [DPMT 1996]
(b) Reduced only
(a) FeSO 4
(c) Proton acceptor only
(b) HNO 3 (d) Both oxidised and reduced
(c) FeSO 4 .( NH 4 )2 SO 4 .6 H 2 O 28. What is the oxidising agent in chlorine water
(d) H 2 SO 4 [JEE Orissa 2004]

19. In which of the following reactions H 2 O2 is a (a) HCl (b) HClO2

reducing agent (c) HOCl (d) None of these

[CPMT 1981; NCERT 1981; BHU 1999] 29. In the reaction
(a) 2 FeCl2  2HCl  H 2 O2  2FeCl3  2H 2 O Ag 2 O  H 2 O2  2 Ag  H 2 O  O 2 , the H 2 O 2 acts as
(b) Cl2  H 2 O2  2 HCl  O2 [BHU 2004]
(c) 2 HI  H 2 O2  2 H 2 O  I2 (a) Reducing agent (b) Oxidising agent
(d) H 2 SO 3  H 2 O2  H 2 SO 4  H 2 O (c) Bleaching agent (d) None of the above

20. When NaCl is dissolved in water the sodium ion 30. In the reaction
becomes HAsO 2  Sn 2   As  Sn 4   H 2 O oxidising agent is
[NCERT 1976]
[BVP 2004]
(a) Oxidised (b) Reduced 2 4
(a) Sn (b) Sn
(c) Hydrolysed (d) Hydrated
(c) As (d) HAsO 2
21. Strongest reducing agent is [MNR 1984, 89]
(a) K (b) Mg 31. Which of the following substances acts as an
oxidising as well as a reducing agent[UPSEAT 2004; DCE 20
(c) Al (d) Br
(e) Na (a) Na 2 O (b) SnCl 2
 554 Redox Reactions
(c) Na2 O2 (d) NaNO2 (a) – 1 (b) 0
32. In the reaction (c) + 1 (d) + 2

P  NaOH  PH 3  NaH 2 PO2 [MP PET 2004] 12. Oxidation number of S in S 2  is [CPMT 1979]
(a) – 2 (b) 0
(a) P is oxidised only
(c) – 6 (d) + 2
(b) P is reduced only 13. Oxidation number of N in (NH 4 )2 SO 4 is [CPMT 1996]
(c) P is oxidized as well as reduced
(a) – 1 / 3 (b) – 1
(d) Na is reduced (c) + 1 (d) – 3
14. In which compound, oxidation state of nitrogen is
Oxidation number and Oxidation state 1
[MP PMT 1989]
1. The oxidation number of C in CO2 is [MP PET 2001]
(a) NO (b) N 2 O
(a) – 2 (b) + 2
(c) NH 2 OH (d) N 2 H 4
(c) – 4 (d) + 4
2. The oxidation number of As is [RPMT 1997] 15. Oxidation number of nickel in Ni(CO)4
(a) + 2 and + 3 (b) + 3 and + 5 [AIIMS 1984; MNR 1985; CPMT 1997;
(c) + 3 and + 4 (d) None of these MP PET/PMT 1998; AMU 2000; 01]
3. The oxidation number of Ba in barium peroxide is (a) 0 (b) + 4
[Pb. PMT 2002] (c) – 4 (d) + 2
(a) + 6 (b) + 2 16. The oxidation number of sulphur in H 2 SO 4 is
(c) 1 (d) + 4
[CPMT 1979Pb. CET 2002]
4. HNO2 acts both as reductant and oxidant, while
(a) – 2 (b) + 2
HNO3 acts only as oxidant. It is due to their [AIIMS 2000]
(c) + 4 (d) + 6
(a) Solubility ability 17. Oxidation state of chlorine in perchloric acid is
(b) Maximum oxidation number [EAMCET 1989]
(c) Minimum oxidation number
(a) – 1 (b) 0
(d) Minimum number of valence electrons
(c) – 7 (d) + 7
5. Chlorine is in +1 oxidation state in
18. Oxidation number of N in HNO 3 is
[MP PMT 1981; NCERT 1974; CPMT 1971, 78]
(a) HCl (b) HClO4 [BHU 1997]

(c) ICl (d) Cl2 O (a) – 3.5 (b) + 3.5

(c) – 3, +5 (d) + 5
6. The valency of Cr in the complex [Cr (H 2 O)4 Cl 2 ]
19. The oxidation number of Mn in MnO 41 is
[MP PMT 2000]
(a) 1 (b) 3 (a) + 7 (b) – 5
(c) 5 (d) 6 (c) + 6 (d) + 5
7. In the conversion Br 2  BrO 3 , the oxidation state 20. Sn   loses two electrons in a reaction. What will
of bromine changes from be the oxidation number of tin after the reaction
[EAMCET 1990; AMU 1999; RPMT 2002] (a) + 2 (b) Zero
(a) – 1 to – 1 (b) 0 to – 1 (c) + 4 (d) – 2
(c) 0 to + 5 (d) 0 to – 5 21. The oxidation state of Mn in K2 MnO4
8. In the chemical reaction Cl2  H 2 S  2 HCl  S , the [CPMT 1982, 83, 84; DPMT 1982;
oxidation number of sulphur changes from [MP PMT 1999] NCERT 1973; AMU 2000]
(a) 0 to 2 (b) 2 to 0 (a) + 2 (b) + 7
(c) – 2 to 0 (d) – 2 to – 1 (c) – 2 (d) + 6
9. Oxidation number of cobalt in K[Co(CO)4 ] is 22. Oxidation number of oxygen in O 2 molecule is
[KCET 1996]
[CPMT 1984]
(a) + 1 (b) + 3
(a) + 1 (b) 0
(c) – 1 (d) – 3
(c) + 2 (d) –2
10. When K2 Cr2 O7 is converted to K2 CrO4 , the change
23. Maximum oxidation state of Cr is [RPMT 2002]
in the oxidation state of chromium is [NCERT 1981] (a) 3 (b) 4
(a) 0 (b) 6 (c) 6 (d) 7
(c) 4 (d) 3
11. The oxidation number of chlorine in HOCl
 Redox Reactions 555
24. In which of the following compound transition (a) SO 2 (b) H 2 SO 4
metal has zero oxidation state [CBSE PMT 1999; BHU 2000] (c) Na2 S 2 O3 (d) Na2 S 4 O6
(a) CrO5 (b) NH 2 .NH 2
36. The oxidation number of Fe and S in iron pyrites
(c) NOClO4 (d) [Fe(CO)5 ] are
25. Carbon is in the lowest oxidation state in [RPMT 1997]
[NCERT 1979; MH CET 1999] (a) 4, – 2 (b) 2, – 1
(a) CH 4 (b) CCl4 (c) 3, – 1.5 (d) 3, – 1
(c) CF4 (d) CO2 37. The oxidation number of nitrogen in NO 3 is
26. Oxidation number of carbon in H 2 C2 O4 is [CPMT 1982]
[CPMT 1982] (a) – 1 (b) +2
(a) + 4 (b) + 3 (c) + 3 (d) +5
(c) + 2 (d) – 2 38. Oxidation state of elemental carbon is [MNR 1983]
 (a) 0 (b) 1
27. The oxidation number of Pt in [Pt (C 2 H 4 ) Cl 3 ] is
(c) 2 (d) 3
[MNR 1993] 39. The sum of the oxidation numbers of all the
(a) + 1 (b) + 2 carbons in C6 H 5 CHO is [EAMCET 1986]
(c) + 3 (d) + 4 (a) + 2 (b) 0
28. The oxidation number of carbon in CH 2 Cl2 is (c) + 4 (d) – 4
[CPMT 1976; Pb. PET 1999; AFMC 2004] 40. Which one of the following has the highest
(a) 0 (b) + 2 oxidation number of iodine [CPMT 1982]
(c)  2 (d) + 4 (a) KI3 (b) KI
29. The oxidation states of phosphorus vary from (c) IF5 (d) KIO4
[CPMT 1976]
(a) – 3 to +5 (b) – 1 to +1 41. The oxidation number of N in N 2 H 5 [Pb. PMT 2001]
(c) – 3 to +3 (d) – 5 to +1 (a) – 3 (b) (– 2)
30. The process in which oxidation number increases is (c) – 1 (d) + 2
known as 42. In which of the following compounds the
[CPMT 1976] oxidation number of carbon is maximum
(a) Oxidation (b) Reduction (a) HCHO (b) CHCl 3
(c) Auto-oxidation (d) None of the above (c) CH 3 OH (d) C12 H 22 O11
31. The oxidation number of S in H 2 S 2O8 is[MP PET 2002]
43. The oxidation state of chlorine in KClO4 is[CPMT 1985]
(a) + 2 (b) + 4
(a) – 1 (b) + 1
(c) + 6 (d) + 7 (c) + 7 (d) – 7
32. The oxidation state of nitrogen in N 3 H is
44. The oxidation state of I in H 4 IO 6 is[CBSE PMT 1994]
[NCERT 1977, 81]
(a) + 7 (b) + 5
1
(a)  (b) + 3 (c) + 1 (d) – 1
3
45. An element which never has a positive oxidation
1
(c) 1 (d)  number in any of its compounds [AIIMS 1981]
3 (a) Boron (b) Oxygen
33. Which of the following statements is correct [AFMC 1997] (c) Chlorine (d) Fluorine
(a) Hydrogen has oxidation number 1 and  1 46. In an oxidation process, oxidation number[CPMT 1976]
(b) Hydrogen has same electronegativity as (a) Decreases
halogens (b) Increases
(c) Hydrogen will not be liberated at anode (c) Does not change
(d) Hydrogen has same ionization potential as (d) First increases then decreases
alkali metals 47. If HNO 3 changes into N 2 O , the oxidation number
34. The oxidation state of Cr in [Cr ( NH 3 )4 Cl 2 ] is is changed by [BHU 1997; AFMC 2001]
[AIEEE 2005] (a) + 2 (b) – 1
(a) +3 (b) +2 (c) 0 (d) + 4
(c) +1 (d) 0 48. The characteristic oxidation number of atoms in
free metals is [NCERT 1975]
35. Sulphur has highest oxidation state in
(a) Minus one (b) Any number
[EAMCET 1991]
(c) One (d) Zero
 556 Redox Reactions
49. In which one of the following changes there are Bihar CEE 1995; RPET 2000]
transfer of five electrons [NCERT 1982] (a) +6 (b) – 7
(a) MnO 4  Mn 2  (b) CrO 42  Cr 3  (c) +2 (d) – 2
60. In which of the following compounds transition
(c) MnO 42   MnO 2 (d) Cr2 O72   2Cr 3 
metal is in oxidation state zero [NCERT 1982]
50. Oxidation number of C in C6 H12O6 is [KCET 1992] (a) [Co(NH 3 )6 ]Cl2 (b) [Fe(H 2 O)6 SO 4 ]
(a) + 6 (b) – 6 (c) [Ni(CO)4 ] (d) [Fe(H 2 O)3 ](OH )2
(c) 0 (d) + 4
61. Oxidation number of osmium (Os ) in OsO4 is
51. In which of the following compounds iron has
lowest oxidation state [MNR 1984] [AIIMS 1999]
(a) FeSO4 .( NH 4 )2 SO 4 .6 H 2 O (a) + 4 (b) + 6
(b) K4 Fe(CN )6 (c) + 7 (d) + 8
62. The atomic number of an element which shows
(c) Fe(CO)5
the oxidation state of + 3 is [CPMT 1989, 94]
(d) Fe2 O (a) 13 (b) 32
(e) K 2 FeO4 (c) 33 (d) 17
52. The oxidation number of hydrogen in MH 2 is 63. The oxidation number of iron in the compound
K4 [Fe(CN )6 ] is
[CPMT 1976]
(a) + 1 (b) – 1 [NCERT 1976; MNR 1986; AIIMS 2000]
(c) + 2 (d) – 2 (a) + 6 (b) + 4
53. Oxidation number of iodine varies from[CPMT 1982] (c) + 3 (d) + 2
(a) – 1 to +1 (b) – 1 to +7 64. The brown ring complex compound is formulated
as [Fe(H 2 O)5 NO] SO 4 . The oxidation state of iron is
(c) +3 to +5 (d) – 1 to +5
54. When SO 2 is passed through acidic solution of [EAMCET 1987; IIT 1987; MP PMT 1994;
AIIMS 1997; DCE 2000]
potassium dichromate, then chromium sulphate is
(a) 1 (b) 2
formed. Change in valency of chromium is[CPMT 1979]
(c) 3 (d) 0
(a) +4 to +2 (b) +5 to +3
65. Oxidation state of oxygen in F2 O is
(c) +6 to +3 (d) +7 to +2
55. The oxidation states of the most electronegative [BHU 1982; UPSEAT 2001; MH CET 2002]
element in the products of the reaction of (a) + 1 (b) + 2
BaO2 with dilute H 2 SO 4 are (c) 1 (d)  2
[IIT 1991; CBSE PMT 1992; BHU 2000] 66. Phosphorus has the oxidation state of +3 in
[NCERT 1982; RPMT 1999]
(a) 0 and – 1 (b) – 1 and – 2
(a) Orthophosphoric acid (b) Phosphorus acid
(c) – 2 and 0 (d) – 2 and + 1
(c) Metaphosphoric acid (d) Pyrophosphoric acid
56. The highest oxidation state of Mn is shown by
67. Oxidation number of P in Mg2 P2 O7 is
[MNR 1983; RPMT 1999]
(a) K2 MnO4 (b) KMnO4 [CPMT 1989; MP PMT 1995]
(a) + 3 (b) + 2
(c) MnO2 (d) Mn2 O2
(c) + 5 (d) – 3
(e) MnO 68. The oxidation state of nitrogen is highest in
57. The oxidation number of carbon in CH 2 O is [MP PMT 2001; BHU 2002]
[IIT 1982; EAMCET 1985; MNR 1990; UPSEAT 2001 (a) N 3 H (b) NH 2 OH
CPMT 1997, 2004] (c) N 2 H 4 (d) NH 3
(a) – 2 (b) + 2 69. Oxidation number of P in KH 2 PO2 is
(c) 0 (d) + 4
[CPMT 1987; MH CET 1999]
58. Oxidation state of oxygen in hydrogen peroxide is
(a) + 1 (b) + 3
[DPMT 1984; 91; CPMT 1988; MNR 1994;
(c) + 5 (d) – 4
UPSEAT 2001; RPMT 2002; JEE Orissa 2004]
70. The most common oxidation state of an element is
(a) – 1 (b) + 1
–2. The number of electrons present in its
(c) 0 (d) – 2 outermost shell is
59. The oxidation number of Cr in K2 Cr2 O7 is [BHU 1983; NCERT 1974; CPMT 1977]
[CPMT 1981, 85, 90, 93, 99; KCET 1992; (a) 4 (b) 2
BHU 1988, 98; AFMC 1991, 99; EAMCET 1986; (c) 6 (d) 8
MP PMT 1996, 99, 2002; MP PET/PMT 1998; 71. Sulphur has lowest oxidation number in
[EAMCET 1993]
 Redox Reactions 557
(a) H 2 SO 3 (b) SO 2 (a) 4 (b) – 6
(c) H 2 SO 4 (d) H 2 S (c) 6 (d) – 2
83. Oxidation state of ‘S’ in H 2 SO 3 [RPET 2003]
72. The oxidation number and covalency of sulphur in
the sulphur molecule (S 8 ) are respectively[NCERT 1977] (a) + 3 (b) + 6
(a) 0 and 2 (b) 6 and 8 (c) + 4 (d) + 2
(c) 0 and 8 (d) 6 and 2 84. Oxidation numbers of two Cl atoms in bleaching
73. In ferrous ammonium sulphate oxidation number powder, CaOCl 2 are
of Fe is (a) – 1, – 1 (b) + 1, – 1
[CPMT 1988] (c) + 1, + 1 (d) 0, – 1
(a) + 3 (b) + 2 85. Select the compound in which chlorine is assigned
(c) + 1 (d) – 2 the oxidation number +5 [NCERT 1984, 94]
74. The oxidation number of nitrogen in NH 2 OH is (a) HClO4 (b) HClO2
[NCERT 1981] (c) HClO3 (d) HCl
(a) + 1 (b) – 1
86. When KMnO4 is reduced with oxalic acid in acidic
(c) – 3 (d) – 2
solution, the oxidation number of Mn changes
75. The oxidation number of phosphorus in
from
Ba(H 2 PO2 )2 is
[MNR 1987; MP PET 2000; CBSE PMT 2000;
[Kurukshetra CEE 1998; DCE 2004] UPSEAT 2000, 02; BHU 2003; AMU 2002]
(a) – 1 (b) + 1 (a) 7 to 4 (b) 6 to 4
(c) + 2 (d) + 3 (c) 7 to 2 (d) 4 to 2
76. A compound is in its low oxidation state. Then its 87. Oxygen has oxidation states of +2 in the
will be [NCERT 1973; DPMT 1983; MP PET 2000]
[DCE 2001]
(a) H 2 O2 (b) CO2
(a) Highly acidic
(c) H 2 O (d) OF2
(b) Highly basic
88. The element exhibiting most stable  2 oxidation
(c) Highest oxidising property
(d) Half acidic, half basic state among the following is [IIT 1995]
(a) Ag (b) Fe
77. The oxidation number and the electronic
configuration of sulphur in H 2 SO 4 is [KCET 2002] (c) Sn (d) Pb
89. Oxidation number of sulphur in S 2 O 32  is[CPMT 1979]
(a) + 4; 1s 2 2 s 2 2 p 6 3 s 2
(a) – 2 (b) + 2
(b) + 2; 1s 2 2 s 2 2 p 6 3 s 2 3 p 2 (c) + 6 (d) 0
(c) + 3; 1s 2 2 s 2 2 p 6 3 s 2 3 p1 90. Carbon has zero oxidation number in
2 2 6 [Kurukshetra CEE 2002]
(d) + 6; 1s 2 s 2 p
(a) CO (b) CH 4
78. The oxidation number of Mn in KMnO4 is
(c) CH 2 Cl2 (d) CH 3 Cl
[CPMT 1982, 83; EAMCET 1992, 93; RPET 1999]
91. Oxidation state of oxygen atom in potassium
(a) + 7 (b) – 7 superoxide is
(c) + 1 (d) – 1 [MNR 1988; NCERT 1980]
79. Oxidation number of As atoms in H 3 AsO4 is (a) 0 (b) – 1
[DPMT 2001] (c)  12 (d) – 2
(a) – 3 (b) + 4 92. Oxidation number of S in S 2 Cl2 is
(c) + 6 (d) + 5
(a) + 1 (b) – 1
80. In XeO3 and XeF6 the oxidation state of Xe is
(c) + 6 (d) 0
[MP PET 2003] 93. What is the oxidation number of sulphur in
(a) + 4 (b) + 6 Na2 S 4 O6
(c) + 1 (d) + 3 [AIIMS 1998; DCE 1999]
81. Oxidation number of carbon in CH 3  Cl is 2 3
(a) (b)
[MP PET 2000] 3 2
(a) – 3 (b) – 2 3 5
(c) (d)
(c) – 1 (d) 0 5 2
82. The oxidation state of Cr in Cr2 O 72  is 94. When CuSO 4 reacts with KI , the oxidation
[BHU 2000; CPMT 2000] number of Cu changes by [BHU 1997]
 558 Redox Reactions
(a) 0 (b) – 1 (a) + 2 (b) + 3
(c) 1 (d) 2 (c) + 4 (d) + 5
95. The oxidation number of N in NH 4 Cl is 107. Which of the following elements never show
(a) + 5 (b) + 3 positive oxidation number [CPMT 2004]

(c) – 5 (d) – 3 (a) O (b) Fe

96. In which reaction there is a change in valency (c) Ga (d) F
[NCERT 1971; CPMT 1971] 108. The oxidation state shown by silicon when it
(a) 2 NO2  N 2 O4 combines with strongly electropositive metals is [MH CET
(a) – 2 (b) – 4
(b) 2 NO2  H 2 O  HNO 2  HNO 3
(c) + 4 (d) – 2
(c) NH 4 OH  NH 4  OH  109. The oxidation number of sulphur in H 2 S is
(d) CaCO3  CaO  CO2 [Pb. CET 2002]
(a) – 2 (b) + 3
97. Oxidation state of Fe in Fe 3 O 4 is
(c) + 2 (d) – 3
[CBSE PMT 1999; AIIMS 2002]
110. Oxidation number of nitrogen in NaNO2 is
3 4
(a) (b) [Pb. CET 2000]
2 5
(a) + 2 (b) + 3
5 8 (c) + 4 (d) – 3
(c) (d)
4 3
111. Oxidation number of S in SO 42  [BCECE 2005]
98. Nitrogen show different oxidation states in the
range (a) + 6 (b) + 3
[Kerala (Med.) 2003] (c) + 2 (d) – 2
(a) 0 to +5 (b) – 3 to + 5 112. The oxidation state of chromium in the final
product formed by the reaction between KI and
(c) – 5 to + 3 (d) – 3 to + 3
acidified potassium dichromate solution is [AIEEE 2005]
99. Oxidation number of Mn in K 2 MnO4 and MnSO 4
(a) +4 (b) +6
are respectively [CPMT 1997] (c) +2 (d) +3
(a) + 7, + 2 (b) + 6, + 2 113. The oxidation state of I in IPO4 is [Orissa JEE 2005]
(c) + 5, + 2 (d) + 2, + 6
(a) +1 (b) +3
100. Identify the element which can have highest
(c) +5 (d) +7
oxidation numbers [AIIMS 1996]
(a) N (b) O Redox reaction and Method for balancing
(c) Cl (d) C Redox reaction
101. What is the oxidation number of Co in
[Co(NH 3 )4 ClNO2 ]
1. The value of x in the partial redox equation
[BHU 1999] MnO 4  8 H   xe ⇌ Mn 2   4 H 2 O is
(a) + 2 (b) + 3 (a) 5 (b) 3
(c) + 4 (d) + 5 (c) 1 (d) 0
102. The oxidation number of nickel in K 4 [ Ni(CN )4 ] is 2. C2 H 6 (g)  nO2  CO2 (g)  H 2 O (l)
[JIPMER 1999] In this equation, the ratio of the coefficients of
(a) – 2 (b) – 1 CO2 and H 2 O is [KCET 1992]
(c) + 2 (d) 0 (a) 1 : 1 (b) 2 : 3
103. The oxidation number of fluorine in F2 O is (c) 3 : 2 (d) 1 : 3
[CPMT 1982; BHU 1982; EAMCET 1986] 3. The number of electrons involved in the reduction
(a) – 1 (b) + 1 of Cr2 O 72  in acidic solution to Cr 3  is[EAMCET 1983]
(c) + 2 (d) – 2 (a) 0 (b) 2
104. Oxidation number of Fe in K3 [Fe(CN )6 ] is (c) 3 (d) 5
[AMU 1988] 4. When KMnO4 acts as an oxidising agent and
(a) + 2 (b) + 3
ultimately forms [ MnO 4 ]2 , MnO 2 , Mn 2 O 3 , Mn 2 then
(c) + 1 (d) + 4
105. Oxidation number of N in NH 3 is the number of electrons transferred in each case
respectively is
[CPMT 1979; Pb CET 2004]
[AIEEE 2002]
(a) – 3 (b) + 3
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7
(c) 0 (d) + 5
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1
106. What is the net charge on ferrous ion [AFMC 2004]
 Redox Reactions 559
5. Starch paper is used to test for the presence of 13. Which of the following is the strongest oxidising
[NCERT 1979] agent
(a) Iodine (b) Oxidising agent [Pb. CET 2000]
(c) Iodide ion (d) Reducing agent (a) BrO 3 / Br 2
, E  1 .50
o

6. How many moles of K2 Cr2 O7 can be reduced by 1

(b) Fe 3  / Fe 2  , E o  0 . 76
mole of Sn 2  [MP PMT 2003]
(a) 1/3 (b) 1/6 (c) MnO 4 / Mn 2  , E o  1 . 52
(c) 2/3 (d) 1
(d) Cr2 O72  / Cr 3  , E o  1 .33
7. 2 MnO 4  5 H 2 O 2  6 H   2 Z  5 O 2  8 H 2 O . In this
reaction Z is [RPMT 2002] 14. In the balanced chemical reaction,

(a) Mn 2
(b) Mn 4 IO3  a I   b H   c H 2 O  d I 2
(c) MnO2 (d) Mn a, b, c and d respectively correspond to[AIIMS 2005]
8. What is ‘A’ in the following reaction (a) 5, 6, 3, 3 (b) 5, 3, 6, 3
2 Fe 3 (aq )  Sn 2 (aq )  2 Fe 2 (aq )  A [MP PET 2003] (c) 3, 5, 3, 6 (d) 5, 6, 5, 5
3 4
(a) Sn (aq ) (b) Sn (aq ) 15. The number of moles of KMnO4 reduced by one
2 mole of
(c) Sn (aq ) (d) Sn
9. For the redox reaction KI in alkaline medium is: [CBSE PMT 2005]

MnO 4  C 2 O 42  H   Mn 2   CO 2  H 2 O (a) One fifth (b) five

the correct coefficients of the reactants for the (c) One (d) Two
balanced reaction are[IIT 1988, 92; BHU 1995; CPMT 1997;
RPMT 1999; DCE 2000; MP PET 2003] Auto oxidation and Disproportionation
MnO 4 C 2 O 42  H
1. In the equation H 2 S  2 HNO 3  2 H 2 O  2 NO2  S
(a) 2 5 16
(b) 16 5 2 The equivalent weight of hydrogen sulphide is[BVP 2003]
(c) 5 16 2 (a) 16 (b) 68
(d) 2 16 5 (c) 34 (d) 17
10. Which of the following is a redox reaction 2. If 1.2 g of metal displace 1.12 litre hydrogen at
[AIEEE 2002] normal temperature and pressure ,equivalent
(a) NaCl  KNO3  NaNO3  KCl weight of metal would be [DPMT 2001]
(b) CaC2O4  2HCl  CaCl2  H 2C2O4 (a) 24 (b) 12
(c) Mg(OH )2  2 NH 4 Cl  MgCl2  2 NH 4 OH (c) 1.2 11.2 (d) 1.2  11.2
(d) Zn  2 AgCN  2 Ag  Zn(CN )2 3. Which one of the following nitrates will leave
behind a metal on strong heating [AIEEE 2003]
11. Which of the following reaction is a redox
reaction (a) Ferric nitrate (b) Copper nitrate
[MP PMT 2003] (c) Manganese nitrate (d) Silver nitrate
(a) P2 O5  2 H 2 O  H 4 P2 O7 4. To prevent rancidification of food material, which
of the following is added [CPMT 1996]
(b) 2 AgNO3  BaCl2  2 AgCl  Ba(NO3 )2
(a) Reducing agent (b) Anti-oxidant
(c) BaCl2  H 2 SO 4  BaSO4  2 HCl
(c) Oxidising agent (d) None of these
(d) Cu  2 AgNO3  2 Ag  Cu(NO3 )2
5. Prevention of corrosion of iron by zinc coating is
12. Which of the following reactions involves oxidation- called
reduction
[MP PMT 1993; CPMT 2002]
[NCERT 1972; AFMC 2000; Pb. CET 2004; CPMT 2004]
(a) Galvanization (b) Cathodic protection
(a) NaBr  HCl  NaCl  HBr
(c) Electrolysis (d) Photo–electrolysis
(b) HBr  AgNO3  AgBr  HNO 3 6. The metal used in galvanizing of iron is
[MP PET 1985, 96]
(c) H 2  Br2  2 HBr
(a) Pb (b) Zn
(d) 2 NaOH  H 2 SO 4  Na2 SO 4  2 H 2 O
(c) Al (d) Sn
 560 Redox Reactions
7. In which of the following reactions there is no
change in valency [NCERT 1974; CPMT 1978]
(a) 4 KClO3  3 KClO4  KCl
1. In which of the following acid, which acid has
(b) SO 2  2 H 2 S  2 H 2 O  3S oxidation reduction and complex formation
(c) BaO2  H 2 SO 4  BaSO4  H 2 O2 properties
[UPSEAT 2001]
(d) 2 BaO  O2  2 BaO2
(a) HNO3 (b) H 2 SO 4
8. The equivalent weight of phosphoric acid (H 3 PO4 )
(c) HCl (d) HNO2
in the reaction NaOH  H 3 PO4  NaH2 PO4  H 2O is
2. The compound which could not act both as
[AIIMS 1999] oxidising as well as reducing agent is[IIT Screening 1991]
(a) 25 (b) 49 (a) SO 2 (b) MnO2
(c) 59 (d) 98 (c) Al2 O3 (d) CrO
9. What is the equivalent mass of IO 4 when it is 3. H 2 S acts only as a reducing agent while SO 2 can
converted into I 2 in acid medium [Kerala PMT 2004] act both as a reducing and oxidizing agent
(a) M/6 (b) M/7 because [AMU 1999]

(c) M/5 (d) M/4 (a) S in H 2 S has – 2 oxidation state

(e) None of these (b) S in SO 2 has oxidation state + 4
10. For decolourization of 1 mole of KMnO4 , the (c) Hydrogen in H 2 S more +ve than oxygen
moles of H 2 O 2 required is [AIIMS 2004] (d) Oxygen is more – ve in SO 2
(a) 1/2 (b) 3/2 4. Of all the three common mineral acids, only
(c) 5/2 (d) 7/2 sulphuric acid is found to be suitable for making
the solution acidic because
11. In the reaction I2  2 S 2 O 3   2 I   S 4 O 6 
[Kurukshetra CEE 2002]
equivalent weight of iodine will be equal to[MP PET 2004] (a) It does not react with KMnO4 or the reducing
(a) 1/2 of molecular weight agent
(b) Molecular weight (b) Hydrochloric acid reacts with KMnO4
(c) 1/4 of molecular weight
(c) Nitric acid is an oxidising agent which reacts
(d) None with reducing agent
12. The equivalent weight of KIO3 in the reaction (d) All of the above are correct
2Cr (OH )3  4 OH  KIO 3  2CrO 42   5 H 2 O  KI is 5. For H 3 PO3 and H 3 PO4 the correct choice is
[MP PMT 2004] [IIT Screening 2003]

Mol.wt. (a) H 3 PO3 is dibasic and reducing

(a) Mole wt. (b)
6 (b) H 3 PO3 is dibasic and non-reducing
Mol.wt. Mol.wt. (c) H 3 PO4 is tribasic and reducing
(c) (d)
2 3 (d) H 3 PO3 is tribasic and non-reducing
13. The product of oxidation of I  with MnO 4 in 6. Match List I with List II and select the correct
alkaline medium is [IIT-JEE Screening 2004] answer using the codes given below the lists
(a) IO 3 (b) I2 List I (Compound) List II (Oxidation state of
N)

(c) IO (d) IO 4 (A) NO2 (1) + 5
14. In alkaline medium ClO2 oxidize H 2 O2 in O 2 and (B) HNO (2) – 3

reduced itself in Cl then how many mole of (C) NH 3 (3) + 4
H 2O2 will oxidize by one mole of ClO2 [Kerala CET 2005] (D) N 2 O5 (4) + 1
(a) 1.0 (b) 1.5 Codes :
(c) 2.5 (d) 3.5 (a) A B C D
(e) 5.0 2 3 4 1
(b) A B C D
3 1 2 4
(c) A B C D
 Redox Reactions 561
3 4 2 1 (a) Cl 2  2 H 2 O  SO 2  4 H   SO 4   2Cl 
(d) A B C D
(b) Cu   Zn  Zn   Cu
2 3 1 4
(c) 2 H 2  O2  2 H 2 O
7. M 3 ion loses 3 e  . Its oxidation number will be
[CPMT 2002] (d) HCl  H 2 O  H 3 O   Cl 
(a) 0 (b) + 3
17. For the reactions, C  O2  CO2 ; H  393 J
(c) + 6 (d) – 3
2 Zn  O2  2 ZnO; H  412 J [AIEEE 2002]
8. In the reaction Zn  2 H   2Cl   Zn 2   2Cl   H 2 ,
the spectator ion is [AIIMS 2001] (a) Carbon can oxidise Zn
 2 (b) Oxidation of carbon is not feasible
(a) Cl (b) Zn
 (c) Oxidation of Zn is not feasible
(c) H (d) All of these
9. The oxidation number of sulphur in H 2 S 2O7 and (d) Zn can oxidise carbon
iron in K4 Fe(CN )6 is respectively [AIIMS 2000] 18. In the reaction B2 H6  2KOH  2 X  2Y  6 H 2 , X
(a) + 6 and + 2 (b) + 2 and + 2 and Y are respectively [EAMCET 2003]
(c) + 8 and + 2 (d) + 6 and + 4 (a) H 2 , H 3 BO3 (b) HCl , KBO3
10. Oxidation number of oxygen in potassium super
oxide (KO2 ) is [UPSEAT 1999, 2002] (c) H 2O, KBO3 (d) H 2 O , KBO2

(a) – 2 (b) – 1 19. In a balanced equation

(c) – 1/2 (d) – 1/4 H 2 SO 4  x HI  H 2 S  y I2  z H 2O , the values of x,
11. One mole of N 2 H 4 loses 10 mol of electrons to y, z are [EAMCET 2003]
form a new compound Y. Assuming that all (a) x = 3, y = 5, z = 2
nitrogen appear in the new compound, what is the
(b) x = 4, y = 8, z = 5
oxidation state of N 2 in Y ? (There is no change in
the oxidation state of hydrogen) (c) x = 8, y = 4, z = 4
[IIT 1981; Pb. PMT 1998] (d) x = 5, y = 3, z = 4
(a) + 3 (b) – 3 20. Which of the following can act as an acid and as a
(c) – 1 (d) + 5 base
12. Amongst the following identify the species with [AMU 1999]
an atom in + 6 oxidation state [IIT Screening 2000]
(a) HClO 3 (b) H 2 PO 4
(a) MnO 4 (b) Cr (CN )63 
(c) HS  (d) All of these
(c) NiF62  (d) CrO2 Cl2
21. MnO 42  (1 mole) in neutral aqueous medium is
13. In which of the following compounds, is the
oxidation number of iodine is fractional [BVP 2003] disproportionate to [AIIMS 2003]
(a) IF3 (b) IF2 (a) 2/3 mole of MnO 4 and 1/3 mole of MnO2
(c) I3 (d) IF7
(b) 1/3 mole of MnO 4 and 2/3 mole of MnO2
14. The compound YBa 2 Cu 3 O7 which shows
(c) 1/3 mole of Mn2 O7 and 1/3 mole of MnO2
superconductivity has copper in oxidation state
........ Assume that the rare earth element Yttrium (d) 2/3 mole of Mn2 O7 and 1/3 mole of MnO2
is in its usual  3 oxidation state
22. The conductivity of a saturated solution of BaSO4
[IIT 1994]
(a) 3/7 (b) 7/3 is 3 .06  10 6 ohm 1 cm 1 and its equivalent
(c) 3 (d) 7 conductance is 1 .53 ohm 1 cm 1 equivalent 1
. The K sp
15. The oxidation number of sulphur in S 8 , S 2 F2 , H 2 S of the BaSO4 will be [KCET 1996]
respectively, are [IIT 1999]
(a) 4  10 12 (b) 2.5  10 9
(a) 0, +1 and – 2 (b) + 2, +1 and – 2
(c) 0, + 1 and + 2 (d) – 2, + 1 and – 2 (c) 2 .5  10 13 (d) 4  10 6
16. Which one of the following reactions is not an
example of redox reaction [Kurukshetra CEE 1998]
 562 Redox Reactions
23. When MnO2 is fused with KOH, a coloured 7. Assertion : The oxidation numbers are
compound is formed, the product and its colour is artificial, they are useful as a ‘book-
[IIT Screening 2003]
keeping’ device of electrons in
reactions.
(a) K2 MnO4 , purple green Reason : The oxidation numbers do not
usually represent real charges on
(b) KMnO4 , purple
atoms, they are simply conventions
(c) Mn2 O3 , brown that indicate what the maximum
charge could possibly be on an atom
(d) Mn3 O4 black in a molecule.
8. Assertion : H 2 SO 4 cannot act as reducing
agent.
Reason : Sulphur cannot increase its
oxidation number beyond + 6.
9. Assertion : Equivalent weight of NH 3 in the
reaction N 2  NH 3 is 17/3 while
that of N 2 is 28/6.
Read the assertion and reason carefully to mark the Reason : Equivalent weight
correct option out of the options given below : Molecular weight
= .
(a) If both assertion and reason are true and the number of e – lost or gained
reason is the correct explanation of the assertion.
(b) If both assertion and reason are true but reason is
not the correct explanation of the assertion.
(c) If assertion is true but reason is false.
(d) If the assertion and reason both are false.
(e) If assertion is false but reason is true.

1. Assertion : SO 2 and Cl2 both are bleaching

agents. Oxidation, Reduction
Reason : Both are reducing agents.[AIIMS 1995]
1 b 2 b 3 c 4 c 5 c
2. Assertion : Fluorine exists only in –1 oxidation
state. 6 a 7 b 8 b 9 a 10 c
Reason : Fluorine has 2 s 2 2 p 5 configuration. 11 b 12 a 13 b 14 b 15 b
[AIIMS 2001] 16 a 17 a 18 b 19 c 20 b
3. Assertion : Stannous chloride is a powerful 21 a 22 c 23 b 24 b 25 b
oxidising agent which oxidises
26 c 27 c 28 d 29 a 30 a
mercuric chloride to mercury.
Reason : Stannous chloride gives grey 31 a 32 a 33 a 34 d 35 b
precipitate with mercuric chloride, 36 d 37 d
but stannic chloride does not do so.[AIIMS 2002]
4. Assertion : HClO4 is a stronger acid than Oxidizing and Reducing agent
HClO3 .
Reason : Oxidation state of Cl in HClO4 is 1 c 2 a 3 b 4 a 5 d

+VII and in HClO3 +V. [AIIMS 2004] 6 b 7 c 8 b 9 a 10 b

5. Assertion : In a reaction Zn(s)  CuSO 4 (aq)  11 c 12 d 13 a 14 d 15 a
ZnSO 4 (aq)  Cu(s) , Zn is a reductant 16 b 17 b 18 bd 19 b 20 d
but itself get oxidized. 21 a 22 b 23 d 24 d 25 b
Reason : In a redox reaction, oxidant is 26 d 27 d 28 c 29 a 30 d
reduced by accepting electrons and
31 d 32 c
reductant is oxidized by losing
electrons.
6. Assertion : Oxidation number of carbon in Oxidation number and Oxidation state
CH 2 O is zero.
1 d 2 b 3 b 4 b 5 d
Reason : CH 2 O formaldehyde, is a covalent
6 b 7 c 8 c 9 c 10 a
compound.
11 c 12 a 13 d 14 b 15 a
 Redox Reactions 563
16 d 17 d 18 d 19 a 20 c
21 d 22 b 23 c 24 d 25 a
26 b 27 b 28 a 29 a 30 a
31 c 32 d 33 a 34 a 35 b Oxidation, Reduction
36 a 37 d 38 a 39 d 40 d
41 b 42 b 43 c 44 a 45 d 1. (b) 2 MnO 4  5 H 2 O 2  6 H   Mn 2   5 O 2  8 H 2 O .
46 b 47 d 48 d 49 a 50 c
2. (b) S  2e   S 2 
51 c 52 b 53 b 54 c 55 b
0 3
56 b 57 c 58 a 59 a 60 c 4. (c) P4  3 NaOH  3 H 2 O  3 NaH 2 PO 2  PH 3 .
Sodium
61 d 62 a 63 d 64 b 65 b hy pophosph ite

66 b 67 c 68 a 69 a 70 c It shows oxidation and reduction (Redox)

71 d 72 a 73 b 74 b 75 b properties.
76 c 77 d 78 a 79 d 80 b 6. (a) In this reaction H 2 S is oxidised because the
81 b 82 c 83 c 84 b 85 c oxidation state of ‘S’ change from – 2 to 0.
86 c 87 d 88 d 89 b 90 c 4 2
91 c 92 a 93 d 94 c 95 d 7. (b) PbO 2  Pb ( NO 3 )2 . In this reaction reduction
96 b 97 d 98 b 99 b 100 c occurs.
101 a 102 d 103 a 104 b 105 a 8. (b) Any substance which is capable of oxidising
106 a 107 d 108 b 109 a 110 b other substances and is capable of
accepting/gaining electron during oxidation is
111 a 112 d 113 b
called oxidising agent or oxidant.

Redox reaction and Method for balancing

Redox reaction

1 a 2 b 3 c 4 c 5 a
6 a 7 a 8 b 9 a 10 d
11 d 12 c 13 c 14 a 15 d

Auto oxidation and Disproportionation

1 d 2 a 3 d 4 b 5 a
6 b 7 c 8 d 9 b 10 c
11 a 12 d 13 a 14 c

Critical Thinking Questions

1 d 2 c 3 a,b 4 d 5 a
6 c 7 c 8 a 9 a 10 c
11 a 12 d 13 c 14 b 15 a
16 d 17 d 18 d 19 c 20 d
21 a 22 d 23 a

Assertion & Reason

1 c 2 b 3 e 4 b 5 a
6 b 7 a 8 a 9 a
 Redox Reactions 563
1 O 2
9. (a) 2 CuI  Cu  CuI 2 . Oxidation and Reduction
In this reaction Zn atom oxidised to Zn 2  ion
both occur so the reaction is redox.
and iodine reduced to I  .
10. (c) H 2 S  X 2 (Cl, Br, I  X )  2HX  S . Here the  

halogen are reduced. 27. (c) CrO42  Cr2 O72 

11. (b) When H 2O2 reduces with K 4 [Fe(CN )6 ] . It is x  [(2)  4 ]  2 2 x  (2)  7  2

present in acidic solution. x  8  2  6 2 x  14  2  12 ,
2 K 4 [Fe(CN )6  H 2 SO 4  H 2 O2  x
12
 6
2
2K 3 [Fe(CN ) 6 ]  K 2 SO 4  2 H 2 O
In this reaction oxidation and reduction are
13. (b) In the given reaction oxidation state of Mg is not involved because there is no change in
changing from 0 to +2 while in nitrogen it is oxidation number.
changing from 0 to –3. So oxidation of Mg and 0 1 5

reduction of nitrogen takes place. 28. (d) 3 Br2  6 CO32   3 H 2 O  5 Br   BrO3  6 HCO 3 . In
this reaction bromine is oxidised as well as
14. (b) When sodium metal is dissolved in liquid reduced.
ammonia to form coloured solution. Dilute
29. (a) P is oxidized as well as reduced (as in option
solutions are bright blue in colour due to the
a).
presence of solvated electrons.
Reduction
Na  (x  y )NH 3  [ Na( NH 3 ) x ]  [e ( NH 3 )y ] 6
Blue Colour 30. (a) Cr2 O72   14 H   6 I   2Cr 3   3 H 2 O  3 I2
15. (b) The metallic iron is oxidised to Fe 3 . 31. (a) In this reaction oxidation occur.

Oxidatio 32. (a) Fluorine has highest E o – value and more

2 n 1 4
reactive than MnO2 .
16. (a) SnCl 2  2 HgCl 2  SnCl 4  Hg 2 Cl 2 (s)
33. (a) Fe 2   Fe3   e  oxidation.
Reductio
n 34. (d) MnO 4  Mn 2  . In this reaction 5 e  are needed
In this reaction HgCl2 is reduced in Hg . for the reduction of Mn 2  as:
MnO 4  5 e   Mn 2  .
17. (a) It is the process in which electrons are lost
(de-electronation). Oxidation
3 2 0 2 0
18. (b) 4 Fe  3 O 2  4 Fe  6O 35. (b) Zn  CuSO 4  ZnSO 4  Cu
19. (c) Cu is above of Ag in electrochemical series Reduction
and thus Cu  2 Ag   Cu 2   2 Ag reaction In this reaction Cu 2  change in Cu o , hence it
occurs. is called as reduction reaction.
0 3
21. (a) Sn 2   Sn 4   2e  . In this reaction Sn 2  36. (d) 4 Fe  3 O 2  4 Fe  6 O 2  , in this reaction
change in Sn 4  it is called an oxidation metallic iron is oxidised to Fe 3
.
reaction.
0 0 2 2
22. (c) 2 S 2 O32   I2  S 4 O62   2 I  . 37. (d) 2 N 2  O 2  2 N O
2 0 Here O.N. of N increases from O in N 2 to +2
23. (b) Zn(aq )  2e   Zn(s) reduction.
in NO, 2– and that of decreased from O in O 2
24. (b) SO 2 bleaches by reduction while chlorine to –2 in O, therefore, it is a redox reaction.
bleaches colour of flowers by oxidation.
Oxidizing and Reducing agent
25. (b) It is the process in which electrons are gained
(electronation). 2 0
1. (c) H 2 S  H 2 O 2  S  2 H 2 O
Oxidation Oxidation
o o 2 1
26. (c) Zn  I2  ZnI 2
Reductio
n
 564 Redox Reactions
The oxidation of S shows oxidising nature of 25. (b) Hydrogen peroxide (H 2O2 ) act as a both
H 2 O2 . oxidising and reducing agent.
2. (a) C 2 O 42   MnO 4 
 H  Mn 2
 CO 2  H 2 O . 27. (d) H 2 O  Br2  HOBr  HBr
0 1 1

In this reaction C 2 O 42  act as a reducing agent.

In the above reaction the oxidation number of
3. (b) A substance which is capable of reducing Br2 increases from zero (in Br2 ) to +1 (in
other substances and is capable of donating HOBr ) and decrease from zero ( Br2 ) to – 1 (in
electrons during reduction is called a HBr ). Thus Br2 is oxidised as well as reduced
reducing agent or reductant.
& hence it is a redox reaction.
4. (a) Fluorine is a most powerful oxidizing agent
because it consist of E o  2 . 5 volt . 28. (c) Cl2  H 2 O  HCl  HOCl

5. (d) HClO is the strongest oxidising agent. The HOCl  HCl  [O]
correct order of oxidising power is HOCl can furnish, nascent oxygen.
1 3 5 7
HClO  H ClO2  H ClO3  H ClO4 . Reduction
(oxidisingagent)
6. (b) It acts both oxidizing and reducing agent. 29. (a) Ag 2 O  H 2 O2  2 Ag  H 2 O  O2
7. (c) Prevent action of water and salt. Oxidation (reducing
agent)
9. (a) In this reaction H 2O2 acts as a oxidizing
30. (d) Oxidizing agent itself, undergoes reduction
agent.
during a redox reaction
10. (b) NaNO2 , SnCl 2 and HI have reducing and 3 2 0 2
HAsO 2  Sn  As  Sn  H 2 O
oxidizing properties but NaNO3 have only
oxidizing property. Hence, here HAsO 2 is acting as oxidizing
11. (c) Because I2 is a reducing agent. agent.
31. (d) NaNO2 (Sodium nitrite) act both as oxidising
13. (a) In this reaction H 2 O acts as oxidising agent.
as well as reducing agent because in it N
 atom is in +3 oxidation state (intermediate
14. (d) I act as a more reducing agent than other
oxidation state)
ions.
Oxidising property
15. (a) When sulphur dioxide is react with H 2 S here
2 NaNO 2  2 KI  2 H 2 SO 4  Na 2 SO 4  K 2 SO 4
SO 2 act as an oxidising agent and H 2 S act as
reducing agent. 2 NO  2H 2O  I2

16. (b) HI (Hydrogen Iodide) is a good reducing agent Reducing property

than other compound. H 2 O 2  NaNO 2  NaNO 3  H 2 O .
17. (b) Hydrogen sulphide (H 2 S ) acts as strong Reduction
reducing agent as it decomposes by evolving 0 3 1
hydrogen. 32. (c) P  NaOH  PH 3  NaH 2 PO 2
o 1 Oxidation
19. (b) Cl2  H 2 O 2  2 HCl  O 2 . In this reaction
chlorine reduced from zero to – 1 oxidation Oxidation number and Oxidation state
state.

20. (d) NaCl  H 2O  NaOH  HCl 1. (d) CO 2
Sodium ion hydrated in water. x  2 (2)  0 ; x  4  0 ; x  4 .
21. (a) Potassium has higher negative value of 3. (b) +2 it is a second group element.
reduction potential hence it shows more 
reducing properties. 4. (b) In HNO 2 oxidation number of N = + 3
22. (b) The oxidation number of Ni changes from 0 to 
1 In HNO 3 oxidation number of N = + 5.

23. (d) HNO 2 (Nitrous acid) acid acts as a oxidising, 5. (d) In case of Cl2O chlorine shows + 1 oxidation
reducing agent and has complex formation state.
properties. 
6. (b) [Cr (H 2 O)4 Cl 2 ]
24. (d) CO2 is an oxidizing agent.
 Redox Reactions 565
x  0  2 (1)  1 ; x  2  1 
26. (b) H 2 C2 O4
x   3 for Cr in complex.
2  2x  2  4  0 ; 2x  8  2  6
5
0 6
7. (c) Br2  BrO3 , in this reaction oxidation state x   3 .
2
change from 0 to + 5.
27. (b) In complex [Pt (C 2 H 4 )Cl 3 ] Pt have + 2 oxidation
8. (c) Oxidation state of sulphur in H 2 S is –2, while
state.
it is zero in ‘S’ i.e. in this reaction oxidation of 
sulphur and reduction of chlorine is takes 28. (a) CH 2 Cl 2
place.
x 220; x 0 .

9. (c) K[Co(CO)4 ] 29. (a) Phosphorus shows – 3 to + 5 oxidation state.
31. (c) The chemical structure of H 2 S 2O8 is as
1  x  0  0; x  1 .
follows:-
6 6
10. (a) K 2 Cr2 O7  K 2 CrO4 .In this reaction no change O O
|| ||
in oxidation state of chromium. H O  SO O  SO H
|| ||
11. (c) In hypochlorous acid chlorine atom has + 1 O O
oxidation number. So the oxidation number of S should be :
12. (a) S  S 2  O.N. of S = –2. 2  (1) 2  X  6  (2) 2  (1)  0 or X  6 .
(for H ) (for S ) (for O ) (for O O )
13. (d) (NH 4 )2 SO 4 ⇌ 2 NH 4   SO 4  
1

32. (d) In hydrazoic acid (N 3 H ) nitrogen shows 
3
NH 4
oxidation state.
x  4  1; x  1  4  3 . 
N3H
14. (b) In N 2 O nitrogen have +1 oxidation state.
15. (a) If any central metal atom combined with 1
3 x  1  0 , 3 x  1 , x   .
corbonyl group than central metal atom shows 3
always zero oxidation state. 33. (a) Hydrogen have oxidation no. + 1 and – 1.

16. (d) H 2 SO 4 34. (a) Cr(NH 3 )4 Cl 2 
2  x  2  4  0 , x  8  2  6 . x  4  (0)  2  1  x  0  2  1

17. (d) HClO4  x = 1 + 2 = + 3.

1  x  2  4  0; 1  x  8  0
35. (b) SO 2  4
x  8  1  7 oxidation state. 
 H 2 SO 4  6
18. (d) H N O 3 ; 1  x  6  0 ; x  5 .

19. (a) Mn shows + 7 oxidation state in MnO 41 Na 2 S 2 O3  2
 
5
MnO41 Na 2 S 4 O6   .
2
x  (2  4 )  1  
x  8  1 36. (a) FeS 2 Fe S 2
x  1  8  7 . x 4 0 4  2x  0
20. (c) Sn 2   Sn 4   2e  x  4 2 x  4

4
21. (d) K 2 MnO4 x  2 .
2
2  x  24  0

x  8  2  6 . 37. (d) NO 3
22. (b) Each molecule always show zero oxidation
state. x  2  3  1 ; x  6  1  5 .
23. (c) Maximum oxi. state for Cr is + 6. 38. (a) Every element always shows zero oxidation
24. (d) In [Fe(CO)5 ] , transition metal Fe has zero state.

oxidation state. 39. (d) In benzaldehyde all carbon atoms show – 4

oxidation state.
25. (a) In (b, c, d) carbon show + 4 oxidation state
while in (a) carbon show – 4 oxidation state.
 566 Redox Reactions
 x 220
40. (d) KIO4
x 0.
1  x  2  4  0 ; x  8  1  7 . 58. (a) In all peroxide oxygen shows – 1 oxidation
 state.
41. (b) N 2 H 5 
59. (a) K 2 Cr2 O7
2 x  5  1 ; 2 x  1  5
2 x  4 ; x  2 . 2  2 x  2  7  0 ; 2 x  14  2  0
42. (b) Oxidation number of C in 12
2 x  12 ; x   6 .
HCHO  0 2
CHCl3  2 60. (c) Nickle shows zero oxidation state in carbonyl
complex.
CH 3 OH  2 

C12 H 22O11  0 61. (d) Os O 4

 x  4 (2)  0
43. (c) KClO4
x 8 0
2  2x  2  7  0 x  8 .
2 x  14  2  0 . 62. (a) Al shows + 3 oxidation state.
 
44. (a) H 4 IO6 63. (d) K 4 [Fe (CN )6 ]
1  4  x  (1  6)  0, 4  x  6  0
4  x  12  1 ; x  1  8   7 .
x  2 .
45. (d) Fluorine always shows – 1 oxidation state.
In this complex compound Iron show + 2
46. (b) In oxidation process oxidation state always
oxidation state.
increases.
64. (b) In this complex iron is a central metal atom

47. (d) HNO3 ⇌ N 2 O showing + 2 oxidation state.
65. (b) Oxygen shows + 2 oxidation state in F2 O . As
1  x  6  0 2x  2  0
F most electronegative element, it always has
x  5 2x  2 an O. No. =–1

2
x  1 . 66. (b) H 3 PO3
2
3  x  2  3  0 ; x  6  3  3 .
48. (d) All free metals always shows zero oxidation 
state. 67. (c) Mg 2 P2 O7
49. (a) MnO 4  Mn 2   5 e  . 4  2 x  2  7  0 ; 2 x  14  4  10
50. (c) C has oxidation number = 0. 10
2 x  10 ; x   5 .
51. (c) Iron has zero oxidation state in carbonyl 2
complexes. 68. (a) 3  x  1(1)  0
52. (b) In all alkali and alkaline earth metal hydride
3x  1  0
hydrogen always shows – 1 oxidation state.
1
53. (b) Iodine shows – 1 to + 7 oxidation state. 3 x  1,  x   in N 3 H
3
Reduction
x  2 (1)  1(2)  1(1)  0
6
54. (c) K 2 Cr2 O7  3 SO 2  H 2 SO 4  x  1 in NH 2 OH
3
K 2 SO 4  Cr2 (SO 4 )3  H 2 O 4
x  2  4 (1)  0 x    2 in N 2 H 4
2
In this reaction chromium change from + 6 to
x  3 (1)  0 x  3 in NH3
+3 oxidation state.
55. (b) In H 2O2 oxygen shows = – 1 (peroxide) Hence, highest in N 3 H .
oxidation state and in BaSO4 oxygen shows = – 
69. (a) In KH 2 PO 2
2 oxidation state.
7 1  2  x  (2  2)  0
56. (b) Mn shows highest oxidation state in KMnO 4 . 3  x  4  0 ; x  1 .

70. (c) Oxygen has 6 electrons in the outer most shell
57. (c) CH 2 O
and shows common oxidation state – 2.
 Redox Reactions 567
  COOH 7
71. (d) H 2 SO 3  4 ; SO 2  4 86. (c) 5 |  2 KMnO4  3 H 2 SO 4 
  COOH
H 2 SO 4  6 ; H 2 S  2 . 2
K 2 SO 4  2 MnSO 4  10 CO 2  8 H 2 O
72. (a) The oxidation number of sulphur in the
sulphur molecule (S 8 ) is 0 and 2. In this reaction oxidation state of Mn change
from + 7 to + 2.
73. (b) In ferrous ammonium sulphate Fe shows +2 87. (d) Oxygen have + 2 oxidation state in OF2 .
oxidation state. 
 89. (b) S 2 O32 
74. (b) NH 2 OH
2 x  3(2)  2 ; x  2 .
x  2 (1)  2  1  0
90. (c) x  2  (1)  2(1)  0
x  2  2  1  0 ; x  1 . x  2  2  0 ; x  0 in CH 2Cl2 .
 
75. (b) Ba(H 2 PO2 )2 ; BaH 4 P2 O4 91. (c) In potassium superoxide (KO2 ) oxygen shows,
2  4  2x  8  0 ; 2x  2 1
 oxidation state.
2 2
x  1 . 
2 92. (a) S 2 Cl 2

77. (d) H 2 SO 4 2 x  2(1)  0 ; 2 x  2  0
x  1 .
2  (1)  x  4  (2)  0 
93. (d) Na2 S 4 O6
2  x  8  0 ; x  8  2  6
2  4 x  12  0
Electronic configuration of sulphur in H 2 SO4
10 5
is 4 x  10 x  x .
4 2
1s 2 , 2 s 2 , 2 p 6 . 2


94. (c) CuSO 4  2 KI ⇌ K2 SO 4  CuI2
78. (a) KMnO 4 1
2 CuI 2  Cu 2 I2  I2
1  x  2  4  0 ; x  8  1  7 .
95. (d) NH4 Cl ⇌ NH 4   Cl 
79. (d) H3 AsO4


3  x  2  4  0 ; x  8  3  5 . NH 4
80. (b) The oxidation state of Xe in both XeO3 and x  4  1 ; x  1  4  3 .
4 5
XeF6 is + 6 96. (b) 2 NO2  H 2 O  HNO 2  HNO 3 . In this reaction
 
oxidation state changes.
XeO 3 XeF 6 
97. (d) Fe 3 O4
x 23  0 x 6 0
3 x  (8 )  0 ; 3 x  8  0
x  6 x  6 .
 8
3x  8 ; x  .
81. (b) CH 3  Cl 3
x  3(1)  (1)  1  0  
99. (b) K 2 MnO4 MnSO 4
x  3 1  0 ; x  2  0
x  2 . 2 x 8 0 x 6 8 0

x  6 x  2 .
82. (c) Cr2 O72 
2 x  2  7  2 ; 2 x  14  2  12 100. (c) Chlorine have oxidation state – 1 to + 7.
12 
x  6 . 101. (a) [Co ( NH 3 )4 ClNO 2 ]
2
 x  4 (0)  1(1)  1(1)  0
83. (c) H 2 SO 3
x  0 1 1  0
2  x  2  3  0 ; x  6  2  4 .
84. (b) Two Cl atom shows +1 and –1 oxidation x  2  0 ; x  2 .
state. 
 102. (d) K 4 [ Ni(CN )4 ]
85. (c) HClO3
4  (1)  x  4  (1)  0
1  x  2  3  0 ; x  6  1  5 .
 568 Redox Reactions
4  x  4  0  x  0 . 3. (c) Cr2 O7 2   3e   Cr 3  .
103. (a) Fluorine always shows – 1 oxidation state in
oxides. Reduction

In this reaction three electrons are required
104. (b) K 3 [Fe (CN )6 ]
for the reduction of Cr2 O72  into Cr 3  .
1  3  x  (1  6)  0
4. (c) Number of e  transferred in each case is 1, 3,
3  x  6  0 ; x  3 .
4, 5.

105. (a) NH 3 5. (a) Starch paper are used for iodine test

x  3(1)  0 , x  3 . as: I   oxidant  I2

106. (a) 26 Fe [ Ar] 3d 6 4 S 2 I2  starch  blue colour

Fe    [ Ar ] 3 d 6 4 S 0 6. (a) Cr2 O72   14 H   6 e   2Cr 3   7 H 2 O

Fe     [ Ar ] 3 d 5 4 S 0 (Sn 2   Sn 4   2e  )  3
In +2 state Fe is called Ferrous & in +3 state
Cr2 O72   14 H   3 Sn 2   3 Sn 4   2Cr 3   7 H 2 O
as ferric.
107. (d) Fluorine is the most electronegative element It is clear from this equation that 3 moles of
in the periodic table so it never shows positive Sn 2  reduce one mole of Cr2 O72  , hence 1 mol.
oxidation state. 1
of Sn 2  will reduce moles of Cr2 O72  .
108. (b) Silicon forms silicides with strongly 3
electropositive metals (like Na, Mg, K etc.) In
7. (a) 2 MnO 4  5 H 2 O 2  6 H   2 Mn 2   5 O 2  8 H 2 O .
these compounds. It has oxidation number
 4 . Reduction

109. (a) H 2 S [O.N. of H  1 ] 8. (b) 2Fe 3  Sn 2  2Fe 2  Sn 4 

(1)  2  x  0 Oxidation
2  x  0 ; x  2
9. (a) MnO 4  8 H   5 e   Mn 2   4 H 2 O  2
110. (b) Let the oxidation number of N in NaNO2 be
x C 2 O 42   2CO 2  2e   5
1  x  (2)  2  0
2 MnO4  5 C 2 O42   16 H   2 Mn 2   10 CO 2  8 H 2 O
1  x  4  0 ; x  3
111. (a) x  8  2  6 Thus the coefficient of MnO 4 , C 2 O 42  and H  in
112. (d) K 2 Cr2 O7  6 KI  7 H 2 SO 4  4 K 2 SO 4  Cr2 (SO 4 )3 the above balanced equation respectively are
2, 5, 16.
7 H 2 O  3 I2 1 2
0 0
* 3 10. (d). Zn  2 AgCN  2 Ag  Zn(CN )2 .
C r2 (SO 4 )3  2 Cr  3 SO 42  Reductio
113. (b) Let the oxidation number of I in IPO4  x n
Oxidatio
n
Oxidation number of PO4  3
Oxidation Reduction
x  (3)  0  x  3
o 1 2 o

Redox reaction and Method for balancing 11. (d) Cu  2 AgNO 3  Cu ( NO 3 )2  2 Ag . This is a redox
Redox reaction reaction.
Oxidatio
1. (a) MnO 4  
 8 H  5 e ⇌ Mn 
 4 H 2O . n
0 0  
12. (c) H 2  Br2  2 H  Br
2. (b) The balanced equation is
2C2 H 6  7O2  4 CO2  6 H 2 O . Ratio of the Reductio
n
coefficients of CO2 and H 2 O is 4 : 6 or 2 : 3.
 Redox Reactions 569
13. (c) Higher is the reduction potential stronger is Molecular weight

the oxidising agent. Hence in the given Change in oxidation number per mole
options. MnO 4 is strongest oxidising agent. Suppose molecular weight is M
14. (a) IO3– + aI– + bH+  cH2O + dI2 Oxidation number of I2 in IO4 in
Step 1 : I–1  I2 (oxidation)
Acidic medium i.e., I  (8)  1e   7
IO3–  I2 (reduction)
So eq. wt.  M / 7 .
Step 2 : 2IO3– + 12H+  I2 + 6H2O
10. (c) 2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO 4
Step 3 : 2IO3– + 12H+ + 10e  I2 + 6H2O
3 H 2O  5O
2I–  I2 + 2e
Step 4 : 2IO3– + 12H+ + 10e–  I2 + 6H2O 5 H 2 O 2  5 O  5 H 2 O  5 O 2

[2I–  I2 + 2e]5 2 KMnO 4  3 H 2 SO 4  5 H 2 O 2  K 2 SO 4  2 MnSO 4

Step 5 : 2IO3– + 10I– + 12H+  6I2 + 6H2O 8 H 2 O  5O2

IO3– + 5I– + 6H+  3I2 + 3H2O Molecular weight
11. (a) = Equivalent weight of Iodine.
On comparing, a = 5, b = 6, c = 3, d = 3 2
15. (d) In alkaline medium Molecular weight
12. (d) Because in KIO3 effective
3
2 KMnO4  KI  H 2 O  2 MnO2  2 KOH  KIO3 .
oxidation number is 3.

Auto oxidation and Disproportionation 13. (a) 6 MnO 4  I   6 OH   6 MnO 42   IO3  3 H 2 O

0 14. (c) ClO 2  Cl 

1. (d) H 2 S  S  2e
ClO 2  2 H 2 O  5 e  Cl   4 OH 
Mol.wt. 34
Equivalent wt. = = =17. H 2 O2  O2
2 2

2. (a) 1.12 ltr H 2  1.2 g; 22 .4 ltr H 2  24 g . H 2 O 2  2 OH   O 2  2 H 2 O  2e

 ClO 2  2 H 2 O  5 e  Cl   4 OH  ]  2
3. (d) 2 AgNO 3  2 Ag  2 NO 2  O 2 .
H 2 O 2  2 OH   O 2  2 H 2 O  2 e ]  2
4. (b) To prevent rancidification of food material we
add anti-oxidant which are called oxidation 2ClO 2  5 H 2 O 2  2OH   2 Cl   5 O 2  5 H 2 O
inhibitor.
2ClO2  5 H 2 O 2
6. (b) Zn 2  / Zn. E o  0 .76 V
 ClO2  2.5 H 2 O 2
Al 3  / Al E o  1 .662
Critical Thinking Questions
Sn 2  / Sn E o  0 . 136
1. (d) HNO2 shows both oxidation and reduction
Pb 2  / Pb E o  0 .126 properties.
In galvanizing action Zn is coated over iron. 2. (c) Al2 O3 could not act as a oxidising and
reducing agent.
8. (d) Molecular weight of H 3 PO4 is 98 and change
3. (a, b) In H 2 S sulphur shows –2 oxidation state
in
and in SO 2 shows +4 oxidation state. Hence
its valency = 1 equivalent wt. of H3 PO4 SO 2 shows both oxidising and reducing

Molecular weight 98 properties.

   98 .
Change in valency 1 4. (d) All the given statements are true.

9. (b) Equivalent mass

 570 Redox Reactions
H 
| H 2 S  2 .
5. (a) H  O  P  OH , hence it is dibasic. It acts as

O 16. (d) In reaction HCl  H 2 O  H 3 O   Cl  , only
reducing agent also. reduction has taken place not oxidation.
 17. (d) Zn can oxidise carbon because heat of
6. (c) (a) NO2 ; x  4  0 ; x   4 combusion of Zn  C .

(b) H N O ; 1  x  2  0 ; x  1 18. (d) B2 H6  2KOH  2H 2O  2KBO2  6 H 2 .

 19. (c) The values of x , y, z are 8, 4, 4 respectively

(c) NH 3 ; x  3  0 ; x  3 hence the reaction is
 10 H 2 SO 4  8 HI  H 2 S  4 I 2  4 H 2 O
(d) N 2 O5 ; 2 x  10  0 ; 2 x  10 ; x  ; x = 5.
2
20. (d) Acid Base
7. (c) 2 × No. of e  losses = Oxi. no.
HClO 3 ClO 32 

2  3 e  6 .
HS  S 2
8. (a) The ion which is not affected during the
course of reaction is known as spectator ion. H 2 PO 4 HPO 42 

9. (a) H 2 S 2 O7 21. (a) MnO 42  in neutral aqueous medium is
2 1
2  (1)  2  x  7  (2)  0 disproportionate to mole of MnO 4 and
3 3
2  2 x  14  0 mole of MnO2 .
2 x  14  2  12
1000 K 1000  3.06  10 6
12 22. (d) m    1.53
x  6 for S S S
2
mol
 S  2  10  3
K 4 Fe (CN )6 litre

4  (1) x  6  (1)  0 Ksp (BaSO 4 )  S 2  (2  10 3 )2  4  10 6 .


4  x 6 0 23. (a) 2 MnO2  4 KOH  O 2  2 K 2 MnO4  2 H 2 O .
purple green
x  6  4  2 for Fe .

10. (c) KO2 ,  1  2 x  0, x  
1
.
Assertion & Reason
2
1. (c) It is true that SO 2 and Cl2 both are bleaching
11. (a) N 22   2 N a   10 e 
agents. But Cl2 is an oxidising agent while
 2a  [2  (2)]  10
SO 2 is a reducing agent. Therefore, in this
 a  3 .
questions assertion is true while reason is

false.
12. (d) CrO 2 Cl 2 , x  4  2  0, x  6 .
2. (b) It is correct that fluorine exists only in –1
13. (c) 3 x  1, x  1 / 3 .
oxidation state because it has 1s 2 2 p 5

14. (b) Ba 2 Cu 3 O7 electronic configuration and thus shows only
–1 oxidation state in order to complete its
3  2  2  3 x  (2  7)  0 octet. Hence, both assertion and reason are
3  4  3 x  14  0 true and reason is not a correct explanation of
3x  7 assertion.

7 3. (e) Here, assertion is false, because stannous

x . chloiride is a strong reducing agent not strong
3
oxidising agent. Stannous chlorides gives Grey

15. (a) S 8  0 precipitate with mercuric chloride. Hence,

reason is true.
S 2 F2  1
 Redox Reactions 571
14  3 17
NH 3   (M. wt. of NH 3 )
3 3
14  2 28
while for N 2  
6 6

4. (b) Both assertion and reason are true but reason

is not the correct explanation of assertion.
Greater the number of negative atoms present
in the oxy-acid make the acid stronger. In
general, the strengths of acids that have
general formula (HO)m ZOn can be related to
the value of n . As the value of n increases,
acidic character also increases. The negative
atoms draw electrons away from the Z-atom
and make it more positive. The Z-atom,
therefore, becomes more effective in with
drawing electron density away from the
oxygen atom that bonded to hydrogen. in turn,
the electrons of H  O bond are drawn more
strongly away from the H -atom. The net
effect makes it easier from the proton release
and increases the acid strength.
5. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
Oxidation loss of 2e

Zn(s)  Cu 2  (aq )  Zn 2  (aq )  Cu (s)

Reduction gain of 2e

6. (b) Both assertion and reason are true but reason

is not the correct explanation of assertion.
Oxidation number can be calculated using
some rules. H is assigned +1 oxidation state
and 0 has oxidation number –2
 O. No. of C in CH 2O :
O. no. of C  2(1)  (2)  0
 O. No. of C  0
7. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
8. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
Maximum oxidation state of S is +6, it cannot
exceed it. Therefore it can’t be further
oxidised as S 2 can’t be reduced further.
9. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
0
N 2  6 e   2 N 3 
 equivalent weight of
 Redox Reactions 571

1. When a piece of wire of copper is dipped in 9. Oxidation number of S in Na2 SO 4 is [CPMT 1989]
AgNO3 solution, the colour of the solution turns
(a) – 2 (b) + 2
blue due to
(c) – 6 (d) + 6
[MP PMT 1992; JIPMER 2002]
(a) Formation of soluble complex 10. A metal ion M 3  after loss of three electrons in a
reaction will have an oxidation number equal to
(b) Oxidation of copper
[CPMT 1980, 83, 84, 94, 99]
(c) Oxidation of silver
(a) Zero (b) + 2
(d) Reduction of copper
(c) + 3 (d) + 6
2. HBr and HI can reduce H 2 SO 4 , HCl can reduce
11. Oxidation number of oxygen in ozone (O3 ) is
KMnO4 and HF can reduce [IIT 1981]
[MP PET 2000; MP PMT 2001]
(a) H 2 SO 4 (b) KMnO4 (a) + 3 (b) – 3
(c) K2 Cr2 O7 (d) None of the above (c) – 2 (d) 0
3. Consider the following statements : 12. The oxidation states of sulphur in the anions
In the chemical reaction SO 32  , S 2 O 42  and S 2 O62  follow the order[CBSE PMT 2003]
MnO2  4 HCl  MnCl2  2 H 2 O  Cl2 (a) S 2 O62   S 2 O 42  SO 32  (b) S 2 O 42   SO 32   S 2 O62 
(1) Manganese ion is oxidised
(c) SO 32   S 2 O 42   S 2 O62  (d) S 2 O 42  S 2 O62   SO 32 
(2) Manganese ion is reduced
(3) Chloride ion is oxidised 13. The oxidation number of hydrogen in LiH is
(4) Chloride ion is reduced (a) + 1 (b) – 1
Which of these statements are correct [NDA 1999] (c) 2 (d) 0
(a) 1 and 3 (b) 1 and 4 14. Which of the following is not a redox reaction
[RPMT 1999]
(c) 2 and 3 (d) 2 and 4
(a) 2 Rb  2H 2O  2RbOH  H 2
4. The oxide which cannot act as a reducing agent is
[CBSE PMT 1995; AIIMS 2000; JIPMER 2002; (b) 2CuI2  2CuI  I2
Kurukshetra CEE 2002] (c) 2 H 2 O2  2 H 2 O  O2
(a) SO 2 (b) NO2
(d) 4 KCN  Fe(CN )2  K4 Fe(CN )6
(c) CO2 (d) ClO2
15. Which of the following equations is a balanced
5. In the reaction between ozone and hydrogen one
peroxide, H 2 O2 acts as [RPET 2000] [EAMCET 1980]
(a) Oxidising agent (a) 5 BiO 3  22 H   Mn 2   5 Bi 3   7 H 2 O  MnO 4
(b) Reducing agent
(b) 5 BiO 3  14 H   2 Mn 2   5 Bi 3   7 H 2 O  2 MnO 4
(c) Bleaching agent
(d) Both oxidising and bleaching agent (c) 2 BiO 3  4 H   Mn 2   2 Bi 3   2 H 2 O  MnO 4
6. The oxidation state of each oxygen atom in (d) 6 BiO 3  12 H   3 Mn 2   6 Bi 3   6 H 2 O  3 MnO 4
Na2 O2 is
16. In the equation
[NCERT 1971]
4 M  8 CN   2 H 2 O  O 2  4[M (CN )2 ]  4 OH 
(a) – 2 each (b) – 2 and zero
(c) – 1 each (d) None of the above Identify the metal M [AFMC 1998]
2 (a) Copper (b) Iron
7. The oxidation state of sulphur in SO 4 is
(c) Gold (d) Zinc
[Bihar MEE 1996]
17. In alkaline condition KMnO4 reacts as
(a) 4 (b) 2
(c) 6 (d) – 6
2KMnO4  2 KOH  2 K2 MnO4  H 2O  O . The
equivalent weight of KMnO4 would be (Atomic
8. The charge on cobalt in [Co (CN )6 ]3  is[CPMT 1985, 93]
mass of K = 39, Mn = 55, O = 16) [MP PMT 2002]
(a) – 6 (b) – 3
(a) 158.0 (b) 79.0
(c) + 3 (d) + 6 (c) 52.7 (d) 31.6
 572 Redox Reactions
18. In acidic medium, equivalent weight of K2 Cr2 O7 (c) M / 6 (d) M / 2
(mol . wt.  M) is [AFMC 1988]
(a) M / 3 (b) M / 4

(SET -13)

1. (b) 2 Ag   Cu  Cu    2 Ag  ; Eo   ECu
o
 .
Ag / Ag / Cu

2. (d) F  can be oxidised to F2 only by electrolysis.

3. (c) Because the oxidation state of chlorine is – 4

to 0 while Manganese ion is reduced because
its oxidation state + 4 to + 2. 11. (d) Molecule and free atoms show zero oxidation
state O3 is a molecule shows zero oxidation
4. (c) CO2 is a acidic oxide.
state.
5. (b) H 2O2 acts as a reducing agent in the reaction
12. (b) S 2 O42   SO 32   S 2 O62 
between O3 and H 2O2 .
Oxi. state of sulphur in S 2 O42   3
6. (c) In Na2 O2 oxygen show – 1 oxidation state.

Oxi. state of sulphur in SO 32   4
7. (c) SO 42 
Oxi state of sulphur in S 2 O62   5 .
x  2  4  2 1 1
x  8  2  6 . 13. (b) Li H .
14. (d) In the reaction 4 KCN  Fe(CN )2  K 4 Fe(CN )6 ,
8. (c) In [Co (CN )6 ]3  complex Co shows + 3 oxidation
change in oxidation state is not taking place.
state.
 15. (b) 5 BiO 3  14 H   2 Mn 2   5 Bi 3   7 H 2 O  2 MnO 4
9. (d) Na 2 SO 4
is the balanced reaction.
2  x  24  0 16. (c) 4 Au  8 CN   2 H 2 O  O 2  4 [ Au (CN )2 ]  4 OH  .
x  6 .
M
17. (a) e   Mn7   Mn 6   E  .
10. (d) M 3   M 6   3e  . Thus the oxidation number 1
of metal = + 6.
18. (c) Cr2 O72   14 H   6 e  2Cr 3   7 H 2 O

*** Equivalent weight of K2Cr2O7

Molecular Mass 294 .2 M

   .
6 6 6
 Surface Chemistry 573

Chapter

14
Surface Chemistry

“The branch of physical chemistry, which deals the Interface : Any surface is a Adsorbate and Adsorbent :
nature of surfaces and also with the chemical and plane which separates any The substance which gets
physical processes which takes place on the surfaces, is two phases in contact with adsorbed on any surface is
called surface chemistry”. each other. The plane which called adsorbate for
separates any two phase is example, if a gas gets
In surface chemistry, we study the phenomenon of generally called an adsorbed on to the surface
adsorption, catalysis and colloidal properties. interface between the two of a solid, then the gas is
Adsorption phases. termed as the adsorbate.
(1) Definition : The phenomenon of attracting The substance on the
surface of which adsorption
and retaining the molecules of a substance on the
takes place is called
surface of a liquid or solid resulting in to higher
adsorbent.
concentration of the molecules on the surface is called
adsorption.
Desorption : The removal Absorption : When the
(2) Causes of adsorption : Unbalanced forces of of the adsorbed substance molecules of a substance are
attraction or free valencies which is present at the from a surface is called uniformly distributed
solid or liquid surface, have the property to attract and desorption. throughout the body of a
retain the molecules of a gas or a dissolved substance solid or liquid. This
on to their surfaces with which they come in contact. phenomenon is called
Example : Ammonia gas placed in contact with absorption.

charcoal gets adsorbed on the charcoal whereas Sorption : The phenomenon Occlusion : When
in which adsorption and adsorption of gases occur on
ammonia gas placed in contact with water gets
absorption occur the surface of metals this is
absorbed into water,
simultaneously is called called occlusion.
Table : 14.1 Some basic terms used in adsorption sorption.
Mc. Bain introduced a
general term sorption
describeing both the
processes, however
adsorption is instantaneous
i.e. a fast process while
absorption is a slow process.

(3) Difference between adsorption and absorption

Adsorption Absorption
It is a surface phenomenon. It concerns with the whole
mass of the absorbent.
 574 Surface Chemistry
In it, the substance is only It implies that a substance is (v) For a process to be spontaneous, the
retained on the surface and uniformly distributed, thermodynamic requirement is that G must be
does not go into the bulk or through the body of the negative, i.e. there is decrease in free energy. On the
interior of the solid or solid or liquid. basis of Gibb’s Helmholtz equation, G  H  T S , G
liquid.
can be negative if H has sufficiently high negative
In it the concentration of the In it the concentration is
value and TS has positive value.
adsorbed molecules is low.
always greater at the free Classification of adsorption
phase.
It is rapid in the beginning It occurs at the uniform Adsorption can be classified into two categories
and slows down near the rate. as described below,
equilibrium.
(1) Depending upon the concentration : In
Examples : (i) Water Examples : (i) Water
adsorption the concentration of one substance is
vapours adsorbed by silica vapours absorbed by
gel. anhydrous CaCl2 different at the surface of the other substance as
(ii) NH3 is adsorbed by (ii) NH3 is absorbed in water compared to adjoining bulk or interior phase.
charcoal. forming NH4OH (i) Positive adsorption : If the concentration of
adsorbate is more on the surface as compared to its
(4) Surface forces : Only the surface atoms of an concentration in the bulk phase then it is called
adsorbent play an active role in adsorption. These positive adsorption.
atoms posses unbalanced forces of various types such Example : When a concentrated solution of KCl is
as, Vander Waal’s forces and chemical bond forces. shaken with blood charcoal, it shows positive
Thus, the residual force-field on a free surface adsorption.
which is responsible for adsorption is produced. For (ii) Negative adsorption : If the concentration of
example, when a solid substance is broken into two the adsorbate is less than its concentration in the bulk
pieces, two new surfaces are formed and therefore, the then it is called negative adsorption.
number of unbalanced forces becomes more. As a result
the tendency for adsorption become large. Example : When a dilute solution of KCl is shaken
with blood charcoal, it shows negative adsorption.
(5) Reversible and Irreversible adsorption : The
adsorption is reversible, if the adsorbate can be easily (2) Depending upon the nature of force existing
removed from the surface of the adsorbent by physical between adsorbate molecule and adsorbent
methods.If the adsorbate can not be easily removed (i) Physical adsorption : If the forces of
from the surface of the adsorbent is called irreversible attraction existing between adsorbate and adsorbent
adsorption. are Vander Waal’s forces, the adsorption is called
Example for reversible adsorption: A gas adsorbed physical adsorption. This type of adsorption is also
on a solid surface can be completely removed in vacuum. known as physisorption or Vander Waal’s adsorption.
It can be easily reversed by heating or decreasing the
Example for irreversible adsorption: Adsorption of
pressure.
O2 on tungusten adsorbent.
(ii) Chemical adsorption : If the forces of
(6) Characteristics of adsorption
attraction existing between adsorbate particles and
(i) Adsorption refers to the existence of a higher adsorbent are almost of the same strength as chemical
concentration of any particular component at the bonds, the adsorption is called chemical adsorption.
surface of a liquid or a solid phase. This type of adsorption is also called as chemisorption
(ii) Adsorption is accompanied by decrease in the or Langmuir adsorption. This type of adsorption
G (free energy change) of the system when G  0 , cannot be easily reversed.
adsorption equilibrium is said to be established. Comparison between physisorption and
chemisorption
(iii) Adsorption is invariably accompanied by
evolution of heat, i.e. it is an exothermic process. In Physisorption Chemisorption
other words, H of adsorption is always negative. (Vander Waal's adsorption) (Langmuir adsorption)
Low heat of adsorption High heat of adsorption in
usually in range of 20-40 the range of 50-400 kJ/mol
(iv) When a gas is adsorbed, the freedom of kJ/mol
movement of its molecules becomes restricted. On Force of attraction are Forces of attraction are
account of it decrease in the entropy of the gas after Vander Waal's forces. chemical bond forces.
adsorption, i.e. S is negative. It is reversible It is irreversible
 Surface Chemistry 575
It is usually takes place at It takes place at high magnitude of adsorption should decrease with rise in
low temperature and temperature. temperature.
decreases with increasing
temperature.
P-
It is related to the case of It is not related. P - Constant
Constant
liquefication of the gas.
It forms multimolecular It forms monomolecular x/m x/m
layers. layers.
It does not require any It requires high activation
activation energy. energy. Temperatur Temperatur
e
Physical e
Chemical
High pressure is favourable. High pressure is favourable.
Decrease of pressure causes Decrease of pressure does adsorption adsorption
desorption not cause desorption. (ii) The relationship between the extent of
It is not very specific. It is highly specific. adsorption and temperature at any constant pressure is
called adsorption isobar.
Factors which affect the extent of adsorption :
The following are the factors which affect the (iii) A physical adsorption isobar shows a
adsorption, decrease in x/m (where ‘m’ is the mass of the adsorbent
and ‘x’ that of adsorbate) as the temperature rises.
(1) Nature of the adsorbate (gas) and adsorbent
(iv) The isobar of chemisorption show an increase
(solid)
in the beginning and then decrease as the temperature
(i) In general, easily liquefiable gases e.g., CO2,
rises.
NH3, Cl2 and SO2 etc. are adsorbed to a greater extent
than the elemental gases e.g. H2, O2, N2, He etc. (while Adsorption isotherms
chemisorption is specific in nature.) A mathematical equation, which describes the
(ii) Porous and finely powdered solid e.g. relationship between pressure (p) of the gaseous
charcoal, fullers earth, adsorb more as compared to the adsorbate and the extent of adsorption at any fixed
hard non-porous materials. Due to this property temperature, is called adsorption isotherms.
powdered charcoal is used in gas masks. The extent of adsorption is expressed as mass of
(2) Surface area of the solid adsorbent the adsorbate adsorbed on one unit mass of the
(i) The extent of adsorption depends directly upon adsorbent.
the surface area of the adsorbent, i.e. larger the surface Thus, if x g of an adsorbate is adsorbed on m g of
area of the adsorbent, greater is the extent of the adsorbent, then
adsorption. x
Extent of adsorption 
(ii) Surface area of a powdered solid adsorbent m
depends upon its particle size. Smaller the particle size, Various adsorption isotherms are commonly
greater is its surface area. employed in describing the adsorption data.
(3) Effect of pressure on the adsorbate gas (1) Freundlich adsorption isotherm
(i) An increase in the pressure of the adsorbate (i) Freundlich adsorption isotherm is obeyed by
gas increases the extent of Adsorption tends to the adsorptions where the adsorbate forms a
adsorption. reach limiting value monomolecular layer on the surface of the adsorbent.
adsorption
Extent of

(ii) At low x
1

temperature, the extent of  kp n (Freundlich adsorption isotherm) or

m
adsorption increases
Adsorption increases x 1
rapidly with pressure. rapidly at the beginning
log  log k  log p
m n
(iii) Small range of Pressure where x is the weight of the gas adsorbed by m
pressure, the extent of
gm of the adsorbent at a pressure p, thus x/m
adsorption is found to be directly proportional to the
represents the amount of gas adsorbed by the
pressure.
adsorbents per gm (unit mass), k and n are constant at
(iv) At high pressure (closer to the saturation a particular temperature and for a particular adsorbent
vapour pressure of the gas), the adsorption tends to and adsorbate (gas), n is always greater than one,
achieve a limiting value. indicating that the amount of the gas adsorbed does
(4) Effect of temperature not increase as rapidly as the pressure.
(i) As adsorption is accompanied by evolution of (ii) At low pressure, the extent of adsorption
x
heat, so according to the Le-Chatelier’s principle, the varies linearly with pressure.  p'
m
 576 Surface Chemistry
(iii) At high pressure, it becomes independent of
x experimental data.
pressure.  p0
m Limitation of Langmuir theory
x
(iv) At moderate pressure depends upon
m
1 is valid only at low pressures and high temperatures.
x
pressure raised to powers  pn
m
x x
 p1  p0
m m
(x/m)
slope 
log
x/m
x
 p1 / n
m intercept = log
x/m k solutions also.
p log p
Freundlich adsorption Plot of log x/m against log p for
isotherm: plot of x/m the adsorption of a gas on a solid
against p
(2) The Langmuir - adsorption isotherms
(i) One of the drawbacks of Freundlich adsorption
isotherm is that it fails at high pressure of the gas.
Irving Langmuir in 1916 derived a simple adsorption
isotherm, on theoretical considerations based on
kinetic theory of gases. This is named as Langmuir
adsorption isotherm.
(a) Adsorption takes place on the surface of the
solid only till the whole of the surface is completely
covered with a unimolecular layer of the adsorbed gas.
(b) Adsorption consists of two opposing
processes, namely Condensation of the gas molecules
on the solid surface and Evaporation (desorption) of
the gas molecules from the surface back into the
gaseous phase.
(c) The rate of condensation depends upon the
uncovered (bare) surface of the adsorbent available for
condensation. Naturally, at start when whole of the
surface is uncovered the rate of condensation is very
high and as the surface is covered more and more, the
rate of condensation progressively decreases. On the
contrary, the rate of evaporation depends upon the
covered surface and hence increases as more and more
of the surface is covered ultimately an equilibrium will
be set up at a stage when the rate of condensation
becomes equal to the rate of evaporation (adsorption
equilibrium).
(d) The rate of condensation also depends upon
the pressure of the gas since according the kinetic
theory of gases, the number of molecules striking per
unit area is proportional to the pressure.
x ap
Mathematically,  , where a and b are
m 1  bp
constants and their value depends upon the nature of
gas (adsorbate), nature of the solid adsorbent and the
temperature. Their values can be determined from the
(a) Langmuir’s theory of unimolecular adsorption
(b) When the pressure is increased or
temperature is lowered, additional layers are formed.
This has led to the modern concept of multilayer
adsorption.
1
Adsorption from solutions
n
(1) The process of adsorption can take place from
(2) In any solution, there are two (or more)
components ; solute and solvent. The solute may be
present in the molecular or ionic form.
(3) The extent of adsorption from solution
depends upon the concentration of the solute in the
solution, and can be expressed by the Freundlich
isotherm.
(4) The Freundlich adsorption isotherm for the
x
1
adsorption from solution is,  kc n where, x is the
m
mass of the solute adsorbed, m is the mass of the solid
adsorbent, c is the equilibrium concentration of the
solute in the solution, n is a constant having value
greater than one,
k is the proportionality constant, (The value of k
depends upon the nature of solid, its particle size,
temperature, and the nature of solute and solvent etc.)
(5) The plot of x/m against c is similar to that
Freundlich adsorption isotherm. The above equations
may be written in the following form,
x 1
log  log k  log c where c, is the equilibrium
m n
concentration of the solute in the solution.
Application of adsorption
The phenomenon of adsorption finds a number of
applications. Important applications are given as
follows.
(1) Production of high vacuum
(2) In Gas masks : This apparatus is used to
adsorb poisonous gases (e.g. Cl2 , CO, oxide of sulphur
etc.) and thus purify the air for breathing.
(3) For desiccation or dehumidification : These
substances can be used to reduce/remove water
vapours or moisture present in the air. Silica gel and
alumina are used for dehumidification in electronic
equipment.
(4) Removel of colouring matter from solution :
(i) Animal charcoal removes colours of solutions by

adsorbing coloured impurities. (ii) Animal charcoal is
used as decolouriser in the manufacture of cane sugar.
(5) Heterogeneous catalysis : Mostly
heterogeneous catalytic reactions proceed through the
adsorption of gaseous reactants on solid catalyst. For
example,
(i) Finely powdered nickel is used for the
hydrogenation of oils.
(ii) Finely divided vanadium pentaoxide (V2 O5 ) is
used in the contact process for the manufacture of
sulphuric acid.
(6) Separation of inert gases : Due to the
difference in degree of adsorption of gases by charcoal,
a mixture of inert gases can be separated by adsorption
on coconut charcoal at different low temperatures.
(7) Softening of hard water
(i) The hard water is made to pass through a
column packed with zeolite (sodium aluminium
silicate)
(ii) Ca++, Mg++ ions which are responsible for
hardness, get adsorbed on zeolite, exchanging sodium
ions.
Na 2 Al 2 Si 2 O8  CaCl 2  CaAl 2 Si 2 O8  2 NaCl
(iii) The exhausted zeolite is regenerated with
10% of sodium chloride solution.
CaAl 2 Si 2 O8  2 NaCl  Na 2 Al 2 Si 2 O8  CaCl 2
(8) De-ionisation of water
(i) Water can be de-ionised by removing all
dissolved salts with the help of cation and anion-
exchanger resin.
(ii) Cation-exchanger is an organic synthetic resin
such as polystyrene-containing a macroanion
 (Sucrose solution)
(R  SO etc .) which has adsorbed
3 H+ ions.
(iii) A resin containing a basic group (R 3 N  etc.)

which has adsorbed OH ions acts as anion exchanger.
(9) In curing diseases : A number of drugs are
adsorbed on the germs and kill them or these are
adsorbed on the tissues and heat them.
(10) Cleaning agents : Soap and detergents get
adsorbed on the interface and thus reduce the surface
tension between dirt and cloth, subsequently the dirt is
removed from the cloth.
(11) Froth floatation process
A low grade sulphide ore is concentrated by
separating it from silica and other earthy matter by
this method.
(12) In adsorption indicators
Surface of certain precipitates such as silver
halide, have the property of adsorbing some dyes like
eosin, fluorescein etc.
(13) Chromatographic analysis
Surface Chemistry 577
The phenomenon of adsorption has given an
excellent technique of analysis known as
chromatographic analysis.
(14) In dyeing : Many dyes get adsorbed on the
cloth either directly or by the use of mordants.
Catalysis
“Catalyst is a substance which speeds up and
speeds down a chemical reaction without itself being
used up.”
Berzelius (1836) introduced the term catalysis and
catalyst.
Ostwald (1895) redefined a catalyst as, “A
substance which changes the reaction rate without
affecting the overall energetics of the reaction is termed
as a catalyst and the phenomenon is known as
catalysis.”
Types of catalysis
Catalytic reactions can be broadly divided into the
following types,
(1) Homogeneous catalysis : When the reactants
and the catalyst are in the same phase (i.e. solid, liquid
or gas). The catalysis is said to be homogeneous. The
following are some of the examples of homogeneous
catalysis.
(i) In the lead chamber process
2 SO 2 (g)  O 2 (g)    2 SO 3 (g)
NO ( g )
(ii) In the hydrolysis of ester
CH 3 COOCH 3 (l)  H 2 O(l)  
HCl (l)
CH 3 COOH (l)  CH 3 OH (l)
(iii) In the hydrolysis of sugar
C12 H 22 O11 (l) H 2 O(l) 2 4

H SO (l )
C 6 H 12 O 6 (l)  C 6 H 12 O 6 (l)
(Glucose solution) (Fructose solution)
(2) Heterogeneous catalysis : The catalytic
process in which the reactants and the catalyst are in
different phases is known as heterogeneous catalysis.
Some of the examples of heterogeneous catalysis are
given below.
(i) In contact process for H2SO4
2 SO 2 (g)  O2 (g)   2 SO 3 (g)
Pt ( s )
BrV 2 O 5
(ii) In Haber’s process for NH 3
N 2 (g)  3 H 2 (g)   2 NH 3 (g)
Fe ( s )
(iii) In Ostwald’s process for HNO 3
4 NH 3 (g)  5 O2 (g)   4 NO (g)  6 H 2 O(g)
Pt ( s )
(3) Positive catalysis : When the rate of the
reaction is accelerated by the foreign substance, it is
said to be a positive catalyst and phenomenon as
 578 Surface Chemistry
positive catalysis. Some examples of positive catalysis (i) Sodium arsenite solution is not oxidised by air.
are given below. If, however, air is passed through a mixture of the
(i) Decomposition of KClO3 solution of sodium arsenite and sodium sulphite, both
of them undergo simultaneous oxidation. The oxidation
2 KClO3 (s) 2  2 KCl(s)  3O2 (g)
MnO (s)
of sodium sulphite, thus, induces the oxidation of
270 o C
sodium arsenite.
(ii) Oxidation of SO 2 (ii) The reduction of mercuric chloride
2SO 2 (g)  O2 (g)  2SO 3 (g)
V2 O5 (s) (HgCl2 ) with oxalic acid is very slow, but potassium
or Pt (s)
permanganate is reduced readily with oxalic acid. If,
(iii) Decon’s process however, oxalic acid is added to a mixture of potassium
permanganate and HgCl2 both are reduced
4 HCl(g)  O2 (g) 2  2Cl2 (g)  2 H 2O(g)
CuCl (s)
450 o C simultaneously. The reduction of potassium
(4) Negative catalysis : There are certain, permanganate, thus, induces the reduction of mercuric
substance which, when added to the reaction mixture, chloride.
retard the reaction rate instead of increasing it. These (7) Acid-base catalysis : According to the
are called negative catalyst or inhibitors and the Arrhenius and Ostwald H+ or H– ion act as a catalyst.
phenomenon is known as negative catalysis. Some (i) For example, Hydrolysis of an ester,
examples are as follows. 
CH 3 COOC 2 H 5 (l)  H 2 O(l)  
 CH 3 COOH (l)  C 2 H 5 OH (l)
H or
(i) Oxidation of sodium sulphite OH 

2 Na 2 SO 3 (s)  O2 (g)    2 Na 2 SO 4 (s)

Alcohol (l )
(ii) Oxidation of benzaldehyde
2C6 H 5 CHO (l)  O2 (g)   2C6 H 5 COOH (l)
Diphenyl
amine (l)
(iii) Tetra ethyl lead (TEL) is added to petrol to
retard the ignition of petrol vapours on compression in
an internal combustion engine and thus minimise the
knocking effect.
(5) Auto-catalysis : In certain reactions, one of
the product acts as a catalyst. In the initial stages the
reaction is slow but as soon as the products come into
existences the reaction rate increases. This type of
phenomenon is known as auto-catalysis. Some
examples are as follows,
(i) The rate of oxidation of oxalic acid by acidified
potassium permanganate increases as the reaction
progresses. This acceleration is due to the presence of
Mn 2  ions which are formed during reaction. Thus
2
Mn ions act as auto-catalyst.
5 H2C2O4  2 KMnO4  3 H2SO4  2MnSO4  K2SO4
10 CO2  8 H 2O
(ii) When nitric acid is poured on copper, the
reaction is very slow in the beginning, gradually the
reaction becomes faster due to the formation of nitrous
acid during the reaction which acts as an auto-catalyst.
(6) Induced catalysis : When one reaction
influences the rate of other reaction, which does not
occur under ordinary conditions, the phenomenon is
known as induced catalysis. Some examples are as
follows,
(ii) Inversion of cane sugar,

C12 H 22 O11 (l)  H 2 O 
H
 C6 H12 O6 (l) C6 H12 O6 (l)
Sugar Fructose Glucose
(iii) Conversion of acetone into diacetone alcohol,

CH 3 COCH 3 (l)  CH 3 COCH 3 (l) 
OH

CH3COCH 2 .C(CH3 )2 OH (l)
Characteristics of catalysis
The following are the characteristics which are
common to must of catalytic reactions.
(1) A catalyst remains unchanged in mass and
chemical composition at the end of the reaction.
(2) A small quantity of the catalyst is generally
sufficient to catalyses almost unlimited reactions
(i) For example, in the decomposition of hydrogen
peroxide, one gram of colloidal platinum can catalyses
10 8 litres of hydrogen peroxide.
(ii) In Friedel craft’s reaction, anhydrous
aluminium chloride is required in relatively large
amount to the extent of 30% of the mass of benzene,
C6 H 6  C2 H 5 Cl   C6 H 5 C2 H 5  HCl
3 AlCl
(3) The catalyst can not initiate the reaction:
The function of the catalyst is to alter the speed of the
reaction rather than to start it.
(4) The catalyst is generally specific in nature:
A substance, which acts as a catalyst for a particular
reaction , fails to catalyse the other reaction , different
catalysts for the same reactant may for different
products.
Examples :
Al2O3 C 2 H 4 ( g )  H 2 O (g )
(Dehydrati on)

C 2 H 5 OH (l)
Cu
CH 3 CHO (g)  H 2 (g)
Cu (Dehy drogenation )

Cu CO 2 (g)  H 2 (g)
(Dehydroge nation)
 Surface Chemistry 579
(i) According to the collision theory, a reaction
occurs on account of effective collisions between the
reacting molecules.
(ii) For effective collision, it is necessary that the
molecules must possess a minimum amount of energy
known as activation energy (Ea).
(iii) After the collision molecules form an
activated complex which dissociate to yield the product
molecules.
(iv) The catalyst provides a new pathway
(5) The catalyst can not change the position of involving lower amount of activation energy. Thus,
equilibrium : The catalyst catalyse both forward and
Ea Ea
backward reactions to the same extent in a reversible Ea
 RT
 – RT 
reaction and thus have no effect on the equilibrium Decreases
–
Decreases Increases
constant.
(6) Catalytic promoters : Substances which
themselves are not catalysts, but when mixed in small e–Ea/RT k
quantities with the catalysts increase their efficiency
 Increases  Reaction speeds
Increases up
are called as promoters or activators.
(i) For example, in Haber’s process for the
synthesis of ammonia, traces of molybdenum increases larger number of effective collisions occur in
the activity of finely divided iron which acts as a the presence of a catalyst in comparison to
catalyst. effective collisions at the same temperature in
absence of a catalyst. Hence the presence of a
(ii) In the manufacture of methyl alcohol from
catalyst makes the reaction to go faster.
water gas (CO  H 2 ) , chromic oxide (Cr2 O3 ) is used as a
(v) Figure shows that activation energy E a ,
promoter with the catalyst zinc oxide (ZnO ) .
in absence of a catalyst is higher than the
(7) Catalytic poisons : Substances which destroy activation energy Ea, in presence of a catalyst.
the activity of the catalyst by their presence are known
(vi) ER and Ep represent the average
as catalytic poisons.
energies of reactants and products. The difference
(i) For example, the presence of traces of
gives the value of G , i.e., G  ER  EP
arsenious oxide ( As2O3 ) in the reacting gases reduces
Uncatalysed
the activity of platinized asbestos which is used as complex
catalyst in contact process for the manufacture of
Energy
sulphuric acid.
Chemical potential

barrier
(ii) The activity of iron catalyst is destroyed by Catalysed
energy

the presence of H 2 S or CO in the synthesis of complex

Ea
ammonia by Haber’s process.
(iii) The platinum catalyst used in the oxidation of Ea
hydrogen is poisoned by CO .
ER
(8) Change of temperature alters the rate of Reactants
Initial G° of
catalytic reaction as it does for the same reaction in (A+B) reaction
state
absence of catalyst : By increasing the temperature, EP
there is an increase in the catalytic power of a catalyst Final state Products (C +
but after a certain temperature its power begins to Reaction D)
decrease. A catalyst has thus, a particular temperature sequence
at which its catalytic activity is maximum. This
Theories of catalysis
temperature is termed as optimum temperature.
(9) A positive catalyst lowers the activation There are two theories of catalysis which is
energy described as follows.
(1) Intermediate compound theory
 580 Surface Chemistry
(i) This theory was proposed by Clement and
Desormes in 1806. According to this theory, the desired
reaction is brought about by a path involving the
formation of an unstable intermediate compound,
followed by its decomposition into the desired end
products with the regeneration of the catalyst.
(ii) The intermediate compund may be formed in
either of two ways
(a) When the intermediate compound is reactive
and reacts with the other reactants.
AB  X  BX  A
intermedia te
BX  C  CB  X .....(i)
(b) When the intermediate is unstable and
decomposes to give the final product.
A  B  X  ABX  AB  X .....(ii)
intermedia te
Where, A, B and C are the reactant molecules and
X is the molecule of the catalyst. The first type of
reaction sums up to, AB  C  CB  A
While the second to, A  B  AB in many cases,
the intermediate compounds postulated to be formed
are known compounds and often their presence is
detected.
(2) Adsorption theory
(i) This theory is applicable to reactions between
gases in the presence of a solid catalyst. Some typical
examples are as follows.
(ii) The contact process for the oxidation of SO 2
to SO 3 with atmospheric oxygen in the presence of
platinum as the catalyst.
(iii) The Haber’s process for the synthesis of
ammonia with iron as the catalyst.
(iv) Adsorption results in the loosening of the
chemical bonds in the reactant molecules, so that their
rupture becomes easier. This is confirmed by the
observed lower activation energies for heterogeneous
catalytic reactions in the presence of the catalysts as
compared to that for the same reaction in the absence
of the catalyst.
Enzyme catalysis
(1) Enzymes are complex nitrogenous substances
these are actually protein molecules of higher
molecular mass.
(2) Enzymes catalyse numerous reactions,
especially those connected with natural processes.
(3) Numerous reactions occur in the bodies of
animals and plants to maintain the life process. These
reactions are catalysed by enzymes. The enzymes are
thus, termed as bio-chemical catalysts and the
phenomenon is known as bio-chemical catalysis.
(4) Nitrogenase an enzyme present in bacteria on
the root nodules of leguminous plants such as peas and
beans, catalyses the conversion of atmospheric N 2 to
NH 3 .
(5) In the human body, the enzyme carbonic
anhydrase catalyses the reaction of CO2 with H 2 O ,
CO2 (aq)  H 2O(l)  H  (aq .)  HCO 3 (aq .)
The forward reaction occurs when the blood takes
up CO2 in the tissues, and the reverse reaction occurs
when the blood releases CO2 in lungs.
(6) In manufacturing of ethyl alcohol
(i)
C12 H 22 O11 (l)  H 2 O(l)   C6 H12 O6 (l) C6 H12 O6 (l)
Invertase
Glucose Fructose
C6 H12 O6 (l)  2C 2 H 5 OH (l)  2CO 2 (l)
Zymase
(ii) Starch (l)   Maltose(l)
Diastase
Maltose    Glucose 
Maltase
 Alcohol
Zyamase
Activity and Selectivity
(1) Activity : Activity is the ability of catalysts to
accelerate chemical reaction, the degree of acceleration
can be as high as 10 10 times in certain reactions. For
example reaction between H 2 and O 2 to form H 2 O in
presence of platinum as catalyst takes place with
explosive violence.
In absence of catalyst, H 2 and O 2 can be stored
indefinitely without any reaction.
(2) Selectivity : Is the ability of catalysts to direct
reaction to yield particular products (excluding other).
Example :
CH 3
(i) n  heptane  Pt
Toluen
e O
||
(ii) CH 3 CH  CH 2   CH 2  CHCH
BiMoO 4
Acrolein
Zeolite (Shape selective catalysis)
(1) Zeolite are alumino–silicates of the general
formula, M x / n [ AlO2 ] x .(SiO2 )y .mH 2 O , where, M may be
simple cation like Na  , K  or Ca 2  , n is the charge on the
simple cation, m is the number of molecules of water of
crystallization.
(2) Some well known zeolites are as follows,
Erionite  Na2 K2CaMg(AlO2 )2 (SiO2 )2 .6 H2O
Gemelinite  Na2Ca(AlO2 )2 (SiO2 )4 .6 H2O
 Surface Chemistry 581
Faujasite (natural)  Na56 (AlO2 )56 (SiO2 )136.250 H2O substances but is a state of matter like solid, liquid and
gas. Any substance can be brought into colloidal state.
ZSM-5  H x [( AlO2 )x (SiO2 )96 x ].16 H2O
(4) The colloidal state depends on the particle
Linde-A (synthetic)  [Na12( AlO2 )12(SiO2 )12.27 H 2O]8
size. If is regarded as intermediate state between true
(3) The characteristic feature of zeolites is the solution and suspension.
openness of the structure, which permits cavities of Table : 14.2 Features of the three types of solutions
different sizes.
Property Suspension Colloid True
(4) The open structure is provided by silica in which solution solution
aluminium occupies x/(x+y) fraction of the telrahedral Nature Heterogeneo Heterogeneo Homogeneo
sites. us us us
(5) The negative charge of the aluminosilicate Particle size > 100 nm 1 nm – 100 < 1 nm
framework is neutralized by the replaceable cations. nm
(6) The void space forms more than 50% of the Separation by
total volume, which is occupied by water molecules. (i) Ordinary Possible Not possible Not
filtration Possible Possible possible
(7) The reaction- selectivity of zeolites depends
(ii) Ultra- Not
upon the size of cavities (cages), pores (apertures) and
filtration possible
the distribution of pores in the structure. The pore size
Settling of Settle under Settle only Do not
in zeolites generally varies from 260 pm to 740 pm.
particles gravity on settle
(8) Zeolite have high porosity due to the presence centrifugati
of one, two, or three dimensional networks of on
interconnected channels and cavities of molecular Appearance Opaque Generally Transpare
dimensions. transparent nt
(9) There is a new class of highly siliceous Tyndall effect Shows Shows Does not
zeolites with an optimal pore diameter of 550pm. ZSM- show
5 is one such zeolite having the formula. Diffusion of Does not Diffuses Diffuses
[H x ( AlO2 )x .(SiO2 )96 x ].16 H 2 O particles diffuse slowly rapidly
Brownian May show Shows Negligible
(10) The zeolite catalyst ZSM-5 converts alcohols movement
to gasoline (petrol) by dehydrating the alcohol and
producing a mixture of wide variety of hydrocarbons.
Colloidal state
(1) The foundation of colloidal chemistry was laid
down by an English scientist, Thomas Graham, in 1861.
The credit for the various advances in this field goes to
eminent scientists like Tyndall, Hardy, Zsigmondy, Suspension Colloidal True
Size > 100 nmsolution
Size solution
Size < 1
N.R. Dhar, S.S. Bhatnagar and others.
between nm
(2) Thomas Graham classified the soluble 1-100types
Fig. 14.1 Three nm solutions
substances into two categories depending upon the rate Phases of colloids and Their classification
of diffusion through animal and vegetable membranes (1) Phases of colloids : We know that a colloidal
or parchment paper.
solution is of heterogeneous nature. It consists of two
(i) Crystalloids : They have higher rate of phases which are as follows
diffusion and diffused from parchment paper.
(i) Internal phase or Dispersed phase
Examples : All organic acids, bases and salts and (Discontinuous phase) : It is the component present in
organic compounds such as sugar, urea etc. small proportion and is just like a solute in a solution.
(ii) Colloids (Greek word, kolla, meaning glue-like) For example in the colloidal solution of silver in water
: They have slower rate of diffusion and can not (silver acts as a dispersed phase)
diffused from parchment paper. (ii) External phase or Dispersion medium
Examples : Starch, gelatin, gums, silicic acid and (continuous phase) : It is generally component present
hdemoglobin etc. in excess and is just like a solvent in a solution. For
(3) The above classification was discarded i.e., the example, in the colloidal solution of silver in water.
terms colloid does not apply to a particular class of Water act as a dispersion medium.
 582 Surface Chemistry
(2) Classification of colloids : The colloids are Surface Lower than that of Same as that of the
classified on the basis of the following criteria tension the medium medium
Viscosity Much higher than Same as that of the
(i) Classification based on the physical state of that of the medium medium
the dispersed phase and dispersion medium : Reversibil Reversible Irreversible
Depending upon the physical state of dispersed phase ity
and dispersion medium whether these are solids, Stability More stable Less stable
Visibility Particles can’t be Particles can be
liquids or gases, eight types of colloidal systems are detected even under detected under
possible. ultramicroscope ultramicroscope.
Table : 14.3 Different types of colloidal systems Migration Particles may Particles migrate either
migrate in either towards cathode or
Disperse Dispersio Colloidal Examples direction or do not anode in an electric
d phase n System migrate in an field because they
Medium electric field carry charge.
Liquid Gas Aerosol of Fogs, clouds, mists, because do not carry
any charge.
liquids fine insecticide
Action of Addition of smaller Coagulation takes place
sprays
electrolyt quantity of
Solid Gas Aerosol of Smoke, volcanic e electrolyte has little
solids dust, haze effect
Gas Liquid Foam or Soap lather. Hydration Extensive hydration No hydration
froth Lemonade froth, takes place
foam, whipped Examples Gum, gelatin, Metals like Ag and Au,
cream, soda water starch, proteins, hydroxides like
rubber etc. Al(OH )3 , Fe(OH ) 3 metal
Liquid Liquid Emulsions Milk, emulsified
oils, medicines sulphides like AS 2 S 3
Solid Liquid Sols Most paints, starch etc.
in water, proteins, (iii) Classification based on types of particle of
gold sol, arsenic
dispersed phase : Depending upon the type of the
sulphide sol, ink
particles of the dispersed phase, the colloids are
Gas Solid Solid foam Pumice stone,
classified as follows.
styrene rubber,
foam rubber (a) Multimolecular colloids
Liquid Solid Gels Cheese, butter, boot  When on dissolution, atoms or smaller
polish, jelly, curd molecules of substances (having diameter less than
Solid Solid Solid sols Ruby glass, some 1nm) aggregate together to form particles of colloidal
(coloured gem stones and dimensions, the particles thus formed are called
glass) alloys multimolecular colloids.
 In these sols the dispersed phase consists of
(ii) Classification based on Nature of interaction
aggregates of atoms or molecules with molecular size
between dispersed phase and dispersion medium: less than 1 nm.
Depending upon the nature of interactions between  For example, sols of gold atoms and sulphur
dispersed phase and the dispersion medium, the (S 8 ) molecules. In these colloids, the particles are held
colloidal solutions can be classified into two types as together by Vander Waal's forces. They have usually
(a) Lyophilic and (b) Lyophobic sols. lyophilic character.
(a) Lyophilic colloids (water loving) : “The (b) Macromolecular colloids
colloidal solutions in which the particles of the  These are the substances having big size
dispersed phase have a great affinity for the dispersion molecules (called macromolecules) which on
dissolution form size in the colloidal range. Such
medium, are called lyophilic collodis.”
substances are called macromolecular colloids.
(b) Lyophobic colloids (water hateing) : “The  These macromolecules forming the dispersed
colloidal solutions in which there is no affinity between phase are generally polymers having very high
particles of the dispersed phase and the dispersion molecular masses.
medium are called lyophobic colloids.”  Naturally occurring macromolecules are starch,
cellulose, proteins, enzymes, gelatin etc. Artificial
Distinction between lyophilic and lyophobic sols
macromolecules are synthetic polymers such as nylon,
Property Lyophilic sols Lyophobic sols
(suspensoid) (Emulsoid)
polythene, plastics, polystyrene etc.

 They have usually lyophobic character.
(c) Associated colloids
 These are the substances which on dissolved in
a medium behave as normal electrolytes at low
concentration but behave, as colloidal particles at
higher concentration due to the formation of
aggregated particles. The aggregates particles thus
formed are called micelles.
 Their molecules contain both lyophilic and
lyophobic groups.
Micelles
 Micelles are the cluster or aggregated particles
formed by association of colloid in solution.
 The common examples of micelles are soaps
and detergents.
 The formation of micelles takes place above a
particular temperature called Kraft temperature
(Tk ) and above a particular concentration called critical
micellization concentration (CMC).
 They are capable of forming ions.
 Micelles may contain as many as 100 molecules
or more.
 For example sodium stearate (C17 H 35 COONa ) is a
typical example of such type of molecules.
 When sodium stearate is dissolved in water, it
gives Na  and C 17 H 35 COO  ions.
C17 H 35 COONa  C17 H 35 COO   Na 
Sodium stearate Stearate ion
The stearate ions associate to form ionic
micelles of colloidal size.
 It has long hydrocarbon part of C17 H 35 radical.
Which is lyophobic and COO  part which is lyophilic.
 In the figure, the chain corresponds to stearate
ion, (C17 H 35 COO  ) . When the concentration of the
3
solution is below from its CMC (10 mol L ) , it behaves
as normal electrolyte. But above this concentration it is
aggregated to behave as micelles.
– colloidal state by treating the aqueous solution of their
Na+
Na+
– Na+ –
Na+
Na+ – –
Na+
Na+ – –
– Na+
Fig. 14.2 Aggregation of several ions to form ionic
micelle
 The main function of a soap is to reduce oily
and greasy dirt to colloidal particles (an emulsion).
Soap therefore, are known as emulsifying agents.
Surface Chemistry 583
 Some other examples of micelles are sodium
palmitate (C15 H31COONa ) , Sodium lauryl sulphate
[CH 3 (CH 2 )11 SO 3 O  Na  ] , Cetyl trimethyl ammonium
 
bromide CH 3 (CH 2 )15 (CH 2 )3 N Br etc.
General methods of preparation of colloids
Lyophilic and lyophobic colloidal solutions (or
sols) are generally prepared by different types of
methods. Some of the common methods are as follows.
(1) Preparation of Lyophilic colloids
(i) The lyophilic colloids have strong affinity
between particles of dispersed phase and dispersion
medium.
(ii) Simply mixing the dispersed phase and
dispersion medium under ordinary conditions readily
forms these colloidal solutions.
(iii) For example, the substance like gelatin, gum,
starch, egg, albumin etc. pass readily into water to give
colloidal solution.
(iv) They are reversible in nature become these
can be precipitated and directly converted into colloidal
state.
(2) Preparation of Lyophobic colloids :
Lyophobic colloids can be prepared by mainly two types
of methods.
(i) Condensation method : In these method,
smaller particles of dispersed phase are condensed
suitably to be of colloidal size. This is done by the
following methods.
(a) By oxidation : A colloidal solution of sulphur
can be obtained by bubbling oxygen (or any other
oxidising agent like HNO 3 , Br2 etc.) through a solution
of hydrogen sulphide in water.
1
2 H 2 S  O2 (or any other oxidising agent)  2 H 2 O  2 S
(b) By reduction : A number of metals such as
silver, gold and platinum, have been obtained in
salts, with a suitable reducing agent such as
formaldehyde, phenyl hydrazine, hydrogen peroxide,
stannous chloride etc.
2 AuCl3  3 SnCl 2  3 SnCl 4  2 Au
Gold sol
2 AuCl 3  3 HCHO  3 H 2 O  2 Au  3 HCOOH  6 HCl
Gold sol
The gold sol, thus prepared, has a purple colour
and is called purple of cassius.
(c) By hydrolysis : Many salt solutions are rapidly
hydrolysed by boiling dilute solutions of their salts. For
example, ferric hydroxide and aluminium hydroxide
 584 Surface Chemistry
sols are obtained by boiling solutions of the  This method is Metal
corresponding chlorides. used to prepare sols of electrode
platinum, silver, copper s
FeCl3  3 H 2 O  Fe(OH )3  3 HCl Arc
Colloidal sol or gold.
 The metal whose ice
Similarly silicic acid sol is obtained by the Water
hydrolysis of sodium silicate. sol is to be prepared is
made as two electrodes
(d) By double decomposition : A sol of arsenic which immerged in Fig. 14.4 Bredig's arc
sulphide is obtained by passing hydrogen sulphide dispersion medium such method
through a cold solution of arsenious oxide in water. as water etc.
As 2 O 3  3 H 2 S  As 2 S 3  3 H 2 O  The dispersion medium is kept cooled by ice.
 An electric arc is struck between the electrodes.
(e) By excessive cooling : A colloidal solution of
ice in an organic solvent like ether or chloroform can  The tremendous heat generate by this method
be prepared by freezing a solution of water in the and give colloidal solution.
solvent. The molecules of water which can no longer be  The colloidal solution prepared is stabilised by
held in solution, separately combine to form particles adding a small amount of KOH to it.
of colloidal size. (c) By peptisation
(f) By exchange of solvent : Colloidal solution of  The process of converting a freshly prepared
certain substances such as sulphur, phosphorus, which precipitate into colloidal form by the addition of
are soluble in alcohol but insoluble in water can be suitable electrolyte is called peptisation.
prepared by pouring their alcoholic solution in excess  The electrolyte is used for this purpose is called
of water. For example, alcoholic solution of sulphur on peptizing agent or stabilizing agent.
pouring into water gives milky colloidal solution of  Cause of peptisation is the adsorption of the
sulphur. ions of the electrolyte by the particles of the
(g) By change of physical state : Sols of substances precipitate.
like mercury and sulphur are prepared by passing their  Important peptizing agents are sugar, gum,
vapour’s through a cold water containing a suitable gelatin and electrolytes.
stabilizer such as ammonium salt or citrate.  Freshly prepared ferric hydroxide can be
(ii) Dispersion methods : In these methods, converted into colloidal state by shaking it with water
larger particles of a substance (suspensions) are containing Fe 3  or OH  ions, viz. FeCl3 or
broken into smaller particles. The following methods NH4 OH respectively.
are employed.
Fe(OH )3  FeCl3  [Fe(OH )3 Fe]3   3 Cl 
(a) Mechanical dispersion Precipitat e electrolyte Colloidal sol

 In this method, Suspension +

+
+ +
+
+ +
+
+
the substance is first Driving Belt
Fe(OH) + Fe3+ + + + + + +
ground to coarse
3 + + + + + +
particles. Discharge Discharge From + + +
Precipitate electrolyte Colloidal particles
 It is then
of Fe(OH)3 FeCl of Fe(OH)3
3
mixed with the
Metal disc Fig. 14.5 Preparation of colloidal sol by
dispersion medium to Fig. 14.3 Colloidal mill peptisation
get a suspension.  A stable sol of stannic oxide is obtained by
 The suspension is then grinded in colloidal mill. adding a small amount of dilute HCl to stannic oxide
 It consists of two metallic discs nearly touching precipitates.
each other and rotating in opposite directions at a very  Similarly, a colloidal solution of Al(OH )3 and
high speed about 7000 revolution per minute. AgCl are obtained by treating the corresponding
 The space between the discs of the mill is so freshly prepared precipitate with very dilute solution
adjusted that coarse suspension is subjected to great of HCl and AgNO3 or KCl respectively.
shearing force giving rise to particles of colloidal size.
Purification of colloidal solution
 Colloidal solutions of black ink, paints,
varnishes, dyes etc. are obtained by this method. The following methods are commonly used for
(b) By electrical dispersion or Bredig’s arc method the purification of colloidal solutions.

(1) Dialysis
(i) The process of separating the particles of
colloid from those of crystalloid, by means of diffusion
through a suitable membrane is called dialysis.
(ii) It’s principle is based upon the fact that
colloidal particles can not pass through a parchment or
cellophane membrane while the ions of the electrolyte
can pass through it.
(iii) The impurities slowly diffused out of the bag
leaving behind pure colloidal solution
(iv) The distilled water is changed frequently to
avoid accumulation of the crystalloids otherwise they
may start diffusing back into the bag.
(v) Dialysis can be used for removing HCl from
the ferric hydroxide sol.
(2) Electrodialysis
(i) The ordinary process of dialysis is slow.
(ii) To increase the process of purification, the
dialysis is carried out by applying electric field. This
process is called electrodialysis.
(iii) The important application of electrodialysis
process in the artificial kidney machine used for the
purification of blood of the patients whose kidneys
have failed to work. The artificial kidney machine
works on the principle of dialysis.
(3) Ultra – filtration
(i) Sol particles directly pass through ordinary
filter paper because their pores are larger (more than
1  or 1000 m  ) than the size of sol particles (less than
200 m  ).
(ii) If the pores of the ordinary filter paper are
made smaller by soaking the filter paper in a solution
of gelatin of colloidion and subsequently hardened by
soaking in formaldehyde, the treated filter paper may
retain colloidal particles and allow the true solution
particles to escape. Such filter paper is known as ultra
- filter and the process of separating colloids by using
ultra – filters is known as ultra – filtration.
(4) Ultra – centrifugation
(i) The sol particles are prevented from setting
out under the action of gravity by kinetic impacts of the
molecules of the medium.
(ii) The setting force can be enhanced by using
high speed centrifugal machines having 15,000 or more
revolutions per minute. Such machines are known as
ultra–centrifuges.
Properties of colloidal solutions
The main characteristic properties of colloidal
solutions are as follows.
Surface Chemistry 585
(1) Physical properties
(i) Heterogeneous nature : Colloidal sols are
heterogeneous in nature. They consists of two phases;
the dispersed phase and the dispersion medium.
(ii) Stable nature : The colloidal solutions are
quite stable. Their particles are in a state of motion and
do not settle down at the bottom of the container.
(iii) Filterability : Colloidal particles are
readily passed through the ordinary filter papers.
However they can be retained by special filters
known as ultrafilters (parchment paper).
(2) Colligative properties
(i) Due to formation of associated molecules,
observed values of colligative properties like relative
decrease in vapour pressure, elevation in boiling point,
depression in freezing point, osmotic pressure are
smaller than expected.
(ii) For a given colloidal sol the number of
particles will be very small as compared to the true
solution.
(3) Mechanical properties
(i) Brownian movement
(a) Robert Brown, a botanist discovered in 1827
that the pollen grains suspended in water do not
remain at rest but move about continuously and
randomly in all directions.
(b) Later on, it was observed that the colloidal
particles are moving at random in a zig – zag motion.
This type of motion is called Brownian movement.
(c) The molecules of the dispersion medium are
constantly colloiding with the particles of the dispersed
phase. It was stated by Wiener in 1863 that the impacts
of the dispersion medium particles are unequal, thus causing
a zig-zag motion of the dispersed phase particles.
(d) The Brownian movement explains the force of
gravity acting on colloidal particles. This helps in
providing stability to colloidal sols by not allowing
them to settle down.
(ii) Diffusion : The sol particles diffuse from
higher concentration to lower concentration region.
However, due to bigger size, they diffuse at a lesser
speed.
(iii) Sedimentation : The colloidal particles settle
down under the influence of gravity at a very slow rate.
This phenomenon is used for determining the molecular
mass of the macromolecules.
(4) Optical properties : Tyandall effect
(i) When light passes through a sol, its path
becomes visible because of scattering of light by particles.
 586 Surface Chemistry
It is called Tyndall effect. This phenomenon was studied
for the first time by Tyndall. The illuminated path of the
beam is called Tyndall cone.
(ii) The intensity of the scattered light depends on
the difference between the refractive indices of the
dispersed phase and the dispersion medium.
(iii) In lyophobic colloids, the difference is
appreciable and, therefore, the Tyndall effect is well -
defined. But in lyophilic sols, the difference is very
small and the Tyndall effect is very weak.
(iv) The Tyndall effect confirms the
heterogeneous nature of the colloidal solution.
(v) The Tyndall effect has also been observed by
an instrument called ultra – microscope.
Some example of Tyndall effect are as follows
(a) Tail of comets is seen as a Tyndall cone due to
the scattering of light by the tiny solid particles left by the
comet in its path.
(b) Due to scattering the sky looks blue.
(c) The blue colour of water in the sea is due to
scattering of blue light by water molecules.
(d) Visibility of projector path and circus light.
(e) Visibility of sharp ray of sunlight passing
through a slit in dark room.
(5) Electrical properties
(i) Electrophoresis
(a) The phenomenon of movement of colloidal
particles under an applied electric field is called
electrophoresis.
(b) If the particles accumulate near the negative
electrode, the charge on the particles is positive.
(c) On the other hand, if the sol particles
accumulate near the positive electrode, the charge on
the particles is negative.
(d) The apparatus consists of a U-tube with two
Pt-electrodes in each limb.
(e) When electrophoresis of a sol is carried out
with out stirring, the bottom layer gradually becomes
more concentrated while the top layer which contain
pure and concentrated colloidal solution may be
decanted. This is called electro decanation and is used
for the purification as well as for concentrating the sol.
(f) The reverse of electrophoresis is called
Sedimentation potential or Dorn effect. The
sedimentation potential is setup when a particle is
forced to move in a resting liquid. This phenomenon
was discovered by Dorn and is also called Dorn effect.
(ii) Electrical double layer theory
(a) The electrical properties of colloids can also
be explained by electrical double layer theory.
According to this theory a double layer of ions appear
at the surface of solid.
(b) The ion preferentially adsorbed is held in
fixed part and imparts charge to colloidal particles.
(c) The second part consists of a diffuse mobile
layer of ions. This second layer consists of both the type
of charges. The net charge on the second layer is exactly
equal to that on the fixed part.
(d) The existence of opposite sign on fixed and
diffuse parts of double layer leads to appearance of a
difference of potential, known as zeta potential or
electrokinetic potential. Now when electric field is
employed the particles move (electrophoresis)
(iii) Electro-osmosis
(a) In it the movement of the dispersed particles
are prevented from moving by semipermeable
membrane.
(b) Electro-osmosis is a phenomenon in which
dispersion medium is allowed to move under the
influence of an electrical field, whereas colloidal
particles are not allowed to move.
(c) The existence of electro-osmosis has suggested
that when liquid forced through a porous material or a
capillary tube, a potential difference is setup between
the two sides called as streaming potential. So the
reverse of electro-osmosis is called streaming
potential.
Origin of the charge on colloidal particles
The origin of the charge on the sol particles in
most cases is due to the preferential adsorption of
either positive or negative ions on their surface. The
sol particles acquire electrical charge in any one or
more of the following ways.
(1) Due to the dissociation of the surface
molecules : Some colloidal particles develope electrical
charge due to the dissociation / ionisation of the
surface molecules. The charge on the colloidal particles
is balanced by the oppositely charged ions in the sol.
For example, an aqueous solution of soap (sodium
palmitate) which dissociates into ions as,
C15 H 31 COONa  C15 H 31 COO   Na 
Sodium palmitate
The cations (Na+) pass into the solution while the
anions (C15 H 31 COO  ) have a tendency to form aggregates
due to weak attractive forces present in the
hydrocarbon chains.
(2) Due to frictional electrification
(i) It is believed that the frictional electrification
due to the rubbing of the dispersed phase particles with
 Surface Chemistry 587
that of dispersion medium results in some charge on Stability of sols
the colloidal particles.
Sols are thermodynamically unstable and the
(ii) The dispersion medium must also get some dispersed phase (colloidal particles) tend to separate
charge, because of the friction. Since it does not carry out on long standing due to the Vander Waal's
any charge, the theory does not seem to be correct. attractive forces. However sols tend to exhibit some
(3) Due to selective adsorption of ions stability due to
(i) The particles constituting the dispersed phase (1) Stronger repulsive forces between the
adsorb only those ions preferentially which are similarly charged particles
common with their own lattice ions. (2) Particle-solvent interactions : Due to strong
(ii) For example, when a small quantity of silver particle-solvent (dispersion medium) interactions, the
nitrate ( AgNO3 ) solution is added to a large quantity of colloidal particles get strongly solvated.
potassium iodide (KI ) solution, the colloidal particles of Coagulation or Flocculation or Precipitation
silver iodide adsorb I  from the solution to become
“The phenomenon of the precipitation of a colloidal
negatively charged, (at this stage KI is in excess, and
solution by the addition of the excess of an electrolyte is
I  being common to AgI ) called coagulation or flocculation.”
AgI  I  ( AgI)I  The coagulation of the lyophobic sols can be
(Colloidal (in excess (Colloidal particle
particle ) in the becomes positivel y carried out by following methods.
medium) charged)
(1) By electrophoresis : In electrophoresis the
But, when a small quantity of potassium iodide colloidal particles move towards oppositely charged
(KI ) solution is added to a large quantity of silver electrode. When these come in contact with the
nitrate solution ( AgNO3 ) ; the colloidal silver iodide electrode for long these are discharged and
precipitated.
particles adsorb Ag  from the solution to become
(2) By mixing two oppositely charged sols :
positively charged, (at this stage AgNO3 is in excess
When oppositely charged sols are mixed in almost
and Ag  is common to AgI ), equal proportions, their charges are neutralised. Both
AgI  Ag   ( AgI) Ag  sols may be partially or completely precipitated as the
(Colloidal (in excess in (Colloidal particle mixing of ferric hydroxide (+ve sol) and arsenious
particle ) the medium) becomes positivel y
charged) sulphide (–ve sol) bring them in precipitated form. This
Ag+
I– type of coagulation is called mutual coagulation or
– +
Ag+ – – Ag I–
+
+
+
I– meteral coagulation.
– AgI – + AgI +
– (3) By boiling : When a sol is boiled, the adsorbed
– + +
Ag+ – – Ag+ I– + + I– layer is disturbed due to increased collisions with the
Ag+ I– molecules of dispersion medium. This reduces the
+ I– ions remain in dispersion
Ag ions remain in dispersed charge on the particles and ultimately they settle down
medium (Agl, I– Sol) medium (Agl, Ag+ Sol)
to form a precipitate.
Fig. 14.6
(4) By persistent dialysis : On prolonged
(iii) Depending upon the nature of charge on the dialysis, the traces of the electrolyte present in the sol
particles of the dispersed phase, the colloidal solutions are removed almost completely and the colloids become
are classified into positively charged and negatively unstable.
charged colloids. Some typical examples are as follows (5) By addition of electrolytes : The particles of
(a) Negatively charged (b) Positively charged the dispersed phase i.e., colloids bear some charge.
colloids colloids When an electrolyte is added to sol, the colloidal
 Metal sulphides :  Metal hydroxides : particles take up ions carrying opposite charge from
As 2 S 3 , CdS Al(OH )3 , Fe(OH )3 the electrolyte. As a result, their charge gets
 Metal dispersions :  Metal oxide : TiO 2 neutralised and this causes the uncharged, particles to
Ag, Au, Pt come closer and to get coagulated or precipitated. For
 Basic dyes : Methylene
example, if BaCl2 solution is added to As 2 S 3 sol the
 Acid dyes : Eosin, congo blue
red  Haemoglobin Ba 2  ions are attracted by the negatively charged sol
 Sols of starch, gums, particles and their charge gets neutralised. This lead to
 Sulphur sol
gold, coagulation.
gelatin etc. (6) Hardy schulze rule : The coagulation capacity
of different electrolytes is different. It depends upon
 588 Surface Chemistry
the valency of the active ion are called flocculating ion,
which is the ion carrying charge opposite to the charge
on the colloidal particles. “According to Hardy Schulze
rule, greater the valency of the active ion or flocculating
ion, greater will be its coagulating power” thus, Hardy
Schulze law state:
(i) The ions carrying the charge opposite to that of
sol particles are effective in causing coagulation of the
sol.
(ii) Coagulating power of an electrolyte is directly
proportional to the valency of the active ions (ions
causing coagulation).
For example to coagulate negative sol of As 2 S 3 ,
the coagulation power of different cations has been
found to decrease in the order as, Al 3   Mg 2   Na
Similarly, to coagulate a positive sol such as
Fe(OH )3 , the coagulating power of different anions has
been found to decrease in the
[Fe (CN )6 ]4   PO 43   SO 42   Cl 
(7) Coagulation or flocculation value
“The minimum concentration of an electrolyte
which is required to cause the coagulation or
flocculation of a sol is known as flocculation value.”
Thus, lyophilic colloids can prevent the coagulation of
any lyophobic sol.
“The phenomenon of preventing the coagulation of
a lyophobic sol due to the addition of some lyophilic
colloid is called sol protection or protection of colloids.”
 The protecting power of different protective
(lyophilic) colloids is different. The efficiency of any
protective colloid is expressed in terms of gold
number.
Gold number : Zsigmondy introduced a term
called gold number to describe the protective power of
different colloids. This is defined as, “weight of the
dried protective agent in milligrams, which when added
to 10 ml of a standard gold sol (0.0053 to 0.0058%) is
just sufficient to prevent a colour change from red to
blue on the addition of 1 ml of 10 % sodium chloride
solution, is equal to the gold number of that protective
colloid.”
order : Thus, smaller is the gold number, higher is the
protective action of the protective agent.
1
Protective power 
Gold number
Table : 14.4 Gold numbers of some hydrophilic
substances

or Hydrophili Gold Hydrophilic Gold

c number substance number
“The number of millimoles of an electrolyte substance
required to bring about the coagulation of one litre of a Gelatin 0.005 - Sodium oleate 0.4 – 1.0
colloidal solution is called its flocculation value.” 0.01
Coagulation value or flocculating value Sodium 0.01 Gum tragacanth 2
1 caseinate

Coagulatin g power Hamoglobi 0.03 – 0.07 Potato starch 25
n
(8) Coagulation of lyophilic sols
Gum arabic 0.15 – 0.25
(i) There are two factors which are responsible
for the stability of lyophilic sols. Congo rubin number : Ostwald introduced congo
(ii) These factors are the charge and solvation of rubin number to account for protective nature of
the colloidal particles. colloids. It is defined as “the amount of protective
colloid in milligrams which prevents colour change in
(iii) When these two factors are removed, a
100 ml of 0.01 % congo rubin dye to which 0.16 g
lyophilic sol can be coagulated.
equivalent of KCl is added.”
(iv) This is done (i) by adding electrolyte (ii) and
Mechanism of sol protection
by adding suitable solvent.
(v) When solvent such as alcohol and acetone are (i) The actual
added to hydrophilic sols the dehydration of dispersed mechanism of sol Lyophilic
protectin
phase occurs. Under this condition a small quantity of protection is very
Lyophobi g
electrolyte can bring about coagulation. complex. However it may c particles
Protection of colloids and Gold number be due to the adsorption particles
 Lyophilic sols are more stable than of the protective colloid
on the lyophobic sol Fig. 14.7 Protection of
lyophobic sols. colloids
particles, followed by its solvation. Thus it stabilises
 Lyophobic sols can be easily coagulated by
the sol via solvation effects.
the addition of small quantity of an electrolyte.
 When a lyophilic sol is added to any lyophobic (ii) Solvation effects contribute much towards the
sol, it becomes less sensitive towards electrolytes. stability of lyophilic systems. For example, gelatin has
a sufficiently strong affinity for water. It is only

because of the solvation effects that even the addition
of electrolytes in small amounts does not cause any
flocculation of hydrophilic sols. However at higher
concentration, precipitation occurs. This phenomenon
is called salting out.
(iii) The salting out efficiency of an electrolyte
depends upon the tendency of its constituents ions to get
hydrated i.e, the tendency to squeeze out water initially
fied up with the colloidal particle.
(iv) The cations and the anions can be arranged in
the decreasing order of the salting out power, such an
arrangement is called lyotropic series.
Cations
2
: Mg  Ca 2   Sr 2   Ba 2   Li   Na   K 
 (iv) Emulsions can be converted into two separate
 NH 4  Rb   Cs 
Anions : Citrate 3   SO 4 2   Cl   NH 3   I   CNS
Ammonium sulphate, due to its very high
solubility in water, is oftenly used for precipitating
proteins from aqueous solutions.
(v) The precipitation of lyophilic colloids can also
be affected by the addition of organic solvents of non-
electrolytes. For example, the addition of acetone or
alcohol to aqueous gelatin solution causes precipitation
of gelatin. Addition of petroleum ether to a solution of
rubber in benzene causes the precipitation of rubber.
Emulsion
“The colloidal systems in which fine droplets of one
liquid are dispersed in another liquid are called
emulsions the two liquids otherwise being mutually
immiscible.” or
“Emulsion are the colloidal solutions in which both
the dispersed phase and the dispersion medium are
liquids.”
A good example of an emulsion is milk in which
fat globules are dispersed in water. The size of the
emulsified globules is generally of the order of 10 6 m.
Emulsion resemble lyophobic sols in some properties.
(1) Types of Emulsion : Depending upon the
nature of the dispersed phase, the emulsions are
classified as;
(i) Oil-in-water emulsions (O/W) : The emulsion
in which oil is present as the dispersed phase and
water as the dispersion medium (continuous phase) is
called an oil-in-water emulsion. Milk is an example of
the oil-in-water type of emulsion. In milk liquid fat
globules are dispersed in water. Other examples are,
vanishing cream etc.
(ii) Water-in-oil emulsion (W/O) : The emulsion
in which water forms the dispersed phase, and the oil
acts as the dispersion medium is called a water-in-oil
emulsion. These emulsion are also termed oil
Surface Chemistry 589
emulsions. Butter and cold cream are typical examples
of this types of emulsions. Other examples are cod liver
oil etc.
(2) Properties of emulsion
(i) Emulsions show all the characteristic
properties of colloidal solution such as Brownian
movement, Tyndall effect, electrophoresis etc.
(ii) These are coagulated by the addition of
electrolytes containing polyvalent metal ions indicating
the negative charge on the globules.
(iii) The size of the dispersed particles in
emulsions in larger than those in the sols. It ranges
from 1000 Å to 10,000 Å. However, the size is smaller
than the particles in suspensioins.
liquids by heating, centrifuging, freezing etc. This

process is also known as demulsification.
(3) Applications of emulsions
(i) Concentration of ores in metallurgy
(ii) In medicine (Emulsion water-in-oil type)
(iii) Cleansing action of soaps.
(iv) Milk, which is an important constituent of
our diet an emulsion of fat in water.
(v) Digestion of fats in intestine is through
emulsification.
Gels
(1) “A gel is a colloidal system in which a liquid is
dispersed in a solid.”
(2) The lyophilic sols may be coagulated to give a
semisolid jelly like mass, which encloses all the liquid
present in the sol. The process of gel formation is
called gelation and the colloidal system formed called
gel.
(3) Some gels are known to liquify on shaking and
reset on being allowed to stand. This reversible sol-gel
transformation is called thixotropy.
(4) The common examples of gel are gum arabic,
gelatin, processed cheese, silicic acid, ferric hydroxide
etc.
(5) Gels may shrink by loosing some liquid help
them. This is known as synereises or weeping.
(6) Gels may be classified into two types
(i) Elastic gels : These are the gels which possess
the property of elasticity. They readily change their
shape on applying force and return to original shape
when the applied force is removed. Common examples
are gelatin, agar-agar, starch etc.
(ii) Non-elastic gels : These are the gels which
are rigid and do not have the property of elasticity. For
example, silica gel.
 590 Surface Chemistry
Application of colloids
(1) Purification of water by alum (coagulation) :
Alum which yield Al 3  ions, is added to water to
coagulate the negatively charged clay particles.
 Chemisorption and physisorption both are
(2) In rubber and tanning industry (coagulation
exothermic.
and mutual coagulation) : Several industrial processes
such as rubber plating, chrome tanning, dyeing,  Charcoal adsorbs many gases. It even adsorbs
lubrication etc are of colloidal nature polluting gases present in air in small
(i) In rubber platting, the negatively charged concentration.
particles of rubber (latex) are made to deposit on the
 The langmuir adsorption isotherm is restricted to
wires or handle of various tools by means of
the formation of unimolecular layer of gas
electrophoresis. The article on which rubber is to be
molecules on the surface of solids. However, it
deposited is made anode.
was suggested that there is possibility of
(ii) In tanning the positively charged colloidal
particles of hides and leather are coagulated by multimolecular layer of gas molecules on the
impregnating, them in negatively charged tanning surface of the solids rather than single layer on
materials (present in the barks of trees). Among the this basis Brunauer, Emmett and Teller proposed
tanning agent chromium salts are most commonly used a new theory known as B.E.T. theory.
for the coagulation of the hide material and the process  All Bronsted acids and bases act as acid base
is called chrome tanning.
catalysts.
(3) Artificial rains : It is possible to cause
artificial rain by throwing the electrified sand or silver  The principle of electrophoresis is employed for
iodide from an aeroplane and thus coagulating the mist the separation of proteins from nucleic acids
hanging in air. removing sludge from sewage waste etc.
(4) Smoke precipitation (Coagulation) : Smoke is  Hydrophilic sols show greater stability than
a negative sol consisting of carbon particles dispersed hydrophobic sols.
in air. Thus, these particles are removed by passing
 Colloidal solution of graphite is called aquadug.
through a chamber provided with highly positively
charged metallic knob.  The phase in which the emulsifier is more soluble
becomes outer phase of the emulsion that is
(5) Formation of deltas (coagulation) : River
water consists of negatively charged clay particles of called Ben croft rule.
colloidal dimension. When the river falls into the sea,
the clay particles are coagulated by the positive
Na  , K  , Mg 2  ions etc. present in sea water and new
lands called deltas are formed.
(6) Clot formation : Blood consists of negatively
charged colloidal particles (albuminoid substance). The
colloidal nature of blood explains why bleeding stops
by applying a ferric chloride solution to the wound.
Actually ferric chloride solution causes coagulation of
blood to form a clot which stops further bleeding.
(7) Colloidal medicine : Argyrol and protargyrol
are colloidal solution of silver and are used as eye
lotions colloidal sulphur is used as disinfectant
colloidal gold, calcium and iron are used as tonics.
(8) Coating of Photographic plates : These are
thin glass plates coated with gelatin containing a fine
suspension of silver bromide. The particles of silver
bromide are colloidal in nature.
 588 Surface Chemistry
(c) Decreased covalent and hydrogen bond forces
(d) Increased attraction between molecules
7. A solid acts as an adsorbent because it has
(a) A definite shape
(b) Small pores in it
(c) Unsaturated valencies
Adsorption and Adsorption isotherm (d) A high lattice energy
8. Point out the wrong statement :
1. Chemisorption Physical adsorption is characterised by
(a) Involves the weak attractive interactions (a) Attraction due to weak Vander Waal's forces
between adsorbent and adsorbate (b) Irreversible nature of adsorption
(b) Is irreversible in nature (c) Multimolecular adsorption layers
(c) Decreases with increase of temperature (d) Decrease in adsorption with increase in
temperature
(d) Involves multilayer formation of adsorbent on
adsorbate 9. When the temperature is lowered and pressure is
raised, the adsorption of a gas on a solid[MP PMT 1997]
2. Chemisorption
(a) Decreases
(a) Increases with temperature
(b) Increases
(b) Decreases with temperature
(c) Remains unaffected
(c) Remains unaffected by change of temperature (d) Decreases first then increases
(d) Either increases or decreases with 10. In physical adsorption, the gas molecules are held
temperature on solid surface by [MP PET 1996; AIIMS 1998]
3. Which among the following statement is false (a) Chemical forces (b) Electrostatic forces
[KCET (Med.) 2002] (c) Gravitational forces (d) Vander Waal's forces
(a) The adsorption may be monolayered or 11. Adsorption is multilayer in the case of[MP PET 1999]
multilayered (a) Physical adsorption (b) Chemisorption
(b) Particle size of adsorbent will not affect the (c) Both (d) None of both
amount of adsorption
12. Physical adsorption
(c) Increase of pressure increases amount of (a) Involves the weak attractive interaction
adsorption between the adsorbent and adsorbate
(d) Increase of temperature may decrease the (b) Involves the chemical interactions between
amount of adsorption the adsorbent and adsorbate
4. Wood charcoal is used to decolourise sugar (c) Is irreversible in nature
because it (d) Increases with increase of temperature
[CPMT 2002] 13. The charge on As2 S 3 sol is due to the adsorbed
(a) Adsorbs coloured material
[MP PMT 1985]
(b) Absorbs decolorised material
(a) H  (b) OH 
(c) Reduces coloured material
(c) O 2  (d) S 2 
(d) None of these
14. In the adsorption of acetic acid on activated
5. If the absorbate is held on a surface by weak charcoal, the acetic acid is an[MP PET 1994; MP PMT 2002]
Vander Waal's forces, the absorption process is (a) Adsorber (b) Absorber
called
(c) Adsorbent (d) Adsorbate
[Kerala (Med.) 2002]
15. Sticking of one substance at the surface of
(a) Physical adsorption (b) Chemical adsorption another is called
(c) Heat of adsorption (d) Enthalpy of (a) Absorption (b) Chemisorption
adsorption
(c) Adsorption (d) Desorption
6. When the temperature is raised, the viscosity of
16. The charge on colloidal particles is due to
liquid decreases, this is because[Kerala (Med.) 2002]
(a) Presence of electrolyte
(a) Decreased volume of the solution
(b) Very small size of particles
(b) Increase in temperature increases the average
(c) Adsorption of ions from the solution
kinetic energy of molecules, which overcome
the attractive force between them (d) None of these
 Surface Chemistry 589
17. Which one of the following statement is not 26. The adsorption of a gas on a solid surface varies
correct with pressure of the gas in which of the following
(a) The extent of adsorption depends on the manner
nature of the adsorbent and adsorbate [CPMT 1999]
(b) The extent of adsorption depends on the (a) Fast  slow  independent of the pressure
pressure of the gas (b) Slow  fast  independent of the pressure
(c) The extent of adsorption depends on the (c) Independent of the pressure  fast  slow
temperature (d) Independent of the pressure  slow  fast
(d) The extent of adsorption has no upper limit 27.
Which of the following statements is not
18. For the adsorption of a gas on a solid, the plot of applicable to chemisorption [KCET (Med.) 1999; BHU 2000]
log (x/m) versus log P is linear with slope equal to (a) It is slow
[CBSE PMT 1994]
(b) It is irreversible
(a) k (b) log k
(c) It is highly specific
(c) n (d) 1/n
(d) It is independent of temperature
19. According to Langmuir adsorption isotherm, the
28. Adsorption is always [DPMT 2000]
amount of gas adsorbed at very high pressures[MP PMT 1993]
(a) Reaches a constant limiting value (a) Endothermic (b) Exothermic
(b) Goes on increasing with pressure (c) Either (a) or (b) (d) None of these
(c) Goes on decreasing with pressure 29. The colloidal system consisting of a liquid
(d) Increases first and decreases later with adsorbent in a solid adsorbate is termed as
pressure (a) Aerosol (b) Sol
20. Which of the following statement is not correct (c) Foam (d) Gel
[MP PET 1993] 30. Which one of the following substances adsorb
(a) Physical adsorption is due to Vander Wall's hydrogen gas most strongly
forces (a) Activated carbon (b) Silica gel
(b) Chemical adsorption decreases at high (c) Platinum black (d) Iron powder
temperature and low pressure 31. According to the adsorption theory of catalysis,
(c) Physical adsorption is reversible the speed of the reaction increases because [CBSE PMT 200
(d) Adsorption energy for a chemical adsorption (a) Adsorption lowers the activation energy of the
is generally greater than that of physical reaction
adsorption (b) The concentration of reactant molecules at the
21. In adsorption of oxalic acid on activated charcoal, active centres of the catalyst becomes high
the activated charcoal is known as due to adsorption
(a) Adsorbent (b) Absorbate (c) In the process of adsorption, the activation
(c) Adsorber (d) Absorber energy of the molecules becomes large
22. Adsorption is phenomenon is which a substance (d) Adsorption produces heat which increases the
(a) Goes into the body of the other substance speed of the reaction
32. In Freundlich adsorption, isotherm adsorption is
(b) Remains close the other substance
proportional to pressure P as
(c) Accumulates on the surface of the other
substance (a) P 0 (b) P
(d) None of these (c) P n (d) P 1 / n
23. Physical adsorption is essentially quite 33. Which one of the following characteristics is not
appreciable correct for physical adsorption
(a) At room temperature (b)At higher temperature (a) Adsorption on solids is reversible
(c) At lower temperature (d) None of these (b) Adsorption increases with increase in
temperature
24. Adsorption increase when
(c) Adsorption is spontaneous
(a) Temperature increases
(d) Both enthalpy and entropy of adsorption are
(b) Temperature decreases
negative
(c) Temperature remains constant
34. Which of the following is not a characteristic of
(d) None of these chemisorption [KCET 2003]
25. In chemical adsorption, how many layers are (a) H is of the order of 400 kJ
adsorbed (b) Adsorption is irreversible
[MP PMT 1996]
(c) Adsorption may be multimolecular layer
(a) One (b) Two (d) Adsorption is specific
(c) Multi (d) Zero 35. The viscosity of the solvent depends on
 590 Surface Chemistry
[Kerala (Med.) 2002] x
(a)  k p1 / n (b) x  mkp 1 / n
(a) Isothermic nature m
(b) Solute - solute interaction
(c) x / m  kpn (d) All of these
(c) Solute - solvent interaction
46. The extent of adsorption of a gas on a solid
(d) Density of the liquid
depends on
36. Which of the following kinds of catalysis can be
[KCET 2005]
explained by the adsorption theory ?[MP PET/PMT 1998]
(a) Nature of the gas (b) Pressure of the gas
(a) Homogeneous catalysis (b)Acid base catalysis
(c) Temperature of the gas (d) A
(c) Heterogeneous catalysis (d) Enzyme catalysis
47. Activated charcoal is used to remove colouring
37. Adsorption due to strong chemical forces is called matter from pure substances. It works by [KCET 2005]
[KCET (Med.) 2001]
(a) Oxidation (b) Reduction
(a) Chemisorption (b) Physiosorption
(c) Bleaching (d) Adsorption
(c) Reversible adsorption (d) Both (b) and (c)
38. In neutralisation of KI by AgNO3 positive charge Catalyst and Catalysis
is due to absorption of [AMU 2000]
(a) Ag  ions (b) Ag 1. Mark the correct statement in a reversible
(c) I ions (d) Both (b) and (c) reaction
39. Physical adsorption is inversely proportional to [CPMT 1974; EAMCET 1978, 79; MP PMT 1993]
the (a) The catalyst catalyses the forward reaction
[AFMC 2000] (b) The catalyst catalyses the backward reaction
(a) Volume (b) Concentration (c) The catalyst influences the direct and the
(c) Temperature (d) All of these reverse reaction to the same extent
40. 50 ml of 1 M oxalic acid is shaken with 0.5 gm of (d) The catalyst increases the rate of forward
wood charcoal. The final concentration of the reaction and decreases the rate of backward
solution after adsorption is 0.5 M. Amount of reaction
oxalic acid absorbed per gm of charcoal is 2. A catalyst is used
[MP PET 2004] [CPMT 1989]
(a) 3.45 gm (b) 3.15 gm (a) Only for increasing the velocity of the reaction
(b) For altering the velocity of the reaction
(c) 6.30 gm (d) None
(c) Only for decreasing the velocity of the
41. Noble gases are adsorbed by [DCE 2004]
reaction
(a) Anhydrous calcium chloride
(d) All (a), (b) and (c) are correct
(b) Ferric hydroxide
3. A catalyst is a substance which [NCERT 1981; CPMT 1996]
(c) Conc. H 2SO4
(a) Alters the equilibrium in a reaction
(d) Activated coconut charcol (b) Is always in the same phase as the reactants
42. Animal charcoal is used in decolourising colour of (c) Participates in the reaction and provides
liquids because it is a good [MHCET 2004]pathway for the same
easier
(a) Adsorbate (b) Adsorbent (d) Does not participate in the reaction but speeds
(c) Oxidising agent (d) Reducing agent it up
43. What will be the effect of increase in temperature 4. In Haber's process for the manufacture of
on physical adsorption [Pb. CET 2000] ammonia
(a) It will decrease [AMU 1984; CPMT 1974, 90]
(b) It will increase (a) Finely divided iron is used as catalyst
(c) First increase then decrease (b) Finely divided molybdenum is used as catalyst
(d) None of these (c) Finely divided nickel is used as catalyst
44. 0.2 gm of fine animal charcoal is mixed with half (d) No catalyst is necessary
litre of acetic acid solution and shaken for 30
5. When KClO3 is heated, it decomposes into
minutes
[DPMT 2004] KCl  O2 . If some MnO2 is added, the reaction
(a) Concentration remains same goes much faster because
(b) Concentration increases [CPMT 1971,76,80,94]
(c) Concentration of the solution decrease (a) MnO2 decomposes to give O 2
(d) None of these (b) MnO2 provides heat by reacting
45. The equation for Freundlich adsorption isotherm
(c) Better contact is provided by MnO2
is
[MHCET 2004] (d) MnO2 acts as a catalyst
 Surface Chemistry 591
6. In the reaction 2 SO 2  O2 

Pt
2 SO 3 , As2O3 acts (c) Forward and reverse reaction
As 2 O 3
(d) Neither (a) nor (b)
as a 16. The role of a catalyst in a reversible reaction is to
[MP PET 1995] [KCET (Med.) 2001]
(a) Autocatalyst (b) Poison (a) Increase the rate of forward reaction
(c) Promotor (d) Positive catalyst (b) Decrease the rate of backward reaction
7. Reactions in Zeolite catalysts depend on[BHU 2000] (c) Alter the equilibrium constant of the reaction
(a) Pores (b) Apertures (d) Allow the equilibrium to be achieved quickly
(c) Size of cavities (d) All of these 17. The catalyst used in the contact process for
manufacturing of sulphuric acid is [MP PMT 1987]
8. What is the role of a catalyst in a catalysed
(a) Copper (b) Iron/aluminium
reaction
oxide
[MP PMT 1996; Pb. PMT 2000;UPSEAT 2001,02]
(c) Vanadium pentoxide (d) Platinized asbestos
(a) Lowers the activation energy
18. For the functioning of enzymes which of the
(b) Increases the activation energy following statements is not correct [MP PMT 2000]
(c) Affects the free energy change (a) An optimum temperature is needed
(d) Affects the enthalpy change (b) An optimum pH is needed
9. The catalyst used in the lead chamber process of (c) They are substrate specific
sulphuric acid manufacture is (d) They always increase activation energy
[CPMT 1977] 19. When a catalyst is added to a system the [JIPMER 2000]
(a) Platinum (b) Oxide of nitrogen (a) Value of equilibrium constant is decreased
(c) Nickel (d) Vanadium (b) The rate of forward reaction is increased and
compounds that of backward reaction is decreased
10. In the following reaction the catalyst used is (c) Equilibrium concentrations are unchanged
CH2 – CH2 (d) Equilibrium concentrations are increased
HC = HC
20. A catalyst can affect reversible reaction by[CPMT 2002]
H2C CH2 HC CH+3H2 (a) Changing equilibrium
(b) Slowing forward reaction
CH2 – CH2 HC – HC (c) Attaining equilibrium in both direction
[AMU (Engg.) 1999] (d) None of these
C12 H 22 O11  H 2 O  2   C6 H 12 O6 (aq ) C6 H 12 O6 (aq )
dil . H SO
(a) Al2O3 (b) Cr2O3 21. 4

Sucrose Fructose Glucose

(c) Cr2O3 and Al2O3 (d) Zn dust
In this reaction, dilute H2SO4 is called [AFMC 1997]
11. Enzymes with two sites are called [AIIMS 2002]
(a) Homogeneous catalysis (b)Homogeneous catalyst
(a) Apoenzyme (b) Holoenzyme (c) Heterogeneous catalysis (d)Heterogeneous catalyst
(c) Allosteric enzyme (d) Conjugate enzyme 22. Which one of the following statement is wrong in
12. Which of the following types of metals make the case of enzyme catalysis [MP PMT 1985, 2001]
most efficient catalysts [DPMT 1985] (a) Enzymes work best at an optimum
(a) Alkali metals (b) Transition metals temperature
(c) Alkaline–earth metals (d)Radioactive metals (b) Enzymes work at an optimum pH
13. An example of autocatalytic reaction is[NCERT 1983] (c) Enzymes are highly specific for substances
(a) The decomposition of nitroglycerine (d) An enzyme raises activation energy
(b) Thermal decomposition of KClO3 and MnO2 23. Which of the following catalyses the conversion of
mixture glucose into ethanol
[CPMT 1983, 84; CBSE PMT 1989; KCET 1993]
(c) Break down of 6 C 14
(a) Zymase (b) Invertase
(d) Hydrogenation of vegetable oil using nickel (c) Maltase (d) Diastase
catalysts 24. Which of the following is used as a catalyst in the
14. In the case of auto catalysis [KCET (Med.) 2002]
manufacture of toluene from benzene with CH 3Cl
(a) Solvent catalyses
[CPMT 1985]
(b) Product catalyses
(a) Ni (b) Anhydrous AlCl3
(c) Reactant catalyses
(d) Heat produced in the reaction catalyses (c) Pd (d) Pt
15. In a reversible reaction, a catalyst will affect the 25. Hydrolysis of ethyl acetate is catalysed by
rate of aqueous
[KCET (Med.) 2002] [MP PMT 2002]
(a) Forward reaction (a) Na2 SO 4 (b) K2 SO 4
(b) Reverse reaction (c) H 2SO4 (d) BaSO4
 592 Surface Chemistry
26. Which of the following statements about a
catalyst is true
[AIIMS 1996]
(a) It lowers the energy of activation
(b) The catalyst altered during the reaction is
regenerated
(c) It does not alter the equilibrium
(d) All of these
27. Which of the following statements is true for a
catalyst
(a) It increases the energy of the reactants
(b) It decreases the energy of the products
(c) It decreases the energy of the reactants
(d) It does not change the enthalpy of the
reactants
28. Which is not a characteristic of a catalyst[AFMC 1992]
(a) It changes the equilibrium constant
(b) It alters the reaction path
(c) It increases the rate of reaction
(d) It increases the average K.E. of the molecules
29. Which one of the following statements is correct
in reversible reaction. A catalyst [MP PET 1994; EAMCET 1987]
(a) Increases the rate of forward reaction
(b) Decreases the rate of forward reaction
(c) Increases the rate of backward and forward
reactions
(d) Alters the equilibrium constant of the reaction
30. A catalyst [MNR 1987; UPSEAT 2002]
(a) Increases the free energy change in the
reaction
(b) Decreases the free energy change in the
reaction
(c) Does not increase or decrease the free energy
change in the reaction
(d) Can either increase or decrease the free
energy change depending on what catalyst we
use
31. Which one of the following changes when catalyst
is used in a reaction
(a) Heat of reaction (b) Product of reaction
(c) Equilibrium constant (d) Activation energy
32. In the reversible reaction a catalyst is the
substance which
[CBSE PMT 1992]
(a) Increases the rate of the forward reaction
(b) Decreases the value of enthalpy change in the
reaction
(c) Reduces the time required for reaching the
equilibrium state in the reaction
(d) Decreases the rate of the reverse reaction
33. In the titration between oxalic acid and acidified
potassium permanganate, the manganous salt
formed catalyses the reaction. The manganous
salt is
[KCET 1992]
(a) A promoter (b) A positive catalyst
(c) An autocatalyst (d) None of these
34. Which one of the following statements is
incorrect in the case of heterogeneous catalysis[CPMT 1990
(a) The catalyst lowers the energy of activation
(b) The catalyst actually forms a compound with
the reactant
(c) The surface of the catalyst plays a very
important role
(d) There is no change in the energy of activation
35. Regarding criteria of catalysis which one of the
following statements is not true [CPMT 1990]
(a) The catalyst is unchanged chemically at the
end of the reaction
(b) A small quantity of catalyst is often sufficient
to bring about a considerable amount of
reaction
(c) In a reversible reaction the catalyst alters the
equilibrium position
(d) The catalyst accelerates the reaction
36. Which of the following reaction is catalysed by
enzyme maltase [MP PMT 2003]
(a) Starch  maltose
(b) Maltose  glucose
(c) Lactose  maltose
(d) Maltose  glucose + fructose
37. The efficiency of an enzyme in catalysing a
reaction is due to its capacity
(a) To form a strong enzyme-substrate complex
(b) To decrease the bond energies of substrate
molecule
(c) To change the shape of the substrate molecule
(d) To lower the activation energy of the reaction
38. A catalyst in a chemical reaction [BHU 1998]
(a) Does not initiate a reaction
(b) Increases the activation energy of the reaction
(c) Changes the equilibrium constant of a
reaction
(d) Does not change the rate of the reaction
39. Platinized asbestos is used as a catalyst in the
manufacture of H2SO4 . It is an example of[CPMT 1975]
(a) Heterogeneous catalyst (b) Autocatalyst
(c) Homogenous catalyst (d) Induced catalyst
40. Catalyst used in hydrogenation of oils is
[CPMT 1975; MNR 1986; DPMT 1982, 85;BHU 1973, 87;
EAMCET 1987; AFMC 1993; CET Pune 1998]
(a) Pt (b) Mo
(c) Fe (d) Ni
41. Addition of catalyst in a system [MP PMT 1992]
(a) Increases equilibrium concentrations
(b) No effect on equilibrium concentrations
(c) Decreases equilibrium concentrations
(d) Increases rate of forward reaction and
decreases rate of backward reaction
42. In which of the following processes, platinum is
used as a catalyst [NCERT 1978, 79]
(a) Oxidation of ammonia to form nitric acid
 Surface Chemistry 593
(b) Hardening of oils (a) A catalyst remains unchanged in composition
(c) Production of synthetic rubber and quantity at the end of the reaction
(d) Synthesis of methanol (b) A catalyst can initiate a reaction
43. Enzymes are [CPMT 1974, 81] (c) A catalyst does not alter the equilibrium in a
(a) Micro-organisms (b) Proteins reversible reaction
(c) Inorganic compounds (d) Moulds (d) Catalyst are sometimes very specific in respect
44. Protons accelerate the hydrolysis of esters. This is of reaction
an example of [MP PMT 1987] 53. The enzyme ptylin used for the digestion of food
(a) A heterogeneous catalysis is present in
[CPMT 1981]
(b) An acid-base catalysis
(c) A promoter (a) Saliva (b) Blood
(d) A negative catalyst (c) Intestine (d) Adrenal glands
45. Which of the following processes does not involve 54. Amongst the following chemical reactions, the one
a catalyst representing homogeneous catalysis is[MP PMT 1999]
[KCET 1991; AIIMS 1996] (a) N 2 (g)  3 H 2 (g) 
 2 NH 3 (g)
Fe

(a) Haber's process (b) Thermite process

(b) 2 SO 2 (g)  O2 (g)   2 SO 3 (g)  2 NO (g)
2 NO

(c) Ostwald process (d) Contact process

46. Which of the statement is wrong among the (c) CO (g)  3 H 2 (g) 

Ni
CH 4 (g)  H 2 O
following (d) 2SO 2 (g)  O2 (g)   2SO 3 (g)
V2 O5

[AFMC 1993]
55. Platinised asbestos helps in the formation of SO 3
(a) Haber's process of NH 3 requires iron as
form SO 2 and O 2 . But, if even a small amount of
catalyst
(b) Friedel–Craft's reaction uses anhydrous AlCl3 As2O3 is present the platinised asbestos does not
help in the formation of SO 3 . As2O3 acts here as[MP PMT
(c) Hydrogenation of oils uses iron as catalyst
(d) Oxidation of SO 2 to SO 3 requires V2 O 5 (a) A positive catalyst (b) A negative catalyst
(c) An autocatalyst (d) A poison
47. A catalyst is a substance which
56. Which of the following statements is wrong
(a) Increases the rate of a reaction
(a) Catalysts can aid a rapid reaching of the
(b) Increases the amount of the products formed in equilibrium position, but do not change the
a reaction position of the equilibrium
(c) Decreases the temperature required for the (b) Homogeneous catalysis generally involves an
reaction equilibrium reaction between at least one of
(d) Alters the speed of the reaction remaining the reactants and the catalyst
unchanged chemically at the end of the (c) Heterogeneous catalysis involves
reaction chemisorption on the surface of the catalyst
48. In the Ostwald's process for the manufacture of (d) Positive catalysts raise the energy of
HNO3 , the catalyst used is[AMU 1982, 83; MP PET 1999] activation of the reaction they catalyse
(a) Mo (b) Fe 57. Which one is false in the following statement
(c) Ni (d) Pt [MP PET 1997]
49. A biological catalyst is essentially (a) A catalyst is specific in its action
[NCERT 1978; AFMC 1998] (b) A very small amount of the catalyst alters the
(a) An amino acid (b) A carbohydrate rate of a reaction
(c) The nitrogen molecule (d) An enzyme (c) The number of free valencies on the surface of
the catalyst increases on subdivision
50. A catalyst added to a reaction mixture
(d) Ni is used as catalyst in the manufacture of
(a) Increases the equilibrium constant
ammonia
(b) Decreases the equilibrium constant
58. In the redox reaction
(c) Does not change the equilibrium constant
2 MnO 4  5 C 2 O42   16 H  ⇌ 2 Mn 2   10 CO 2  8 H 2 O
(d) None of these
51. The components of Zigler Natta catalyst, used in The ion acting as autocatalyst is [

the polymerisation of propylene, are (a)
[MP MnO
PMT 2003]
4 (b) C 2 O42 
(a) TiCl3  Al(C2 H5 )3 (b) TiCl4  Al(C2 H5 )3 (c) H 
(d) Mn 2 
(c) Ti(C2 H5 )3  AlCl3 (d) Ti(C2 H5 )4  AlCl3 59. In a homogeneous catalysis
52. Which of the following statements regarding (a) The catalyst and the reactants should be gases
catalyst is not true (b) The catalyst and the reactants should form a
[CPMT 1983, 84; MNR 1993; KCET 1999] single phase
 594 Surface Chemistry
(c) Catalyst and the reactants are all solids (b) Increase or decrease the rate of reaction
(d) The catalyst and the reactions are all liquids (c) Increase or decrease the products
60. Which of the following statements is incorrect (d) Decrease the products
[CPMT 1985]
71. The transition metal used as a catalyst is[Pb. PMT 2004]
(a) Enzymes are in colloidal state
(b) Enzymes are catalysts (a) Nickel (b) Platinum
(c) Enzymes can catalyse any reaction (c) Cobalt (d) All of these
(d) Urease is an enzyme 72. Which of the following is true about catalyst[Pb.CET 2000]
61. Enzymes are [BHU 1982] (a) It initiates reaction
(a) Substances made by chemists to activate
(b) It changes equilibrium point
washing powder
(c) It increase average kinetic energy
(b) Very active vegetable catalysts
(c) Catalysts found in organism (d) It accelerates the rate of reaction
(d) Synthetic catalysts 73. Which of the following types of metals form the
62. Catalyst used in the oxidation of SO 2  SO 3 most efficient catalysts [KCET 2005]

[AIIMS 1996] (a) Alkali metals

(a) Nickel (b) ZnO.Cr2O3 (b) Alkaline earth metals
(c) V2 O 5 (d) Iron (c) Transition metals
(d) All of these
63. Which requires catalyst [AFMC 1987; MP PET 1999]
(a) S  O2  SO 2 (b) 2SO 2  O2  2SO3 74. Formation of ammonia from H2 and N2 by
Haber's process using Fe is an example of [J & K 2005]
(c) C  O2  CO2 (d) All
(a) Heterogeneous catalysis (b)Homogeneous catalysis
64. The process which is catalysed by one of the (c) Enzyme catalysis (d) Non-catalytic
products is called[MP PET 1999; AIIMS 2000; J & K 2005] process
(a) Acid-base catalysis (b) Autocatalysis
(c) Negative catalysis (d) None of these Colloids, Emulsion, Gel and Their properties
65. Adam's catalyst is [Pb.CET 2001]
with application
(a) Platinum (b) Iron 1. Gold number is [MP PET/PMT 1988]
(c) Molybdenum (d) Nickel (a) The number of mg of lyophilic colloid which
66. A catalyst remains unchanged at the end of the should be added to 10 ml of ferric hydroxide
reaction regarding [MP PET 1995] sol so as to prevent its coagulation by the
(a) Mass addition of 1 ml of 10% sodium chloride
solution
(b) Physical state
(b) The number of mg of lyophilic colloid which
(c) Physical state and chemical composition should be added to 10 ml of standard gold sol
(d) Mass and chemical composition so as to prevent its coagulation by the
67. Wilhem Ostwald redefined the action of addition of 1 ml of 10% NaCl
[Kerala (Med.) 2002] (c) The mg of gold salt to be added to a lyophilic
colloid to coagulate it
(a) Anamers
(d) The mg of an electrolyte required to coagulate
(b) Isomers a colloid
(c) Catalyst 2. Which of the following statement is wrong for
(d) Geometry of monomers lyophobic sol
68. In a reversible reaction, a catalyst used (a) Dispersed phase is generally in organic
material
(a) Increases the speed of the forward reaction
(b) Can be easily coagulated by small addition of
(b) Decreases the speed of the backward reaction electrolyte
(c) Does not alter the final state of equilibrium (c) Dispersed phase particles are poorly hydrated
(d) Increases the amount of the products formed and colloid is stabilised due to charge on the
69. Enzyme activity is maximum at [KCET 1989] colloidal particles
(d) Reversible in nature that is after coagulation
(a) 300 K (b) 310 K
can be easily set into colloidal form
(c) 320 K (d) 330 K
3. Which of the following statements is not true for
70. A catalyst is used to [Pb.CET 2000] a lyophobic sol
(a) Increase the product (a) It can be easily solvated
 Surface Chemistry 595
(b) It carries charge 14. Tyndall effect would be observed in a
(c) The coagulation of this sol is irreversible in [CPMT 1973, 79, 90, 91, 94; MP PET 1999;
nature MP PMT 1973, 89; DPMT 1982, 83; AFMC 1999]
(d) It is less stable in a solvent (a) Solution (b) Colloidal solution
4. As2 S 3 sol has a negative charge. Capacity to (c) Precipitate (d) Solvent
15. Ferric hydroxide sol is positively charged colloid.
precipitate it is highest in
[CPMT 1982, 89, 93; DPMT 1983;MP PET 1999] The coagulating power of NO 3 , SO 42  and PO 43 
(a) AlCl3 (b) Na3 PO4 ions would be in the order
(c) CaCl2 (d) K 2 SO 4 (a) NO 3  SO 42   PO 43  (b) SO 42   NO 3  PO 43 

5. Starch dispersed in hot water is an example of (c) PO 43   SO 42   NO 3 (d) NO 3  SO 42   PO 43 

(a) Emulsion (b) Hydrophobic sol 16. A colloidal solution can be purified by
(c) Lyophilic sol (d) Associated colloid [MP PET 1993; CPMT 1990; MP PMT 2001]
6. Which of the following is most effective in (a) Filtration (b) Peptization
(c) Coagulation
coagulating a ferric hydroxide sol[MP PET 1993, 97; MP PMT 2000] (d) Dialysis
(a) KCl (b) KNO3 17. Gold number is associated with
(c) K 2 SO 4 (d) K3 [Fe(CN )6 ] (a) Only lyophobic colloids
(b) Only lyophilic colloids
7. Sky looks blue due to [MNR 1986; MP PET 1992]
(c) Both lyophobic and lyophilic colloids
(a) Dispersion effect (b) Reflection (d) None of these
(c) Transmission (d) Scattering 18. Which of the following forms a colloidal solution
8. Which one is an example of gel in water
(a) Soap (b) Cheese [MP PET 1990; CPMT 1988]
(c) Milk (d) Fog (a) NaCl (b) Glucose
9. The random or zig-zag motion of the colloidal (c) Starch (d) Barium nitrate
particles in the dispersion medium is referred to 19. A negatively charged suspension of clay in water
as will need for precipitation the minimum amount
[CPMT 1985; JIPMER 1997; MP PET 2000] of [CPMT 1973]
(a) Electro-osmosis (a) Aluminium chloride (b) Potassium sulphate
(b) Electrophoresis (c) Sodium hydroxide (d) Hydrochloric acid
20. Difference between colloids and crystalloids is of
(c) Brownian movement
[CPMT 1979]
(d) Tyndall effect (a) Particle composition (b) Particle size
10. Which of the following electrolytes is least (c) Concentration (d) Ionic character
effective in causing flocculation of ferric
21. The purification of the colloidal particles from
hydroxide sol
crystalloid dimensions through semipermeable
[MNR 1991; UPSEAT 1999]
membrane is known as
(a) K4 [Fe(CN )6 ] (b) K2CrO4
[BHU 1979; MP PMT 1999; CBSE 1996; Pb. CET 2002]
(c) KBr (d) K 2 SO 4 (a) Coagulation (b) Dialysis
11. If the dispersed phase is a liquid and the (c) Ultrafiltration (d) Peptisation
dispersion medium is a solid, the colloid is known 22. The stability of lyophilic colloids is due to
as [CPMT 1971, 81, 83, 93, 96; AFMC 1998;
[NCERT 1981; CBSE PMT 1989; KCET 1998] MP PMT 1990, 95; MP PET 1992]
(a) A sol (b) An emulsion (a) Charge on their particles
(c) A gel (d) A foam (b) A layer of dispersion medium on their
12. Zig-zag motion (eratic motion) of particles in particles
colloid was observed by [CPMT 1985] (c) The smaller size of their particles
(a) Tyndall (b) Zsigmondy (d) The large size of their particles
(c) Robert brown (d) Thomas Graham 23. Milk is a colloid in which
13. On addition of one ml solution of 10 % NaCl to 10 [MP PMT 1985, 2002; MP PET 2001;
ml gold sol in the presence of 0.25 gm of starch, JIPMER (Med.) 2002]
the coagulation is just prevented. Starch has the (a) A liquid is dispersed in liquid
following gold number (b) A solid is dispersed in liquid
[MP PET/PMT 1988] (c) A gas is dispersed in liquid
(a) 0.025 (b) 0.25 (d) Some suger is dispersed in water
(c) 0.5 (d) 250 24. Smoke is an example of [CPMT 1984; BIT 1992]
 596 Surface Chemistry
(a) Gas dispersed in liquid (b)Gas dispersed in solid (a) Milk is an emulsion of protein in water
(c) Solid dispersed in gas (d)Solid dispersed in solid (b) Milk is an emulsion of fat in water
25. Gold number is minimum in case of [MP PMT 1985] (c) Milk is stabilised by protein
(a) Gelatin (b) Egg albumin (d) Milk is stabilised by fat
(c) Gum arabic (d) Starch 36. Which of the following electrolytes have
26. Movement of colloidal particles under the maximum coagulating power
influence of electrostatic field is (a) CCl4 (b) ZnCl2
[AMU 1985, 88,02; MP PMT 1987, 89; CPMT 1988,94; (c) KCl (d) NaCl
Roorkee 1995; MP PET 1992; AIIMS 2001; UPSEAT 2004]
37. Which one of the following is not a colloidal
(a) Electrophoresis (b) Electrolysis solution
(c) Dialysis (d) Ionisation [MADT Bihar 1983]
27. Which of the following substances gives a (a) Smoke (b) Ink
positively charged sol [CPMT 1983, 84; MP PMT 1990; MP PET 1992]
(c) Air (d) Blood
(a) Gold (b) A metal sulphite 38. Detergent action of soap is due to
(c) Ferric hydroxide (d) An acidic dye (a) Emulsification properties (b) H
28. Light scattering in colloidal particles is (c) Ionization (d) High molecular
(a) Visible to naked eye weight
(b) Not visible by any means 39. When dispersion medium is water, the colloidal
(c) Visible under ordinary microscope system is called [MP PMT 1986]
(d) Visible under ultra-microscope (a) Sol (b) Aerosol
29. Flocculation value is expressed in terms of[MP PMT 1986] (c) Organosol (d) Aquasol
(a) millimole per litre (b) mole per litre 40. When a freshly precipitated substance is
(c) gram per litre (d) mole per millilitre converted into a colloidal solution with the help
30. Which of the following is an emulsifier of a third substance, the process is known as
(a) Soap (b) Water (a) Coagulation (b) Peptization
(c) Oil (d) NaCl (c) Electrodispersion (d) Dialysis
31. Suspensions are [CPMT 1984] 41. Which of the following will have highest
(a) Visible to naked eye coagulating power for As2 S 3 colloid
(b) Invisible through microscope [CPMT 1988; DPMT 1984; Pb. PMT 2001; Pb. CET 2004]
(c) Not visible by any means (a) PO 43 (b) SO 42
(d) Invisible under electron microscope
32. Gelatin is mostly used in making ice cream in (c) Na  (d) Al 3 
order to 42. Which one of the following is a hydrophobic sol
[NCERT 1979; MP PET/PMT 1988] [MP PET 1991]
(a) Prevent making of colloid (a) Starch solution
(b) To stabilise the colloid and prevent (b) Gum solution
crystallisation (c) Protein solution
(c) To stabilise mixture (d) Arsenic sulphide solution
(d) To enrich the aroma 43. Purification of colloids is done by the process of
33. In emulsions, the dispersion medium and [CPMT 1988]
dispersed phase are (a) Electrophoresis (b) Electrodispersion
(a) Both solids (c) Peptization (d) Ultra-filteration
(b) Both gases 44. Which of the following terms is not related with
(c) Both liquids colloids
(d) One is solid and other is liquid [CPMT 1985, 87, 88]
34. Lyophilic sols are more stable than lyophobic sols (a) Dialysis (b) Ultrafiltration
because
(c) Wavelength (d) Brownian movement
[NCERT 1982, 83]
45. When dispersed phase is liquid and dispersion
(a)The colloidal particles have positive charge
medium is gas, then the colloidal system is called[CPMT 19
(b)The colloidal particles have no charge
(a) Smoke (b) Clouds
(c)The colloidal particles are solvated
(d)There are strong electrostatic repulsions (c) Emulsion (d) Jellies
between the negatively charged colloidal 46. Tyndall phenomenon is exhibited by [CPMT 1985]
particles (a) NaCl solution (b) Starch solution
35. Which is the correct statement in case of milk (c) Urea solution (d) FeCl3 solution
[CPMT 1977; MNR 1988; UPSEAT 2000, 01, 02]
47. The colloidal solution of gelatin is known[CPMT 1984]
 Surface Chemistry 597
(a) Solvent loving sol (b) Reversible sol 57. According to Graham, colloids are those
(c) Hydrophilic colloids (d) All of these substances which are
48. The zig-zag motion of colloidal particles is due to (a) Insoluble in water
(b) In solution do not pass through filter paper
(a) Small size of colloidal particles
(c) Of definite size of particles
(b) Large size of colloidal particles
(d) Separated from crystalloids by parchment
(c) The conversion of potential energy into paper
kinetic energy 58. The reason for exhibiting Tyndall effect by the
(d) Bombardment on colloidal particles by colloidal particle is [CPMT 1980, 86; MP PMT 1989]
molecules of dispersion medium (a) Reflection of light (b) Refraction of light
49. Which is a natural colloidal [DPMT 1985] (c) Polarisation of light (d) Scattering of light
(a) Sodium chloride (b) Urea 59. Which of the following shows the maximum
(c) Canesugar (d) Blood hydrophobic behaviour [NCERT 1982]
(a) Glycerine (b) Stearic acid
50. Sodium stearate forms in water
(c) Glucose (d) Adenine
(a) True solution (b) A suspension
60. A liquid aerosol is a colloidal system of[MP PMT 1987]
(c) An emulsion (d) A colloidal solution
(a) A liquid dispersed in a solid
51. Blood contains (b) A liquid dispersed in a gas
(a) Positively charged particles (c) A gas dispersed in a liquid
(b) Negatively charged particles (d) A solid dispersed in a gas
(c) Neutral particles 61. The blue colour of water in the sea is due to[NCERT 1983]
(d) Negatively as well as positively charged (a) Refraction of blue light by the impurities in
particles sea water
52. Brownian motion is due to (b) Reflection of blue sky by sea water
(c) Scattering of blue light by water moleules
[MNR 1987; CPMT 1987; UPSEAT 2001, 02]
(d) Absorption of other colours except the blue
(a) Temperature fluctuation within the liquid
colour by water molecules
phase
62. Butter is a colloid. It is formed when
(b) Attraction and repulsion between charge on [MNR 1982; MP PET 1991;
the colloidal MP PMT 1994; CPMT 2002]
(c) Impact of molecules of the dispersion medium (a) Fat is dispersed in solid casein
on the colloidal particles (b) Fat globules are dispersed in water
(d) Convective currents (c) Water is dispersed in fat
53. Milk can be preserved by adding a few drops of (d) Casein is suspended in H 2 O
[MADT Bihar 1981] 63. Colloidal solution cannot be obtained from two
(a) Formic acid solution such substances which are
(b) Formaldehyde solution (a) Insoluble in each other (b)In same physical state
(c) Acetic acid solution (c) In different physical state (d) N
64. Which of the following reactions leads to the
(d) Acetaldehyde solution
formation of a substance in the colloidal state
54. When a colloidal solution is observed under a [MP PMT 1984; MP PET/PMT 1988]
microscope we can see [CPMT 1985]
(a) Cu  HgCl2  CuCl2  Hg
(a) Light scattered by colloidal particles
(b) 2HNO3  3 H2S  3S  4 H2O  2 NO
(b) Size of colloidal particles
(c) 2Mg  CO2  2MgO  C
(c) Shape of colloidal particles
(d) Cu  CuCl2  Cu2Cl2
(d) Relative size of the colloidal particles
55. Property of the colloidal solution is due to (in presence of excess of HCl )
(a) Nature of dispersed phase 65. Lyophobic colloids are [MP PMT 1986; DPMT
1996]
(b) Nature of dispersion medium
(a) Reversible colloids (b) Irreversible colloids
(c) Physical state of dispersed phase
(c) Protective colloids (d) Gum proteins
(d) Temperature of the system
66. Substances whose solutions can readily diffuse
56. Which of the following has minimum value of through parchment membranes are
flocculating power [MP PET 1989, 90]
(a) Colloids (b) Crystalloids
(a) Pb 2 (b) Pb 4 (c) Electrolytes (d) Non-electrolytes
2
(c) Sr (d) Na  67. Size of colloidal particles varies from
[CPMT 1982, 90, 93, 97; CBSE PMT 1996;
 598 Surface Chemistry
MP PMT 1995; AIIMS 2002; KCET 2004] (d) None of these
(a) 10 7 to 10 9 m (b) 10 9 to 10 17 m 79. When a substance comes in colloidal state the
5 7 4 10 surface area of the particles
(c) 10 to 10 m (d) 10 to 10 m
(a) Increases
68. Which of the following pairs of ions would be
expected to form precipitate when their dilute (b) Decreases
solution are mixed (c) Remains unchanged
[CPMT 1976] (d) First increases then decreases
(a) Na  , SO 32  (b) NH 4 , CO 32  80. Which of the impurity can be separated from a
solution by electrodialysis
(c) Na  , S 2 (d) Fe 3 , PO 43
(a) Alcohol (b) Alum
69. Jelly is a form of (c) Sugar (d) Parchment paper
(a) Suspension (b) Colloidal solution
81. The reason for the stability of a lyophobic sol is
(c) Supersaturated solution (d) True solution
(a) Brownian movement
70. Bleeding is stopped by the application of ferric
(b) Tyndall effect
chloride. This is because
(c) Electric charge
(a) Ferric chloride seal the blood cells.
(d) Brownian movement and electric charge
(b) Blood starts flowing in the other direction
(c) Blood is coagulated and blood vessel is sealed 82. For coagulating As2 S 3 colloidal sol, which of the
(d) None of these following will have the lowest coagulation value
71. The colloidal particles can pass through [MP PMT 1996; DCE 2000]
(a) Filter paper as well as animal membrane (a) NaCl (b) KCl
(b) Animal membrane but not through filter paper (c) BaCl2 (d) AlCl3
(c) Filter paper but not through animal 83. Some substances behave as electrolytes in dilute
membrane solutions and as colloids in their concentrated
(d) Semipermeable membrane solutions. Their colloidal forms are said to form[AMU 2002
72. The emulsifying agent in milk is (a) Emulsions (b) Gels
(a) Lactic acid (b) Casein (c) Micelles (d) Sols
(c) Lactose (d) Fat 84. Which one can act as semipermeable membrane
73. Butter is [MP PMT 1990] [Pb. PMT 2002]
(a) A gel (b) An emulsion (a) Phenol layer (b) Ca3 (PO4 )2
(c) A sol (d) Not a colloid (c) Cu2 Fe(CN )6 (d) All of these
74. An emulsion is a colloidal dispersion of[BCECE 2005]
85. In which particles can pass through
(a) A liquid in a gas (b) A liquid in a liquid
semipermeable membrane [
(c) A solid in a liquid (d) A gas in a solid
(a) Molecules of solvent (b) Complex ions
75. The colloidal solution of mercury in water can be
(c) Simple ions (d) Molecules of solute
easily obtained by
(a) Mechanical precipitation (b)Bredig's arc method 86. Silver iodide is used for producing artificial rain
because AgI
(c) Repeated washing (d) Ultrasonic dispersion
[NCERT 1984]
76. The rate of dialysis depends upon
(a) Nature of colloidal substance (a) Is easy to spray at high altitudes
(b) Temperature of the solution (b) Is easy to synthesize
(c) Both of these (c) Has crystal structure similar to ice
(d) None of these (d) Is insoluble in water
77. An emulsifier [MP PET 1995] 87. Surface water contains [AFMC 2003]
(a) Accelerates the dispersion (a) Salt
(b) Homogenises the emulsion (b) Salt and organic compound
(c) Stabilizes the emulsion (c) Organic compounds
(d) Aids the flocculation of emulsion (d) Suspended impurities
78. The difference between a lyophilic and lyophobic 88. Gelatin is mixed in ice-cream
colloid is in their (a) As a coagulant (b) For taste
(a) Particle size (c) For colour (d) As a protective
(b) Behaviour towards dispersion medium colloid
(c) Filtrability 89. Which of the following is an example of `water in
oil' type emulsion
 Surface Chemistry 599
(a) Butter (b) Milk (c) Disc like (d) Thread like
(c) Cream (d) Face cream (e) All of these
90. In which of the following Tyndall effect is not 99. Colloidal solution of arsenious sulphide is
observed coagulated by
[MP PET/PMT 1998] [MP PMT 1992]
(a) Suspensions (b) Emulsions (a) Addition of electrolyte
(c) Sugar solution (d) Gold sol (b) Addition of non-electrolyte
91. Which of the following is a lyophilic colloid (c) Addition of solid As2 S 3
[MP PET/PMT 1998]
(d) None of these
(a) Milk (b) Gum
100. Different colloidal particles of gold having
(c) Fog (d) Blood different colours, obtained from different
92. Which characteristic is true in respect of colloidal methods due to
particle [MP PET 1989; UPSEAT 2001, 02; EAMCET 2003]
[CPMT 1993; UPSEAT 2000]
(a) Variable valency of gold
(a) They always have two phases (b) Different concentration of gold particles
(b) They are only in liquid state (c) Different types of impurities
(c) They can't be electrolysed (d) Different radius of colloidal particles
(d) They are only hydrophilic 101. Which one of the following is lyophilic colloid
93. Gold number is a measure of the [MP PET 1989]
[MP PMT 1989; MP PET 1989,90; (a) Gelatin (b) Sulphur
DCE 1999; BHU 1999; CBSE PMT 1989]
(c) Gold (d) Carbon
(a) Protective action by a lyophilic colloid on a 102. Which one of the following properties of colloids
lyophobic colloid is related with scattering of light [MP PMT 1989]
(b) Protective action by a lyophobic colloid on a (a) Diffusion (b) Peptization
lyophilic colloid
(c) Tyndall effect (d) Brownian movement
(c) Number of mg of gold in a standard red gold
103. Which one of the following is a hydrophilic
sol colloidal sol
(d) Stability of gold sol (a) Barium hydroxide sol (b)Arsenic sulphide sol
94. Sulphur sol contains [UPSEAT 2002] (c) Starch solution (d) Silver chloride sol
(a) Discrete sulphur atoms 104. The coagulation power of an electrolyte for
(b) Discrete sulphur molecules arsenious sulphide decreases in the order [JIPMER 1997]
(c) Large agreegates of sulphur molecules (a) Na  , Al 3 , Ba 2 (b) PO 43 , SO 42 , Cl 
(d) Water dispersed in solid sulphur
(c) Al 3 , Ba 2 , Na  (d) Cl  , SO 42 , PO 43
95. Pick out the statement which is not relevant in
the discussion of colloids 105. Size2003]
[KCET of colloidal particle is [BCECE 2005]
(a) Sodium aluminium silicate is used in the (a) 1 nm (b) 1 – 100 nm
softening of hard water (c) > 100 nm (d) > 1000 nm
(b) Potash alum is used in shaving rounds and as 106. The concentration of electrolyte required to
antiseptic in medicine coagulate a given amount of As2 S 3 sol is
(c) Artificial rain is caused by throwing minimum in the case of
electrified sand on the clouds from an [KCET 2003]
aeroplane (a) Magnesium nitrate
(d) Deltas are formed at a place where the river (b) Potassium nitrate
pours its water into the sea (c) Potassium sulphate
96. Surface tension of lyophilic sols is [MP PMT
(d) 1992]
Aluminium nitrate
(a) Lower than H 2 O (b) More than H 2 O 107. When a strong beam of light is passed through a
(c) Equal to H 2 O (d) None of these colloidal solution, the light will[BHU 1996; JIPMER 1997]
(a) Give a rainbow
97. When excess of electrolyte is added to a colloid it
[CBSE PMT 1989] (b) Be scattered
(c) Be reflected
(a) Coagulates (b) Precipitates
(d) Absorbed completely
(c) Gets diluted (d) Does not change
108. A cleared solution which is again converted into
98. The shape of colloidal particles is
colloidal solution, the process is called [DPMT 1996]
(a) Sphere like (b) Rod like
(a) Peptisation (b) Electrolytic addition
 600 Surface Chemistry
(c) Electrophoresis (d) None of these (c) Hydrolysis (d) Precipitation
109. In dialysis, colloidal particles are separated from 121. Tyndall effect is more pronounced in
[DPMT 1996] (a) Hydrophilic sols (b) Hydrophobic sols
(a) Solvent (c) Starch solution (d) Both (b) and (c)
(b) Dispersed phase 122. Emulsifier is mixed to
(c) Ions of electrolytes (a) Increase the stability of emulsion
(d) Particles of dispersion medium (b) Decrease the stability of emulsion
110. Colour of colloidal solution is due to [CPMT 1996] (c) Change oil into water like emulsion
(a) Different size of colloidal particles (d) None of these
(b) Due to formation of complex 123. White of an egg is partly coagulated by heating
(c) Due to formation of hydrated crystal which can be again obtained back by some pepsin
(d) None of these and little HCl . This process is called
111. Which of the following is property of colloid [CPMT 1996] (a) Peptization (b) Coagulation
(a) Scattering of light (b) They show attraction (c) Precipitation (d) None of these
(c) Dialysis (d) Emulsion 124. When sugar is added to a colloidal solution it
112. The size of particles in suspension, true solution brings about
and colloidal solution varies in the order[BHU 1997] (a) Ionization (b) Coagulation
(a) Suspension > Colloidal > True solution (c) Peptization (d) None of these
(b) Suspension > (Colloidal + True solution)
125. Colloidal solutions of metals like gold, silver and
(c) True solution > Suspension > Colloidal
platinum are generally prepared by using[DPMT 1984]
(d) None of these
(a) Peptization (b) Bredig's arc method
113. Which of the following represents surfactant
molecule (c) Exchange of solvent (d) Oxidation method
[JIPMER 1997] 126. Liquid–liquid sols are known as [CPMT 1999]
(a) C17 H36 (b) C17 H 25 COO  Na  (a) Aerosols (b) Emulsions
(c) H 2 O (d) None of these (c) Foam (d) Gel
127. Tyndall effect depends upon the
114. In lyophilic sols the attraction of sol particles
(a) Charge on the colloidal particles
towards the medium is due to
(b) Osmotic pressure of colloidal solution
(a) Covalent bond (b) Vander Waal's force
(c) Difference between the refractive indices of
(c) Hydrogen bond (d) None of these
dispersed phase and dispersion medium
115. If some gelatin is mixed in colloidal solution of
(d) Size of colloidal particles
gold, then it does
128. Which one of the sols acts as protective colloid
(a) Coagulation of gold
[MP PMT 1990; MP PET 1990, 92; RPET 2003]
(b) Peptization of gold
(a) As2 S 3 (b) Gelatin
(c) Protection of gold sol
(d) Protection of gelatin (c) Au (d) Fe(OH )3
116. Emulsifiers are generally 129. The example of heteropolar sol is
(a) Soap (b) Synthetic detergents (a) Starch sol in water (b) Rubber sol in water
(c) Lyophilic sols (d) All of these (c) Protein sol in water (d) Sulphur sol
117. In shaving cream, the dispersion medium is 130. In Bredig's arc method some alkali is added
(a) Liquid (b) Gas because
(c) Solid (d) None of these (a) It increases electrical conductance
118. The minimum quantity of sodium chloride which (b) To obtain molecular colloid
is necessary to precipitate 10 litres of sol in two (c) To obtain colloidal particles of same size
hours is 0.585 gm. The flocculation value of (d) To stabilise the sol
sodium chloride is 131. Which one of the following is not a colloid[BIT 1992]
(a) 0.585 (b) 0.0585 (a) Milk (b) Blood
(c) 0.1 (d) One (c) Solution of urea (d) Ice cream
119. Which one is an example of miceller system 132. Milk is an example of [BIT 1992; CPMT 1994;
(a) Soap + water (b) Protein + water MP PET 1996; BHU 1996]
(c) Rubber + benzene (d) As2O3  Fe(OH )3 (a) Pure solution (b) Emulsion
120. “Delta” at the rivers are formed due to (c) Gel (d) Suspension
(a) Peptization (b) Coagulation 133. Dialysis is the process of separation of
(a) Suspended particles from colloids
 Surface Chemistry 601
(b) Suspended particles from crystalloids (b) Fe 3  ion coagulates blood, which is a
(c) Colloidal particles from crystalloids positively charged sol
(d) Colloidal particles from gel (c) Cl  coagulates blood, which is a positively
134. Minimum concentration of electrolyte which can charged sol
precipitate any sol is [BIT 1992]
(d) Cl  ion coagulates blood, which is a
(a) Peptization value (b) Gold number
negatively charged sol
(c) Avogadro's number (d) Flocculation value
145. At the critical micelle concentration, the
135. Whipped cream is an example of [MNR 1978]
surfactant molecules
Dispersion medium Dispersed phase [CBSE PMT 1998]
(a) Gas Liquid (a) Decompose
(b) Liquid Gas
(b) Dissociate
(c) Liquid Liquid
(c) Associate
(d) Liquid Solid
(d) Become completely soluble
136. Milk is
146. The decomposition of H 2O2 can be slowed down
[MP PMT 1995;CPMT 1988; MP PET 1991; MNR 1982]
(a) Dispersed fats in oil (b)Dispersed fats in water by the addition of small amount of phosphoric
(c) Dispersed water in fats (d) acid which
Dispersed actin
water asoil
[JIPMER 2000]
137. A coagulating agent frequently added to water to
remove the suspended and colloidal impurities is (a) Promoter (b) Inhibitor
(a) Mohr salt (b) Alum (c) Detainer (d) Stopper
(c) Bleaching powder (d) Copper sulphate 147. Which of the following molecules is most suitable
138. Fe(OH )3 when treated with FeCl3 solution a to disperse benzene in water [AIIMS 2005]
O
(a)
reddish-brown solution is formed. The process
O- Na+
involved is
-
O
[AFMC 1982] +
(b) Na O O- Na+
(a) Dispersion (b) Exchange of solvent O
(c) Peptization (d) None of these
139. Alum purifies muddy water by
(c)
(a) Dialysis (b) Absorption
CH3
(c) Coagulation (d) Forming a true
solution (d)
140. Which of the following statements is not true for Cl
a lyophilic sol
(a) It can be easily solvated 148. Luminosity observed as a result of scattering of
(b) It carries no charge light by particles is observed in [RPET 2000]
(c) Coagulation of this sol is reversible in nature (a) Suspension (b) Colloidal solution
(d) It is not very stable in a solvent (c) True solution (d) None of these
141. High concentration of gelatin in water on heating 149. Which of the following makes the lyophilic
gives colloidal solution, which is called solution unstable
(a) Foam (b) Gel [MP PMT 1994]
(c) Gas (d) Air (a) Dialysis
142. Size of colloidal particle is (b) Addition of electrolyte
[CPMT 1988; MP PMT 1991; RPET 2000] (c) Addition of alcohol
(a) 1 to 10 Å (b) 20 to 50 Å (d) Addition of alcohol and electrolyte both
(c) 10 to 1000 Å (d) 1 to 280 Å 150. A detergent is a [CPMT 1993]
143. Which one is Freundlich's equation (a) Cleaning agent (b) Drug
x 1 x (c) Catalyst (d) Vitamin
(a)  log K  log P (b)  exp ( KP)
m n m 151. Gold number is related with [MP PET 2000]
x x 1 (a) Colloids (b) Radioactivity
(c)  KP 2 (d) log  log K  log C
m m n (c) Gas equation (d) Kinetic energy
144. Ferric chloride is applied to stop bleeding cut 152. Small liquid droplets dispersed in another liquid
because is called
[Pb. PMT 2000]
(a) Fe 3  ion coagulates blood, which is a
(a) Gel (b) Emulsion
negatively charged sol
(c) Suspension (d) True solution
 602 Surface Chemistry
153. Which of the following is used for the destruction (b) Only solvation
of colloids (c) Only charge
[CBSE PMT 2000] (d) None of these
(a) Dialysis (b) Condensation 164. The impurities present in rain water possess .....
(c) By ultrafiltration (d) By adding electrolyte charge
154. An example of an associated colloid is (a) Positive (b) Negative
[CBSE PMT 2000; MP PET 2000] (c) Zero (d) Positive and negative
(a) Milk (b) Soap solution 165. Sodium lauryl sulphate is [RPET 2003]
(c) Rubber latex (d) Vegetable oil (a) Cationic sol (b) Anionic sol
155. The movement of colloidal particles towards the (c) Neutral sol (d) None of these
oppositely charged electrodes on passing 166. Which of the following statement is false
electricity is known as (a) Every solid substance can be brought into
[AFMC 2000] colloidal state
(a) Cataphoresis (b) Tyndall effect (b) Colloidal particles carry electrical charges
(c) Brownian movement (d) None of these (c) Every solid substance can be made to behave
156. Tyndall effect is shown by [Pb. PMT 1999] like a lyophilic colliod
(a) Sol (b) Solution (d) Addition of electrolytes causes flocculation of
(c) Plasma (d) Precipitation colloidal particles
157. Colloidal solutions of gold prepared by different 167. Which is a colloid [CPMT 1984]
methods have different colours owing to[JIPMER 1999] (a) Sugar solution (b) Urea solution
(a) The difference in the size of the colloidal (c) Silicic acid (d) NaCl solution
particles 168. Alum helps in purifying water by [AIEEE 2002]
(b) The fact that gold exhibits a variable valency (a) Forming Si complex with clay particles
of + 1 and + 3 (b) Sulphate part which combines with the dirt
(c) Different concentrations of gold and removes it
(d) Presence of different types of foreign particles (c) Aluminium which coagulates the mud
depending upon the method of preparation of particles
the colloid (d) Making mud water soluble
158. Which of the following colloids are formed when 169. Maximum coagulation power is in [
hydrogen sulphide gas is passed through a cold  
(a) Na (b) Ba
solution of arsenious oxide [CPMT 2000]
(c) Al    (d) Sn    
(a) As2 S 3 (b) As2O3 170. Which of the following is not an emulsion [MP PET 2003]
(c) As 2 S (d) As 2 H 2 (a) Butter (b) Ice cream
159. The simplest way to check whether a system is (c) Milk (d) Cloud
colloidal, is 171. Colloidal solution of gold cannot be prepared by
[KCET (Med.) 2002] (a) Bredig's arc method (b) Mechanical
(a) Tyndall effect (b) Electro dialysis dispersion
(c) Brownian movement (d) Finding out particle (c) Reduction of gold chloride(d)Exchange of solvents
size 172. Which of the following ions can cause coagulation
160. Fog is an example of colloidal system of proteins [KCET 2000]
[MNR 1985; NCERT 1985; CPMT 1988; MP PMT 1991; (a) Ag  (b) Na 

MP PET 1996; UPSEAT 1999, 2000] (c) Mg (d) Ca  
(a) Liquid dispersed in gas (b)Gas dispersed in gas 173. Light scattering takes place in
(c) Solid dispersed in gas (d)Gas dispersed in liquid [MP PMT 1991; BHU 2000; AFMC 2001; Kerala PET 2002]
161. In the measurement of gold number, the useful (a) Solutions of electrolyte (b)Colloidal solutions
electrolyte is
(c) Electrodialysis (d) Electroplating
(a) AuCl3 (b) NaCl
174. Which of the following can stabilize gold sol from
(c) AlCl3 (d) FeCl3 coagulation by NaCl solution
162. Blood may be purified by [MP PMT 2000] (a) Fe(OH )3 (b) Gelatin
(a) Dialysis (b) Electro-osmosis (c) As2 S 3 (d) None of these
(c) Coagulation (d) Filtration 175. At isoelectric point
163. The stability of lyophilic colloidal sol is due to (a) Colloidal sol becomes highly stable
(a) Both charge and solvation (b) Precipitation of a colloidal sol takes place
 Surface Chemistry 603
(c) Colloidal particles becomes uncharged 187. Gold sol is an electronegative sol. The amount of
(d) Peptization can be carried out electrolyte required to coagulate a certain amount
176. Which one is an example of multimolecular of gold sol is minimum in the case of
colloid system (a) CaCl2 (b) NaCl
(a) Soap dispersed in water (b)Protein dispersed in water (c) AlCl3 (d) Na2 SO 4
(c) Gold dispersed in water (d)Gum dispersed in water 188. In the case of small cuts, bleeding is stopped by
177. Metals like Pt and Pd can adsorb large volume of applying potash alum. Here alum acts as [KCET (Med.) 200
hydrogen under specific conditions. Such (a) Fungicide (b) Disinfectant
adsorbed hydrogen by the metal is known as (c) Germicide (d) Coagulating agent
(a) Occluded hydrogen (b) Absorbed hydrogen 189. If gold number of A,B,C and D are 0.005, 0.05, 0.5
(c) Reactive hydrogen (d) Atomic hydrogen and 5 respectively, then which of the following
178. A colloidal system in which gas bubbles are will have the highest protective power [Pb. CET 2001; CPM
dispersed in a liquid is known as [MP PMT 1993] (a) A (b) B
(a) Foam (b) Sol (c) C (d) D
(c) Aerosol (d) Emulsion 190. Bredig arc method can not be used to prepare
179. On adding few drops of dilute HCl or FeCl3 to colloidal solution of which of the following [AFMC 2004]
freshly precipitated ferric hydroxide a red (a) Pt (b) Fe
coloured colloidal solution is obtained. The (c) Ag (d) Au
phenomenon is known as 191. Gold number is maximum for the lyophilic sol is
[NCERT 1981; AFMC 1982; MP PMT 1989, 97] [BVP 2004]
(a) Peptisation (b) Dialysis (a) Gelatin (b) Haemoglobin
(c) Protective action (d) Dissolution (c) Sodium oleate (d) Potato starch
180. Surface tension of lyophilic sols is [MP PMT 2002] 192. Which of the following is the best protective
(a) Lower than that of H 2O (b)More than that of H 2O colloid
[UPSEAT 2004]
(c) Equal to that of H 2O (d) None of these
(a) Gelatin (Gold No. = 0.005)
181. Which of the following is not true of a detergent (b) Gum arabic (Gold No. = 0.15)
molecule (c) Egg albumin (Gold No. = 0.08)
[JIPMER 2002] (d) None of these
(a) It has a non-polar organic part and a polar 193. The gold number of A, B C and D are 0.04, 0.002,
group 10 and 25 respectively. Protective power of A, B, C
(b) It is not easily biodegraded and D are in order [DCE 2003]
(c) It is a sodium salt of fatty acid (a) A  B  C  D (b) B  A  C  D
(d) It is a surface active agent (c) D  C  B  A (d) C  A  B  D
182. Which of the following can act as protective 194. A catalyst is a substance which [Pb. CET 2004]
colloids (a) Is always in the same phase as in the
(a) Hydrophobic sols (b) Hydrophilic sol reactions
(c) Gold sol (d) None of these (b) Alters the equilibrium in a reaction
183. Which of the following substances is not used for (c) Does not participate in the reaction but alters
preparing lyophilic sols [MP PET 2002] the rate of reaction
(a) Starch (b) Gum (d) Participates in the reaction and provide an
(c) Gelatin (d) Metal sulphide easier pathway for the same
184. Hydrophilic sols are 195. Cod liver oil is [MHCET 2004]
(a) Reversible (b) Irreversible (a) An emulsion (b) Solution
(c) Unstable (d) None of these
(c) Colloidal solution (d) Suspension
185. Soap essentially forms a colloidal solution in
196. Paste is [MHCET 2004]
water and removes the greasy matter by
(a) Suspension of solid in a liquid
(a) Absorption (b) Emulsification
(b) Mechanical dispersion of a solid in liquid
(c) Coagulation (d) None of these
186. Toilet soap is a mixture of [UPSEAT 2001]
(c) Colloidal solution of a solid in solid
(a) Calcium and sodium salts of fatty acids (d) None of these
(b) Fatty acids and glycerol 197. A precipitate is changed to colloidal solution by
(c) Sodium salts of fatty acids the following process [UPSEAT 2004]

(d) Potassium salt of fatty acids (a) Dialysis (b) Ultrafiltration

(c) Peptization (d) Electrophoresis
198. An aerosol is a [UPSEAT 2004]
 604 Surface Chemistry
(a) Dispersion of a solid or liquid in a gas (c) Gas in liquid (d) Gas in solid
(b) Dispersion of a solid in a liquid 208. Lyophilic sols are more stable than lyophobic sols
(c) Dispersion of a liquid in a liquid because their particles are [Karala CET 2005]
(d) Solid solution (a) Positively charged (b) Negatively charged
(c) All soluble (d) Attract each other
199. Lyophilic sols are [IIT 2005]
(e) Are heavier
(a) Irreversible sols
209. Oils and fats are obtained by saponification of
(b) They are prepared from inorganic compound
potassium stearate. Its formula is
(c) Coagulated by adding electrolytes
CH 3  (CH 2 )16  COO  K  . Lyophobic end of atom is
(d) Selfstabilizing
200. The volume of a colloidal particle, VC as (CH 3 ) and lyophilic end is COO  K  . potassium
compared to the volume of a solute particle in a stearate is example of
true solution VS , could be [Kerala CET 2005]
[AIEEE 2005] (a) Lyophobic colloids (b) Lyophilic colloids
V V (c) Poly molecular colloids (d) M
(a) C ~– 1 (b) C ~– 10 23
VS VS (e) Combined colloids or Miscells
VC ~ VC ~
(c) – 10  3 (d) – 10 3
VS VS
201. The disperse phase in colloidal iron (III)
hydroxide and colloidal gold is positively and
negatively charged, respectivley. Which of the
following statements is NOT correct [AIEEE 2005]
(a) Magnesium chloride solution coagulates, the 1. Which of the following is contributed towards the
gold sol more readily than the iron (III) extra stability of lyophilic colloids
hydroxide sol (a) Hydration (b) Charge
(b) Sodium sulphate solution causes coagulation in (c) Colour (d) Tyndall effect
both sols
2. Which of the following methods is used for sol
(c) Mixing the sols has no effect destruction
(d) Coagulation in both sols can be brought about [CPMT 1988]
by electrophoresis
(a) Condensation
202. The surface tension of which of the following
(b) Dialysis
liquid is maximum ? [CBSE PMT 2005]
(a) H 2 O (b) C6 H 6 (c) Diffusion through animal membrane
(d) Addition of an electrolyte
(c) CH3 OH (d) C2 H 5 OH
3. A catalyst is a substance which [IIT 1983]
203. Which one of the following forms micelles in
(a) Increases the equilibrium concentration of the
aqueous solution above certain concentration ? [CBSE PMT 2005]
product
(a) Urea
(b) Changes the equilibrium constant of the
(b) Dodecyl trimethyl ammonium chloride
reaction
(c) Pyridinium chloride
(c) Shortens the time to reach equilibrium
(d) Glucose
204. Alum is a water purifier because it [KCET 2005] (d) Supplies energy to the reaction
(a) Coagulates the impurities 4. The decomposition of hydrogen peroxide can be
(b) Softens hard water slowed by the addition of a small amount of
(c) Gives taste acetamide. The latter acts as a
(d) Destroys the pathogenic bacteria (a) Detainer (b) Stopper
205. An emulsifier is a substance which [KCET 2005] (c) Promoter (d) Inhibitor
(a) Stabilises the emulsion 5. The ability of an ion to bring about coagulation of
(b) Homogenises the emulsion a given colloid depends upon[CPMT 1980; MP PET/PMT 1988
(c) Coagulates the emulsion CBSE PMT 1997; MP PMT 1989; MP PET 1994]
(d) Accelerates the dispersion of liquid in liquid (a) Its size
206. Muddy water can be purified through coagulation (b) The magnitude of its charge only
using (c) The sign of its charge
[J & K 2005] (d) Both the magnitude and the sign of its charge
(a) Common salt (b) Alums
6. Which one of the following is an incorrect
(c) Sand (d) Lime
statement for physisorption [
207. Fog is a colloidal solution of [J & K 2005]
(a) It is a reversible process
(a) Solid in gas (b) Liquid in gas
 Surface Chemistry 605
(b) It requires less heat of adsorption (d) None of these
(c) It requires activation energy 17. Point out the false statement [MP PET 1997]
(d) It takes place at low temperature (a) Brownian movement and Tyndall effect is
7. Which is not colloidal [CPMT 1984; MP PET 1989, 91] shown by colloidal systems
(b) Gold number is a measure of the protective
(a) Chlorophyll (b) Egg
power of a lyophilic colloid
(c) Ruby glass (d) Milk
(c) The colloidal solution of a liquid in liquid is
8. Which one of the following is not a surfactant[AIIMS 2003]
called is gel
CH (d) Hardy–Schulze rule is related with
3
|
  coagulation
(a) CH 3  (CH 2 )15  N  CH 3 Br
| 18. Which of the following does not contain a
CH hydrophobic structure [NCERT 1983]
3
(a) Linseed oil (b) Lanolin
(b) CH3  (CH 2 )14  CH 2  NH 2
(c) Glycogen (d) Rubber
(c) CH 3  (CH 2 )16  CH 2 OSO 2 Na  19. The function of gum-arabic in the preparation of
indian ink is
(d) OHC  (CH 2 )14  CH 2  COO  Na 
(a) Coagulation (b) Peptization
9. Size of colloidal particles is (c) Protective action (d) Absorption
[CPMT 1984; MP PMT 1990, 92] 20. Identify the gas which is readily adsorbed by
(a) 0.1 m  to 0.001 m  (b) 10  to 20  activated charcol
(c) 0.05 m  to 0.1 m  (d) 25  to 30  [KCET 2004]
(a) N 2 (b) SO 2
10. Which of the following electrolytes is most
effective in the coagulation of gold solution [KCET 1996] (c) H 2 (d) O 2
(a) NaNO3 (b) K4 [Fe(CN )6 ] 21. The density of gold is 19 g / cm 3 . If 1.9  10 4 g of
(c) Na3 PO4 (d) MgCl2 gold is dispersed in one litre of water to give a sol
11. A catalyst is used in a reaction to having spherical gold particles of radius 10 nm,
[CPMT 1972, 75, 97; DPMT 1982] then the number of gold particles per mm 3 of the
(a) Change the nature of reaction products sol will be [Pb.CET 2004]
(b) Increase the reaction yield (a) 1 . 9  10 12 (b) 6 .3  10 14
(c) Decrease the need for reactants
(c) 6 .3  10 10 (d) 2 . 4  10 6
(d) Decrease the time required for the reaction
22. Which of the following forms cationic miscelles
12. Which one of the following is not represented by
above certain concentration [
sols
(a) Urea
[MP PMT 1992]
(b) Cetyltrimethylammonium bromide
(a) Absorption (b) Tyndall effect
(c) Sodium dodecyl sulphate
(c) Flocculation (d) Paramagnetism
(d) Sodium acetate
13. Example of intrinsic colloid is
(a) Glue (b) Sulphur
(c) Fe (d) As2 S 3
14. Colloidal solution of arsenious sulphide can be
prepared by
[AMU 1985]
(a) Electrodispersion method
(b) Peptization Read the assertion and reason carefully to mark the
(c) Double decomposition correct option out of the options given below :
(d) Hydrolysis]
(a) If both assertion and reason are true and the
15. The capacity to bring about coagulation increases
reason is the correct explanation of the assertion.
with
(b) If both assertion and reason are true but reason is
(a) Ionic radii (b) Atomic radii
(c) Valency of an ion (d) Size of an ion not the correct explanation of the assertion.
16. Gold number gives (c) If assertion is true but reason is false.
[NCERT 1987; MNR 1987; UPSEAT 2002; (d) If the assertion and reason both are false.
Kurukshetra CET 2002; MP PMT 2004] (e) If assertion is false but reason is true.
(a) The amount of gold present in the colloid
(b) The amount of gold required to break the 1. Assertion : When a finely divided active carbon
colloid or clay is stirred into a dilute
(c) The amount of gold required to protect the
colloid
 606 Surface Chemistry
solution of a dye, the intensity of 11. Assertion : An emulsion becomes stable if soap
colour in the solution is decreased. is added to it .
Reason : The dye is adsorbed on the solid Reason : Soap contains hydrophilic and
surface. hydrophobic parts.
2. Assertion : The enthalpy of physisorption is 12. Assertion : Deep electric shock causes death of
greater than chemisorption. an animal.

Reason : Molecules of adsorbate and Reason : Electric shock coagulate the blood.
adsorbent are held by van der [AIIMS 1995]

Waals forces in physisorption and 13. Assertion : A catalyst is more effective in finely
by chemical bonds in divided form.
chemisorption. Reason : Finely divided form has more
3. Assertion : Silica gel is used for drying air. surface area.
[AIIMS 1998]
Reason : Silica gel adsorbs moisture from
air. 14. Assertion : NH 3 absorb more readily over

x activated charcoal than CO2 .

4. Assertion : According to Freundlich: k .P 1 / n .
m Reason : NH 3 is non-polar. [AIIMS 2000]
Reason : The isotherm shows variation of the 15. Assertion : Sky appears blue colour.
amount of gas adsorbed by the
Reason : Colloidal particles of dust scatter
adsorbent with temperature. blue light.
5. Assertion : A reaction cannot become fast by [AIIMS 2000]
itself unless a catalyst is added.
16. Assertion : Physical absorption of molecules
Reason : A catalyst always increases the takes place on surface only.
speed of a reaction. Reason : In this process, the bonds of the
6. Assertion : ZSM – 5 is used as a catalyst in absorbed molecules are broken.[AIIMS 2002
petrochemical industries. 17. Assertion : The micelle formed by sodium
Reason : Zeolites are three dimensional stearate in water has  COO  groups
network silicates in which some at the surface.
silicon atoms are replaced by Reason : Surface tension of water is reduced
aluminium atoms. by the addition of stearate.[AIIMS 2003]
7. Assertion : Lyophilic colloids are called as 18. Assertion : Aqueous gold colloidal solution is
reversible sols. red in colour.
Reason : Lyophilic sols are liquid loving. Reason : The colour arises due to scattering
8. Assertion : Colloidal sols scatter light while of light by colloidal gold particles.[AIIMS 20
true solutions do not. 19. Assertion : Increase in surface area, increase in
Reason : The particles in the colloidal sol rate of evaporation.
more much slower than that of the Reason : Stronger the intermolecular
true solution. attractive forces, fast is the rate of
evaporation at a given temperature.
9. Assertion : Colloidal particles show Brownian
movement.
Reason : Brownian movement arises because
of the impact of the molecules of
the dispersion medium with the
colloidal particles.
10. Assertion : For the coagulation of sols carrying
positive charge, PO 43  ions are more Adsorption and Adsorption isotherm
2 
efficient than SO 4 or Cl ions.
1 b 2 a 3 b 4 a 5 a
Reason : This follows Hardy – Schulze rule.
6 b 7 c 8 b 9 b 10 d
 Surface Chemistry 607
11 a 12 a 13 d 14 d 15 c 86 c 87 d 88 d 89 a 90 c
16 c 17 d 18 d 19 a 20 b 91 b 92 a 93 a 94 c 95 a
21 a 22 c 23 c 24 b 25 a 96 a 97 a 98 e 99 a 100 d

26 a 27 d 28 b 29 b 30 c 101 a 102 c 103 c 104 c 105 b

31 a 32 d 33 b 34 c 35 d 106 d 107 b 108 d 109 c 110 a

36 c 37 a 38 a 39 c 40 c 111 a 112 a 113 b 114 c 115 c

41 d 42 a 43 a 44 c 45 d 116 d 117 a 118 d 119 a 120 b

46 d 47 d 121 b 122 a 123 a 124 d 125 b

126 b 127 c 128 b 129 c 130 d

Catalyst and Catalysis 131 c 132 b 133 c 134 d 135 b

136 b 137 b 138 c 139 c 140 d
1 c 2 d 3 d 4 a 5 d 141 b 142 c 143 d 144 a 145 c

6 b 7 d 8 a 9 d 10 c 146 b 147 c 148 b 149 d 150 a

11 c 12 b 13 a 14 b 15 c 151 a 152 b 153 d 154 b 155 a

16 d 17 c 18 d 19 c 20 c 156 a 157 a 158 a 159 a 160 a

21 b 22 d 23 a 24 b 25 c 161 b 162 a 163 a 164 b 165 a

166 c 167 c 168 c 169 d 170 d
26 d 27 d 28 a 29 c 30 c
171 d 172 a 173 b 174 b 175 c
31 d 32 c 33 c 34 d 35 c
176 c 177 a 178 a 179 a 180 a
36 b 37 d 38 a 39 a 40 d
181 c 182 b 183 d 184 a 185 b
41 b 42 a 43 b 44 b 45 b
186 d 187 c 188 d 189 a 190 b
46 c 47 d 48 d 49 d 50 c
191 d 192 a 193 b 194 c 195 a
51 b 52 b 53 a 54 b 55 d
196 a 197 c 198 a 199 d 200 d
56 d 57 d 58 d 59 b 60 c
201 c 202 a 203 b 204 a 205 a
61 c 62 c 63 b 64 b 65 a
206 b 207 b 208 c 209 e
66 d 67 c 68 c 69 b 70 b
71 d 72 d 73 c 74 a Critical Thinking Questions

Colloids, Emulsion, Gel and Their properties 1 a 2 d 3 c 4 d 5 d

with application 6 c 7 a 8 b 9 a 10 b
11 d 12 d 13 a 14 c 15 c
1 b 2 d 3 a 4 a 5 c 16 d 17 c 18 d 19 c 20 b
6 d 7 d 8 b 9 c 10 c 21 d 22 d
11 c 12 c 13 d 14 b 15 c
16 d 17 b 18 c 19 a 20 b Assertion & Reason
21 b 22 b 23 a 24 c 25 a
1 a 2 e 3 a 4 c 5 d
26 a 27 c 28 d 29 a 30 a 6 b 7 b 8 b 9 a 10 a
31 a 32 b 33 c 34 c 35 b 11 a 12 a 13 a 14 c 15 a
36 b 37 c 38 a 39 d 40 b 16 d 17 b 18 a 19 c
41 d 42 d 43 d 44 c 45 b
46 b 47 d 48 d 49 d 50 d
51 b 52 c 53 b 54 a 55 c
56 d 57 d 58 d 59 d 60 b
61 c 62 c 63 d 64 b 65 b
66 b 67 a 68 d 69 b 70 c
71 c 72 b 73 a 74 b 75 d
76 b 77 c 78 b 79 a 80 b
81 d 82 d 83 c 84 c 85 a
 606 Surface Chemistry
used to separate these gases. Helium is not
adsorbed by charcoal (as it is very difficulty
liquifiable gas).
42. (a) Animal charcoal is a good adsorbate. The
impurities adsorbs on its surface and thus it
decolourises colour of liquids.
Adsorption and Adsorption isotherm 43. (a) Since adsorption is an exothermic process
(taking place with the evolution of heat)
1. (b) Chemical adsorption is irreversible due to therefore in accordance with Lechatelier's
formation of new bonds and compounds. principle, the magnitude of physical
adsorption will decrease with the increase in
2. (a) Chemical adsorption increases with
temperature. In case of chemisorption the
temperature. adsorption first increase and then decreases
6. (b) When the temperature is raised, the viscosity with increase in temperature.
of liquid decreases, this is because increase in 44. (c) Concentration of the solution decreases
temperature increases the average kinetic because acetic acid gets adsorbed on charcoal.
energy of molecules which overcome the x
attractive force between them. 45. (d)  k p1 / n or x  m . kp 1 / n or x / m  kpn
m
13. (d) Charge on As 2 S 3 sol is due to the adsorbed
All of these equation represent freundlich
sulphide ion. adsorption isotherm.
19. (a) According to langmuir Adsorption isotherm 47. (d) It has been observed that the surface of a
the amount of gas adsorbed at very high solid (or liquid) has the tendency to attract
pressures reaches a constant limiting volume. and retain the molecules of other immiscible
21. (a) According to definition of adsorbent. phase with which it is brought into contact.
24. (b) Adsorption increase when temperature These molecules remian only at the surface
decreases (Adsorption  1/Temperature) and do not go deeper into the bulk. This
25. (a) In chemical adsorption, one layers are tendency of accumulation of molecular species
adsorbed. at the surface than in the bulk of a solid (or
liquid) it termed adsorption.
26. (a) Adsorption of a gas on solid independent of the
pressure start fast and after some time becomes
Catalyst and Catalysis
slow.
27. (d) Chemisorption first increases and then
3. (d) A catalyst does not take part in the reaction
decreases with temperature.
but can speed it up. It can be recovered after
28. (b) Adsorption is an exothermic process. the reaction.
1
32. (d) log x / m  log k  log p ; this is Freundlich 4. (a) N 2  3 H 2    2 NH 3
Fe Catalyst

n (g) (g) Mo promoter (g)

1 (d) 2 KClO 3 

 2 KCl  3 O 2
MnO 2
isotherm. Thus p  . 5.
n
36. (c) Heterogeneous catalysis can be explained by 6. (b) 2 SO 2  O 2   2 SO 3
Pt (Catalyst )
As 2 O 3 ( poison )
the adsorption theory.
7. (d) It is a shape-selective catalyst.
37. (a) Adsorption due to strong chemical bond is
8. (a) All substance have average energy and before
called chemical adsorption or chemisorption
the reaction occurs energy of the reactant
or Langmuir adsorption.
should be higher than the average energy. We
39. (c) Physical adsorption decreases with increase of also know that catalyst lower the activation
temperature. energy. Therefore, rate of reaction is
126  1  50 increased.
40. (c) W   6.3
1000 9. (b) 2 SO 2  O 2  2 SO 3
NO

(Molecular weight of oxalic acid 163)

12. (b) Transition metals are most efficient catalysts
6.3
0 .5 gm  due to half filled d-orbitals.
2 16. (d) An increase in rate of reaction in forward
6.3 direction by a catalyst for a reaction in
1 gm   1  6.3 gm.
2  0 .5 equilibrium brings in an increase in
41. (d) Noble gases are adsorbed by coconut charcoal. concentration of products and thus rate of
The adsorption of different noble gases occur backward reaction also increase to same
at different temperatures, hence charcoal is
 Surface Chemistry 607
magnitude and so allow the equilibrium to be 58. (d) Mn   is a product in reaction so it is auto
achieved quickly. catalyst (according to definition).
17. (c) 2 SO 2  O 2   2 SO 3
V2 O5
62. (c) 2 SO 2  O 2   2 SO 3
V2 O5

(g) (g) (g) (Catalyst )

(b) 2 SO 2  O 2     2 SO 3 (g)
Pt Catalyst
19. (c) Catalyst never change the equilibrium 63.
(g) ( g ) Asbestos(p romoter)
constant.
21. (b) Because reactant and catalyst are present in 65. (a) Generally transition elements acts as
same physical state. catalysts. Adam's catalyst is another name of
platinum.
23. (a) C 6 H 12 O 6   2C 2 H 5 OH  2CO 2
Zymase

Glucose Enzyme Ethanol

69. (b) Enzyme activity is maximum at 310K.
70. (b) Catalyst is a substance which changes the rate
24. (b) C6 H 6  CH 3 Cl    C6 H 5 CH 3  HCl
Anhydrous
of reaction without affecting the overall
AlCl 3
energetics of the reaction.
(c) CH 3 COOC 2 H 5  HOH    
Conc . H 2 SO 4
25. 71. (d) Ni, Pt and Co all three transition metals are
Catalyst
used as a catalysts.
CH 3 COOH  C 2 H 5 OH
72. (d) Catalyst is a substance which changes the rate
27. (d) Catalyst does not depend on the enthalpy of of reaction without affecting the overall
the reactants. energetics of the reaction.
30. (c) Catalyst does not depend on the free energy 73. (c) Many of the d -block (transition) elements
change in the reaction. and their compounds act as catalyst. Catalytic
31. (d) Activation energy changes when catalyst is property is probably due to the utilisation of
used in a reaction. (n  1)d orbitals or formation of interstitial
32. (c) In the reversible reaction a catalyst is the
compounds.
substance which reduces the time required for
reaching the equilibrium state in the reaction. 74. (a)The catalytic process in which the reactants
and the catalyst are in different phases is
36. (b) Maltose  GlucoseMaltase
enzyme known as heterogenous catalysis.
37. (d) Efficiency of catalysing property is inversely N 2(g)  3 H 2(g)   2 NH 3(g)
Fe (s)

proportional of activation energy.

The reactants are in gaseous state while the
39. (a) 2SO 2  O 2    2SO 3 ;
Platinized
Example of
(g ) (g ) Asbestose catalyst is in solid state.
(s )

heterogeneous catalyst. Colloids, Emulsion, Gel and Their properties

40. (d) Oil  H 2 
Ni
Ghee . with application
41. (b) Catalyst is not effect on equilibrium
concentrations. 4. (a) Negatively charged As 2 S 3 sol coagulated most
42. (a) 4 NH 3  5 O 2  4 NO 
 4 NO 2
Pt guage O2
effectively by AlCl3 . This is because oppositely
1100 K
charged Al    ions have maximum charge.
2 H 2 O  O2
  4 HNO 3 As 3   Ca 2   Na 
6. (d) K 3 [Fe(CN )6 ] is most effective in coagulating a
(d) 4 NH 3  5 O 2  4 NO 
  4 NO 2
Pt guage O
48. 2
1100 K ferric hydroxide sol.
7. (d) Sky looks blue due to scattering of light by
2 H 2O  O2
   4 HNO 3 dust particles present in the atmosphere.
51. (CH 3 CH 2 )3 Al  TiCl 4
(b) nCH 3  CH  CH 2    10. (c) KBr is least effective in causing flocculation of
Propylene ferric hydroxide sol due to minimum charge at
(KBr ) Br 
 CH 3  11. (c) Liquid  Solid  Gel (e.g. Butter)
 |  (Dispersed (Dispersio n (Colloid)
 CH 2  CH   phase) medium

  13. (d) By definition gold number of starch is the

 n
Polypropyl ene amount of starch in mg added to 10 ml
53. (a) Ptyline (enzyme) is present in saliva. standard gold sol which prevents the
54. (b) 2 SO 2  O 2   2 SO 3 2 NO(g) ,
2 NO ( g )
reactants coagulation of gold on adding 1 ml of 10%
(g) (g) (g) NaCl solution. So the amount of starch is
and catalyst present in same phase. 0.25g = 250 mg. Hence gold number is 250.
15. (c) According to Hardy schulze rule the ions
(d) 2SO 2  O2  2SO 3
Platinised asbestos(c atalyst )
55.
As 2 S 3 (Poison ) having opposite charge to sol particle cause
coagulation and greater the valency of
 608 Surface Chemistry
oppositely charged ion more is the coagulating 79. (a) When a substance comes in colloidal state the
power (PO 43   SO 42   NO 3 ). surface area of the particles increases due to
small size than substance.
17. (b) Gold number is associated with only lyophilic
colloids due to protective nature. 80. (b) Alum can be separated from a solution by
19. (a) Negatively charged sols require minimum electrodialysis due to alum give Al 3  ion in
amount of electrolyte having higher valence of solution.
cation. 82. (d) The amount of electrolyte required to
22. (b) Lyophilic possesses solvent loving nature and coagulate a fixed amount of a solution
thus a thin layer of dispersed phase is formed depends upon the valency of the flocculation
round sol particles. ion. The flocculating power of the various ions
23. (a) Milk is a colloid of liquid ( H 2 O ) dispersed in follows the following order, larger the valency
lesser will be coagulating value.
liquid (fat).
Al 3   Mg 2   Na  , hence lowest coagulation
24. (c) Smoke is an example of solid dispersed in gas.
value is of AlCl3 .
26. (a) Movement of (charged) colloidal particles
under the influence of electrostatic field is 88. (d) Gelatin is a protective colloid in ice-cream.
called electrophoresis due to opposite charge. 90. (c) Tyndall effect is not observed in sugar
27. (c) Fe(OH )3 gives a positively charged sol as it solution due to homogeneous nature.
adsorbs Fe 3  ions from FeCl3 solution. 92. (a) Dispersion medium and dispersed phase are
phase of colloid.
29. (a) Flocculation value is expressed in terms of
millimole per litre. 99. (a) As 2 S 3 is coagulated by addition of electrolyte
32. (b) Gelatin is a protective colloid. due to opposite charge.
36. (b) ZnCl 2 has maximum coagulation power due to 104. (c) According to Hardy-Schulze rule.
more charge on the Zn 111. (a) Scattering of light is a property of colloid.
37. (c) Air is not a colloidal solution because it is a 115. (c) Some gelatin is mixed in colloidal solution of
homogeneous mixture. gold to form ppt of gold (peptization of gold).
43. (d) In Purification separation of colloids from Because formation of layer on colloidal
crystalloids is done by the process of ultra- particle.
filtration. 120. (b) “Delta” at the rivers are formed due to
45. (b) dispersed phase  dispersion medium coagulation between sea water (+ve charged
(liquid) (gas)
particles) and river water (–ve charged
 colloidal system particles)
(clouds)
121. (b) Tyndall effect expressed by hydrophobic sols.
46. (b) Tyndall phenomenon is exhibited by starch 129. (c) Protein sol in water is a example of
solution because starch solution is a colloidal heteropolar sol.
solution.
130. (d) For stabilise the sol.
53. (b) Milk can be preserved by adding a few drops
of HCHO solution. HCHO is an emulsifier. 131. (c) Solution of urea is not a colloid.
55. (c) Properties of the colloidal solution depend 135. (b) Liquid  Gas  Whipped cream
(Dispersion (Dispersed Colloidal solution
upon physical state of dispersed phase and medium) phase)
mol. wt.
137. (b) Alum is a coagulating agent, frequently added
57. (d) According to Graham, colloids are separated
to water to remove impurities from water
from crystalloids by parchment paper.
because impurities contain negative charge
60. (b) Liquid aerosol involves liquid dispersed in and alum give positive charge particle for
gas, e.g. cloud, fog, mist etc. coagulation.
64. (b) 2 HNO3  3 H 2 S  3S  4 H 2O  2 NO 139. (c) Alum is purifies muddy water by coagulation
(Sol)
due to opposite charge.
65. (b) Lyophobic colloids are irreversible colloids.
142. (c) The particle size is in the order 10 Å  1000 Å .
66. (b) Crystalloids are diffuse through parchment
membranes. 144. (a) FeCl3 is a electrolyte give Fe 3  and blood
contain negatively colloid so stop bleeding due
67. (a) Colloidal particles range between 10 7 to
to coagulation.
10 9 m or 10 5 to 10 7 cm.
145. (c) AT (CMC) critical micellization concen-
70. (c) Fe 3  ion coagulates –ve sol particles of blood tration, the surfactant molecules associate to
and seals the cut. form miscelles. For soap CMC is 10 3
mol/litre

146. (b) Inhibitors are also known as negative catalyst.
147. (c) Benzene is non polar in nature. As we know
that non-polar disperses more to non-polar
substances. Therefore, meta-metyl
nonylbenzene being nonpolar from both sides
will disperse more to benzene. All other
substances (a, b and d) have either one side
polar or both sides polar.
CH
non-polar end (metamethyl nonylbenzene) non-polar
3
end
 H19C9  C6 H 4  CH 3
151. (a) The protective action of different colloids is
expressed in terms of Gold number.
156. (a) Tyndall effect may be defined as the scattering
of light by the colloidal particles present in a
colloidal sol.
158. (a) It is due to adsorption of S 2  ions on the
surface of the colloidal particles and H  ions
in the diffused layer.
168. (c) Alum helps in purifying water by Al 3  ions
which coagulate the negative mud particles.
169. (d) Sn 4 contain maximum coagulation power
(coagulation power  number of charge on
ion)
170. (d) It is liquid in gas colloidal solution.
175. (c) Colloidal particles becomes uncharged
isoelectric point.
176. (c) Example of multimolecular colloid system is a
gold dispersed in water.
179. (a) The phenomenon of converting of fresh mass
into colloidal state by the action of solute or
solvent is known as peptization.
180. (a) Surface tension of lyophilic sol is lower than
that of the dispersion medium (i.e. H 2 O in
this case.)
182. (b) Hydrophilic sol can act as protective colloids
for hydrophobic solution.
183. (d) Metal sulphide is not used for preparing
lyophilic sol.
185. (b) According to definition emulsification.
186. (d) Toilet soap is a mixture of potassium salt of
higher fatty acids.
187. (c) Coagulation is governed by Hardy Schulze
rule.
1 207. (b) Fog is an example of aerosol where the
189. (a) Protective power 
Gold number
Gold number of A is least, therefore, it has the
highest protective power.
190. (b) Bredig's arc method is suitable for the
preparation of colloidal solution of metal like
gold silver, platinum etc. An arc is struck
between the metal electrode under the surface
Surface Chemistry 609
of water containing some stabilizing agent such
as a trace of KOH. However, Fe does not react
with alkalies that is why it is not obtained by
Bredig's arc method.
191. (d) Gold number shows the protective power of a
lyophilic solution. Lesser the gold number,
greater will be the protecting power of that
colloid. Gelatin is one of the best protective
colloid. Among the given colloids, potato
starch has maximum gold number.
1
192. (a) Protective power 
Gold number
Thus gelatin is the best protective colloid.
1
193. (b) Protective power 
Gold number
Hence, the correct order of protective power
is B  A  C  D .
194. (c) A catalyst does not participate in the reaction
but alters the rate of reaction.
195. (a) A colloid of liquid in liquid is called emulsion
cod liver oil is such an emulsion.
196. (a) Suspension of solid in a liquid.
197. (c) By the peptization, precipitate is changed to
colloidal solution.
198. (a) An aerosol is a dispersion of a solid or liquid
at in a gas.
199. (d) Lyophilic sols are self stabilizing because
these sols are reversible and are highly
hydrated in the solution.
Vc 10 5
200. (d)   10 3
Vs 10 7
204. (a) Alum contains many cations and water has
many anionic impurities. On adding alum
coagulates the suspended impurities and make
water fit for drinking purposes.
205. (a) For the stabilisation of an emulsion a third
component called emulsifying agent is usually
added. The emulsifier forms an interfacial
film between suspended particles and the
medium.
206. (b) Alum is added to muddy water so as to
destroy the bacteria as well as to coagulate
the suspended impurities.
dispersed phase is liquid and
dispersionmedium is gas.
208. (c) Lyophilic sols, are more stable than Lyophobic
sols because after vaporization its remaining
residue, convert into colloidal state after the
addition of solvent.
 610 Surface Chemistry
209. (e) The substance, whose molecules associate As 2 O3  3 H 2 S  As 2 S 3  3 H 2 O
with given solvent to form colloidal particle 15. (c) The amount of electrolyte required to
known as association colloidal. The molecule coagulate a fixed amount of a sol depends
of soap & detergent are generally smaller than upon the valency of flocculating ion.
colloidal particle. These molecules associate
in concentration solution to form colloidal 16. (d) Gold no. is a measure of protective power of a
size particle. These association of soap & lyophillic colloid.
detergent known as miscelle. 17. (c) The colloidal solution of liquid in liquid is
called emulsion not gel.
Critical Thinking Questions
18. (d) Linseed oil, lanolin and Glycogen attract
water hence contain a hydrophobic structure
1. (a) Lyophillic means liquid loving hence
but rubber does not attract water and does
hydration is contributed toward the extra
not contain a hydrophobic structure.
stability of lyophillic colloids.
2. (d) Traces of electrolytes are essential for 19. (c) Gum-arabic has protective power hence the
stabilising the sales hence for sales function of it ion in preparation of indian ink
destruction addition of electrolytes are is protective action.
required. 20. (b) Easily liquefiable gases like SO 2 , NH 3 , CO2 are
3. (c) A catalyst is a substance which alters the rate adsorbed to a greater extent than the
of reaction and shortens the time to reach elemental gases like N 2 , O2 , H 2 .
equilibrium.
21. (d) Volume of the gold dispersed in one litre
4. (d) Inhibitors are also catalysts but they slow
Mass 1 . 9  10 4 gm
down the rate of reaction. water    1  10 5 cm 3
5. (d) The ability of an ion to bring about Density 19 gm cm  3
coagulation of a given calloid depend upon Radius of gold sol particle  10 nm
both the magnitude and sign of its charge.
 10  10 9 m  10  10 7 cm  10 6 cm
6. (c) Physiorption is a process in which the
particles of adsorbate are held to the surface 4 3
Volume of the gold sol particle  r
of adsorbent by physical forces hence does not 3
requires activation energy. 4 22
   (10 6 )3  4 .19  10 18 cm 3
7. (a) Egg is a calloid of solid and liquid; Ruby glass 3 7
is a colloid of solid and solid. Milk is a colloid
No. of gold sol particle in
of liquid and liquid but chlorophyll is a
1  10 5
complex of magnesium. 1  10 5 cm 3 
8. (b) Surfactant are those which have charge on 4.19  10 18
their tail e.g., cetyltrimethyl ammonium  2 .38  10 12
bromide.
No. of gold sol particle in one mm 3
CH 3
| 2.38  10 12
    2.38  10 6
CH 3  (CH 2 )15  N  CH 3  Br 10 6
|
CH 3 22. (d) Sodium acetate forms cationic micelles in the
Surfactants are those, which dissociate in molecule of soap and detergent the negative
water to yield positively charged ion. ions aggregate to form a micelle of colloidal
size. The negative ion has a long hydrocarbon
9. (a) The size of colloidal particles is of the order
0 . 1m  to 0 . 001 m  . chain and a polar group (COO  ) at one end.

10. (b) K 4 [Fe(CN )6 ] is most effective in the

Assertion & Reason
coagulation of gold-solution.
11. (d) A catalyst is used to decrease the time
1. (a) Both assertion and reason are true and reason
required for the reaction hence it can decease
is the correct explanation of assertion.
or increase the rate of reaction.
The surface of a solid (or liquid) tends to
12. (d) Absorption, Tyndall effect and flocculation all
attract and retain other molecules when it is
are related to sol but paramagnetism is not
brought in contact with a gas or a solution.
represented by sol.
13. (a) On shaking with the dispersion medium, 2. (e) Assertions is false but reason is true.
colloids directly form the colloidal sol. Hence The enthalpy of chemisorption is of the order
they are called intrinsic colloids. i.e., glue. of 200 kJmol 1 while for physical adsorption it
14. (c) Arsenious sulphide can be prepared by double is of the order of 20 kJmol 1
.
decomposition
 Surface Chemistry 611
3. (a) Both assertion and reason are true and reason the polar nature of NH 3 due to which it
is the correct explanation of assertion . readily absorb. Hence assertion is true but
4. (c) Assertion is true but reason is false. reason is false.
Freundlich adsorption isotherm gives an 15. (a) The sky appears blue because the colloidal
empirical relation ship between the quantity particles of dust, dirt in air scatter blue light
of gas adsorbed by unit mass of solid to the maximum extent. Here both assertion
adsorbent and pressure at a particular and reason are correct and reason is the
temperature. correct explanation of assertion.
5. (d) Both assertion and reason are false. 16. (d) The assertion that physical absorption of
molecules takes place on surface only is false.
There are reactions in which one of the
Actually absorption takes place on the whole
products acts as catalyst (autocatalysis) and
body. In physical absorption the bonds of
no catalyst is added.
absorption molecules are not broken. Hence,
6. (b) Both assertion and reason are true but reason both assertion and reason are false.
is not the correct explanation of assertion. 17. (b) Here both assertion and reason are correct
ZSM – 5 converts alcohols directly into but reason is not a correct explanation of
gasoline (petrol) by dehydrating them so that assertion. Micelle is formed if molecules with
a mixture of hydrocarbons is formed. polar and nonpolar ends assemble in bulk to
7. (b) Both assertion and reason are true but reason give nonpolar interior and polar exterior.
is not the correct explanation of assertion. 18. (a) Both assertion and reason are true and
If the dispersion medium is separated from reason is the correct explanation of assertion.
the dispersed phase, the lyophilic sol can be Scattering of light is the main phenomenon of
reconstituted by simply remixing with the colloidal particles. In which colloidal particles
dispersion medium. That is why these sols are scatter a particular wavelengths light.
also called reversible sols. 19. (c) It is true that if we increase the surface area
8. (b) Both assertion and reason are true but reason the rate of evaporation also increase as
is not the correct explanation of assertion. evaporation is always takes place from the
The size of colloidal particles is large enough surface. But if the intermolecular attraction is
to scatter light while particles of a true stronger than the rate of evaporation is
solution are too small to scatter light. slower.
9. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
The impact of the molecules of the dispersion
medium on the colloidal particle are unequal
leading to zig-zag motion i.e., Brownian
movement.
10. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
According to Hardy – Schulze rule :
Coagulating power of an electrolyte is directly
proportional to the fourth power of the
valency of the ions causing coagulation.
11. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
Soap coats the drops of an emulsion and
checks them from coming together and the
emulsion is thus stabilised.
12. (a) It is fact that deep electric shock causes death
of an animal and the reason for this is that
blood is coagulated by electric shock.
Therefore, here both assertion and reason are
true.
13. (a) A catalyst is more effective in finely divided
form because finely divided form has more
surface area. Therefore there is an increase in
active centres on the surface.
14. (c) NH 3 absorbs more readily over activated
charcoal than CO2 it is correct. The reason is
 Surface Chemistry 611

1. In which of the following commercial processes a (c) Being used up

catalyst is not used [CPMT 1989]
(d) Being proteinous in nature
(a) Haber's process
8. Commercial detergents mainly contain[CPMT 1993]
(b) Deacon's process
(a) RCOONa
(c) Solvay process
(b) RONa
(d) Lead chamber process
(c) RSNa
2. A catalyst [IIT 1984; AFMC 1995; CBSE PMT 1995]
(d) ROSO 2 Na
(a) Increases the average kinetic energy of
reacting molecules 9. In which of the following processes shape-
(b) Increases the activation energy selective catalysis is occurring

(c) Alters the reaction mechanism (a) Conversion of alcohol to gasoline

(d) Increases the frequency of collisions of (b) Synthesis of methanol from CO and H 2
reacting species
(c) Polymerisation of ethylene
3. The coagulation of 100 ml of a colloidal sol of gold
(d) Synthesis of ammonia
is completely prevented by addition of 0.25 g of a
substance `X' to it before adding 10 ml of 1% 10. Which one of the following is used for reviving
NaCl solution. The gold number of `X' is the exhausted permutite [EAMCET 2003]
(a) 0.25 (b) 25 (a) HCl solution
(c) 250 (d) 2.5 (b) 10 % CaCl2 solution
4. Which one of the following is not a property of (c) 10% MgCl2 solution
hydrophilic sols [AIIMS 1983, 84]
(a) High concentrations of dispersed phase can be (d) 10% NaCl solution
easily attained 11. The ability of a catalyst to accelerate the chemical
(b) Coagulation is reversible reaction is known as [CPMT 2000; KCET 2000]

(c) Viscosity and surface tension are about the (a) Selectivelty
same as for water (b) Activity
(d) The charge of the particle depends on the pH (c) Negative catalyst
values of the medium; it may be positive,
(d) None of these
negative or even zero
12. AlCl3 , in reactions, acts as [
5. Peptising agent is
(a) Always an electrolyte (a) Oxidizing agent
(b) Always a non-electrolyte (b) Reducing agent
(c) Electrolyte or non-electrolyte (c) Acid catalyst
(d) A lyophilic colloid (d) None of these
6. The catalyst used in the manufacture of methanol 13. On addition of one ml of 10% NaCl solution to 10
from water gas is [MP PET 2002] ml gold sol in the presence of 0.25 gm of starch.
(a) V2 O5 (b) Ni + Mo The coagulation is just prevented, starch has gold
number [MP PET 2004]
(c) ZnO + Cr2O3 (d) Pt + W
(a) 0.025 (b) 0.25
7. Organic catalysts differ from inorganic catalysts
(c) 2.5 (d) None
[AFMC 1989]
14. Milk is an example of
(a) By acting at very high temperature
[MP PET 2001; JIPMER 2002; MP PMT 2002,04]
(b) By acting at low temperature
(a) Pure solution
 612 Surface Chemistry
(b) Gel (d) Suspension
(c) Emulsion

(SET -14)

1. (c) In Haber's process we use iron as a catalyst, In

Deacon's process we use Cu 2 Cl2 as a catalyst
and in lead chamber process we use N 2 O5 as a
catalyst but in solvay process no catalyst is
used.
2. (d) A catalyst can increase the rate or reaction
and hence increases the frequency of collision
7. (d) Organic catalyst are proteinous in nature and
of reacting species.
obtain from living cell.
3. (b) 250 mg of X is present in 100 ml of colloidal
8. (a) Commercial detergents mainly contain salts of
sol of gold. By definition, gold no. of X is that higher fatty acids.
amount of it in mg which is present in 10 ml
9. (a,c) Shape selective catalyst are zeolites
of colloidal gold solution. Hence in 10 ml, the
and zeolites are alminosilicates of general
amount of X present is 25 mg which is the formula M x / n [( AlO2 ) x .(SiO2 )y ].mH 2 O . Zeolites
gold number of X.
are used in conversion of alcohol to gasoline
4. (c) Viscosity and surface tension are not same for and in polymerisation of ethylene.
water in hydrophillic sols. 10. (d) 10% NaCl solution is used for reviving the
5. (a) Process of converting precipitate into colloidal exhaust permutite.
particles by adding suitable electrolyte called 11. (b) The ability of a catalyst to accelerate the
peptisation and stabilizing agent chemical reaction is known as its activity.
(electrolytes) as peptizing agent. Degree of acceleration can be as high as
ZnO  Cr 2 O 3 10 10 times in certain reactions.
6. (c) [CO  H 2 ]  H 2    CH 3 OH
12. (c) AlCl3 may be written as Al 3 Cl  and all the

*** tri-positive ions are Lewis acid hence it can be

acts as acid catalyst.
13. (d) 0 . 25  1000  250
14. (c) Milk is the example of emulsion of fat
globules in water.

Periodic table is an arrangement of elements
with similar properties placed together. The periodic
table evolved largely as a result of experimental
observations.
Earlier attempt to classify elements
(1) Dobereiner’s law of triads (1829) : It was the
classification of elements into groups of three elements
each with similar properties such that the atomic
weight of the middle element was the arithmetic mean
of the other two e.g. Ca, Sr, Ba, Cl, Br, I etc.
(2) Telluric screw or Helix (1862): It was
proposed by Chancourtois.
(3) Newlands law of octaves (1864) : It was an
arrangement of elements in order of increasing atomic
weights in which it was observed that every eighth
element had properties similar to those of the first just
like the eighth node of an octave of music.
(4) Mendeleef’s period law (1869) : The first
significant classification was given by Mendeleeff in
the form of periodic table, commonly known as
Mendeleeff's periodic table. His periodic table was
based on periodic law, ''The physical and chemical
properties of elements are periodic functions of their
atomic weights.''
In Mendeleef’s periodic table elements are
arranged in order of their increasing atomic weights in
such a way that elements with similar properties are
placed in the same group. It consists of seven
horizontal rows called periods. These are numbered
from 1 to 7.
Chemical Periodicity 613
Chapter
15
Chemical Periodicity
Mendeleef’s original table consists of 8 vertical
columns called groups. These are numbered as I, II
III….. VIII. However, 9th vertical column called Zero
group was added with the discovery of inert gases.
Except for group VIII and zero, each group is further
divided into two sub-groups designated as A and B.
Group VIII consists of 9 elements arranged in three sets
each containing three elements.
(5) Modern Periodic Law : The recent work has
established that the fundamental property of an atom
is atomic number and not atomic weight. Therefore,
atomic number is taken as the basis of the
classification of the elements. The modern periodic law
was given by Moseley, it may be stated as : ''The
properties of elements are periodic functions of their
atomic number".
When atomic number is taken as the basis for
classification of elements, many anomalies of Mendeleef's
table disappear, such as the,
(i) Position of hydrogen : Dual behaviour of
hydrogen is explained on the fact that it has one electron
in its outermost orbit. When it loses its electron it gives
H+ and behaves like alkali metals and when it gains an
electron it gives H– and behaves like halogens. Thus, it
resembles with both the alkali metals and the halogens.
(ii) Dissimilar elements placed together : The
lengths of periods are determined by the arrangement
of electrons in different orbits. The period ends on the
completion of last orbits (last members always being
the inert gas). Different periods contain 2, 8, 18 or 32
elements. Now out of the two elements which every
 614 Chemical Periodicity
long period adds to the group, one resembles the
typical elements while the other does not. This gives
rise to formation of subgroups. This explains the
inclusion of dissimilar elements in the same group but
different subgroups.
(iii) Position of rare earth elements : The
electronic arrangement of rare earths can be written as
2, 8, 18, (18 + x), 9, 2 where x varies from 0 to 13, i.e.,
from Lanthanum to Lutecium. The number of electrons
in valency shell, in case of all the elements remain the
same although the atomic number increases. Since they
possess the same number of valency electrons, the
chemical behaviour is also similar. This justifies their
positions in the same group and in the same place of
the periodic table.
(iv) Anomalous pairs of elements : Now the basis of
classification is atomic number, therefore, this anomaly
disappears as the elements occupy their normal position
in the new periodic table.
(v) Position of isotopes : Since the isotopes of
same element possess same atomic number they should
occupy one and the same position in the periodic table.
(vi) Position of VIII group elements : In long
periods 18 elements are to be distributed among 8
groups; 1 to 7 groups get 2 elements each and zero
group accommodates inert elements, the rest three
elements are placed at one place in a new group, known
as VIII group. This lack of space justifies the induction
of VIII group in the periodic table.
(vii) Transuranic elements : These elements form
a series known as actinide series, it begins from
actinium and ends at lawrencium (89–103). This series
has been placed outside the periodic table. The
electronic configuration of these elements can be
written as 2, 8, 18, 32, (18 + x), 9, 2, where x varies
from zero (for actinium) to 14 (for lawrencium). The
number of valency electrons remains the same for all
these elements although atomic number increases.
Therefore, their chemical behaviour is similar. This
justifies their position outside the periodic table at one
place.
Classification of element on the basis of
electronic configuration
According to Bohr the element have been grouped
into four types
(1) Inert gases : These atom have been full fill
outer most s and p subshell and having the
configuration ns 2np 6 (Exception helium having 1s 2 )
due to stable configuration these element do not show
chemical activity under normal condition and thus
termed as inert gases. Under special conditions, the
higher members do form some compounds with other
elements and hence, the name has been changed to
Noble gases. Six element He , Ne, Ar, Kr, Xe and
Rn belongs to this group.
(2) Representative or normal elements :
Element in which atom have all shells complete except
outermost shell which is incomplete. The number of
electrons in the outermost shell varies from 1 to 7 i.e.
the configuration of the outermost shell varies from
ns 1 to ns 2np 5 . These consist of some metals, all non
metals and metalloid. These are the elements which are
found in nature in abundance and active in nature. On
account of this, these elements are called
representative elements. All the three types of
valencies are observed in the case of these elements.
These elements have one of the following configuration
in their outermost shell.
ns 1 ns 2 ns 2 np 1 ns 2 np 2 ns 2 np 3 ns 2 np 4 ns 2 np 5
1 2 2 4 5 6 7
The number of electrons present in the outermost
shell signify the group to which these element belong.
(3) Transition elements : In the atoms of these
elements the outermost shell and the penultimate shell
(Next to the outermost) are incomplete. These elements
have the general configuration (n  1) d 1  9 ns 0 or 1 or 2 either
in the ground state or in excited state. These elements
are present in IV th , V th , VI th and VII th period of periodic
table and called transition elements. There are four
transition series every series consists 9 elements each.
(4) Inner transition elements : Atoms of these
elements have three outermost shell incomplete. The
general configuration is (n  2) f 1 14 (n  1) d 0 or 1 ns 2 . There
are two series of elements.
(i) Lanthanides or rare earths from Ce (58 ) to
Lu (71) .
(ii) Actinides from Th(90 ) to Lr (103 )
Each series consists of 14 elements i.e. in the
lanthanides, 4 f is gradually filled up while in actinides,
5 f is gradually filled up.
The properties of these elements are similar to
transition elements. The members of actinide series are
radioactive and majority of them are not found in
nature. The elements from atomic number of 93
onwards are called transuranic elements and have been
discovered artificial means.
In this classification the element, Zn, Cd and Hg
have not been included in any of the four groups of
elements. The elements Lu and Lr of the inner
transition group have (n  2) f shell complete consisting
14 electron hence their inclusion in this group is not
justified.

Extended or long form of periodic table
Modern periodic table is also called long form of
the periodic table or Bohr’s table. In this table, the
elements are arranged in order of their increasing
atomic number. It consists of 4 blocks (s, p, d and f), 18
groups numbered from 1 to 18 and 7 periods numbered
from 1 to 7.
Blocks : The periodic table is divided into four
main blocks (s, p, d and f) depending upon the subshell
to which the valence electron enters into.
(1) Elements of group 1 and 2 constitute s-Block.
(2) Elements of group 13, 14, 15, 16, 17, 18
constitute p-Block
(3) Elements of group 3, 4, 5, 6, 7, 8, 9, 10, 11, 12
constitute d-Block
(4) The f-Block elements comprise two horizontal
rows placed at the bottom of the periodic table to avoid
its unnecessary expansion.
Discovery of element 104, 105 and 112 has recently been reported
(4f1–145d0–106s2)
(5f1–146d0–107s2)
All the other groups are named after the first
member of each group.
Chemical Periodicity 615
Elements of s- and p-blocks are called normal or
representative elements, those of d-block are called
transition elements while the f-block elements are
called inner transition elements.
Groups : The 18 vertical columns are called
groups. The elements belonging to a particular group is
known as a family and is usually named after the first
number. Apart from this some of the groups are given
typical names as examplified beneath,
(1) Elements of group 1 are called Alkali-Metals.
(2) Elements of group 2 are called Alkaline
Earths.
(3) Elements of group 3 are called Pnicogens.
(4) Elements of group 16 are called Chalcogens.
(5) Elements of group 17 are called Halogens.
(6) Elements of group 18 are called Noble Gases
or Aerogens.
[(n–2)f1–14(n–1)d0–
10
ns2]
 616 Chemical Periodicity
Periods : The horizontal rows are called periods.
There are seven periods in the long form of the periodic
table,
(1) Ist period 1H 2 He ) contains 2 elements. It is
the shortest period.
(2) 2nd period (3 Li 10 Ne) and 3rd
(11 Na 18 Ar) contains 8 elements each. These are short
periods.
(3) 4th period (19 K 36 Kr) and 5th
(37 Rb 54 Xe ) contains 18 elements each. These are long
periods.
(4) 6th period (55 Cs 86 Ra) consists
elements and is the longest period.
(5) 7th period starting with 87 Fr is incomplete
and consists of 19 elements.
Periodicity in properties
''The repetition of similar electronic configuration
after a definite period is the cause of periodicity of the
properties of elements.''
It can be explained with the help of electronic
arrangement of elements. According to the modern
views, the valency of an element is indicated by the
number of electrons present in the outermost orbit. The
chemical properties of elements are dependent on
valency electrons. Variation in electronic arrangement
leads to the variation in properties. After a definite
interval, recurrence of similar electronic arrangement
takes place when the number of valency electrons is the
same. Thus, there is a regular gradation and repetition
in the properties of elements.
Periodic properties are directly or indirectly
related to their electronic configuration and show a
regular gradation on moving from left to right in a
period or from top to bottom in a group. Some period
or from top to bottom in a group. Some important
periodic properties are : oxidation number, shielding
effect, atomic radii, ionization energy, electron
affinity, electro-negativity, valency, density, m.pt.
and b.pt.
The screening effect or shielding effect
A valence-electron in a multi-electron atom is
attracted by the nucleus, and repelled by the electrons
of inner-shells. The combined effect of this attractive
and repulsive force acting on the valence-electron
experiences less attraction from the nucleus. This is
called shielding or screening effect. The magnitude of
the screening effect depends upon the number of inner
electrons, i.e., higher the number of inner electrons,
greater shall be the value of screening effect. The
screening effect constant is represented by the symbol
'  ' is determined by the Slater's rules.
The magnitude of screening constant in the case of
s- and p- block elements increases in a period as well as
period in a group as the atomic number increases.
Effective nuclear charge
Due to screening effect the valency electron
period experiences less attraction towards nucleus. This
brings decrease in the nuclear charge (Z) actually
present on the nucleus. The reduced nuclear charge is
termed effective nuclear charge and is represented by
of 32
Z * . It is related to actual nuclear charge (Z) by the
following formula,
Z *  (Z   ) where  is screening constant.
It is observed that magnitude of effective nuclear
charge increases in a period when we move from left
to right.
In a subgroup of normal elements the magnitude
of effective nuclear charge remains almost the same.
Covalent, Ionic and Vander waal's radii
The radius of an atom is the distance between
the centre of its nucleus and electrons in the last
orbit. However, according to quantum mechanics,
there is no certainty about the exact position of
electrons at any time. Theoretically, an electron, at
one time, may be very close to the nucleus while at
other time it may be far away from the nucleus. In
spite of these limitations we need to have some
operational definition of the term atomic radius.
There are three operational concepts of atomic
radius.
(1) If the bonding is covalent, the radius is called
a covalent radius.
(2) If the bonding is ionic, the radius is called
ionic radius.
(3) If the two atoms are not bonded by a chemical
bond (as in noble gases) the radius is called vander Waal's
radius.
(1) Covalent radius : It is half of the distance
between the nuclei of two like atoms bonded together by a
single bond. Thus covalent radius of carbon in a
compound having C – C single bond can be determined
by dividing the bond length by 2, i.e.,
C C
rc   C  C  2rc or rc  rc
2

where, rc is the single bond covalent radii (SBCR)
of carbon. However, if atoms forming the covalent bond
are different i.e., one is more electronegative than the
other then the atomic radius is determined by the
relation
A  B  rA  rB  0.009 ( A   B )
where  A and  B are electronegativities of the
atoms A and B respectively. This relation was given by
Stevenson in 1941.
In a given period, atomic radius generally
decreases from left to right and thus in any period,
alkali metal is the largest and halogen is the smallest
atom. For example, in second period elements the
covalent radii decrease from Li to F.
3Li 4Be 5B 6C 7N 8O 9F
1.23 0.8 0.8 0.77 0.7 0.7 0.72
9 0 4 4
The decrease in size along a period is due to the
effect of successive increasing nuclear charge without
addition of a new shell, i.e., in each element of a given
period a new electron is added in the same principal
quantum number. For example, in the second period
the nuclear charge increases from + 3 in Li to + 9 in F.
The increased nuclear charge attracts the electrons
more strongly to the nucleus and thus decreases the
size of the atom. In case of noble gases, the atomic
radii are only the vander Waal's radii which are
naturally higher than the covalent radii of other
elements.
In a given group, Atomic radius generally increases as
one moves from top to bottom, e.g., in group 1 atomic size
increases steadily from lithium to cesium,
rCs  rRb  rK  rNa  rLi
The increase in size on descending a group is due
to addition of extra shell which outweighs the effect of
increased nuclear charge. Remember that He and Fr are
smallest and largest atom respectively.
(2) Ionic radius : It is the effective distance from
the nucleus of an ion upto which it has its influence on
its electron cloud.
A cation is always much smaller than the
corresponding atom. Further, more the number of
electrons removed smaller will be the size of the
resulting positive ion. For example, rFe  r 2   r 3  .
Fe Fe
1.26 0.76
This is due to following two factors
Chemical Periodicity 617
(i) A cation formed by the loss of electrons may
result in the complete disappearance of the outer shell
and since the remaining inner shells do not extend so
far in space, the cation is much smaller than the metal
atom. For example,
Sodium atom (Na)  Sodium ion (Na+)
(2, 8, 1) (2, 8)
(ii) Whenever a cation is formed, the ratio of
nuclear charge to the number of electrons (Z/e ratio) is
increased with the result the effective nuclear charge is
increased and the electrons are pulled towards the
nucleus. Consequently, the cation becomes smaller. An
anion is always larger than the corresponding atom.
For example, Atomic radius of I = 1.23 ; Ionic radii of I–
= 2.16
10Ne
This is again due to following two factors : (a)
1.6
Since in the formation of an anion, one or more
electrons are added, the electron cloud expands and the
ionic size increases. (b) In the formation of anion, the
effective nuclear charge decreases with the result the
electrons get away from the nucleus and thus the anion
becomes larger than the corresponding atom.
In any particular group, the ions of elements
increase in size on moving from top to bottom.
In case of isoelectronic ions (ions having same
number of electrons but different nuclear charge); the
greater the nuclear charge, the greater is the attraction
for electrons and smaller is ionic radius. Hence size of
such ions decreases. Which is as follows
C 4  N 3  O 2  F 1  Ne  Na   Mg 2  Al 3  Si 4  P 5  S 6  Cl 7
Size of ions (in decreasing order)
i.e.
(3) Vander Waal's radius : It is one–half of the
distance between the nuclei of two adjacent atoms
belonging to two neighbouring molecules of an element
in the solid state.
The covalent radius is always smaller than the
corresponding vander Waal's radius. This is because of
the fact that in the formation of a chemical bond, the
two atoms have to come closer to each other. This also
explains why covalent bonds are much stronger than the
vander Waal's forces. It is important to note that since
the noble gases ordinarily do not form any covalent
bond, in crystals of noble gases, no chemical forces are
operating between the atoms. Hence the vander Waal's
0.64 forces are the only attractive forces in these cases. In
other words, the vander Waal's radii constitute the
 618 Chemical Periodicity
atomic radii of noble gases and since vander Waal's
radii are larger than covalent radii, atomic radii of
noble gases are largest in their respective periods
(anomaly).
Ionisation potential or ionisation energy
The electrons in an atom are attracted by the
nucleus. When an electron is to be removed then work
is done against this nuclear attraction. In other words
energy is required to remove an electron from an atom.
To understand the details of chemical behaviour of an
element we must have an indication of the energy with
which an atom binds its electrons. This is obtained by
the measurement of ionisation potential or ionisation
energy. It may be defined as the energy required to
remove an electron from the outermost orbit of an
isolated gaseous atom in its ground state. It is
expressed in electron volts (eV) or kilo calories per
gram atom. In an atom, the energy required to remove
first electron from a gaseous atom is called first
ionisation energy. The energy required to remove one
electron from a unipositive ion to form a bipositive ion
is called second ionisation energy. Second ionisation
energy is higher than the first. The reason is that in
unipositive ion left after the removal of one electron
from the atom, the electrons are more firmly bound to
the nucleus than in the atom. Hence more energy is
needed to remove the second electron.
A  A e 1
(First I. E.)
 2 1
A A e (Second I. E.)
A 2  A 3  e 1 (Third I. E.)
Similarly, third ionisation energy is even more
than second ionisation energy.
(1) Variation of ionisation energy in periodic
table
(i) Ionisation energy decreases in a group as the
atomic number increases. It is based on the fact that as
we move down a group, the size of atom increases, and
the outer electrons become farther away from the
nucleus thus reducing the force of attraction and hence
ionisation energy decreases.
Li Na K Rb
5.4 eV 1. eV 4.3 eV 4.2 eV
(ii) Ionisation energy increases along a period with
increase in atomic number. This is due to the size of
atom since it decreases along a period and outer
electrons are most strongly attracted by the nucleus
and hence more energy is required to remove the
electron.
Li Be B C N O F Ne
5.4eV 9.3eV 8.3eV 11.3e 14.6 eV 13.6e 17.0e 21.6e
V V V V
(iii) The ionisation energies of inert gases are
greater than that of their immediate neighbour. It is due
to their complete octet ns2p6 configuration which is
highly stable. Therefore, it is very difficult to remove an
electron from the outermost orbit of an inert gas.
(2) Factors affecting the value of ionisation
energy
(i) Size of atom : With an increase in atomic size,
the ionisation potential is reduced, since the distance of
the outermost electron from the nucleus increases and
hence the force of attraction decreases.
(ii) The charge on the nucleus : With an increase
in the nuclear charge, there is an increase in force of
attraction of nucleus for electrons making the removal
of the electrons more difficult. Thus an increase in
nuclear charge increases the ionisation potential.
(iii) The shielding or screening effect of inner
shells : The valence electrons in a multi–electron atom
are pulled by the nucleus but are repelled by the
electrons of the inner shells. The valence electrons,
therefore, do not experience the total pull of the
nucleus. Instead the total pull of the nucleus is reduced
by the electrons in inner shells. This effect of reducing
the force of attraction of nucleus by the inner shells is
called screening effect. This effect is exhibited
maximum by s2p6 (the most stable) shell. Therefore, the
ionisation energy of K is much less than Cu, however,
both have one electron in their fourth shell.
K 19  1s 2 , 2 s 2 p 6 , 3 s 2 p 6 , 4 s1
Cu 29  1s 2 , 2 s 2 p 6 , 3 s 2 p 6 d 10 , 4 s 1
The ionisation energy of K is 4.33 eV while that of
Cu is 7.72 eV. This is due to a large screening effect of
s 2 p 6 , penultimate orbit in K while s 2 p 6 d 10 , penultimate
orbit in Cu which exhibit little screening effect.
Cs
(iv) Type of electrons involved : Ionisation
3.9 eV energy also depends upon the type, i.e., s, p, d or f,
electrons which are to be removed, s –electrons are
closer to the nucleus and are more tightly held as
compared to p, d or f electrons. Hence, ionisation
energy decreases in the order of s > p > d > f orbitals.

(v) Completely filled or half filled sub-shells :
According to Hund's rule, completely filled or half filled
orbitals are more stable. Therefore, it is comparatively
difficult to remove the electrons from these shells. The
ionisation energy of Be (9.3 eV) is more than B (8.3 eV)
because Be has 2s2 configuration of the outermost orbit
which is fully filled. Similarly, nitrogen (14.6 eV) has
more ionisation energy than oxygen (13.6 eV) because
nitrogen has outermost shell configuration as 2s2p3 in
which p shell is half filled and is more stable. Similarly,
ionisation energy of Mg is more than Al and that of P is
more than S.
(3) Relative ionisation energies
 IE1 and IE2 of the 2nd period elements
IE1 : Li < B < Be < C < O < N < F < Ne
IE2 : Be < C < B < N < F < O < Ne < Li
 IE1 and IE2 of the 3rd period elements
IE1 : Na < Al < Mg < Si < S < P < Cl < Ar
IE2 : Mg < Si < Al < P < S < Cl < Ar < Na
 IE1 of elements with very high values
Cl < H < O < Kr < N < Ar < F < Ne < He
(4) Importance of ionisation energy
(i) Lower is the ionisation potential of an
element, more would be its reducing power and also
reactivity.
(ii) It gives rough estimate about the basic
character of the elements.
(iii) The relative values of ionisation potential
and electron affinity of two elements are related to the
nature of bond formed during their combination.
(iv) The ionisation potentials provide
indication about the number of valence electron (s) in
an atom; the abnormally high value indicates that the
electron removed is other than the valence electron.
For example, IE1, IE2 and IE3 values are 5.39,
75.62 and 122.42 eV. Since the values shows sudden
jump, it indicates that the number of valence electron
in its atom is one. Similarly, values of IE1, IE2 and IE3 as
9.32, 18.21 and 153.85 eV indicate that the number of
valence electrons in its atom is two.
Electron affinity
Those atoms whose nuclear forces are
completely screened by electronic shells,
Chemical Periodicity 619
attraction for electrons. Such atoms capture electrons if
these are available with in their effective fields to
neutralise the electrostatic forces of the nucleus.
Energy is always liberated whenever there is a force of
attraction offered by an atom or ion, and this energy is
called electron affinity. This may be defined as, ''the
energy released when an extra electron is added to a
neutral gaseous atom''.
When first electron is added in a neutral atom
then some energy is released that is called first
electron affinity but in case of second electron affinity
energy will be absorbed due to electronic repulsion.
Example as
(a) O(g)  e   O(g)  E1 (H  ve , Exoenergic )
(b) O(g)  e   O 2  E2 (H  ve , Endoenergic)
Thus, higher the energy released in the process of
taking up an extra electron, the higher will be the
electron affinity. Higher the value of electron affinity
of an atom, the more is its tendency to change into
anion. It is very difficult to determine the electron
affinity experimentally. The values have been
calculated on the basis of thermodynamic concepts. It is
expressed in electron volts. The values of inert gases
are assumed to be zero because they have stable ns2p6
configuration and unable to accept any electron. The
values for alkali metals are between zero and one.
The electron affinities of Be, Mg and zero since
they have complete ns2 configuration which can not
accommodate extra electron. Similarly, the values for N
and P are very low because they also have completely
half–filled p orbitals (ns2p3) and are more stable.
(1) Factors affecting the value of electron
affinity
an (i) Atomic size : The value of electron affinity
decreases with the increase in the size of atom since
the nuclear attraction decreases down a group as the
atomic number increases. Its value increases as we
move along a period since the size of atoms decreases
along a period. The lower value of F than Cl is due to
the very small size of F in which negative charge is
highly concentrated and repels the incoming electron
thereby reducing the force of attraction of the nucleus
towards the adding electron and hence decreasing the
electron affinity. Thus, chlorine has a highest value of
electron affinity.
(ii) Nuclear charge : The value of electron
affinity increases with increasing nuclear charge. Thus,
not
offer
 620 Chemical Periodicity
its value increases with increase in nuclear charge
along a period. This trend is observed especially in IA, IIA and
(iii) Screening or shielding effect : The value of IIIA elements.
electron affinity increases with the decrease in
(d) The basic nature of the oxides decreases in
shielding effect of inner electrons. Besides, the value of
a period while acidic nature increases. In a group, basic
electron affinity also depends to some extent upon the
nature increases while acidic nature decrases.
type of orbital in which electron is added. The value is
greater when electron enters 's' orbital and decreases
Basic nature of Acidic nature of
successively for p, d and f orbitals. oxides oxides
(2) Importance of electron affinity : Certain Basic Decreas Acidic Increas
nature es nature
properties of the elements are predicted on the basis es
of oxides of oxides
of values of electron affinity. Increase Decreases

(i) The elements having high value high values of

electron affinity are capable of accepting electron
easily. They form anions and electrovalent compounds.
These elements are electronegative in nature.
(ii) The elements having high values of electron
affinity act as strong oxidising agents, for example,
F, Cl , Br , O, S , etc.
On the basis of the general trend of ionisation
potential and electron affinity, the following properties
can be predicted,
(a) Metallic nature decreases in a period while
nonmetallic nature increases. Metallic nature increases
in a group while non-metallic nature decreases. The
arrow () represents a group and () represents a
period.
Metallic Non-Metallic
Electronegativity
The tendency of an atom in a compound to attract
a pair of bonded electrons towards itself is known as
electronegativity of the atom. It is important to note
that electron affinity and electronegativity both
measure the electrons attracting power but the former
refers to an isolated gaseous atom while the latter to an
atom in a compound. Thus electron affinity is attraction
for a single electron while electronegativity is for a
pair of bonded electrons. Further electron affinity is
energy while electronegativity is a tendency.
Activity of the
metal
Activity of Decreas
the metal es
Increases

Metallic Decrease Non- Increas (1) Factors affecting the value of

(Electro s Metallic es electronegativity
+Ve) (Electro –
Increases Decrease (i) The size of the atom.
Ve)
s
(b) Reducing nature decreases in a period while (ii) Electronic configuration. Small atoms attract
oxidising nature increases. The reducing nature electrons more than the larger one and are therefore
increases in a group while oxidising nature decreases. more electronegative. Secondly, atoms with nearly
filled shell of electrons, will tend to have higher
Reducing Oxidising
nature nature electronegativity than those sparsely occupied ones.
Reducin Decreas Oxidising Increas (2) Variation of electronegativity in the
g es nature es periodic table
nature
Increase Decreases
s (i) In a period, electronegativity increases from
(c) Stability of metal increases while activity of left to right. This is due to decrease in size and increase
the metal decreases in a period and in a group stability in nuclear charge. Thus the alkali metals possess the
decreases while activity increases. lowest value, while the halogens have the highest. Inert
Stability of the gases have zero electronegativity.
metal
(ii) In a group, electronegativity decreases from
Stability Increase
top to bottom. This is due to increase in atomic size.
of s
the
metal Decreas
es
 Chemical Periodicity 621
If an element exhibits various oxidation state, the (d) The difference X A  X B is very high, the bond is
atom in the higher oxidation state will be more more ionic and less covalent. The molecule will be
negative due to greater attraction for the electron, e.g.,
represented in such case as BA (B  A  ) . Percentage ionic
Sn II (1.30) and Sn IV (1.90).
character may be calculated as,
(3) Electronegativity may be expressed on the
Percentage of ionic character
following three scales
 16 ( X A  X B )  3 .5( X A  X B )2
(i) Mulliken's scale : Mulliken regarded
electronegativity as the average value of ionization where X A and X B represents electronegativity of
potential and electron affinity of an atom. bonded atoms A and B.

Ionization potential  Electron affinity This relation was given by A.L. Allerd (1961).
Electroneg ativity 
2 (ii) Greater the value of difference (X A  X B )
(ii) Allred-Rochow scale : Allred and Rochow more stable will be the bond.
defined electronegativity as the electrostatic force HF H  Cl H  Br H I
exerted by the nucleus on the valence electrons. Thus
(X A  X B ) 1.9 0.9 0.7 0.4
0 .359 Z
  0 .744 where Z is the effective nuclear
r2 Stability decreases
charge and r is the covalent radius of the atom in Å. Stability of compounds in which X A  X B is very
(iii) Pauling scale : Pauling scale of small are unstable in nature, SiH 4 (0.3), NCl3 (0.0) , PH3 (0),
electronegativity is the most widely used. It is based on AsH 3 (0.1) are unstable.
excess bond energies. He determined electronegativity
difference between the two atoms and then by (iii) (XO  X A ) difference predicts the nature of the
assigning arbitrary values to few elements (e.g. 4.00 to oxides formed by the element A. X O is the
fluorine, 2.5 to carbon and 2.1 to hydrogen), he electronegativity of oxygen.
calculated the electronegativity of the other elements.
XO  X A is large, the oxide shows basic nature,
 A   B  0.208 E where A and B are
(e.g., Na2O ).
electronegativities of the atoms A and B respectively,
XO  X A is small, the oxide shows acidic nature,
the factor 0.208 arises from the conversion of kcal to
electron volt (1 eV = 23.0 kcal/mole), (e.g., SO 2 ).

while E  Actual bond energy  (E A  A  E B  B ) (iv) Ionic compounds having percentage ionic
character less than 20% were found coloured, e.g.,
Pauling and Mulliken values of electronegativities AgCl AgBr AgI Ag2 S
are related as below  (Pauling) = 0 .34  (Mulliken) –
22% 18% 11% 8%
0.2
White Light Dark Black
(4) Importance of electronegativity : The yellow yellow
following predictions can be made from value of
Lesser the percentage ionic character, darker will
electronegativity,
be the colour.
(i) Nature of the bond between two atoms can be
Some other periodic properties
predicted from the eelctronegativity difference of the two
atoms. (1) Atomic volume : It is defined as the volume
occupied by one gram atom of an element.
(a) The difference X A  X B  0, i.e., X A  X B the
Mathematically,
bond is purely covalent.
Gram atomic weight
(b) The difference X A  X B is small, i.e., X A  X B , Atomic volume 
Density in solid state
the bond is polar covalent.
Units of atomic volume are c.c./mole. Atomic
(c) The difference X A  X B is 1.7, the bond is 50% volume signifies the volume occupied by one mole
covalent and 50% ionic. (Avogadro number) of atoms of the given element in
solid state. Lower atomic volume generally leads to
 622 Chemical Periodicity
higher density, increased hardness and brittleness,
higher melting and boiling points, less malleability and
ductility.
(i) While descending a group, the atomic volume
generally increases which is due to increase in the
number of shells though the valence electrons in a
given group remains constant.
(ii) While going left to right across a period the
atomic volume first decreases to a minimum and then
increases. Francium has the highest atomic volume and
boron has lowest atomic volume.
(2) Density : The density of the elements in solid
state varies periodically with their atomic numbers. At
first, the density increases gradually in a period and
becomes maximum somewhere for the central members
and then starts decreasing afterwards gradually.
(3) Melting and boiling points : The melting
points of the elements exhibit some periodicity with
rise of atomic number. It is observed that elements
with low values of atomic volumes have high melting
points while elements with high values of atomic
volumes have low melting points. In general, melting
points of elements in any periodic at first increase and
become maximum somewhere in the centre and
thereafter begins to decreases.
Tungsten has the maximum melting point
(3410°C) amongst metals and carbon has the maximum
melting point (3727°C) amongst non-metals. Helium
has the minimum melting point (–270°C). The metals,
Cs, Ga and Hg are known in liquid state at 30°C.

The boiling points of the elements also show

similar trends, however, the regularities are not so
striking as noted in the case of melting points.
(4) Oxidation state (Oxidation number, O.N.) :
Oxidation number of an element in a compound is the
total number of electrons it appears to have gained or
lost (negative and positive oxidation states
respectively) during the formation of that particular
compound.
Note : For detail see chapter redox reaction.

(5) Magnetic properties : Magnetic properties of
matter depend on the properties of the individual
atoms. A substance (atom, ion or compound) capable of
being attracted into a magnetic field is known as
paramagnetic. The paramagnetic substances have a net
magnetic moment which in turn is due to the presence
of unpaired electron(s) in atoms, ions or molecules.
Since most of the transition metal ions have unpaired
d–electrons, they show paramagnetic behaviour. The
exceptions are Sc 3  , Ti 4  , Zn 2  , Cu  , etc. which do not
contain any unpaired electron and hence
diamagnetic.
Chemical Periodicity 623
(i) Hydration energy is the enthalpy change that
accompanies the dissolving of 1 mol of gaseous ions in
water.
(ii) Size of ions and its charge determines extent
of hydration. Greater the charge smaller the size of the
ion, greater the attraction for the lone pair of O of
H 2 O , hence greater the extent of hydration energy.
(a) Size of the hydration ion increases.
(b) Ionic mobility decreases i.e. heavier
(hydrated) ions moves slower.
are
(7) Acid-base-character of oxides

On the other hand, a substance which is repelled (i) On moving across a period, the basic character
by a magnetic field is known as diamagnetic. Such of the oxides gradually changes first into amphoteric
substances do not have any net magnetic moment and finally into acidic character.
because they do not have any unpaired electron. (ii) On moving down a group, reverse behaviour is
Electrons determine the magnetic properties of matter observed i.e., from more acidic to more basic.
in two ways,
(iii) Stability of oxides decreases across a period.
 Each electron can be treated as a small sphere of
negative charge spinning on its axis. The spinning of (8) Hydrides
charge produces magnetic moment. (i) Hydrogen combines with a number of other
 An electron travelling in closed path around a elements including metals and non-metals to form
nucleus will also produce magnetic moment just as compounds called hydrides.
does electric current travelling in a loop of wire.
(ii) Covalent nature of hydrides increases across a
The observed magnetic moment is therefore the sum period and decreases down the group.
of the two moments: the spin moment and the orbital
moment. It is expressed in units called Bohr Magnetons (iii) Ionic hydride are better reducing agents than
(BM). In terms of n (number of unpaired electron), covalent hydride and reducing nature of hydride
decreases across a period and increases down the
magnetic moment is given by the formula,   n (n  2)
group.
Greater the number of unpaired electrons in a
substance, the greater is the magnetic moment of the (A (B)(C) LiH NaH Mg AlH3 SiH3
) H2
substance. The value of magnetic moment has been covalent
Na (A)
used to calculate the number of unpaired electrons in
H
ionic
an ion. In some cases, even the structure of the KH (B)
molecule or complex is indicated by its magnetic reducing nature
moment. Rb (C)
H
Paramagnetism is generally measured by a
CsH (Minimum Maximum)
simple device known as Guoy's balance which involves
weighing the species in presence of a magnetic field.
Ferromagnetism is a special property observed in
(iv) Covalent and ionic hydrides are classified as
some substances in the solid state. Such substances are
follows,
strongly attracted to magnetic field and may retain the
magnetic properties for some time even after the Diagonal relationship
removal of the field. The most common example is of Fe
Certain elements of 2nd period show similarity
followed by Co and Ni.
with their diagonal elements in the 3rd period as shown
(6) Hydration and hydration energy below :
Group 1 Group 2 Group 13 Group
14
 624 Chemical Periodicity
2nd perio Li Be B
C

3rd period Na Mg Al Si

Thus, Li resembles Mg, Be resembles Al and B

resembles Si. This is called diagonal relationship and is
due to the reason that these pairs of element have
almost identical ionic radii and polarizing power (i.e.
charge/size ratio). Element of second period are known
as bridge elements.

Anomalous behaviour of the first elements of a

group: The first element of a group differs
considerably from its congeners (i.e. the rest of the
element of its group). This is due to (i) small size (ii)
high electronegativity and (iii) non availability of d-
orbitals for bonding. Anomalous behaviour is observed
among the second row elements (i.e. Li to F).
 622 Chemical Periodicity
Uus
118 un-un-octium
Uuo
119 un-un-ennium
Uue
 Elements of second period are known as Bridge
 The IUPAC nomenclature of elements > 100 elements. Their properties resemble with the
properties of diagonal elements of third period.
In IUPAC system, the names are derived by using
roots for the three digits in the atomic number of the  For isoelectronic ions the size depends on the
element and adding the ending : ium. The roots for nuclear charge. Greater is the nuclear charge
the numbers are smaller is the size.
Number 0 1 2 3 4 5 6 7  The incease in magnitude of radii is more in the
8 9 beginning of a group because the difference in
energy between energy shells is more.
Root nil un bi tri quad pent hex hept
oct enn  The ionisation potentials provide an indication
Atomic about the number of valence electrons (s) in an
Number Name atom e.g., Na has IE2 >>> IE1 (because it has one
Symbol valence electron) while Mg has IE3 >>> IE2 > IE1
101 un-nil-unium because it has two valence electrons and attains
Unu noble gas configuration after losing 2 electrons.
102 un-nil-bium  The highest I.E. in a period is shown by noble
Unb gas.
103 un-nil-trium
Unt
 The electronegativity of a series of transition
metals is almost similar. The electronegativity of
104 un-nil-quadium
all lanthanide’s are identical (1.1).
Unq
105 un-nil-pentium  The most electronegative elements is Fluorine
Unp (value is 4.0 on the Pauling scale). The least
106 un-nil-hexium electronegative elements is Cs and Fr with a
Unh value of 0.700.
107 un-nil-septium  The electron affinity of exactly half-filled
Uns
configuration is approximately zero and exactly
108 un-nil-octium zero for fully filled configuration.
Uno
 The electron affinities of gaseous anions are
109 un-nil-ennium
Une always negative.

110 un-un-nilium  Some of the polar crystals when heated produce

Uun electric current. This phenomena is termed as
111 un-un-unium piezoelectric effect.
Uuu  All the elements of f- block (4f series –
112 un-un-bium Lanthanides and 5f series – Actinides) are placed
Uub
in 3rd group (IIIB) and form a separate block at
113 un-un-trium the bottom of the periodic table.
Uut
114 un-un-quadium
Uuq
115 un-un-pentium
Uup
116 un-un-hexium
Uuh
117 un-un-septium Extended or long form of periodic table
 Chemical Periodicity 623
(a) Cerium (b) Actinium
1. Which of the following statement is not correct (c) Uranium (d) Lanthanum
for the element having electronic configuration 13. The d -block elements consists mostly of [MP PMT 1994]
1 s 2 , 2 s 2 p 6 , 3 s1 (a) Monovalent metals
(a) It is a monovalent electropositive (b) All non-metals
(b) It forms basic oxide (c) Elements which generally form stoichiometric
(c) It is a non-metal metal oxide
(d) It has low electron affinity (d) Many metals with catalytic properties
2. Which of these dose not reflect the periodicity of 14. “The 6 properties of the elements are periodic
the elements [UPSEAT 2001; BIT 1990; MP PMT 2001] function of their atomic numbers.” The statement
(a) Bonding behaviour (b) Electronegativity was given by
(c) Ionization energy (d) Neutron/proton ratio [MNR 1995]
3. If an atom has electronic configuration (a) N. Bohr (b) J.W. Dobereiner
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 3 4 s 2 , it will be placed in (c) D.I. Mendeleef (d) H.G.J. Moseley
[CBSE PMT 2002] 15. The long form of periodic table has
(a) Second group (b) Third group [CPMT 1986; KCET 1998]
(c) Fifth group (d) Sixth group (a) Eight horizontal rows and seven vertical
4. All the s–block elements of the periodic table are columns
placed in the groups … [Orissa JEE 2002] (b) Seven horizontal rows and eighteen vertical
(a) IA and IIA (b) IIIA and IVA columns
(c) B sub groups (d) VA to VIIA (c) Seven horizontal rows and seven vertical
5. The electronic configuration of halogen is columns
[MP PET/PMT 1998; Pb. PMT 2001] (d) Eight horizontal rows and eight vertical
(a) ns 2 np 6 (b) ns 2 np 3 columns
(c) ns 2 np 5 (d) ns 2 16. The telluric helix was given by [AFMC 1990]

6. Hydrogen by donating one electron forms H . In  (a) De Chan Courtois (b) Newlands
this property, it resembles with (c) L. Meyer (d) Mendeleef
(a) Transitional metals (b) Alkaline earth metals 17. Which one of the following belongs to
(c) Alkali metals (d) Halogens representative group of elements in the periodic
table [Kurukshetra CEE 1991]
7. The tenth elements in the periodic table
resembles with the (a) Lanthanum (b) Argon
[CPMT 1988] (c) Chromium (d) Aluminium
(a) First period (b) Second period 18. An element of atomic number 29 belongs to
[CPMT 1991; Kurukshetra CEE 1991; MP PET 2001]
(c) Fourth group (d) Ninth group
8. The element with quantum numbers (a) s -block (b) p -block
n  2, l  1, m  1, s  1 / 2 has the following position (c) d -block (d) f -block
in the periodic table 19. The element californium belongs to the family
(a) Group VII-A, period II (b) Group 0, period II [MNR 1987]
(c) Group VII-A, period III (d)Group 0, period III (a) Actinide series (b) Alkali metal family
9. Who developed the long form of periodic table (c) Alkaline earth family (d) Lanthanide series
[MP PET 1997] 20. On moving from left to right across a period in the
(a) Lothar Meyer (b) Niels Bohr table the metallic character [CPMT 1986]
(c) Mendeleef (d) Moseley (a) Increases
10. The electronic configuration of an element is (b) Decreases
1 s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 3 . What is the atomic number of (c) Remains constant
the element which is just below the above (d) First increases and then decreases
element in the periodic table [CBSE PMT 1995] 21. An element with atomic number 20 will be placed
(a) 33 (b) 34 in which period of the periodic table[MNR 1986; UPSEAT 19
(c) 31 (d) 49 (a) 4 (b) 3
11. In the periodic table, the element with atomic (c) 2 (d) 1
number 16 will be placed in the group [MP PET/PMT 1998]
22. The electronic structure (n  1) d 1 10 ns 0  2 is
(a) Third (b) Fourth characteristic of
(c) Fifth (d) Sixth [CET Pune 1998]
12. The first element of rare–earth metals is[AFMC 1992] (a) Transition elements (b) Lanthanides
 624 Chemical Periodicity
(c) Actinides (d) Rare gases 34. The element with atomic number 36 belongs to
23. The elements with atomic number 10, 18, 36, 54 …… block in the periodic table [KCET 2003]
and 86 are all [CPMT 1976] (a) p (b) s
(a) Light metals (b) Inert gases (c) f (d) d
(c) Halogens (d) Rare–earths 35. Which group of the periodic table contains only
24. Elements of atomic number 6 is placed in [CPMT 1978] metals
(a) IV group (b) IV period [UPSEAT 2003]
(c) VI group (d) III group (a) IIA (b) IB
25. Which of the following elements is a lanthanide (c) IA (d) None of these
(Rare–earth element) [Manipal MEE 1995] 36. The elements in which s and p-orbitals are
(a) Cadmium (b) Californium present
(c) Cerium (d) Cesium (a) Common elements
26. Mendeleef's periodic law is based on (b) Inert gases
(a) Atomic weight (b) Atomic number (c) Halogens
(c) Number of neutrons (d) None of the above (d) Transitional elements
27. The heaviest atom amongst the following is 37. Aluminium is diagonally related to (in periodic
[CPMT 1976; NCERT 1976] table)
(a) U (b) Ra [MP PET 1993]
(c) Pb (d) Hg (a) Li (b) C
28. Which of the following pairs has both members (c) B (d) Be
from the same group of the periodic table
38. An element has the electronic configuration
[CPMT 1985; MP PET/PMT 1998]
(a) Mg  Ba (b) Mg  Na 1s 2 ,2 s 2 2 p 6 , 3 s 2 3 p 6 3 d 5 , 4 s 1 . It is a

(c) Mg  Cu (d) Mg  K (a) s-block element (b) p-block element

29. Which of the following pairs has both members (c) d-block element (d) Inert gas
from the same period of the periodic table 39. Which of the following show diagonal relationship
[CPMT 1985; UPSEAT 2001; BHU 2003] [KCET 2003; MP PMT 2003]
(a) Na  Ca (b) Na  Cl (a) B and Si (b) B and Al
(c) Ca  Cl (d) Cl  Br (c) B and Ga (d) B and C
30. Diagonal relationship is shown by [DPMT 1984] 40. Which of the following dinegative anion is quite
(a) Elements of first period common
(b) Elements of second period [CPMT 2000]
(c) Elements of third period
(a) S 2  (b) Se 2

(d) (b) and (c) both

(c) Te 2  (d) O 2 
31. The elements having the electronic
41. An element has electronic configuration
configuration, [ Kr ] 4 d 10 f 14 , 5 s 2 p 6 d 2 , 6 s 2 belongs
1s 2 2 s 2 2 p 6 3 s 2 3 p 4 . Predict their period, group and
to [CPMT 1982]
block
(a) s-block (b) p-block
[CPMT 2000]
(c) d-block (d) f-block
(a) Period = 3rd, block = p, group = 16
32. Chemical property of Li and Mg similar because
(b) Period = 5th, block = s, group = 1
[RPMT 2002]
(a) These belong to same group (c) Period = 3rd, block = p, group = 10
(b) Both ionisation potential is same (d) Period = 4th, block = d, group = 12
(c) Shows diagonal relationship 42. If the atomic number of an element is 33, it will
be placed in the periodic table in the [RPET 1999; UPSEAT 2
(d) Both electron affinity is same
(a) First gp (b) Third gp
33. According to the periodic law of elements, the
variation in properties of elements is related to (c) Fifth gp (d) Seventh gp
their [AIEEE 2003] 43. Which of the following is the atomic number of a
(a) Atomic masses metal
[AIIMS 2000]
(b) Nuclear masses
(a) 32 (b) 34
(c) Atomic numbers
(c) 36 (d) 38
(d) Nuclear neutron-proton number
44. Which of the following statement is not correct
regarding hydrogen atom [AIIMS 2000]
 Chemical Periodicity 625
(a) It resembles halogens in some properties 53. The element X, Y, Z and T have the indicated
(b) It resembles alkali metals in some properties electronic configurations. Starting with the
(c) It can be placed in 7th group of periodic table innermost shell, which is the most metallic
(d) It can not be placed in first group of periodic element [CPMT 1979, 93]
table (a) X  2, 8, 4 (b) Y  2, 8, 8
45. Lithium shows similarities to magnesium in its (c) Z  2, 8, 8, 1 (d) T  2, 8, 8, 7
chemical behaviour because [AFMC 2000]
54. Which pair of atomic numbers represents s -block
(a) Similar size, same electronegativity and lower elements
polarizing power [EAMCET 1990; RPMT 1997; MP PET 2003]
(b) Similar size, greater electronegativity and (a) 7, 15 (b) 6, 12
similar polarizing power (c) 9, 17 (d) 3, 12
(c) Similar size, same electronegativity and 55. Which pair of elements has same chemical
similar high polarizing power properties
(d) None of these [EAMCET 1987]
46. On going left to right in a period, in transition (a) 13, 22 (b) 3, 11
metals, their atomic volumes [MP PMT 2003]
(c) 4, 24 (d) 2, 4
(a) Decrease (b) Increase 56. Mosley's name is most closely associated with the
(c) Remain same (d) None of these of discovery of
correct
(a) Positron (b) Deutrons
47. Electronic configuration of chalcons in their
(c) Atomic number (d) Atomic weight
outermost orbit is
57. In the periodic table going down in fluorine group
(a) s 2 p 3 (b) s 2 p 4 [CPMT 1981]
(c) s2 p5 (d) s 2 p 6 (a) Reactivity will increase
48. Which configuration represents a noble gas [DPMT 2000] (b) Electronegativity will increase
(c) Ionic radius will increase
(a) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2
(d) Ionization potential will increase
(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 58. Beryllium resembles much with [CPMT 1988]
(c) 1s 2 2 s 2 2 p 6 3 p 6 (a) Zn (b) Al
(d) 1s 2 2 s 2 2 p 6 3 s 2 (c) Li (d) Ra
59. The last member in each period of the periodic
49. Which of the following pair has elements
table is
containing same number of electrons in the
[DPMT 2001]
outermost orbit
[Kurukshetra CEE 1998; AFMC 2000] (a) An inert gas element (b) A transition element
(a) N , O (b) Na , Ca (c) A halogen (d) An alkali metal
(c) As , Bi (d) Pb , Sb 60. Which one of the following combination
represents a metallic element [EAMCET 1979]
50. Dobereiner traids is [RPMT 1997]
(a) 2, 8, 7 (b) 2, 8, 8
(a) Na , K , Rb (b) Mg , S , As
(c) 2, 8, 4 (d) 2, 8, 2
(c) Cl , Br, I (d) P , S , As
61. The electronic configuration of an atom A is 1 s 2 ,
51. As per the modern periodic law, the physical and
chemical properties of elements are periodic 2s 2 p 6 , 3 s 2 p 6 d 10 , 4 s 2 p 3 . The chemistry of A is
functions of their therefore likely to be similar to that of [MP PMT 1995]
[RPMT 1997; EAMCET (a) Chlorine (b) Nitrogen
1998] (c) Oxygen (d) Boron
(a) Atomic volume 62. The element having the electronic configuration
(b) Electronic configuration 1 s 2 , 2 s 2 2 p 6 , 3 s 2 3 p 1 is
(c) Atomic weight
(a) A transition element
(d) Atomic size
(b) A representative element
52. Elements after atomic number 103 have been
discovered till now. If an element with atomic (c) An inert gas
number 106 were ever discovered which of the (d) An inner–transition element
following electronic configuration will it possess[AIIMS63. The element with configuration
1982] 1s 2 , 2 s 2 p 6 , 3 s 2
14 4 2 14 5 1
(a) [Rn ] 5 f 6d 7 s (b) [Rn ] 5 f 6d 7 s would be
[CPMT 1986; MP PMT 1993]
(c) [Rn ] 5 f 14 6 d 6 7 s 0 (d) [Rn ] 5 f 14 6 d 1 7 s 2 7 p 3
(a) A metal (b) A non-metal
 626 Chemical Periodicity
(c) An inert gas (d) A metalloid (c) Highest ionization potential
64. The long form of periodic table is based on[CPMT 1997] (d) Highest electronegativity
(a) Shape of the atom 73. The elements on the right side of the periodic
(b) Mass of the atom table are
(c) Atomic number of the atom [CPMT 1976]
(d) Electronegativity (a) Metals (b) Metalloids
65. Chloride of an element A gives neutral solution (c) Non-metals (d) Transition elements
in water. In the periodic table, the element A 74. The screening effect of d-electons is [RPMT 2000]
belongs to (a) Equal to that of p-electrons
[AIIMS 1992; UPSEAT 2001]
(b) More than that of p-electrons
(a) First group (b) Third group
(c) Same as f-electrons
(c) Fifth group (d) First transition (d) Less than p-electrons
series
75. Chemical behaviour of an atom is determined by
66. The fundamental basis of the present-day Periodic
(a) Atomic number (b) Mass number
Table is that elements are [JIPMER 1999]
(c) Binding energy (d) Number of isotopes
(a) Arranged in the order of increasing atomic
weights 76. Which of the following is a inert element
(b) Grouped according to chemical properties (a) Na (b) Fe
(c) Arranged in the order of increasing number of (c) Li (d) He
neutrons in the atomic nucleus 77. The lightest metal is
[CPMT 1976; NCERT 1976; AFMC 1988]
(d) Arranged in the order of increasing number of
protons in the nucleus (a) Li (b) Mg
67. All the elements in a group in the periodic table (c) Ca (d) Na
have the same [NCERT 1974; MP PET 1996; MP PMT 1996]78. Choose the typical element
(a) Atomic number (a) K (b) Na
(b) Electronic configuration (c) Sc (d) He
(c) Atomic weight 79. Of the following pairs, the one containing
(d) Number of electrons in the outermost shell or example of metalloid elements in the periodic
number of electrons for bonding table is
68. The most predominantly ionic compounds will be (a) Sodium and potassium
obtained from the combination of elements (b) Fluorine and chlorine
belonging to (c) Calcium and magnesium
(a) 1 and 7 groups (b) 2 and 6 groups (d) Boron and silicon
(c) 3 and 5 groups (d) 0 and 7 groups 80. The number of elements in each of the long
69. An atom with atomic number 21 belongs to the periods in the periodic table is
category of (a) 2 (b) 8
[Kurukshetra CEE 1991] (c) 18 (d) 32
(a) s -block elements (b) p -block elements 81. In the long form of the periodic table, all the non-
(c) d -block elements (d) f -block elements metals are placed under [EAMCET 1988]

70. Which metal has 2 electrons in the outermost (a) s-block (b) p-block
orbit (c) d-block (d) f-block
(a) Na (b) Cu 82. Elements with outer electronic configuration
(c) Au (d) Be ns 2 np 6 are
71. In the modern periodic table, elements are [MP PET/PMT 1998]
arranged in (a) Alkaline earth metals(b) Transition elements
[MP PMT 1990; MP PET 1995; CPMT 1971, 73, 78, 80] (c) Chalcogenes (d) Noble gases
(a) Increasing mass 83. Highest density is of ………. [RPET 2000]
(b) Increasing volume (a) Ir (b) Os
(c) Increasing atomic number (c) Pb (d) Hg
(d) Alphabetically 84. Lithium shows diagonal relationship with
72. Alkali metals in each period have [MP PMT 1995] [MP PET 1995, 96; EAMCET 1990]
(a) Smallest size (a) Al (b) Mg
(b) Lowest ionization potential (c) Be (d) B
 Chemical Periodicity 627
85. 1s 2 2 s 2 2 p 6 3 s 2 is the electronic configuration of the (c) p -block (d) f – block
metal 98. Last element of group-IV is found to be [DPMT 1996]
[RPET 2000] (a) Strong metallic
(a) Na (b) Mg (b) Weak metallic
(c) Fe (d) Al (c) Strong non-metallic
86. Element having atomic number 17 is placed in (d) Weak non-metallic
[MP PET 1995]
99. Elements of d group are called [DPMT 1996]
(a) I-group (b) V-group
(a) Transition elements (b) Transuranic
(c) VIII-group (d) VII-group elements
87. The most importasnt active step in the (c) Metals (d) Metalloids
development of periodic table was taken by[CPMT 1976]
100. Which of the following is a normal element
(a) Mendeleef (b) Dalton
(a) Ce (b) He
(c) Avogadro (d) Cavendish
88. Who is called the father of chemistry [CPMT 1972] (c) Li (d) Ar
(a) Faraday (b) Priestley 101. Which of the following is metalloid[BHU 1996; AMU 2000]
(c) Rutherford (d) Lavosier (a) Pb (b) Zn
89. The total number of rare–earth elements is[CPMT 1993] (c) As (d) None of these
(a) 8 (b) 32 102. Under normal condition which of the following
(c) 14 (d) 10 electronic configuration is able to form dipositive
90. Which is metalloid [Bihar MEE 1997] ion [RPET 2000]
(a) Pb (b) Sb (a) [ Ar ] 4 s1 (b) [ Ne ] 2 s 2 3 p 6
(c) Bi (d) Zn (c) [ Ne ] 3 s 2 (d) None of these
(e) Mg
103. The statement that is true for the long form of the
91. The element or elements whose position is periodic table is [IIT 1988]
anomalous in the periodic table is (a) It reflects the sequence of filling the electrons
(a) Halogens (b) Fe, Co and Ni in the order of sub-energy levels s, p, d and f
(c) Inert gases (d) Hydrogen (b) It helps to predict the stable valency states of
92. An element M has an atomic mass 19 and atomic the elements
number 9. Its ion is represented by (c) It reflects trends in physical and chemical
  properties of the elements
(a) M (b) M
2 (d) It helps to predict the relative ionicity of the
(c) M (d) M 2 
bonds between any two elements
93. The number of elements in the 5th period of the
104. To which block is related an element having
periodic table are
electronic configuration 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 1
(a) 8 (b) 10
in the periodic table [MP PMT 1995]
(c) 18 (d) 32
(a) s - block (b) p - block
94. The element with atomic number 55 belongs to
(c) d - block (d) f – block
[MP PMT 1995]
(a) s-block (b) p-block 105. Ce  58 is a member of

(c) d-block (d) f-block (a) s-block elements (b) p-block elements
95. Coloured salts are formed by [Bihar MEE 1996] (c) d-block elements (d) f-block elements
(a) Alkali metals (b) Lanthanides 106. Atomic number of elements represent
(c) Actinides (d) Transition metals (a) Number of protons in the nucleus
(e) None of these (b) Number of neutrons in the nucleus
96. Which one of the following is an s - block element (c) Number of protons and neutrons in nucleus
[MP PMT 1999] (d) The valency of an element
(a) Aluminium (b) Chromium 107. As we go from left to right in period two of the
(c) Niobium (d) Potassium periodic table, gram atomic volume of the
97. In the modern periodic table, the place of the elements
element with atomic number 31 is in[MP PMT 1999] (a) Will change indefinitely
(a) s - block (b) d- block (b) Increases at a constant rate
 628 Chemical Periodicity
(c) First increases then decrease 115. Group comprising of all metals is [RPET 2000]
(d) Decreases (a) IIIA (b) IVA
108. The electronic configuration of the element which (c) VIIA (d) IIA
is just above the element with atomic number 43
116. Whose name is not associated with the
in the same periodic group is[MNR 1992; UPSEAT 1999, 2000, 02]
development of Periodic Table [
(a) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 5 4 s 2
(a) Prout’s (b) Newlands
(b) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 10 4 s 2 4 p 5 (c) Rutherford (d) Loother Meyer
(c) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 6 4 s 1 117. Element of atomic number 23 is placed in the
periodic table in [MP PMT 1996]
(d) 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 10 4 s 1 4 p 6
(a) s - block (b) p – block
109. The elements indicating following atomic
(c) d - block (d) f - block
numbers belong to same group [RPMT 1997]
(a) 11 and 37 (b) 19 and 15 118. In which of the following groups all the three
members are of the alkaline earth metals family
(c) 39 and 88 (d) None of these
(a) Al, Sr , Ti (b) Li, Na, K
110. Elements in which 4 f orbitals are progressively
filled are called as [MP PET 1996] (c) Mg, Ba, Ca (d) Rb, Cs, Fr
(a) Transition elements (b) Lanthanides
119. Astatine is a [RPET 2000]
(c) Actinides (d) Inert gases
(a) Halogen
111. Hydrogen can be put in halogen group because
(b) Rare earth element
[RPMT 2000]
(a) It has deuterium and tritium as isotopes (c) Alkaline earth metal
(b) It forms hydrides like chlorides (d) None of these
(c) It contains one electron only 120. The nitride ion in lithium nitride is composed of
(d) It is light [CBSE PMT 2001]
112. In the main group elements (i) as we proceed (a) 7 P  7 e (b) 10 P  7e
down the same group in the periodic table and (ii)
(c) 7 P  10 e (d) 10 P  10 e
as we proceed from left to right in the same
period, the atomic radius 121. Which set has the same number of unpaired
(a) (i) Increase continuously; (ii) Decreases electrons in their ground state [JIPMER 2000]
continuously (a) Cl , Fe3  , Cr 3  (b) Na  , Mg 2  , Al
(b) (i) Decreases continuously; (ii) Increases
(c) Na, P, Cl (d) N, P, V
continuously
(c) (i) Increases continuously; (ii) Decreases upto 122. Which of the following doesn’t decompose on
the group IV and then increases upto the end heating
of the period. [AMU 2002]

(d) (i) Decreases continuously; (ii) Decreases (a) MgCO3 (b) Na2 CO3
upto the group IV and then increases upto the (c) Li2 CO3 (d) Ca (HCO 3 )2
end of the period.
123. Which of the following has smallest bond angle
113. Cause of diagonal relationship is
[AMU 2002]
(a) Similar electronic configuration of the
elements (a) H 2 O (b) NH 3

(b) Similar e / r ratio of the elements (c) CH 4 (d) CO2

(c) Same number of valency electrons in the 124. The metal-having highest melting point is
elements [AMU 2002]
(d) Same atomic weights of the elements (a) Chromium (b) Tungston
114. From which of the following the hydration energy (c) Diamond (d) Silver
of Mg 2  is larger [MP PET 2000] 125. The elements with atomic numbers 9, 17, 35, 53,
 3 85 are all
(a) Na (b) Al
2
[KCET 2004]
(c) Be (d) Cr 3 
(a) Noble gases (b) Halogens
 Chemical Periodicity 629
(c) Heavy metals (d) Light metals (c) F  (d) N 3 
126. The atomic number of an element is derived from 4. Which of the following has largest size
[Kerala PMT 2004] [MP PMT 1995, 2003; JIPMER (Med.) 2002]

(a) Number of electrons (a) Al (b) Al 

(b) Number of protons (c) Al 2 (d) Al 3

5. Of the following, the one with largest size is
(c) Number of neutrons
[EAMCET 1997; BHU 1999]
(d) Number of isotopes (a) Cl  (b) Ar
(e) Number of nucleons (c) K  (d) Ca 2 
127. Beryllium shows diagonal relationship with [Pb.CET 2003]
6. Which cation has smallest radius [RPET 2000]
(a) Mg (b) Na (a) K  (b) Na 
(c) B (d) Al (c) Li  (d) Be 2 
128. Which of the properties remains unchanged on 7. The radii of F, F  , O and O 2 are in the order of
descending a group in the periodic table [AIIMS 1999; CPMT 1999]
2 
[MP PMT 1997; RPMT 2002] (a) O F OF (b) O 2   F   F  O
 2
(a) Atomic size (b) Density (c) F  O  F  O (d) O 2   O  F   F
(c) Valence electrons (d) Metallic character 8. Which of the following has the smallest size
[CBSE PMT 1996]
129. Which of the following element does not occur in
liquid form (a) Na  (b) Mg 2
[RPMT 2002] (c) Cl  (d) F 
(a) Hg (b) Li 9. Which of the following is largest [CBSE PMT 1996]
(c) Ga (d) Br (a) Cl  (b) S 2 
130. The cause of periodicity of properties is (c) Na  (d) F 
(a) Increasing atomic radius 10. Which of the following property displays
progressive increase down a group in the Bohr's
(b) Increasing atomic weights
periodic table
(c) Number of electrons in the valency orbit (a) Electronegativity (b) Electron affinity
(d) The re-occurrence of similar outer electronic (c) Ionization potential (d) Size of the atom
configuration 11. Atomic radii of fluorine and neon in angstrom
131. The chemistry of lithium is very similar to that of units are respectively given by [IIT 1987]
magnesium even though they are placed in (a) 0.762, 1.60 (b) 1.60, 1.60
different groups (c) 0.72, 0.72 (d) None of these values
[NCERT 1982] 12. Which ion has greatest radius in the following
(a) Both are found together in nature [CPMT 1976; NCERT 1977]

(b) Both have nearly the same size (a) H (b) F 

(c) Both have similar electronic configuration (c) Br (d) I 
(d) The ratio of their charge to size is nearly the 13. Which has the maximum atomic radius
same [CPMT 1975; AIIMS 1982; DPMT 1982]
(a) Al (b) Si
Atomic and Ionic radii (c) P (d) Mg
14. Which one of the following ions has the highest
1. The ratio between radii of He  ion and H atom is value of ionic radius [AIEEE 2004]
[MP PET 1996]
(a) O 2  (b) B 3 
1
(a) (b) 1 (c) Li  (d) F 
2
15. On going down a main sub-group in the periodic
3
(c) (d) 2 table (example Li to Cs in IA or Be to Ra in
2 IIA), the expected trend of changes in atomic
2. The smallest among the following ions is[JIPMER 1999] radius is a
(a) Na  (b) Mg 2 [CPMT 1981; NCERT 1979]
(c) Ba 2
(d) Al 3 (a) Continuous increase
3. Which is smallest in size [RPMT 1997] (b) Continuous decrease
(a) O 2  (b) C 4 
 630 Chemical Periodicity
(c) Periodic one, an increase followed by a 25. Which one of the following indicates the correct
decrease order of atomic size [EAMCET 1989]
(d) A decrease followed by increase (a) Be > F > C > Ne (b) Be < C < F < Ne
16. Which one of the following is the smallest in size (c) Be > C > F > Ne (d) F < Ne < Be < C
[IIT 1989] 26. Which has the smallest size [MP PET 1999]
3 2
(a) N (b) O (a) Na  (b) Mg 2 
 
(c) F (d) Na
(c) Al 3  (d) P 5 
17. Which one is the correct order of the size of the
27. A sodium cation has a different number of
iodine species
electrons from
[Pb. CET 1986; CBSE PMT 1997; Kurukshetra CEE 1998;
RPMT 1999; DCE 1999; MP PET 2000; (a) O 2  (b) F 

MP PMT 2001; BCECE 2005] (c) Li (d) Al 3 
(a) I  I   I  (b) I  I   I  28. Which of the following statement concerning
 
(c) I  I  I (d) I   I  I  lanthanides elements is false [CBSE PMT 1994]
18. Which one has larger radius[CPMT 1997; KCET 2005] (a) Lanthanides are separated from one another
(a) Na 
(b) F by ion exchange method
(c) F  (d) Na (b) Ionic radii of trivalent lanthanides steadily
increases with increase in the atomic number
19. In third row of periodic table the atomic radii from
Na to Cl (c) All lanthanides are highly dense metals
[MP PMT 1986] (d) More characteristic oxidation state of
(a) Continuosly decreases lanthanide elements is +3
(b) Continuosly increases 29. The lanthanide contraction is responsible for the
(c) Remains constant fact that
(d) Increases but not continuously [CBSE PMT 1997]
20. The size of the following species increases in the (a) Zr and Y have about the same radius
order (b) Zr and Nb have similar oxidation state
[IIT-JEE 1990; AFMC 1995]
(c) Zr and Hf have about the same radius
(a) Mg 2   Na   F   Al
(d) Zr and Zn have the same oxidation state
(b) F   Al  Na   Mg 2  30. Elements of which group form anions most
(c) Al  Mg  F   Na  readily
[CBSE PMT 1992]
(d) Na   Al  F   Mg 2 
(a) Oxygen family (b) Nitrogen group
21. In K  F  ionic radius of F  is more while atomic
(c) Halogens (d) Alkali metals
radius of K  is [CPMT 1997]
31. The unit representing atomic radii and ionic radii
(a) Less than F  (b) More than F  is
(c) Equal of F  (d) None of these (a) nm (b) cm
22. Which one of the following species possesses (c) Å (d) m
maximum size 32. The atomic radii in periodic table among elements
[EAMCET 1993; MP PET 2001] from right to left [MP PET 1995]
(a) Na  (b) F  (a) Decreases
(c) Ne (d) O 2  (b) Increases
23. The ionic radii of N 3  , O 2  , F  and Na  follow (c) Remain constant
the order [MP PET/PMT 1998; MP PMT 2000] (d) First decreases and then increases
(a) N 3   O 2   F   Na  33. Of the following the ion with the smallest ionic
3  2  radius is
(b) N  Na O F
 2 3
[MP PET 1996]
(c) Na  O N  F  2
(a) K (b) Ca
(d) O 2   F   Na   N 3  3
(c) Ti (d) Ti 4 
24. On moving down a group of regular elements,
both atomic and ionic radii increases with 34. Which of the following does not represent the
increasing [BMEE 1995] correct order of the property indicated[CBSE PMT 1997]
(a) Atomic number (b) Atomic weight (a) Sc 3   Cr 3   Fe 3   Mn 3  ionic radii
(c) Atomic mass (d) None of these (b) Sc  Ti  Cr  Mn Density
(c) Mn 2   Ni 2   Co 2   Fe 2  ionic radii
 Chemical Periodicity 631
(d) FeO  CaO  MnO  CuO Basic nature (d) Low positive charge, large cation and small
35. The order of magnitude of ionic radii of ions anion
Na  , Mg 2 , Al 3  and Si 4  is [MP PMT 1996] 45. Which of the following has largest ionic radius
[AFMC 1999; BHU 2003]
(a) Na   Mg 2   Al 3   Si 4 
(a) Cs  (b) Li 
(b) Mg 2  Na   Al 3   Si 4 
(c) Na  (d) K 
(c) Al 3   Na   Si 4   Mg 2 
46. Point out the wrong statement :
(d) Na   Mg 2   Al 3   Si 4  On moving horizontally from left to right across a
36. The order of the magnitude of ionic radii of ions period in the periodic table
N 3  , O 2  and F  is [MP PMT 1996] (a) Metallic character decreases
(b) Electronegativity increases
(a) N 3   O 2   F  (b) N 3   O 2   F 
3 2  (c) Gram atomic volume first decreases and then
(c) N  O  F (d) N 3   O 2   F 
increases
37. Which statement is correct
(d) Size of the atoms increases for normal
(a) For potassium, the atomic radius < ionic elements
radius; but for bromine, the atomic radius >
47. Which of the following statements is correct
ionic radius
[MP PET 1997]
(b) For potassium and bromine both, the atomic

radii > ionic radii (a) X ion is larger in size than X atom

(c) For potassium and bromine both, the atomic (b) X ion is larger in size than X atom
radii < ionic radii (c) X  ion is larger in size than X  ion
(d) For potassium, the atomic radius > ionic
(d) X  and X  ions are equal in size
radius but for bromine, the atomic radius <
ionic radius 48. The atomic radius of elements of which of the
38. Which of the following ion is the smallest ion following series would be nearly the same[MP PET 1997]
[AIIMS 2001] (a) Na K Rb Cs (b) Li Be B C
(a) O 2 (b) O 2 (c) Fe Co Ni Cu (d) F Cl Br I
49. The decreasing order of size of isoelectronic
(c) O 2 (d) O 22
series K  , Ca 2  , Cl  and S 2  is [Roorkee 1995]
39. The correct order of radii is[IIT-JEE (Screening) 2000]
(a) K   Ca 2   S 2   Cl 
(a) N  Be  B (b) F   O 2   N 3 
(b) K   Ca 2   Cl   S 2 
(c) Na  Li  K (d) Fe 3   Fe 2  Fe 4 
40. Which one of the following should be most stable (c) Ca 2   K   Cl   S 2 
[MP PET 2000] (d) S 2   Cl   K   Ca 2 
(a) H 2 (b) H  50. Which of the following sets of elements have the
strongest tendency to form anions [MP PET 1993]
(c) H (d) H  (a) N, O, F (b) P, S, Cl
41. Which of the following is the correct order of (c) As, Se, Br (d) Sb, Te, I
ionic radii
51. Radius of the isoelectronic species [MP PET 1994]
[BHU 2002]
(a) Increases with the increase of nuclear charge
(a) F  Li  Na  K (b) F  K  Na  Li
(b) Decreases with the increase of nuclear charge
(c) Na  K  F  Li (d) Li  Na  K  F
(c) Is the same for all
42. Smallest among these species is [KCET 2002]
(d) First increases and then decreases
(a) Lithium ion (b) Hydrogen
52. In which of the following pairs the difference
(c) Lithium (d) Helium
between the covalent radii of the two metals is
43. Which of the following ionic radius would be maximum
maximum [MP PET 1994]
[MP PET 1997]
(a) K, Ca (b) Mn , Fe
(a) C 4  (b) N 3  (c) Co , Ni (d) Cr , Mn
(c) O 2  (d) Mg 2  53. An atom of an element has electronic
44. Which is helpful in the formation of ionic bond configuration 2, 8, 1. Which of the following
(a) Only small cation statement is correct [MP PMT 1994]

(b) Only small anion (a) The element's valency is 7

(b) The element exists as a diatomic molecule
(c) Small cation and small anion both
 632 Chemical Periodicity
(c) The element is of non-metallic nature (c) Their size are same
(d) The element forms a basic oxide (d) Chloride ion is bigger than potassium ion
54. Which of the following ions has the smallest 63. Which of the following has the largest ionic
radius radius
[KCET 1992] [Pb. PMT 2002; BHU 2003]
2  (a) Na  (b) Ni 
(a) Be (b) Li
2 (c) Cs  (d) Mg 2
(c) O (d) F 
55. Point out the wrong statement : 64. The ionic radii of Li  , Na  , K  are in which of the
In a given period of the periodic table the s - block following order [MP PMT 2002]
element has, in general, a lower value of [MP PMT 1997] (a) K   Na   Li  (b) K   Na   Li 
  
(a) Ionisation energy (b) Electronegativity (c) K  Na  Li (d) Li   Na   K 
(c) Atomic radius (d) Electron affinity 65. Which of the following has smallest size
[JIPMER (Med.) 2002]
56. Arrange the following in increasing order of their
atomic radius : Na, K, Mg, Rb [AFMC 1995, 97; CPMT 1999] (a) Mg 2  (b) Na 

(a) Mg < K < Na < Rb (b) Mg < Na < K < Rb (c) Al 3  (d) Si 4 
(c) Mg < Na < Rb < K (d) Na < K < Rb < Mg 66. Which one of the following is expected to have
57. In the isoelectronic species the ionic radii (Å) of largest size
[UPSEAT 2004]
N 3  , O 2  and F  are respectively given by[Pb. CET 1989]
(a) F  (b) O 2
(a) 1.36, 1.40, 1.71 (b) 1.36, 1.71, 1.40 3
(c) 1.71, 1.40, 1.36 (d) 1.71, 1.36, 1.40 (c) Al (d) N 3
67. The trivalent ion having largest size in lanthanide
58. Al 3
has a lower ionic radius than Mg 2  because
series is
[EAMCET 1992]
[Pb.PMT 2004]
(a) Mg atom has less number of neutrons than
(a) Ti (b) Zr
Al
(c) Hf (d) La
(b) Al 3  has a higher nuclear charge than Mg 2 
68. Which of the following alkali metal ions has
(c) Their electronegativities are different
lowest ionic mobility in aqueous solutions [DPMT 2004]
(d) Al has a lower ionisation potential than Mg
atom (a) Rb  (b) Cs 
59. When a neutral atom is converted into cation, (c) Li  (d) Na 
there is 69. Ionic radii are [CBSE PMT 2003, 04]
[EAMCET 1986]
(a) Directly proportional to effective nuclear
(a) Decrease in the atomic number
charge
(b) An increase in the atomic number
(b) Directly proportional to square of effective
(c) A decrease in size
nuclear charge
(d) An increase in size
60. A trend common to both groups I and VII elements (c) Inversely proportional to effective nuclear
in the periodic table as atomic number increases charge
is (d) Inversely proportional to square of effective
[NCERT 1981; EAMCET 1980] nuclear charge.
(a) Oxidising power increases 70. The correct sequence of increasing covalent
(b) Atomic radius increases character is represented by [CBSE PMT 2005]
(c) Maximum valency increases (a) LiCl  NaCl  BeCl2 (b) BeCl 2  NaCl  LiCl
(d) Reactivity with water increases
(c) NaCl  LiCl  BeCl (d) BeCl 2  LiCl  NaCl
61. Increasing order of atomic radii is [RPET 2003]
(a) Mg 2  Na   Ne  F   O 2 71. Correct energy value order is [Orissa JEE 2004]

(b) Na   Mg   Ne  F   O 2 (a) ns np nd(n  1) f (b) ns np(n  1)d (n  2) f

2   2
(c) O  F  Ne  Na  Mg (c) ns np(n  1)d (n  1) f (d) ns(n  1)d n(n  1) f
2   2
(d) Ne  O  F  Na  Mg 72. The ionic conductance of following cation in a
62. Chloride ion and potassium ion are isoelectronic. given concentration are in the order [Orissa JEE 2004]
Then (a) Li   Na   K   Rb 
[KCET 2002]
(a) Potassium ion is relatively bigger (b) Li   Na   K   Rb 
(b) Depends on the other cation and anion (c) Li   Na   K   Rb 
 Chemical Periodicity 633
(d) Li   Na   K   Rb  (d) For transition elements the d -sub-shells are
filled with electrons monotonically with
increase in atomic number
Ionisation energy
6. Choose the correct statement
(a) Ionization energy and electron affinity
1. The incorrect statement among the following is increases across a period
[IIT-JEE 1997]
(b) Ionization energy increases but electron
(a) The first ionisation potential of Al is less than affinity decreases along a period
the first ionisation potential of Mg
(c) Ionization energy decreases but electron
(b) The second ionisation potential of Mg is affinity increases
greater than the second ionisation potential of (d) Both decreases along a period
Na
7. In halogens, with the increase of atomic number
(c) The first ionisation potential of Na is less which habit is found
than the first ionisation potential of Mg
(a) Habit to loose electrons decreases
(d) The third ionisation potential of Mg is greater
(b) Ionic radii decreases
than the third ionisation potential of Al
(c) Ionization potential decreases
2. The second ionisation potential of an element M
is the energy required to [JIPMER 1997] (d) In MX 2 (M  metal and X  halogen), covalent
(a) Remove one mole of electron from one mole of properties decreases
gaseous anion 8. Ionization potential is lowest for
(b) Remove one mole of electron from one mole of [CPMT 1989; MP PET 2001]
gaseous cation of the element (a) Halogens (b) Inert gases
(c) Remove one mole of electron from one mole of (c) Alkaline earth metals(d) Alkali metals
monovalent gaseous cation of the element
9. Which of the following explanation is best for not
(d) Remove 2 moles of electrons from one mole of placing hydrogen in either the group of alkali
gaseous atoms metals or halogens
3. The ionization energy of an element is [NCERT 1978]
(a) The same as the electron affinity of the
(a) The ionization energy of hydrogen is to high
element for group of alkali metals, but too low of
(b) Equal in magnitude but of opposite sign to the halogen group
electron affinity of the element
(b) Hydrogen can form compounds with all other
(c) The energy released when an electron is elements
added to an atom of the element
(c) Hydrogen is much lighter element than the
(d) The energy required to remove the outermost alkali metals or the halogens
electron of an atom of the element
(d) None of the above
4. The first ionisation energies of alkaline earth
10. The ionization energy of nitrogen is more than
metals are higher than those of the alkali metals.
that of oxygen because [MP PET 1993]
This is because
(a) Nitrogen has half filled p-orbitals
[MP PET 1996]
(b) Nitrogen is left to the oxygen in the same
(a) There is increase in the nuclear charge of the
period of the periodic table
alkaline earth metals
(c) Nitrogen contains less number of electrons
(b) There is a decrease in the nuclear charge of
(d) Nitrogen is less electronegative
the alkaline earth metals
11. The energy required to remove an electron of a
(c) There is no change in the nuclear charge
gaseous atom from its ground state is called[CPMT 1989, 9
(d) None of the above
(a) Potential energy (b) Ionization energy
5. The statement that is not correct for the periodic
(c) Electrode potential (d) Activation energy
classification of elements is [IIT-JEE 1992]
12. The first ionization energy of boron is less than
(a) The properties of elements are the periodic
that of beryllium because
functions of their atomic numbers
(a) Boron has higher nuclear charge
(b) Non-metallic elements are lesser in number
(b) Atomic size of boron is more than that of
than metallic elements
beryllium
(c) The first ionisation energies along a period do
(c) Boron has only one electron in p-sub-shell
not vary in a regular manner with increase in
(d) Atomic size of boron is less than that of
atomic number
beryllium
 634 Chemical Periodicity
13. A  A   e , E1 and A   A 2   e , E 2 . The energy (c) 3 (d) 4
required to pull out the two electrons are E1 and 25. Which of the following has least ionization
potential
E 2 respectively. The correct relationship between
[CPMT 1982, 93]
two energy would be (a) Li (b) Cs
(a) E1  E2 (b) E1  E 2 (c) Cl (d) I
(c) E1  E 2 (d) E1  E 2 26. Which of the following element has the lowest
ionization potential [CPMT 1976; RPMT 2002]
14. Which of the following element has maximum,
first ionisation potential [AIIMS 2001]
(a) Fe (b) H
(c) Li (d) He
(a) V (b) Ti
27. As one moves along a given row in the periodic
(c) Cr (d) Mn
table, ionization energy
15. Highest energy will be absorbed to eject out the [CPMT 1976, 89; NCERT 1978; EAMCET 1985]
electron in the configuration [RPMT 2000]
(a) Remains same
(a) 1s 2 2 s 2 2 p 1 (b) 1s 2 2 s 2 2 p 3 (b) Increases from left to right
(c) 1s 2 2 s 2 2 p 2 (d) 1s 2 2 s 2 2 p 4 (c) First increases, then decreases
16. In which of the following process highest energy (d) Decreases from left to right
is absorbed 28. Ionization energy is highest for[AFMC 2001; BVP 2003]
[RPET 2000] (a) Noble gases
(b) Platinum metals
(a) Cu  Cu  (b) Br  Br 
(c) Transition elements
(c) I  I (d) Li  Li 
(d) Inner–transition elements
17. The first ionization potential of Na, Mg, Al and Si 29. Which one of the following elements has the
are in the order [IIT 1988; MP PMT 2000] highest ionisation energy [IIT-JEE 1990]
(a) Na < Mg > Al < Si (b) Na > Mg > Al > Si (a) [ Ne ] 3 s 2 3 p 1 (b) [ Ne ] 3 s 2 3 p 2
(c) Na < Mg < Al > Si (d) Na > Mg > Al < Si
18. How many ionisation energies can carbon have (c) [ Ne ] 3 s 2 3 p 3 (d) [ Ar ] 3 d 10 4 s 2 4 p 2
(a) 1 (b) 2 30. Which of the following elements has the lowest
(c) 4 (d) 6 ionistion potential [EAMCET 1993]
19. Which of the following gaseous atoms has highest (a) N (b) O
value of IE (c) F (d) Ne
[JIPMER 1997; CPMT 1997; AIIMS 2000] 31. Which of the following has lowest first ionisation
(a) P (b) Si potential
[CPMT 1993]
(c) Mg (d) Al
(a) B (b) C
20. Hydrogen has high ionization energy than alkali
(c) N (d) O
metals, due to its [AIIMS 1999]
(a) Large size (b) Small size 32. If first orbit energy of He  is – 54.4 eV, then the
second orbit energy will be [Roorkee 1995]
(c) Ionic bond (d) Covalent bond
The first ionization potentials eV  of Be and B
(a) – 54.4 eV (b) – 13.6 eV
21.
(c) – 27.2 eV (d) + 27.2 eV
respectively are [CBSE PMT 1998]
33. The screening effect of inner electrons of the
(a) 8 . 29 eV , 9 . 32 eV (b) 9 . 32 eV , 9 . 32 eV
nucleus causes
(c) 8 . 29 eV , 8 . 29 eV (d) 9 . 32 eV , 8 . 29 eV
[MP PMT 1994]
22. Which ionisation potential IP  in the following
(a) A decrease in the ionisation potential
equations involves the greatest amount of energy[Pune CET 1998]
(b) An increase in the ionisation potential
(a) Na  Na   e  (b) K   K 2  e 
(c) No effect on the ionisation potential
(c) C 2   C 3   e  (d) Ca   Ca 2  e  (d) An increase in the attraction of the nucleus to
23. Which of the following has maximum ionization the electrons
potential 34. Which of the following has highest first ionization
[MH CET 1999] energy
(a) K (b) Na [MP PET 1994]
(c) Al (d) Mg (a) Sulphur (b) Oxygen
24. The first four ionization energy values of an
(c) Nitrogen (d) Phosphorus
element are 191, 578, 872 and 5962 kcal. The
number of valence electrons in the element is 35. The second ionization potential is
(a) 1 (b) 2 [Bihar CEE 1995; CET Pune 1998]
(a) Less than the first ionization potential
 Chemical Periodicity 635
(b) Equal to the first ionization potential (d) Li  Be  B  C -1st ionisation potential
(c) Greater than the first ionization potential 47. Which of the following has the least ionization
(d) None of these potential
36. When the first ionization energies are plotted [MP PET 2002]
against atomic number the peaks are occupied[CET Pune 1998]
(a) Lithium (Li) (b) Helium (He)
(a) Alkali metals (b) Halogens (c) Nitrogen (N) (d) Zinc (Zn)
(c) Rare gases (d) Transition elements 48. The first ionisation energy of lithium will be
37. Among the following which has the highest first [EAMCET 1990]
ionization energy (a) Greater than Be (b) Less than Be
(a) K (b) Na (c) Equal to that of Na (d) Equal to that of F
(c) B (d) Kr
49. Spectrum of Li 2  is similar to that of [AIIMS 2002]
38. The first ionisation potential will be maximum for
(a) H (b) He
[CPMT 2000]
(c) Be (d) Ne
(a) Lithium (b) Hydrogen
50. Highest ionisation energy stands for [DPMT 2000]
(c) Uranium (d) Iron
39. Arrange S, P, As in order of increasing ionisation (a) He (b) C
energy (c) N (d) H
[JIPMER (Med.) 2002] 51. Which of the following electrons should have the
(a) S  P  As (b) P  S  As highest value of ionisation energy (for the same
(c) As  S  P (d) As  P  S value of the principal quantum number)
40. With reference to concept of ionisation potential, (a) s (b) p
(c) d
which one of the following sets are correct[Kurukshetra CEE 1991] (d) f
(a) U  K  Cs (b) B  U  K 52. The correct sequence of elements in decreasing
(c) Cs  U  B (d) Cs  U  K order of first ionisation energy is [MP PET 1997]
41. Which among the following species has the (a) Na  Mg  Al (b) Mg  Na  Al
highest ionisation potential [KCET 2001] (c) Al  Mg  Na (d) Mg  Al  Na
(a) B (b) Li
53. Correct order of polarising power is
(c) Ne (d) F
[MP PMT 2003; BHU 2003]
42. The set representing the correct order of first
  2 3
ionisation potential is [IIT-JEE (Screening) 2001] (a) Cs  K  Mg  Al
(a) K  Na  Li (b) Be  Mg  Ca (b) K   Cs   Mg 2  Al 3 
(c) B  C  N (d) Ge  Si  C
(c) Cs   K   Al 3   Mg 2
43. Among the following options, the sequence of
increasing first ionisation potential will be (d) K   Cs   Al 3   Mg 2
[AIIMS 2000; MP PMT 2002] 54. Correct increasing order of first ionistion
(a) B  C  N (b) B  C  N potential is
(c) C  B  N (d) N  C  B [UPSEAT 2003]
44. The decreasing order of the ionisation potential in (a) Na  Mg  Al  Si (b) Na  Mg  Al  Si
the following elements is [MP PMT 2001]
(c) Na  Mg  Al  Si (d) Na  Mg  Al  Si
(a) Ne  Cl  P  S  Al  Mg
55. The ionisation potential of hydrogen from ground
(b) Ne  Cl  P  S  Mg  Al
state to the first excited state is [DCE 2001]
(c) Ne  Cl  S  P  Mg  Al (a) 13 .6 eV (b) 13 .6 eV
(d) Ne  Cl  S  P  Al  Mg
(c) 3.4 eV (d) 3.4 eV
45. Which is the correct order of the first ionization
potential of N, O and C [AMU 2000] 56. In view of their low ionisation energies the alkali
metals are
(a) C  N  O (b) C  N  O
[MP PMT 2002]
(c) O  N  O (d) C  N ~ O
(a) Weak oxidising agents
46. Which of the following order is wrong [CBSE 2002]
(b) Strong reducing agents
(a) NH 3  PH 3  AsH 3 -acidic nature
(c) Strong oxidising agents
(b) Li   Na   K   Cs  -ionic radius (d) Weak reducing agents
(c) Al2 O3  MgO  Na2 O  K 2 O -basic
 636 Chemical Periodicity
57. Of the following iso-electronic ions, the one which 69. In the long form of periodic table, the element
has the lowest ionisation potential is [AMU 1999] having lowest ionisation potentials are present in[EAMCET
(a) Na  (b) Mg   (a) I group (b) IV group
(c) VII group (d) Zero group
(c) F  (d) O  
70. The process requiring the absorption of energy is
58. Ionisation energy in group I-A varies in the [Roorkee 1990]
decreasing order as [Orissa JEE 2005] 
(a) F  F (b) Cl  Cl 
(a) Li  Na  K  Cs (b) Na  Li  K  Cs
(c) O  O 2 (d) H  H 
(c) Li  Cs  K  Na (d) K  Cs  Na  Li
71. In a period from Li to F , ionization potential
59. Which of the following relation is correct with [CPMT 1982]
respect to first (I) and second (II) ionization
(a) Increases (b) Decreases
potentials of sodium and magnesium [CPMT 1999]
(c) Remains same (d) None of the above
(a) I Mg  IINa (b) I Na  I Mg
72. Ionization energy increases in the order
(c) IIMg  IINa (d) II Na  IIMg (a) Be, B, C, N (b) B, Be, C, N

60. The order of the magnitude of first ionisation (c) C, N , Be, B (d) N , C, Be, B
potentials of Be, B, N and O is [MP PMT 1996] 73. A neutral atom will have the lowest ionization
(a) N  O  Be  B (b) N  Be  O  B potential when its electronic configuration is
(c) Be  B  N  O (d) B  Be  O  N [NCERT 1978; CBSE PMT 1991]

61. Which of the following transitions involves (a) 1s 1 (b) 1 s 2 , 2 s 2 p 6

maximum amount of energy [AIIMS 1992] (c) 1 s 2 , 2 s 2 p 2 (d) 1s 2 , 2 s 2 p 6 , 3 s 1
 
(a) M (g)  M (g) (b) M (g)  M (g) 74. Which has maximum first ionization potential
 2 2 3 [IIT 1982; EAMCET 1997;
(c) M (g)  M (g) (d) M (g)  M (g)
KCET (Med.) 1999; KCET 2000]
62. Which of the following species has lowest
(a) C (b) N
ionization potential [KCET 1996]
(c) B (d) O
(a) O (b) O 2
75. Which one of the following elements has the
(c) O 2 (d) O 2 highest ionisation energy
(a) Na (b) Mg
63. Which of the following has minimum ionization
(c) C (d) F
energy
76. Order of first ionization potentials of elements Li,
[JIPMER 1999]
Be, B, Na is [Kerala CET 2005]
(a) Ge (b) Se
(a) Li > Be >B > Na (b) Be >B > Li > Na
(c) As (d) Br
(c) Na > Li > B > Be (d) Be > Li > B > Na
64. First I.P. of Mg is ...... than Al [CPMT 1997] (e) B > Be > Li > Na
(a) Less (b) More 77. The ionization energy of nitrogen is larger than
(c) Equal (d) None of these that of oxygen because of [RPMT 1997; DCE 1999]
65. The element with highest value of ionization (a) Greater attraction of electrons by the nucleus
potential is (b) The size of nitrogen atom being smaller
(a) Potassium (b) Helium (c) The half-filled p -orbitals possess extra
(c) Hydrogen (d) Xenon stability
66. Which has the highest second ionisation potential (d) Greater penetration effect
[AIIMS 1991] 78. If the IP of Na is 5.48 eV, the ionisation potential
of K will be [EAMCET 1988]
(a) Nitrogen (b) Carbon
(a) Same as that of Na (b) 5.68 eV
(c) Oxygen (d) Fluorine
(c) 4.34 eV (d) 10.88 eV
67. In ionisation of hydrogen, the energy required is
79. Mg and Li are similar in their properties due to
[CPMT 1996]
[AFMC 2004]
(a) 13 . 6 eV (b)  13 . 6 eV (a) Same e/m ratio (b) Same electron
(c)  13 . 6 eV (d) 1 . 5 eV affinity
68. Which of the following elements will have the (c) Same group (d) Same ionic potential
lowest first ionisation energy [KCET 1992] 80. The formation of the oxide ion O(g2) requires first
(a) Mg (b) Rb
an exothermic and then an endothermic step as
(c) Li (d) Ca shown below
O(g)  e   O(g) H 0  142 kJmol 1
 Chemical Periodicity 637
O(g)  e   O(2g) H 0  844 kJmol 1
This is because [AIEEE 2004] Electron affinity
(a) O  ion will tend to resist the addition of
another electron 1. Electron affinity depends on [MP PMT 2002]

(b) Oxygen has high electron affinity (a) Atomic size

(c) Oxygen is more electronegative (b) Nuclear charge
(d) O  ion has comparatively larger size than (c) Atomic number
oxygen atom (d) Atomic size and nuclear charge both
81. 2.
Which is correct about ionisation potential [MHCET 2003] Increasing order of electron affinity is [RPET 2003]
(a) It is independent of atomic radii (a) N  O  Cl  Al (b) O  N  Al  Cl
(b) It increases with increase in atomic radii (c) Al  N  O  Cl (d) Cl  N  O  Al
(c) It remains constant with increase in atomic 3. The correct order of electron affinity of B, C, N, O
radii is
[MP PET 1997; J & K 2005]
(d) It decreases with increase in atomic radii
(a) O  C  N  B (b) B  N  C  O
82. Flourine is the best oxidising agent because it has
(c) O  C  B  N (d) O  B  C  N
[CPMT 2004]
4. Which one has maximum electron affinity[Roorkee 1995]
(a) Highest electron affinity
0
(a) N (b) Be
(b) Highest E red
(c) B (d) Cl
0
(c) Highest E oxid 5. The electron affinity for the inert gases is
(d) Lowest electron affinity [Kurukshetra CEE 1998; MP PMT 2002]

83. Which among the following elements have lowest (a) Zero (b) High
value of IE1 [CPMT 2004] (c) Negative (d) Positive
6. The electron affinities of halogens are F  322 ,
(a) Pb (b) Sn
Cl  349 , Br  324 , I  295 kJ mol 1 . The higher
(c) Si (d) C
value for Cl as compared to that of F is due to[MP PMT 19
84. In a given shell, the order of screening effect is
(a) Weaker electron-electron repulsion in Cl
[Kerala PMT 2004]
(b) Higher atomic radius of F
(a) s  p  d  f (b) f  d  p  s
(c) Smaller electronegativity of F
(c) p  d  s  f (d) d  f  s  p
(d) More vacant P - subshell in Cl
(e) f  p  s  d 7. Which one of the following is an incorrect
85. Which of the following has the highest first statement
ionisation energy [MP PMT 2001]
[BHU 2004] (a) The ionisation potential of nitrogen is greater
(a) Li (b) Be than that of oxygen
(c) B (d) C (b) The electron affinity of fluorine is greater
than that of chlorine
86. Which one of the following sets of ions represents
the collection of isoelectronic species [AIEEE 2004] (c) The ionisation potential of beryllium is
greater than that of boron
(a) K  , Cl  , Mg 2 , Sc 3  (b) Na  , Ca 2 , Sc 3  , F 
(d) The electronegativity of fluorine is greater
(c) K  , Ca 2 , Sc 3  , Cl  (d) Na  , Mg 2 , Al 3  , Cl than that of chlorine
87. The correct order of reactivity of halogens is 8. Electron affinity is the [MP PMT 1993]
[MHCET 2003] (a) Energy absorbed when an electron is added to
(a) F  Cl  Br  I (b) F  Cl  Br  I an isolated atom in the gaseous state

(c) F  Cl  Br  I (d) F  Cl  Br  I (b) Energy released when an electron is added to

an isolated atom in the gaseous state
88. The first ionisation potential is maximum for [CPMT 2004]
(c) Energy required to take out an electron from
(a) B (b) N an isolated gaseous atom
(c) O (d) Be (d) Power of an atom to attract an electron to
89. The correct order of ionisation energy for itself
comparing carbon, nitrogen and oxygen atoms is [UPSEAT
9. 2004]
The electron affinity values for the halogens show
(a) C  N  O (b) C  N  O the following trend [Kerala PET 2002]
(c) C  N  O (d) C  N  O (a) F  Cl  Br  I (b) F  Cl  Br  I
 638 Chemical Periodicity
(c) F  Cl  Br  I (d) F  Cl  Br  I (b) Electron affinity generally increases along a
10. Which element has maximum electron affinity period
(a) Na (b) S (c) Nitrogen atom has half filled p-orbital
(c) Mg (d) Al (d) Nitrogen is a p-block element
21. Electron affinity is the lowest for
11. Which of the following has the least electron
(a) Nitrogen (b) Carbon
affinity in kJmol 1 [AFMC 2000]
(c) Oxygen (d) Sulphur
(a) Oxygen (b) Carbon
22. Which one of the elements has the maximum
(c) Nitrogen (d) Boron electron affinity
12. Fluorine has low electron affinity than chlorine [CPMT 1986; AFMC 1992, 95; Bihar MEE 1996; BHU 1997;
because of CBSE PMT 1996, 99; MP PET 1995, 2001; AMU 2000]
[CPMT 1997] (a) F (b) Cl
(a) Smaller radius of fluorine, high density (c) Br (d) I
(b) Smaller radius of chlorine, high density 23. Which among the following factors is the most
(c) Bigger radius of fluorine, less density important in making fluorine the strongest
(d) Smaller radius of chlorine, less density oxidizing halogen
13. For electron affinity of halogens which of the [AIEEE 2004]
following is correct [AIIMS 2004] (a) Hydration enthalpy
(a) Br  F (b) F  Cl (b) Ionization enthalpy
(c) Br  Cl (d) F  I (c) Electron affinity
14. Ionic compounds are formed most easily with (d) Bond dissociation energy
[DPMT 2005] 24. Which of the following pairs show reverse
(a) Low electron affinity, high ionisation energy properties on moving along a period from left to
(b) High electron affinity, low ionisation energy right and from top to down in a group [DCE 2003]
(c) Low electron affinity, low ionisation energy (a) Nuclear charge and electron affinity
(d) High electron affinity, high ionisation energy (b) Ionisation energy and electron affinity
15. In comparison with alkali metals, the electron (c) Atomic radius and electron affinity
affinity of halogens is
(d) None of these
(a) Very high (b) Very low
(c) Nearly same (d) Exactly same 25. Which of the following properties show gradual
decrease with increase in atomic number across a
16. The electron affinity of [CPMT 1994]
period in the periodic table [Pb. CET 2003]
(a) Carbon is greater than oxygen
(a) Electron affinity (b) Ionization potential
(b) Sulphur is less than oxygen
(c) Iodine is greater than bromine (c) Electronegativity (d) Size of atom
(d) Bromine is less than chlorine 26. Order of electron affinity of F, Cl, Br and I is .....
17. The amount of energy which is released due to [AFMC 1999; Orissa JEE 2004,05]
addition of extra electron to the outermost orbit (a) F  Cl  Br  I (b) F  Cl  Br  I
of gaseous atom is called [BHU 1996]
(c) F  Cl  Br  I (d) F  Cl  Br  I
(a) Electron capacity (b) Electron affinity
27. Which one of the following arrangements
(c) Ionisation potential (d) Electronegativity
represents the correct order of electron gain
18. Which of the following species has the highest
enthalpy (with negative sign) of the given atomic
electron affinity [KCET 1996]
species. [CBSE PMT 2005]
(a) F (b) O
(a) Cl  F  S  O (b) O  S  F  Cl
(c) O  (d) Na 
(c) S  O  Cl  F (d) F  Cl  O  S
19. The electron affinity values (in kJ mol 1 ) of three
halogens X, Y and Z are respectively – 349, –
Electronegativity
333 and – 325. Then X, Y and Z are respectively[EAMCET 2003]
(a) F2 , Cl 2 and Br2 (b) Cl 2 , F2 and Br2
1. Between HF , HCl , HBr and HI, HF has the highest
(c) Cl 2 , Br2 and F2 (d) Br2 , Cl 2 and F2 ionic character because
20. Nitrogen has lower electron affinity than its (a) F has the highest electron affinity
preceeding element carbon because (b) In HF , electronegativity difference is highest
(a) Electron affinity decreases along a period
(c) F  ion has the highest value of ionic radius
 Chemical Periodicity 639
(d) Atomic orbitals of H and F have almost similar 11. The outermost electronic configuration of the
energy most electronegative element is
2. On going from right to left in a period in the [MP PET 1996; RPMT 1997; MP PET 2004]
periodic table the electronegativity of the 2
(a) ns np 3
(b) ns 2 np 4
elements
(c) ns 2 np 5 (d) ns 2 np 6
[MP PET/PMT 1998; MP PMT 2002]
(a) Increases 12. Going from fluorine to chlorine, bromine and
iodine, the electronegativity [MP PMT 2000]
(b) Decreases
(a) Increases
(c) Remain unchanged
(b) Decreases
(d) Decreases first then increases
(c) First decreases then increases
3. On Pauling scale which of the following does not
(d) Changes randomly
have electronegativity  3.0 [MP PET 1994]
13. Of the following elements, which one has highest
(a) Oxygen (b) Nitrogen
electro-negativity[CPMT 1988; CBSE PMT 1991; BHU 1996;
(c) Chlorine (d) Bromine Kurukshetra CET 2002; Pb. PMT 2004]
4. Which one of the following represents the (a) I (b) Br
electronic configuration of the most (c) Cl (d) F
electropositive element
14. Which of the following is most electronegative[CPMT 1999
[AIIMS 1982; CPMT 1994; MP PMT 2000]
(a) Carbon (b) Silicon
(a) [ He ] 2 s 1 (b) [ Xe ] 6 s 1 (c) Lead (d) Tin
(c) [He ] 2 s 2 (d) [ Xe ] 6 s 2 15. The property of attracting electrons by the
halogen atom in a molecule is called [CPMT 1996]
5. An atom with high electronegativity has
(a) Ionisation potential (b) Electron affinity
[Kerala (Med.) 2003]
(c) Electronegativity (d) Electronic attraction
(a) Large size
16. In third row of periodic table from Na to Cl
(b) High ionisation potential
[MP PET 1986]
(c) Low electron affinity
(a) Electronegativity increases
(d) Low ionisation potential
(b) Electronegativity decreases
6. Two elements whose electronegativities are 1.2
(c) Ionization energy decreases
and 3.0 the bond formed between them would be[MP PET 2002]
(a) Ionic (b) Covalent (d) Atomic volume increases
(c) Coordinate (d) Metallic 17. Which of the following is the most electropositive
element
7. The solubilities of carbonates decreases down the
[AIIMS 1998]
magnesium group due to a decrease in[AIEEE 2003]
(a) Aluminium (b) Magnesium
(a) Lattice energies of solids
(c) Phosphorus (d) Sulphur
(b) Hydration energies of cations
18. Which of the following sets of atoms is arranged
(c) Inter-ionic attraction
in order of increasing electronegativity
(d) Entropy of solution formation (a) S, Si, P (b) S, P, Si
8. Which element has the highest electronegativity (c) Si, P, S (d) Si, S, P
or 19. Which of the following property displays
Which of the following is the most electronegative progressive increase with the rise in atomic
[CPMT 1981; Roorkee 1995; MP PMT 2003; EAMCET 1980; number across a period in the periodic table
CPMT 1989; MNR 1994; MP PMT 1999] (a) Electronegativity (b) Electron affinity
(a) F (b) He (c) Ionization potential (d) Size of the atom
(c) Ne (d) Na 20. With respect to chlorine, hydrogen will be
9. Which element has the highest electronegativity [NCERT 1978; MP PMT 2003]
[MP PET/PMT 1998] (a) Electropositive (b) Electronegative
(a) C (b) Mg (c) Neutral (d) None of the above
(c) O (d) S 21. The correct order of electropositive nature of Li,
10. Keeping in view the periodic law and the periodic Na and K is
table suggest which of the following elements (a) Li > Na > K (b) Li > K > Na
should have the maximum electronegative (c) Na > K > Li (d) K > Na > Li
character [MNR 1985]
22. Electronegativity is a measure of the capacity of
(a) P (b) As an atom to
(c) Bi (d) Sb [CPMT 1989]
 640 Chemical Periodicity
(a) Attract electrons (b) Attract protons [UPSEAT 2004]
(c) Repel electrons (d) Repel protons (a) Br (b) Cl
23. With increasing atomic number in a certain (c) P (d) Si
period 33. Which or these have no unit [AFMC 2004]
[MP PMT 1987] (a) Electronegativity (b) Electron affinity
(a) The chemical reactivity decreases (c) Ionisation energy (d) Excitation potential
(b) The chemical reactivity increases 34. The polarising ability of which one of the
(c) The electropositive character increases following is highest
(d) The electronegative character increases [DCE 2003]
24. Which of the following have maximum (a) Small highly +ve ion (b) Large +ve ion
electronegativity (c) Small highly –ve ion (d) Large –ve ion
[CPMT 1982] 35. Among Al 2 O3 , SiO2 , P2 O3 and SO 2 the correct order
(a) Al (b) S of acid strength is [AIEEE 2004]
(c) Si (d) P (a) Al 2 O3  SiO2  SO 2  P2 O3
25. Which element has the lowest electronegativity
(b) SiO2  SO 2  Al 2 O3  P2 O3
[CPMT 1976]
(a) Li (b) F (c) SO 2  P2 O3  SiO2  Al 2 O3
(c) Fe (d) Cl (d) Al 2 O3  SiO2  P2 O3  SO 2
26. The attraction that an atom exerts on a pair of
electrons that are being shared between that atom Valency and oxidation state
and another atom to which it is bonded by a
covalent bond is referred to as its
1. Which one of the following oxides is neutral
[Manipal MEE 1995]
[IIT-JEE 1996]
(a) Electron affinity (b) Electronegativity
(a) CO (b) SnO 2
(c) Ionisation energy (d) Valence
27. The electronegativity of the following elements (c) ZnO (d) SiO 2
increases in the order [IIT 1987] 2. All element in 3rd period have [JIPMER 1997]
(a) C, N, Si, P (b) N, Si, C, P (a) An atomic number 3
(c) Si, P, C, N (d) P, Si, N, C (b) 3 complete sub-shells
28. Choose the correct statement (c) Valence electrons shell
(a) Electronegativity increases down a group (d) 3 electrons less than the octet
(b) Electronegativity decreases down a group
3. Which shows variable valency [RPMT 1997]
(c) Electronegativity decreases from left to right
(a) s - block elements (b) p - block elements
along a period
(c) d - block elements (d) Radioactive elements
(d) Electronegativity changes along a group but
remains constant along a period 4. Most reducing agent is [UPSEAT 1999]
29. In C, N, O and F the electronegativity [DPMT 2001] (a) K (b) Mg
(c) Al (d) Ba
(a) Decreases from carbon to fluorine
(b) Increases from carbon to fluorine 5. Acidity of pentoxides in VA group [CPMT 1982]

(c) Increases from carbon to oxygen and then (a) Decreases (b) Increases
decreases (c) Remains same (d) None
(d) Decreases from carbon to oxygen and then 6. If the valency shell electronic structure for an
increases element is ns 2 np 5 , this element will belong to the
30. Which is the correct order of electronegativities group of
[EAMCET 1990] [CBSE PMT 1992]
(a) F > N < O > C (b) F > N > O > C (a) Alkali metals (b) Inert metals
(c) F < N < O < C (d) F > N > O < C (c) Noble gases (d) Halogens
31. In the following, the element with the highest 7. The order in which the following oxides are
electropositivity is [MP PET/PMT 1998] arranged according to decreasing basic nature is [CPMT 19
(a) Na 2 O, MgO, Al 2 O3 , CuO
(a) Copper (b) Caesium
(c) Barium (d) Chromium (b) MgO, Al 2 O3 , CuO, Na 2 O
32. Which one of the following has the highest (c) Al 2 O3 , MgO, CuO, Na 2 O
electronegativity (d) CuO, Na 2 O, MgO, Al 2 O3
 Chemical Periodicity 641
8. Strongest reducing agent is [RPMT 1997] (a) It belongs to II group of the periodic table
(a) Cl 2 (b) Cl  (b) It has 20 neutrons
(c) The formula of its oxide is MO2
(c) Br  (d) I 
9. Metallic nature and basic nature of the oxides (d) It belongs to 4th period of the periodic table
........ as we move along a period 19. Which of the following oxides is most basic
(a) Increases [MP PET 1994]
(b) Decreases (a) Na 2 O (b) Al 2 O3
(c) First increases then decreases (c) SiO 2 (d) SO 2
(d) Remains constant 20. In the periodic table, the metallic character of
10. The correct order of increasing order of oxidising elements
power is [MP PET 1993]
[DCE 2000] (a) Decreases from left to right across a period
(a) F2  Cl2  Br2  I2 (b) F2  Br2  Cl 2  I2 and on descending a group
(c) Cl2  Br2  F2  I2 (d) I2  Br2  Cl2  F2 (b) Decreases from left to right across a period
and increases on descending a group
11. The most basic among these hydroxides, is[MP PMT 2003]
(c) Increases from left to right across a period
(a) Be (OH )2 (b) Mg (OH )2
and on descending a group
(c) Ca (OH )2 (d) Ba (OH )2 (d) Increases from left to right across a period
12. In any period the valency of an element with and decreases on descending a group
respect to oxygen [Kerala (Med.) 2003] 21. The halogen that most easily reduced is [MP PMT 2000]
(a) Increases one by one from IA to VIIA (a) F2 (b) Cl2
(b) Decreases one by one form IA to VIIA (c) Br2 (d) I2
(c) Increases one by one from IA to IVA and then
22. Which of the following is the correct order of
decreases from VA to VIIA one by one
gradually decreasing basic nature of the oxides[MP PMT 19
(d) Decreases one by one from IA to IVA and then
(a) Al 2 O3 , MgO , Cl 2 O7 , SO 3
increases from VA to VIIA one by one
13. Which will show maximum non-metallic character (b) MgO , Al 2 O3 , SO 3 , Cl 2 O7
[UPSEAT 2003] (c) Cl 2 O7 , SO 3 , Al 2 O3 , MgO
(a) B (b) Be
(d) SO 3 , Cl 2 O7 , MgO , Al 2 O3
(c) Mg (d) Al
23. The correct order of reactivity of halogen is [BHU 2000]
14. Which of the following halogen acids is least
acidic (a) Flourine > bromine > chlorine > iodine
[RPET 2003] (b) Flourine > chlorine > bromine > iodine
(a) HI (b) HCl (c) Iodine > bromine > chlorine > flourine
(c) HF (d) HBr (d) Bromine > chlorine > flourine > iodine
15. Pentavalency in phosphorus is more stable when 24. Elements A and B with their respective electronic
compared to that of nitrogen even through they configurations 3 d 10 4 s 1 and 4 d 10 5 s 1 in their
belong to same group is due to [KCET 2002]
outermost shell are
(a) Reactivity of phosphorus
(a) Both non-metals
(b) Inert nature of nitrogen
(b) Both coinage metals
(c) Dissimilar electronic configuration
(c) A is a non-metal and B is coinage metal
(d) Larger size of phosphorus atom
(d) A is a coinage metal and B is non-metal
16. In the ground state of cobalt atom (Z = 27) there
are ....... unpaired electrons and thus the atom 25. Which is the best reducing agent [MP PET 2000]
is....... (a) F  (b) Cl 
(a) 2, diamagnetic (b) 2, paramagnetic (c) Br  (d) I
(c) 3, diamagnetic (d) 3, paramagnetic 26. Which of the following group of elements
17. Variable valency in general, is exhibited by eliminates electron easily
[CPMT 1974, 84, 89; DPMT 1981, 82; MP PET 2001] (a) N, P, As (b) O, S, Se
(a) Transition elements (b) Gaseous elements (c) Li, Na, K (d) Cl, Ba, I
(c) Non-metals (d) s -block elements
27. The maximum valency of an element with atomic
18. An element of atomic weight 40 has 2, 8, 8, 2 as number 7 is [AFMC 2002]
the electronic configuration. Which one of the
(a) 2 (b) 5
following statements regarding this element is
not correct (c) 4 (d) 3
 642 Chemical Periodicity
28. Which of the following metals exhibits more than (c) Cu (d) Na
one oxidation state [MP PET 1999] 37. The basis of keeping the elements in the group of
(a) Na (b) Mg a periodic table is [RPET 1999]
(c) Fe (d) Al (a) Ionisation potential
29. Out of the following elements which one do you (b) Electronegativity
expect to be most reactive chemically [CPMT 1983] (c) Electron affinity
(a) Mg (b) Ca (d) Number of electrons in the valence shell
(c) Sr (d) Ba 38. Which of the following electronic configurations
30. Thalium shows different oxidation states because in the outermost shell is characteristic of alkali
metals
[AIIMS 1982]
[Bihar CEE 1992]
(a) It is a transition element
(b) Of inert pair effect (a) (n  1) s p , ns p
2 6 2 1
(b) (n  1) s 2 p 6 d 10 , ns 1

(c) Of its amphoteric character (c) (n  1) s 2 p 6 , ns 1 (d) ns 2 p 6 d 1

(d) Of its higher reactivity 39. On moving down the group gradually increase
31. Oxidising action increases in halogen in the (a) Oxidising property (b) Electronegativity
following order
(c) Acidic property (d) Metallic property
[DPMT 1990]
40. An ion which has 18 electrons in the outermost
(a) Cl < Br < I < F (b) Cl < I < Br < F
shell is
(c) I < F < Cl < Br (d) I < Br < Cl < F
(a) K  (b) Ca 2 
32. Fluorine, chlorine, bromine and iodine are placed
in the same group (17) of the periodic table, (c) Na  (d) Cu 
because 41. Increasing order of acid strength of halogen acid
[KCET (Med.) 1999] is
(a) They are non-metals [DCE 2000]

(b) They are electronegative (a) HF  HCl  HBr  HI

(c) Their atoms are generally univalent (b) HCl  HBr  HI  HF
(d) They have 7 electrons in the outermost shell (c) HF  HI  HBr  HCl
of their atom (d) None of these
33. Which of the following sequence correctly 42. Which is the weakest base [KCET 1993]
represents the decreasing acid nature of oxides [AMU 2000] (a) NaOH (b) KOH
(a) Li 2 O  BeO  B2 O3  CO2  N 2 O3 (c) Ca(OH )2 (d) Zn(OH )2
(b) N 2 O3  CO2  B2 O3  BeO  Li 2 O 43. Which of the following elements shows maximum
(c) CO2  N 2 O3  B2 O3  BeO  Li 2 O number of different oxidation states in its
compounds
(d) B2 O3  CO2  N 2 O3  Li 2 O  BeO [CBSE PMT 1998]
34. Which of the following aqueous acid is most (a) Eu (b) La
acidic (c) Gd (d) Am
[AMU 2000]
44. The valency shell of calcium contains [JIPMER 2000]
(a) HCl (b) HF
(a) 8 electrons (b) 6 electrons
(c) HI (d) HBr
(c) 4 electrons (d) 2 electrons
35. The correct order of the increasing ionic character
45. 3 and 6 electrons are present in the outermost
is
orbit of A and B respectively. The chemical
[MP PET 2000] formula of its compound will be
(a) BeCl 2  MgCl2  CaCl2  BaCl2 (a) A 3 B 2 (b) A 2 B 3
(b) BeCl 2  MgCl2  BaCl2  CaCl2 (c) A2 B (d) AB
(c) BeCl 2  BaCl2  MgCl2  CaCl2
46. Which of the following halogens doesn’t exhibit
(d) BaCl2  CaCl2  MgCl2  BeCl 2 positive oxidation state in its compounds [MH CET 1999]
36. Which of the following elements is found in native (a) Cl (b) Br
state (c) I (d) F
[RPET 1999] 47. The most basic element is [MP PET 2000; JIPMER 2000]
(a) Al (b) Au (a) Fluorine (b) Iodine
 Chemical Periodicity 643
(c) Chlorine (d) Bromine 5. Arrange S, O and Se in ascending order of
48. Which of the following set has the strongest electron affinity
tendency to form anions [AFMC 1999] [Roorkee 1990]
(a) Ga, In and Te (b) Na, Mg and Al (a) Se < S < O (b) Se < O < S
(c) N, O and F (d) V, Cr and Mn (c) S < O < Se (d) S < Se < O
49. An element X which occurs in the first short 6. Which of the following is not the correct
period has an outer electronic structure s 2 p 1 . increasing order of ionisation energy [RPMT 2000]
What are the formula and acid-base character of (a) Cl   Ar  K  (b) Au  Ag  Cu
its oxides [DCE 1999]
(c) Cs  Rb  K (d) K  Ca  Sc
(a) XO 3 , basic (b) X 2 O 3 , basic
7. In which of the following arrangements the order
(c) X 2 O 3 , amphoteric (d) XO 2 , acidic is NOT according to the property indicated
50. Which of the following gas does not have an octet against it [AIEEE 2005]
or eight electrons in the outer shell[CBSE PMT 2001] (a) Al 3   Mg 2   Na  F  : Increasing ionic size
(a) Ne (b) Ar (b) B  C  N  O : Increasing first ionization
(c) Rn (d) He enthalpy
51. Beryllium and aluminium exhibit many properties (c) I  Br  F  Cl : Increasing electron gain
which are similar. But, the two elements differ in[AIEEE 2004] enthalpy (with negative sign)
(a) Forming covalent halides (d) Li  Na  K  Rb : Increasing metallic radius
(b) Forming polymeric hydrides 8. Which element has the greatest tendency to loose
(c) Exhibiting maximum covalency in compounds electrons
[NCERT 1980]
(d) Exhibiting amphoteric nature in their oxides
(a) F (b) S
(c) Fe (d) Be
9. Strongest acid is [RPMT 1997]
(a) Al 2 O3 (b) MgO
(c) Na 2 O (d) CaO
10. Which one of the following arrangements
1. Which of the following statement is correct with represents the correct order of electron gain
respect to the property of elements with an enthalpy (with negative sign) of the given atomic
increase in atomic number in the carbon family species [CBSE PMT 2005]
(group 14) [BHU 2004] (a) Cl  F  S  O (b) O  S  F  Cl
(a) Atomic size decrease (c) S  O  Cl  F (d) F  Cl  O  S
(b) Ionization energy increase 11. Increasing order of electronegativity is [RPET 2003]
(c) Metallic character decrease (a) Bi  P  S  Cl (b) P  Bi  S  Cl
(d) Stability of +2 oxidation state increase (c) S  Bi  P  Cl (d) Cl  S  Bi  P
2. The pair of amphoteric hydroxides is [AIIMS 2005] 12. What will be the order of Ist ionisation energy[BHU 2005]
(a) Al(OH )3 , LiOH (a) Li > Na > K (b) K > Li > Na
(b) Be(OH )2 , Mg(OH )2 (c) Na > Li > K (d) Li > K > Na

(c) B(OH )3 , Be(OH )2 13. Which of the following configurations represents

atoms of the elements having the highest second
(d) Be(OH )2 , Zn(OH )2 ionization energy
3. Which of the following oxides is amphoteric in [Pb. PMT 1998]
character 2
(a) 1s 2 s 2 p2 4
(b) 1s 2 s 2 p 6
2 2

[AIEEE 2005]
(c) 1s 2 2 s 2 2 p 6 3 s 1 (d) 1s 2 2 s 2 2 p 6 3 s 2
(a) CaO (b) CO2
(c) SiO2 (d) SnO2 14. The first ionization potentials in electron volts of
nitrogen and oxygen atoms are respectively given
4. Which has highest melting point [RPMT 1997]
by [IIT 1987]
(a) LiCl (b) BeCl 2
(a) 14.6, 13.6 (b) 13.6, 14.6
(c) BCl 3 (d) CCl4 (c) 13.6, 13.6 (d) 14.6, 14.6
 644 Chemical Periodicity
15. The elements which occupy the peaks of
ionisation energy curve, are [CBSE 2000] 1. Assertion : Positive ions will be wider than parent ato
(a) Na, K, Rb, Cs (b) Na, Mg, Cl, I Reason : Nuclear charge pulls them closer
(c) Cl, Br, I, F (d) He , Ne, Ar, Kr 2. Assertion : Dinegative anion of oxygen (O 2 ) is
quite common but dinegative anion
16. Which is the correct order of ionic sizes (At. No. :
Ce = 58, Sn = 50, Yb = 70 and Lu = 71)[AIEEE 2002] of sulphur (S 2 ) is less common
(a) Ce  Sn  Yb  Lu (b) Sn  Ce  Lu  Yb Reason : Covalency of oxygen is two
[AIIMS 2002]
(c) Lu  Yb  Sn  Ce (d) Sn  Yb  Ce  Lu
3. Assertion : The atomic radii of calcium is
17. A sudden large jump between the values of second smaller than sodium.
and third ionisation energies of an element would
Reason : Calcium has a lower nuclear charge
be associated with the electronic configuration
than sodium [AIIMS 1999]
[CBSE PMT 1992; AFMC 1998; CPMT 1999]
4. Assertion : The first ionization energy of Be is
(a) 1s , 2 s p 6 , 3 s 1
2 2
(b) 1s 2 , 2 s 2 p 6 , 3 s 2 p 1 greater than that of B
Reason : 2p orbital is lower in energy than 2s
(c) 1s 2 , 2 s 2 p 6 , 3 s 2 p 2 (d) 1 s 2 , 2 s 2 p 6 , 3 s 2
of
18. Which element having following electronic [IIT-JEE Screening 2000]
configurations has minimum ionization potential 5. Assertion : LiCl is predominantly a covalent
[NCERT 1978; KCET 1991; CBSE PMT 1991; compound
Pb. PET 1999; BHU 2000] Reason : Electronegativity difference
(a) 1s 1 2
(b) 1s , 2 s 2 p 2 6 between Li and Cl is too small[IIT-JEE 1998]
2 2 6 1
6. Assertion : F atom has a less negative electron
(c) 1s , 2 s 2 p , 3 s (d) 1s 2 , 2 s 2 2 p 2 affinity than Cl atom
19. Arrange F, Cl, O, N in the decreasing order of Reason : Additional electrons are repelled
electronegativity more effectively by 3p electrons in
(a) O  F  N  Cl (b) F  N  Cl  O Cl atom than by 2p electrons in F
atom
(c) Cl  F  N  O (d) F  O  N  Cl
[IIT-JEE 1998]
20. Ionic radii of [IIT-JEE 1999] 7. Assertion : Noble gases have maximum
(a) Ti 4   Mn 7  (b) 35
Cl   37 Cl  electron affinity. [AIIMS 1995]
Reason : High electron affinity shows that
(c) K   Cl  (d) P 3   P 5 
the electron is loosely bonded to the
21. Which of the following have high electron affinity atom.
[BHU 2000, 05] 8. Assertion : The first ionisation energy of Be is
(a) F (b) Cl greater than boron [AIIMS 2002]
(c) N (d) O Reason : 2p orbitals have lower energy than
22. In which block 106th element belongs [DCE 2000] 2s orbitals.
(a) s-block (b) p-block 9. Assertion : Atomic number of the element
(c) d-block (d) f-block ununbium is 112.
Reason : Name for digits 1 and 2 is un-and
bi-respectively in latin words.
10. Assertion : Chemistry of Actinoids is more
complicated than Lanthanoids.
Reason : Actinoid elements are radioactive.
11. Assertion : Ionization enthalpy is always
negative.
Reason : Energy is always released when
electrons are removed.
Read the assertion and reason carefully to mark the
12. Assertion : Shielding effect increases as we go
correct option out of the options given below :
down the group.
(a) If both assertion and reason are true and the Reason : More is the number of electrons in
reason is the correct explanation of the assertion. the penultimate shell, more is
(b) If both assertion and reason are true but reason is shielding.
not the correct explanation of the assertion.
13. Assertion : Ionization potential across the
(c) If assertion is true but reason is false.
period is Na < Al < Mg < Si.
(d) If the assertion and reason both are false.
(e) If assertion is false but reason is true.
 Chemical Periodicity 645
Reason : Ionization potential decreases with
decrease in atomic size.
14. Assertion : More is the electron affinity greater
is the reducing character.
Reason : Reducing character depends on
number of electrons gained.
15. Assertion : Ground state configuration of Cr is
3d5, 4s1.
Reason : A set of half filled orbitals
containing one electron each with
their spin parallel provides extra
stability to the system.
16. Assertion : I.E. of 7N is more than that of 8O as
well as 6C.
Reason : This is due to difference in
reactivity towards oxygen.
17. Assertion : NO– ion is isoelectronic with CN–
ion.
Reason : Isoelectronic ions have same
number of elelctrons.
18. Assertion : Outermost electronic configuration
of most electropositive elements is
ns2 np3.
Reason : ns2 np3 is stable due to half filled
subshell.
19. Assertion : First ionization energy for nitrogen
is lower than oxygen.
Reason : Across a period effective nuclear
charge decreases. [AIIMS 2005]
 Chemical Periodicity 643
46 d 47 a 48 c 49 d 50 a
51 b 52 a 53 d 54 a 55 c
56 b 57 c 58 b 59 c 60 b
61 a 62 d 63 c 64 a 65 d
66 d 67 d 68 c 69 c 70 c

Extended or long form of periodic table 71 b 72 a

1 c 2 d 3 c 4 a 5 c Ionisation energy
6 c 7 b 8 b 9 b 10 a
1 b 2 c 3 d 4 a 5 c
11 d 12 a 13 d 14 d 15 b
6 a 7 c 8 d 9 a 10 a
16 a 17 d 18 c 19 a 20 b
11 b 12 c 13 a 14 d 15 b
21 a 22 a 23 b 24 a 25 c
26 a 27 a 28 a 29 b 30 d 16 a 17 a 18 c 19 a 20 b

31 c 32 c 33 c 34 a 35 b 21 d 22 b 23 d 24 c 25 b

36 b 37 d 38 c 39 a 40 d 26 c 27 b 28 a 29 c 30 b
41 a 42 c 43 d 44 d 45 c 31 a 32 b 33 a 34 c 35 c
46 a 47 b 48 b 49 c 50 c 36 c 37 d 38 b 39 c 40 a
51 b 52 b 53 c 54 d 55 b 41 c 42 b 43 a 44 b 45 b
56 c 57 c 58 b 59 a 60 d
46 d 47 a 48 b 49 a 50 a
61 b 62 b 63 a 64 c 65 a
51 a 52 d 53 a 54 a 55 c
66 d 67 d 68 a 69 c 70 d
56 b 57 a 58 a 59 d 60 a
71 c 72 b 73 c 74 c 75 a
61 d 62 d 63 a 64 b 65 b
76 d 77 a 78 b 79 d 80 c
66 c 67 a 68 b 69 a 70 c
81 b 82 d 83 b 84 b 85 b
86 d 87 a 88 d 89 c 90 b 71 a 72 b 73 d 74 b 75 d

91 d 92 b 93 c 94 a 95 d 76 b 77 c 78 c 79 d 80 a

96 d 97 c 98 b 99 a 100 c 81 d 82 b 83 b 84 a 85 d
101 c 102 c 103 abcd 104 c 105 d 86 c 87 a 88 b 89 c
106 a 107 d 108 a 109 a 110 b
111 b 112 a 113 b 114 a 115 d Electron affinity
116 c 117 c 118 c 119 a 120 c
1 d 2 c 3 c 4 d 5 a
121 d 122 b 123 a 124 b 125 b
6 a 7 b 8 b 9 a 10 b
126 b 127 d 128 c 129 b 130 d
11 c 12 a 13 c 14 b 15 a
131 d
16 d 17 b 18 a 19 b 20 c
Atomic and Ionic radii 21 b 22 b 23 d 24 c 25 d
26 a 27 b
1 b 2 d 3 c 4 a 5 a
6 d 7 a 8 b 9 b 10 d
Electronegativity
11 a 12 d 13 d 14 a 15 a
16 d 17 d 18 d 19 a 20 a 1 b 2 b 3 d 4 b 5 b
21 b 22 d 23 a 24 a 25 c 6 a 7 b 8 a 9 c 10 a
26 d 27 c 28 b 29 c 30 c 11 c 12 b 13 d 14 a 15 c
31 c 32 b 33 d 34 a 35 d 16 a 17 b 18 c 19 a 20 a
36 a 37 d 38 a 39 b 40 d 21 d 22 a 23 d 24 b 25 a
41 b 42 a 43 a 44 d 45 a 26 b 27 c 28 b 29 b 30 a
 644 Chemical Periodicity
31 b 32 b 33 a 34 a 35 d 2s and three 2 p ) which can have eight
electrons, hence second period contains 8
elements from atomic no. 3 to 10.
Valency and oxidation state 9. (b) Neils Bohr developed the long form of periodic
table on the basis of Mosley’s principle.
1 a 2 c 3 c 4 a 5 a 10. (a) 33  1s 2 2 s 2 2 p 6 3 s 2 3 p 6 3d 10 4 s 2 4 p 3
6 d 7 a 8 d 9 b 10 d
11. (d) 16- 1s 2 2 s 2 2 p 6 3 s 2 3 p 4 there are 6 e  in outer
11 d 12 c 13 a 14 c 15 d most shell therefore its group is VIthA.
16 d 17 a 18 c 19 a 20 b 13. (d) Many metals with catalytic properties because
21 a 22 b 23 b 24 b 25 d (i) They provide surface area for reaction to
occur
26 c 27 b 28 c 29 d 30 b
(ii) They decreases the ionisation energy.
31 d 32 d 33 b 34 c 35 a
(iii) They have vacant d -orbitals.
36 b 37 d 38 c 39 d 40 d
17. (d) Aluminium. As it belongs to p -block element.
41 a 42 d 43 d 44 d 45 b
18. (c) Cu29   Ar  3 d 10 4 s1 .
46 d 47 b 48 c 49 c 50 d
21. (a) 1 s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 principal quantum no. is 4
51 d
so it belongs to 4th period.

Critical Thinking Questions 23. (b) Inert gases, these have ns 2 np 6 configuration.
24. (a) 1s 2 2 s 2 2 p 2  there are 4 e  in valence shell
1 d 2 d 3 d 4 b 5 a therefore it goes to IV- group.
6 b 7 b 8 c 9 a 10 b 27. (a) U  Ra  Pb  Hg
11 a 12 a 13 c 14 a 15 d 28. (a) Mg – Ba. Both belongs to II-A group.
16 b 17 d 18 c 19 d 20 d 29. (b) Na  Cl . Both belongs to III period.
21 b 22 c 30. (d) Elements of second and third period
Diagonal relationship
Assertion & Reason II Li Be B C N O F
III Na Mg Al Si P S Cl
1 d 2 b 3 c 4 c 5 c
31. (c) d-Block because the last electron enters d-
6 c 7 d 8 a 9 a 10 b subshell.
11 d 12 a 13 c 14 e 15 a 34. (a) Kr has atomic no. 36 which is a noble gas and
16 c 17 e 18 e 19 b all noble gases are included in the p-block.
38. (c) d-block. As the last e  enters in d-subshell.
40. (d) Due to its vacant p-orbital.
41. (a) By obserbing principal quantum number (n),
Orbital (s, p, d , f ) and equating no. of e  ’s we
are able to find the period, block and group of
element in periodic table.
42. (c) 33 : 1s 2 , 2 s 2 , 2 p 6 , 3 s 2 , 3 p 6 , 4 s 2 , 3 d 10 , 4 p 3
Extended or long form of periodic table
In its valence shell 5e  are present so it is
2. (d) n / p ratio is a cause of radioactivity. fifth (A) group element.
5. (c) Halogens has 7 electrons in his valance shell 43. (d) 38 is the atomic no. of strontium (Sr ) which is
(ns 2np 5 ) . s-block element and all the elements of s-
block are metals.
6. (c) As alkali metals have tendency to loose e  .
44. (d) Hydrogen resembles alkali metals in some
7. (b) Each period consists of a series of elements
properties so it can be placed in the first
whose atom have the same principal quantum
no. (n) of the outer most shell i.e. In second group of periodic table.
period n  2 , this shell has four orbitals (one 47. (b) Chalcons are oxygen family.
49. (c) Both belongs to VA group.
 Chemical Periodicity 645
50. (c) According to Dobernier law of triads the 102. (c) Mg has only two electrons in the 3s-orbital
atomic mass of the central element was nearly and hence its I.E. is lowest, i.e. it has the
the arithmetic mean of atomic masses of other maximum tendency to form di-positive ions.
two elements. 103. (a,b,c,d) It reflects trends in physical and
Cl Br I Arithmetic mean chemical properties of the elements.
120  31
31 75 120  75 .5 104. (c) As last e  goes to d-subshell.
2
107. (d) First decreases to a minimum and then
53. (c) Z = 2,8,8,1.  it would donate e  more easily. increases
54. (d) Last electron goes to s-subshell. Mn  3 d 5 4 s 2 .
108. (a) 25
55. (b) Because they belong to same group.
111. (b) Hydrogen, forms hydrides like halides, e.g.
57. (c) Ionic radius will increase as number of shells
HCl.
increases
58. (b) Al. Due to diagonal relationship. 114. (a) Hydration energy increases along the period.

60. (d) 2,8,2.  it would donate e  more easily. 115. (d) In IIA group all elements are metal while in
IIIA, IVA and VIIA groups non-metallic
62. (b) A representative element as last e  enters p- elements are also present.
orbital.
118. (c) Mg, Ba, Ca have ns 2 configuration.
63. (a) The configuration represents on alkaline earth
metals. 119. (a) Elements of group halogen are :
65. (a) First group F, Cl, Br I and At .

e.g. NaCl  H2O ⇌ NaOH  HCl 121. (d) N and P have 3 unpaired electrons in 2 p and
3 p respectively; V has 3 unpaired electrons
68. (a) Ionic bond is formed when there is large
difference of electro-negativities between the in 3 d .
atoms. 124. (b) Tungston (W ) having highest m.p.

69. (c) d-block - [ Ar ] 3 d 1 4 s 2 125. (b) These atomic no. gives the configuration
ns 2np 5 which are of halogen group or VIIth
70. (d) Be : 1 s 2 2 s 2
group.
71. (c) Increasing atomic number. Mosley found that 126. (b) The atomic no. of an element is derived from
atomic no. was better fundamental property the no. of proton because during chemical
than atomic weight. reaction no. of electron undergoes for change
72. (b) Lowest ionisation energy due to largest size. 127. (d) Due to identical ionic radii and polarising
73. (c) Elements on the right side of the periodic power
table are p-block. Mostly non-metals.  Charge 
74. (c) Screening effect of d and f block elements is  Size ratio of pairs of these elements 
 
nearly same.
77. (a) Li because of its smallest size.
78. (b) In third group Na is a typical element.
Atomic and ionic radii
85. (b) On equating no. of e  ’s atomic no. is 12 which 1. (b) Value of Z for hydrogen =1
is for Mg . Value of Z for helium = 2
86. (d) 17  1s 2 2 s 2 2 p 6 3 s 2 3 p 5 . Value of n for both is = 1
0 .52  12 0 .52  12
89. (c) Lanthanide’s are called rare earth metals. rH  rHe  
1 1
91. (d) It show similarities with both alkali metals as
rH
well as halogens.  1 : 1 or rHe  : rH  1 : 1
rHe 
92. (b) M  After gaining an e  the metal attains
stable configuration. 2. (d) The size of an species decreases with
increasing nuclear charge because the
95. (d) Due to presence of vacant d-orbitals and they attraction for the electrons increases. Thus
show d-d transition.
Al 3  is smaller in size.
96. (d) Potassium, K  Ar  4 s1 .

97. (c) p-block; 31 Ga  Ar 3 d 10 4 s 2 p 1 .

 646 Chemical Periodicity
3. (c) As the nuclear charge per electron is 26. (d) As the nuclear charge per electron is
maximum in F  . Therefore it is smallest in maximum in P 5  . Therefore its size is
size. smallest.
4. (a) During the formation of cation the size 27. (c) Na   10 electron ; Li   4 electron
decreases.
6. (d) Highest the nuclear charge smallest the 28. (b) Ionic radius of trivalent lanthanide’s almost
remains constant with increase in the atomic
atomic size as well as radius also.
number.
7. (a) Atomic radius decreases on going from left to
30. (c) Halogens are most electronegative elements.
right in a period. Thus size of O  F . As O 2 
33. (d) On moving from left to right in a period value
and F  are isoelectronic, therefore, size of
of radius decreases.
O 2  F.
34. (a) Sc 3   Cr 3   Fe 3   Mn 3  the correct order is
8. (b) As the nuclear charge per e  is maximum in
Cr 3  Mn 3  Fe 3  Sc 3
Mg 2 , it has smallest size among
35. (d) Na  Mg 2   Al 3   Si 4  . All are isoelectronic
Na  , Mg 2 , Cl  and F  .
but nuclear charge per electron is greatest for
9. (b) S 2  and Cl  both are isoelectronic but nuclear
Si 4  . So it has smallest size and nuclear
charge of Cl  is more than S 2  . So it has
charge per electron for Na  is smallest. So it
largest size.
has largest size.
10. (d) In completely filled shell inter atomic
repulsion is more so have greater size. 36. (a) N 3   O 2   F  . All are isoelectronic but
12. (d) I  as it has the biggest size. nuclear charge per electron is highest for F  ,
13. (d) Mg, as we move across the period atomic so it has smallest size.
radius decreases. 38. (a) Cation has small size than parent atom and
anion has greater size than parent atom.
14. (a) O 2 has the highest value of ionic radii as this
can be explained on the basis of 39. (b) Ionic radii decreases significantly from left to
 Nucleaus charge  right in a period among representative
Z /e   elements.
 No. of electron 
Whereas Z / e ration increases, the size 40. (d) H  is most stable due to its full filled 1s-
decreases and when Z / e ration decreases the orbital.
size increases. 43. (a) C 4  has largest radius due to least nuclear
15. (a) Continuous increase as no. of shells increases charge per electron.
down the group. 44. (d) For ionic bond formation low I.E., high
16. (d) Na   F   O 2   N 3  electron affinity and high lattice energy is
All are isoelectronic, effective number charge needed.
is highest for Na  so it has smallest size. 45. (a) Ionic radii increases in a group.
17. (d) I   I  I  46. (d) Size of elements decreases across a period.
54 53 52 atmoic number
47. (a) X  ion larger in size than X atoms. Because of
19. (a) Continuously decreases as the effective low effective nuclear charge on X  , X has a
nuclear charge increases. bigger size.
20. (a) Mg 2   Na  F   Al 48. (c) Fe, Co, Ni , Cu . Due to shielding of d-electrons,
 2  the effect of increased nuclear charge due to
F has bigger size than Mg and Na due to
small nuclear charge. increase in atomic no. neutralised.
Consequently atomic radius remains almost
21. (b) More than F  as K  has more no of shells in unchanged after chromium.
atomic state.
49. (d) S 2   Cl   K   Ca 2 
22. (d) All are isoelectronic but O 2  has lowest
52. (a) Covalent radii decreases on going from left to
charge among them. So it is largest in size.
right in periods. However among the transition
23. (a) As effective nuclear charge on Na  is elements the size do not changes much because
maximum. It has smallest size. the electrons add to the pneultimate d-subshells
25. (c) Be  C  F  Ne . Atomic size decreases across i.e. (n  1) d - subshell.
a period.
 Chemical Periodicity 647
59. (c) During the conversion of neutral atom to 1. (b) I.E.(II) of Na is higher than that of Mg
cation size decreases because after removal because in case of Na , the second e  has to
one e  or more be remove from the noble gas core while in
(i) Nuclear charge per electron increases. case of Mg removal of second e  gives a
(ii) Outermost shell is completely removed. noble gas core.
Mg has high first ionisation potential than
60. (b) Atomic radius increases as no. of shells
increases. Na because of its stable ns 2 configuration.
7. (c) Ionization potential decreases. Since, atomic
62. (d) Chloride ion and potassium ion are
size increases.
isoelectronic, isoelectronic ions are those ions
having same number of electrons. 8. (d) Alkali metals, lower the no. of valence e  ,
lower is the value of ionization potential.
K  2, 8, 8, 1 K   2, 8 , 8
9. (a) The ionization energy of hydrogen is to high
Cl  2, 8, 7 Cl  2, 8, 8 for group of alkali metals, but too low for
halogen group.
63. (c) Cs  has the largest ionic radius in the periodic 13. (a) E1  E2 because second I.E. is greater than
table. first I.E.
64. (a) Ionic radii increases down the group. 15. (b) Due to high stability of half-filled orbitals.
4 16. (a) In Cu it has completely filled d-orbital so
65. (d) Si is smallest in size due to their greater +ve
charge. highest energy is absorbed when it convert in
Cu  ion.
66. (d) Due to having three electrons atomic size
increases. 18. (c) The energy required to remove an electron
from outermost orbit of an isolated gaseous
F   9  1  10 electrons ; O 2  8  2  10 atom is called I.E. Now carbon has 4 e  in
electrons outermost shell. Thus it has 4 ionization
Al  3  13  3  10 electrons ; N 3   7  3  10 e  . energies.
19. (a) Since, stable half filled configuration.
Because electrostatic force between nucleus
21. (d) First I.P. of Be  B because of stable ns 2
and e cloud is least in nitrogen.
configuration.
67. (d) The trivalent ion having largest size in
22. (b) K   K 2   e  . Since e  is to be removed from
lanthanide series is lanthanum. This is due to
lanthanide contraction. stable configuration.
24. (c) Since the IV, I.E. is very high. Thus electron is
68. (c) As we know that hydration power decreases to be removed from stable configuration.
on moving down the group hence among alkali
25. (b) Li and Cs belong to Ist group but Cs has
metals Li has excessive hydration & hence it
larger size, hence low nuclear attraction
has low mobility in aqeous solution.
force, thus low ionization energy.
n 2a (c) Li belongs to Ist group. There is 1 e  in
69. (c) Ionic radius in the nth orbit is given by rn  26.
z outermost shell. Thus low I.E.
1 27. (b) Increases from left to right. Since, the size
or rn  where n is principal equation no.,
Z decreases.
ao. bohr's radius of hydrogen atom and Z is
28. (a) As the e  is to be removed from stable
the effective nuclear energy.
configuration.
70. (c) Order of polarising power Be    Li   Na  29. (c) Since e  is to be removed from exactly half
Hence order of covalent character filled p-orbital.
BeCl2  LiCl  NaCl 31. (a) Ionisation potential increases across the
period.
71. (b) Higher the (n+1) value higher is the energy
E 54 .4
associated with orbitals. 32. (b) E  20   13 .6 eV
n 4
72. (a) With the increase in size of cation the size of
34. (c) Due to stable half-filled orbitals.
the hydrated ion decreases hence ionic
conductance increases. 35. (c) Greater than the first ionization energy
because after removal one e  , effective
nuclear charge increases.

Ionisation energy 36. (c) Rare gases as the e  is to removed from

stable electron configuration.
 648 Chemical Periodicity
37. (d) Since it is a noble gas. 75. (d) It has maximum no. of e  in outermost shell.
38. (b) The first I.P. is maximum for hydrogen due to So it has maximum I.E.
its small size. 76. (b) Ionization potential increases as we go from
41. (c) Due to his fullfilled configuration. left to right in a period, while it decreases as
we come down a group.
42. (b) 1st I.P. decreases down the group.
Be B Li Na
43. (a) 1st I.P. increases from left to right in a period.
9.3 8.3 5.4 5.1
45. (b) First I.P. for C is 11.3, for N is 14.5 and for O is
13.6 77. (c) Half filled p-orbitals possess extra stability.
47. (a) Li has least I.P about 5 . 4 . 78. (c) Ionization potential decreases down the
48. (b) I.E. increases across the period. group.
50. (a) He has highest ionisation energy due to it full 79. (d) Li  and Mg 2 ions have similar polarising
fill 1s-orbital. power or ionic potential and therefore have
51. (a) s-electrons are strongly bonded to the similar properties. This type of relationship of
nucleus. So large amount of energy is required the first element of a group with the second
to remove an e  . element of the next group is known as
52. (d) Mg  Al  Na . This is due to the presence of diagonal relationship.
fully filled s-orbital in Mg. 80. (a) The addition of second electron in an atom or
55. (c) The 1st I.P. for hydrogen is 13.6 volts ion is always endothermic.
56. (b) Alkali metals are strong reducing agents 81. (d) We know that ionisation potential gradually
58. (a) Due to the large size of group IA elements, the decreases of moving down the group while
outermost electron is far from the nucleus and atomic size increases as we move down the
can easily be removed. their ionisation group. Hence larger the atomic size, smaller is
energies or ionisation potentials are relatively ionisation potential.
low. 82. (b) Fluorine has highest E o red {Equal to +2.9 V}
Li Na K Rb due to which it can easily accept an electron &
Cs hence it is the best oxidising agent.
Ionisation potential (eV) 5.4 5.1 4.3 83. (b) The ionisation energy of tin {Sn} is less than
4.2 3.9 that of lead (Pb). It is due to the poor
60. (a) N  O  Be  B Ist ionisation energy of N  O shielding of d- and f-electron in Pb due to
because of half filled p -orbital. which it feels greater attraction from nucleus.
84. (a) The order of screening effect in a given shell
61. (d) M 2   M 3  After the removal of 2e  the
are in order s  p  d  f .
nuclear charge per e  increases, due to which
85. (d) The ionisation energy of Li, Be, B and C is 520,
high energy is required to remove 3 e  .
899, 801, 1086 kJ / mol respectively hence,
63. (a) I.E. increases from left to right in a period.
carbon has highest IE1 .
64. (b) More because of stable configuration of Mg.
86. (c) Isoelectronic species are those which have
65. (b) He and Xe belongs to same group but He has
same no. of electrons.
higher ionisation energy because of small size.
66. (c) In second transition electron is to be removed K   19  1  18 ; Ca 2  20  2  18
from half filled orbital. Sc 3  21  3  18 ; Cl   17  1  18
68. (b) As it belongs to IA group and has maximum 87. (a) We know that atomic no. of fluorine (F),
size. chlorine (Cl), Bromine (Br) and Iodine (I) are
69. (a) Since, they have larger size as compared to 9, 17, 35 and 53 respectively. Therefore
other. correct reactivity of halogens is F  Cl  Br  I
70. (c) The second I.E. is greater than first I.E. 88. (b) Ionisation potential generally increases when
similarly second E.A. is greater than first E.A. we more in a period from left to right but IE1
the energy is to be supplied to force the of N 2 is greater than that of O 2 . It is due to

second e into the anion. the more stable (half-filled orbitals)
71. (a) Increases as the atomic size decreases and configurations of N.
hence effective nuclear charge increases. 89. (c) Nitrogen has more ionisation potential than
72. (b) B, Be, C, N as I.E. increases across the period. carbon & oxygen because, if outermost orbit is
half filled so it is more stable & order is
73. (d) Ionization potential is least for alkali metals
CN O
and it decreases down the group.
74. (b) It has maximum ionization energy due to half Electron affinity
filled orbitals.
 Chemical Periodicity 649
3. (c) O  C BN Value of electron affinity 4. (b) Electropositive nature increases down the
140 .9 122 .3 83 0
group and decreases across the period.
increases on going from left to right in
periods but the value of electron affinity of Vth 5. (b) An atom with high electronegativity has high
A elements is less than that of IVth A element, I.P.
this is due to half filled p-orbitals presence. 6. (a) If electronegativity difference is greater than
4. (d) Halogens have maximum electron affinity due 1.7 bond is ionic, if less than 1.7, the bond is
to their smaller size. covalent.
5. (a) Zero, because of the stable electronic 7. (b) Due to decrease in hydration energy of cation
configuration the noble gases do not show any and lattice energy remains almost unchanged.
force of attraction towards the incoming 8. (a) F, because of its smallest size.
electron. 9. (c) Because of small size and high nuclear charge.
8. (b) Energy released when an electron is added to 10. (a) Electronegativity decreases down the group.
an isolated atom in gaseous state. 11. (c) Halogens are most electronegative.
9. (a) Electron affinity value of Cl is greater the F 12. (b) Electronegativity decreases down the group.
and then decreases down the group.
13. (d) Because of smallest size.
10. (b) Electron affinity increases across the period.
14. (a) Electronegativity decreases down the group.
13. (c) Electron affinity of chorine is maximum.
16. (a) Electronegativity increases since the size
14. (b) The formation of ionic bond depends upon
decreases.
easy formation of cation and anion. therefore
the ionisation energy value of the metal atom 17. (b) Electropositive character decreases across the
should be low, so that it can easily form period as metallic character decreases.
cation. on the other hand, the electron affinity 18. (c) Si, P, S. As across the period electronegativity
value of the non-metal atom should be high so increases.
that it can easily form anion. 19. (a) Both electronegativity and electron affinity
 increases. This is because decrease in the size
15. (a) Because it can easily accept an e .
and increase in the nuclear charge. But
18. (a) Halogens have the highest e  affinity.
electronegativity increases continuously.
19. (b) In IB group all elements are metals.
20. (a) Electropositive nature increases down the
22. (b) Flourine although have highest group.
electronegativity due to its very small size,
21. (d) Electropositive nature increases down the
effective inter electronic repulsions are
group.
observed which brings down its electron
affinity. 23. (d) The electronegative character increases as the
size decreases.
23. (d) The bond dissociation energy of F-F bond is
very low. The weak F-F bond makes fluorine 24. (b) Electronegativity increases across a period.
the strongest oxidising halogen. 25. (a) Li3  1 s 2 2 s1 donates 1e  easily.
24. (c) Atomic radius increase from top to bottom in
28. (b) Electronegativity decreases down the group as
a group while decrease from left to right in a
atomic radius increases.
period on the other hand electron affinity
shows severe trends i.e. decrease from top to 30. (a) Electronegativity increases across the period
bottom in a group and increase from left to because size decreases.
right in a period. 31. (b) Alkali metals are most electropositive and
25. (d) It is a fact. moreover, electropositive character increases
down the group.
26. (a) Electron affinity of Cl is greater than fluorine
so the order are as F  Cl  Br  I 32. (b) Electronegativity increases when moves
towards period & decrease when moves
27. (b) Halogens have very high electron affinity. It
toward group.
may be rated that the electron affinity of
fluorine is unexpectedly low ( Cl ) . This may 33. (a) Electronegativity is the property of a bonded
atom. The relative tendency on an atom to
perhaps be due to small size of F atom. The
attract the shared pair of electron toward
value of electron gain enthalpies for Cl, F, S
itself is called electronegativity.
and O are respectively 349, 333, 200 & 142 KJ 34. (a) Due to Raving small in size and electron
/ mol hence correct order is Cl  F  S  O defficient in nature it has highest polarising
ability we can use Fazan's rule to understand
Electronegativity it further.
35. (d) With decrease in size from Al to S the basic
2. (b) Decrease as atomic size increases. nature of oxide decrease and acidic nature
increases.
 650 Chemical Periodicity
Al2O3  SiO2  P2O3  SO 2 33. (b) On passing from left to right in a period acidic
character of the normal oxides of the element
Al2 O3 is amphoteric, SiO2 is slightly acidic
goes on increasing with increase in
whereas P2O3 and SO 2 are the anhydrides of electronegativity.
acids H3 PO3 and H 2 SO 3 . 36. (b) Gold is found in native state.
37. (d) The elements which having same number of
Valency and Oxidation state electrons in the valence shell are placed in the
same group of periodic table.
1. (a) Examples of neutral oxides are CO, H 2O, N 2O . 38. (c) Alkali metals have the configuration
These oxides are neutral towards litmus (n  1)s 2 p 6 , ns1
paper. 41. (a) As going down the group size increases, an
5. (a) Basic or metallic character of pentaoxides in liberation of H  ion becomes easy. So the
VA group increases down the group. Hence order of acidity is : HI  HBr  HCl  HF
acidity decreases. 44. (d) Valence shell configuration for IIA group
7. (a) Na2O, MgO, Al2O3 , CuO . More the metallic elements is : ns 2
character higher the e  donating tendency. 45. (b) A 2 B 3
 
Therefore lower the I.E. more the basic nature 3 e
A   A 3 ; B  2 e
 B 2
of oxide.
47. (b) Lower the value of I.P. of an element, the
8. (d) As it can donate e  easily due to low greater will be the basic character of the
comparative attraction by the nucleus to the element.
valence e  . 48. (c) N, O and F have strong tendency to attract the
9. (b) Because of the non-metallic character shared pair of electrons i.e. by gaining
increases. electrons to form anions.
10. (d) Oxidizing power increases in a group. 49. (c) B2 O3 , Al2 O3 are amphoteric oxides.
14. (c) HF is least acidic due to the small size of 50. (d) He has the atomic number 2 so it does not
fluorine. have octet.
16. (d) Co  [ Ar]3d 7 4 s 2 , it has 3 unpaired e  so it is a 51. (c) Beryllium has the valency of +2 while
paramagnetic. aluminum exhibits its valency as +3
17. (a) Transition elements due to presence of vacant
Critical Thinking Questions
d-orbitals.
18. (c) Its valency is 2. So it will form MO type
compound. 1. (d) As we go down the group inertness of ns 2 pair
19. (a) Oxides of alkali metals are most basic. increase hence tendency to exhibit +2
21. (a) Fluorine is the most easily reduced in oxidation state increases and that of +4
halogens. oxidation state decreases.
22. (b) Across the period non-metallic character 2. (d) Both Be(OH)2 and Zn(OH)2 are amphoteric in
increases. Hence basic nature of oxide nature.
decreases. 3. (d) CaO is basic; CO2 is acidic; SiO2 is weakly
23. (b) Fluorine is more reactive than chlorine, acidic. SnO 2 is amphoteric.
bromine and iodine.
4. (b) In BeCl 2 has the highest melting point due to
24. (b) Both are coinage metals
ionic bond.
3 d 10 4 s1  Cu ; 4 d 10 5 s1  Ag
5. (a) Correct order of electron affinity is Se < S < O.
26. (c) Li, Na, K, contains only one e  in outer most In a group electron affinity decreases with
orbit. increase in atomic number.
27. (b) Valency is according to valence shall 6. (b) The correct increasing order of I.E. is,
configuration which here is 1 s 2 , 2 s 2 , 2 p 3 , ie . 5 Cu  Ag  Au .
28. (c) Fe belongs to first transition series. 7. (b) B  C  N  O ; When we move from B to O in a
29. (d) Reactivity of alkaline earth metals increases periodic table the first ionisation enthalpy
down the group. increase due to the attraction of nucleous
31. (d) Tendency to gain e  and oxidising power are towords the outer most of electron.
related. Among halogens F is the directly 8. (c) Both Fe and Be are metal but Be has stable
most powerful oxidising agent. configuration so it is difficult to release e 
32. (d) Electronic configuration of outermost shell of from it. So it has less metallic character than
group-17 or halogens are ns 2 np 5 . Fe .

9. (a) The basic nature of oxide decreases across the
period as metallic character decreases.
Therefore acidic nature of oxide increases.
10. (b) Halogens have very high electron affinities. It
may be noted that the electron affinity of
fluorine is unexpectedly low ( Cl ) . This may
perhaps be due to the small size of the F atom.
The values of electron gain enthalpies for Cl,F,
S and O are respectively 349, 333, 200 and
142 kJ/mole hence correct order is Cl>F>S>O.
11. (a) Increasing order of electronegativity
Bi<P<S<Cl.
12. (a) In a group, the ionisation potential decreases
from top to bottom. In the alkali group, the
ionisation potential decreases from Li to Cs.
Li Na K Rb Cs
eV 5.3 5.1 4.3 4.2 3.9
13. (c) Because for removing second electron, it has
to be taken out from stable configuration that
needs a large amount of energy.
14. (a) First I.E. of N  First I.E. of O.
15. (d) All the nobal gases occupy the peaks of I.E.
curve.
16. (b) Correct order of ionic size is Sn > Ce > Lu >
Yb.
17. (d) 1s 2 2 s 2 p 6 3 s 2 - In III transition e  is to be
removed from stable configuration.
18. (c) 1s 2 2 s 2 2 p 6 3 s1 . It belongs to IA group which has
least ionization potential and it decreases
down the group
19. (d) Electronegativity increases on going from left
to right in a period. Thus electronegativity of
F  O  N ~ Cl .
20. (d) Nuclear charge per electron is greater in P
Therefore, its size is smaller.
21. (b) The electron affinities of some of the elements
of second period (i.e., N, O, F etc.) are
however, lower than the corresponding
elements (i.e., P, S, Cl, etc.) of the third
period. This is due to the reason that the
elements of second period have the smallest
atomic size amongst the elements in their
respective groups. As a result, there are
considerable electron-electron repulsion
within the atom itself and hence the
additional electron is not accepted with the
same ease as is the case with the remaining
elements in the same group.
22. (c) Element belongs to d-block is unnilhexium
(Unh)106 .
Assertion and Reason
Chemical Periodicity 651
1. (d) Positive ions will be smaller than parent
atoms.
3. (c) Calcium has a higher nuclear charge than
sodium.
4. (c) 2s orbital has lower energy than 2p.
5. (c) Cl is more electronegative than Li. Although
the difference is not much. Therefore the
electron pair moves equally to both an thus
is forming a covalent compound.
6. (c) The lower value of electron affinity of F is due
to electron-electron repulsion in 2-p orbitals
of F-atom is stronger.
7. (d) All noble gases have stable configuration.
Therefore, they can not take any electron
means that they have no affinity for electrons.
High electron affinity shows that electron is
strongly bonded to the atom. Here both
assertion and reason are false.
8. (a) The first ionization energy of Be is greater
than Boron because it is difficult to remove
electron from Be in comparison to boron. It is
also true that the 2P orbitals have lower
energy than 2 s-orbitals. Both assertion and
reason are true and reason is correct
explanation.
9. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
10. (b) Both assertion and reason are true but reason
is not the correct explanation of assertion.
Actinoids are more complicated due to the
opssibility of large number oxidation states.
11. (d) Both assertion and reason are false.
Ionization enthalpies are always positive.
5
. Energy is always absorbed when electrons are
removed from an atom.
12. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
The phenomenon is which the Penultimate
Shell (n  1) electrons act as screen or shield in
between nucleus and valence shell electrons
thereby reducing the effective nuclear charge
is known as shielding effect.
13. (c) Assertion is true but reason is false.
Ionisation potential decreases with increase
in atomic size and also for a given a shell. I.E.
is in given order.
s pd  f
14. (e) Assertion is false but reason is true.
More is the electron affinity, greater is the
Oxidising character.
15. (a) Both assertion and reason are true and reason
is the correct explanation of assertion.
 652 Chemical Periodicity
I.E. of N is more than that of 8O as well as
6 C.

16. (c) Assertion is true but reason is false.

N is half-filled (1s 2 2 s 2 2 p 3 ) and therefore more
stable and hence energy required to lose
electron is greater.
17. (e) Assertion is false but reason is true.
NO   7  8  1  16 e  whereas

CN   6  7  1  14 e  . So both are not

isoelectronic.
18. (e) Assertion is false but reason is true.
Outermost electronic configuration of most
electropositive elements is ns 1
19. (b) First ionization energy for nitrogen is lower
than oxygen due to decrease nuclear charge in
nitrogen comparison than oxygen.
 Chemical Periodicity 651

1. If the difference in electronegativities of two (c) Sb (d) Bi

elements is very large, then 9. For a p - block element, its 3d, 3s, 3p and 4s
(a) The bond is 50% ionic orbitals are completely filled and the
differentiating electron goes to the 4p orbital. The
(b) The bond is 100% covalent
element should have its atomic number in the
(c) The bond is more covalent than ionic range
(d) The bond is more ionic than covalent (a) 13 - 18 (b) 21 - 26
2. Which of the following elements will have the (c) 31 - 36 (d) 49 - 54
lowest electron affinity
10. The most common lanthanide is [AFMC 1995]
(a) Nitrogen (b) Flourine
(a) Lanthanum (b) Cerium
(c) Chlorine (d) Phosphorus
(c) Samarium (d) Plutonium
3. The correct order of second ionization potential of
11. In a period, elements are arranged in strict
carbon, nitrogen, oxygen and fluorine is
sequence of
[IIT-JEE 1981; CBSE PMT 1991; MADT Bihar 1995;
[CPMT 1989]
MP PMT 2003]
(a) Decreasing charges in the nucleus
(a) C > N > O > F (b) O > N > F > C
(b) Increasing charges in the nucleus
(c) O > F > N > C (d) F > O > N > C
(c) Constant charges in the nucleus
4. Which of the following species has the highest
ionisation potential [EAMCET 1998] (d) Equal charges in the nucleus
12. Some of the polar crystal when heated produce
(a) Li  (b) Mg 
electric current. This phenomena is termed as[AMU 2001]
(c) Al  (d) Ne (a) Ferroelectric effect (b) Phyroelectric effect
5. Which of the following elements are analogous to (c) Antiferroelectric effect (d)Piezoelectric effect
the lanthanides [AIIMS 1998]
13. Which of the following pairs has elements
(a) Actinides (b) Borides containing same number of electrons in the
(c) Carbides (d) Hydrides outermost orbit
6. Which of the order for ionisation energy is correct [CPMT 1985]

[CPMT 1999; CBSE PMT 2001] (a) N  O (b) Na  Cl

(a) Be  B  C  N  O (b) B  Be  C  O  N (c) Ca  Cl (d) Cl  Br
(c) B  Be  C  N  O (d) B  Be  N  C  O 14. Coinage metals are present in [DCE 2000]

7. Modern periodic table is based on the atomic (a) s-block (b) d-block
number of the elements. The experiment which (c) p-block (d) f-block
proved the significance of the atomic number was[CBSE PMT 1989]
15. In which of the following metal carbonate which
(a) Millikan's oil drop experiment metal carbonate is decomposed on heating[UPSEAT 1999]
(b) Moseley's work on X -ray spectra
(a) MgCO3 (b) Na 2 CO 3
(c) Bragg's work on X -ray diffraction
(c) K 2 CO 3 (d) Pb2 CO3
(d) Discovery of X -rays by Rontgen
8. Which one of the elements is most metallic 16. Which one of the following is the correct
decreasing order of boiling point [AMU 2000]
[MP PMT 2002]
(a) P (b) As (a) H 2 O  H 2 S  H 2 Se  H 2 Te
 652 Chemical Periodicity
(b) H 2 Te  H 2 Se  H 2 S  H 2 O (d) H 2 Te  H 2 O  H 2 Se  H 2 O

(c) H 2 O  H 2 Te  H 2 Se  H 2 S

(SET -15)

1. (d) If the difference in electronegativities of two

elements is very high then the bond is more
ionic than covalent.
2. (d) Phosphorus have the lowest electron affinity
due to half filled p orbital, but in nitrogen
electron affinity is greater than phosphorus
because of large nuclear attraction in 8. (d) The metallic property of an element increases
comparison with phosphorus. from top to bottom in group.
3. (c) The ionization potential increases across the P  As  Sb  Bi
period but the second ionization potential of
9. (c) 31– 36  Ga to Kr .
oxygen is highest among them because after
the removal of 1 e  the 2 e  is to be removed 10. (b) The most common lanthanide is cerium.
from half filled orbital which is difficult. 11. (b) Increasing charges in the nucleus as atomic
number increases across a period.
4. (d) As, now the e  is to be removed from stable
12. (d) This phenomena is called piezoelectric effect.
configuration. Li+ has the highest ionisation
potential due to its stability. 13. (d) Cl  Br . Both belong to VII-A group having 7 e 
5. (a) Actinides are homologous of Lanthanides. in valence shell.
6. (b) Ionisation energy increases across the period 14. (b) Copper, Silver and Gold are coinage metals
but due to stable half filled configuration of 15. (a) MgCO3  MgO  CO2
VA group, its I.E. is more than VI-A group.
16. (c) Correct decreasing order of boiling point is,
7. (b) Moseley’s work on X-ray spectra was proved
the significance of the atomic number. H 2O > H 2Te > H 2 Se > H 2S .

***
 General Principles of Extraction of Metals 653

Chapter

16
General Principles of Extraction of Metals

All the materials found in the earth are composed of pure metals are also found. These are termed
of elements. There are about 112 elements known nuggets. Iron is found in free state as meteroites which
which constitute the entire matter on the earth. also have 20 to 30% nickel.
Therefore, the elements are regarded as the building (ii) Sulphurised and arsenical ores : These ores
blocks of the universe. These are distributed in all the consist of sulphides and arsenides in simple and
three main parts of the earth; atmosphere and complex forms of metals. Important ores of this group
are
lithosphere. Among these, lithosphere constitutes the
Metal Name of the ore Composition
main source of most of the elements. The elements
have been broadly divided into metals and non-metals Pb Galena PbS
on the basis of their physical and chemical properties. Zn Zinc blende ZnS
Hg Cinnabar HgS
Occurrence of Metals
Ag Argentite or silver Ag2S
Element which have low chemical reactivity glance Pyrargyrite or 3Ag2S.Sb2S3
generally occur native or free or metallic state. e.g. ruby silver
Au, Pt, noble gas etc. Element which are chemically
Fe Iron pyrites FeS2
reactive, generally occur in the combined state. e.g. Ni Kupfer nickel NiAs
halogens, chalcogens etc. The natural materials in
Cu Copper pyrites CuFeS2
which the metals occur in the earth are called
minerals. The mineral from which the metal is Chalcocite or Copper Cu2S
conveniently and economically extracted is called an glance
ore. All the ores are minerals but all minerals cannot be (iii) Oxidised ores : In these ores, metals are
ores. Ores may be divided into four groups, present as their oxides or oxysalts such as carbonates,
(1) Metallic core (siderophile) of the earth crust nitrates, sulphates, phosphates, silicates, etc.
contains (Mn, Fe, Co, Ni, Cu, Ru, Rb, Pd, Ag, Re, Os, Ir, Important ores of this group are listed below,
Pt, Au). Entire composition of metals in earth crust may Oxides
be given as, Haematite Fe2O3
Al (8.3%); Ca(3.6%); Na (2.8%); K (2.6%); Mg Magnetite Fe3O4
(2.1%); Ti (0.4%); Mn (0.1%); Fe (5.1%) other metals Limonite Fe2O3.3H2O
(0.1%).
Bauxite Al2O3.2H2O
(i) Native ores : These ores contain metals in
Corundum Al2O3
free state, e.g., silver, gold, platinum, mercury, copper,
etc. These are found usually associated with rock or Diaspore Al2O3.H2O
alluvial materials like clay, sand, etc. sometimes lumps Chromite FeO.Cr2O3
 654 General Principles of Extraction of Metals
Chromeochre Cr2O3 (iv) Halide ores : Metallic halides are very few in
nautre. Chlorides are most common. For example.
Tinstone (Cassiterite) SnO2
Common salt NaCl ; Horn silver AgCl
Chrysoberyl BeO.Al2O3
Carnallite KCl. MgCl2 .6 H 2 O
Cuprite (Ruby copper) Cu2O
Pyrolusite MnO2 The important fluoride ores are

Zincite ZnO Fluorspar CaF2 ; Cryolite Na3 AlF6

Rutile TiO2 Metals in Biology

Ilmenite FeO.TiO2 Metals are also found in living organisms, e.g.,
Carbonates
(1) Magnesium is found in chlorophyll.
Magnesite MgCO3
(2) Potassium is present in plant roots.
Lime stone CaCO3
(3) Manganese, Iron and copper are present in
Dolomite CaCO3.MgCO3
chloroplast. (4) Zinc is present in eyes of cats and
Calamine ZnCO3
cows.
Malachite CuCO3.Cu(OH)2
(5) Iron is present in haemoglobin.
Azurite Cu(OH)2.2CuCO3
(6) Calcium is present in bones.
Cerussite PbCO3
Siderite FeCO3 (7) Vanadium is present in cucumbers.
(8) Chromium is present in prown.
Nitrates
Chile saltpetre NaNO3 Extraction of Metals: Metallurgy
Salt petre KNO3 The extraction of a pure metal from its ore is
Sulphates called metallurgy. In order to extract the metal from
Epsom salt MgSO4.7H2O ores, several physical and chemical methods are used.
The method used depending upon chemical properties
Barytes BaSO4
and nature of the ore from which it is to be extracted. It
Gypsum CaSO4.2H2O
involves four main steps,
Glauber’s salt Na2SO4.10H2O
Anglesite PbSO4 (1) Crushing and grinding of the ore.
Kainite KCl.MgSO4.3H2O (2) Concentration or dressing of the ore.
Schonite K2SO4.MgSO4.6H2O (3) Reduction to free metal.
Polyhalite K2SO4.MgSO4.CaSO4.2H2O
(4) Purification or refining of the metal.
Phosphates and Silicates
(1) Crushing and grinding of the ore : Those ores
Lepidolite (an ore of (Li, Na, K)2 Al2(SiO3)3
occur in nature as huge lumps. They are broken to small
lithium) (F,OH)2
pieces with the help of crushers or grinders. These pieces
Petalite (an ore of LiAl(Si2O5)2 are then reduced to fine powder with the help of a ball
lithium) mill or stamp mill. This process is called
Triphylite (an ore of (Li, Na)3PO4, (Fe, Mn)3 pulverisation.
lithium) (PO4)2 (2) Concentration or dressing of the ore : The
Beryl (an ore of 3BeO. Al2O3.6SiO2 ore are usually obtained from the ground and therefore
berylium) contained large amount of unwanted impurities, e.g.,
earthing particles, rocky matter, sand, limestone etc.
Willemite Zn2SiO4 These impurities are known collectively as gangue or
China clay Al2O3.2SiO2.2H2O matrix. It is essential to separate the large bulk of
Chlor-apatite 3Ca3(PO4)2.CaCl2 these impurities from the ore to avoid bulk handling
and in subsequent fuel costs. The removal of these
Mica K2O.3Al2O3.6SiO2.2H2O
impurities from the ores is known as concentration.
Fluor-apatite 3Ca3(PO4)2.CaF2 The concentration is done by physical as well as
Felspar KAlSi3O8 chemical methods.
Talc Mg2(Si2O5).Mg(OH)2 Physical Methods (i) Gravity Separation or
Asbestos CaMg3.(SiO3)4 levigation: This process of concentration is based on the
difference in the specific gravity of the ore and gangue.

Crushed
 General Principles of Extraction of Metals 655
The sieved ore is either subjected to dry centrifugal xanthate (Collector) along with sodium cynamide and
separation or is placed in big shallow tanks in which a alkali (depressants) where by the floatation property
strong current of water blows. Heavy ore particles settle of ZnS and FeS2 is depressed. Mainly PbS passes into
down to the bottom of the tanks while lighter gangue the froth when air current in flown in, which is
particles are carried away by the current of water. The collected. After PbS is removed with the froth, same
process removes most of the soluble and insoluble CuSO4 (activator) is added and air is blown. The
impurities. For this purpose wilfley table and hydraulic floatation property of ZnS is increased which is now
classifier are widely used. The method is particularly removed with the froth. The slurry is acidified and
suitable for heavy oxide and carbonate ores like process is repeated when FeS2 passed into the froth and
Cassiterite (SnO2) and haematite. is collected.
(iii) Electromagnetic separation : If the mineral
and not gangue is attracted by a magnet, it can be
concentrated by magnetic separation. For example
chromite ore, FeCr2O4 being magnetic can be separated
from non–magnetic silicons impurities by this method.
Sometimes two minerals occur together, in which one
happens to be magnetic. By magnetic separation
method the nonmagnetic minerals is separated from
(ii) Froth floatation process : In some cases for
the magnetic mineral. For example tin–stone or
example, sulphides ores of copper, zinc and lead
concentration is brought by this method. In this method cassiterite, SnO2 (non-magnetic) containing wolfram,
advantage is taken of the preferential wetting of the FeWO4 (magnetic) is separated by this method. In this
ore by an oil. The finely ground ore is taken in a tank method a thin layer of finely ground ore is spread over
containing water and 1% of pine oil or terpentine oil. a rubber belt carried over a pulley in a magnetic field.
A strong current of air is blown through the The gangue particles or the particles of non–magnetic
suspension, producing a heavy froth or foam on the mineral fall off as the belt becomes vertical, and the
surface. The metal sulphide is wetted by the oil but the magnetic particles collect.
gangues is not and the sulphide-oil mixture is carried
Chemical methods (i) Calcination : In this
to the surface by films of oil The froth is skimmed off,
process the concentrated ore is heated in a suitable
the gangue settles down on the bottom or remains
underneath the froth. By this floatation method it is furnace generally in reveratory furnace much below its
possible to concentrate over 90% of a sulphite ore to melting point in absence of air. As a result of which
1/10 of its original bulk. the ore dries up and moisture and volatile impurities are
Compressed air driven off and carbonates are converted into oxides and the
Powdered
ore becomes porous. For example,
ore + oil + Light ore
water Al2 O3 .2 H 2 O  Al2 O3  2 H 2 O
particles in
froth 2 Fe2O3 .3 H2O  2Fe2O3  6 H2O
ZnCO3  ZnO  CO2 ; CaCO3  CaO  CO2
CuCO3 . Cu(OH )2  2CuO  CO2  H 2 O
(ii) Roasting : The process of heating the ores
Concentrate strongly in presence of air with or without certain
Gangue d substances, below its melting point is termed as
ore roasting. It differs from calcination in the respect that
Fig. 16.2. Froth floatation process heating is done in presence of air and at a higher
(ii) Activators and Depressants : During the temperature. In this process the impurities of sulphur
floatation process of some ores, these substances are and arsenic etc. are volatilized away as oxides and the
added which activate or depress the floatation property ore is converted into oxide. For example zinc oxide is
of the minerals and thus help in the separation of formed by the oxidation of zinc blende,
minerals present in the Powdered 2 ZnS  3O2  2 ZnO  2SO 2
ore. For instance, ore Electromagn
galena (PbS) is usually (iii) Leaching : It involves the treatment of the ore
ets
associated with with a suitable reagent as to make it soluble while
sphalerite (ZnS) and impurities remain insoluble. The ore is recovered from
pyrites (FeS2). Gangue the solution by suitable chemical method. For example,
Moving belt
Concentration of galena the chief ore of aluminium, bauxite (Al2O3.2H2O) contains
is carried out by Magnetic
ore varying amounts of ferric oxides, titanium oxide and
passing potassium ethyl
silica. Since alumina is amphoteric, it can be separated
Fig. 16.3 Electromagnetic
separation
 656 General Principles of Extraction of Metals
from the other two oxides. Finely powdered bauxite is
digested with caustic soda solution at 150–170oC under
pressure for some hours. Alumina dissolves forming
soluble sodium aluminate.
Al2O3. 2H2O + 2NaOH  2NaAlO2 + 3H2O
The impurities remain unaffected and separated
as insoluble red mud which is filtered off. The filtrate
is diluted and some freshly precipitated aluminium
hydroxide is added when Al(OH)3 is precipitated as
follows,
NaAlO2 + 2H2O  NaOH + Al(OH)3
The precipitated hydroxide is filtered off and
calcified to get highly pure aluminium oxide (alumina).
2 Al (OH )3    Al 2 O 3  3 H 2 O
calcinatio n
Gold and silver are also extracted from their
native ores by Leaching (Mac-Arthur forest cyanide
process).
(3) Reduction to free metal : Some of the
methods commonly used to get free metal from the
concentrated ore are given below,
(i) Smelting : The process of extracting a metal in
the state of fusion is called smelting. In this process the ore
is mixed with carbon, obtained after the above reactions
and heated in suitable furnace. A suitable flux is added
during the operation to convert the non–fusible gangue to
fusible slag. The metallic oxide is reduced by carbon and
the metal may be obtained in the molten state or as
vapours which are condensed. Metals like tin, zinc or lead
are obtained by this process.
SnO 2  2C  Sn  2CO ; ZnO  C  Zn  CO
Fe2 O3  3CO  2Fe  3CO2
Flux and slag : Flux is a substance that is added
during smelting to convert infusible silicons or earthy
impurities into fusible material known as slag.
Impurities + Flux = Slag. The slag is immiscible with
the metal and has a low melting point and density. The
slag floats on the metal and protects it from oxidation.
It is removed from the furnance through the slag hole.
If the impurities in the ore are acidic (SiO2) in nature, a
basic flux e.g., CaO, MgO, FeO etc. are added; and if the
impurities are basic (CaO, FeO, etc.) then on acidic flux
(SiO2) is used. The gangue or matrix present in the ore
is refractory or non–fusible in nature but it reacts with
the flux forming fusible slag which does not mix with
the molten metal and forms the upper layer. Slag are
usually silicates.
CaO  SiO 2  CaSiO SiO 2  FeO  FeSiO
3 ;
Flux Impurities Slag Impurities Slag
(ii) Reduction by Aluminium (Gold-schmidt
alumino thermic process) : The process of reduction is
used in the case of those oxides which can not be easily
reduced by carbon. In this process, metallic oxides ore
are mixed with aluminium powder commonly called as
thermite and placed in a steel crucible lined inside with
a refractory material and ignited by magnesium ribon.
By the use of this process a number of metals such as
chromium and manganese are obtained on a
commercial scale in highly pure state.
Cr2O3  2 Al  Al2O3  2Cr ; 2MnO2  4 Al  2 Al 2 O3  3 Mn
Large amount of heat energy is released during
reduction, which fuses both the alumina and the metal.
(iii) Self reduction process : This process is also
called autoreduction process or air reduction process.
The sulphide ores of less electropositive metals like Hg,
Pb, Cu etc., are heated in air as to convert part of the
ore into oxide or sulphate which then reacts with the
remaining sulphide ore to give the metal and sulphur
dioxide. No external reducing agent is used in this
process.
(iv) Electrolytic reduction process : This process
is used in the extraction of the alkali and alkaline earth
metals, zinc and aluminium. The material from which a
metal to be obtained is first smelted by heating and
then electrolysed. Sometimes, some other salt is mixed
to lower the melting point of the substance taken. For
example,
NaCl Na   Cl 

e
At anode (Oxidation) : Cl   Cl ; Cl  Cl  Cl2 ,
At cathode (Reduction) : Na  e   Na
(v) Precipitation or metal displacement method
(Hydrometallurgy) : This method is used for extraction
of metals such as cadmium, copper, gold and silver. A
metal having higher electrode potential is added into
the solution of a metal of lower electrode potential
with the result that the latter is displaced or
precipitated.
CuSO 4  Fe  Cu  FeSO4 ;
CdSO 4  Zn  Cd  ZnSO 4
2K[ Ag(CN )2 ]  Zn  2 Ag  K 2 [Zn(CN )4 ]
2K[ Au(CN )2 ]  Zn  2 Au  K 2 [Zn(CN )4 ]
(vi) Amalgamation process : This method is used
for the extraction of noble metals like gold, silver, etc.,
from the native ores. the finely powdered ore is
brought in contact with mercury which combines with
the particles of the metal present in the ore and form
amalgam. The metal recovered from the amalgam by
subjecting it to distillation, where the mercury distills
over leaving behind the metal.
3
(4) Purification or refining of metals : Metals
obtained as above are usually impure and need
purification. Some of the methods used in the refining
of metals are given below,
 General Principles of Extraction of Metals 657
(i) By poling : The molten metals is stirred with deposited on the cathode. The electrolyte used in the
green wood poles. Wood at the high temperature of the bath is usually a complex salt of the metal to enable the
molten metals form hydrocarbons like methane which smooth deposition of pure metal on the cathode.
being about the reduction of any oxide present in the (viii) Special methods
metal e.g., copper oxide present in the blister copper. In
(a) Mond's process : Nickel is purified by this
the case of the tin the impurities are oxidised and float on
the molten metal as scum which is removed. method. Impure nickel is treated with carbon monoxide
at 60-80°C when volatile compound, nickel carbonyl, is
(ii) By cupellation : In this method the impure formed. Nickel carbonyl decomposes at 180°C to form
metal is heated in a blast of air when impurities are pure nickel and carbon monoxide which can again be
oxidised and blown away. For example, when impure used.
silver is heated in air, lead present in it is oxidised to
(b) Van Arkel process : This methods is generally
litharge (PbO) and blown away leaving a shining of
applied for obtaining ultrapure metals. The impure
silver.
metal is converted into a volatile compound while the
(iii) By liquation : This process is used for refining impurities are not affected. The volatile compound is
easily fusible metals like lead and tin. The impure metal is then decomposed electrically to get the pure metal. Ti,
heated on the slopy hearth of a reverberatory furnace. Zr, Hf, Si etc., have been refined by this method.
The metal melts and flows down leaving the impurities.
(c) Zone refining or fractional crystallisation :
(iv) By distillation : Some metals have very low Elements such as Si, Ge, Ga, etc., which are used as
melting point and soon vaporize on behind heating, semiconductors are refined by this method. Highly pure
while the associated impurities remains in the solid metals are obtained. The method is based on the
state. Zinc, mercury and arsenic are purified by this
difference in solubility of impurities in molten and
method. Vacum distillation gives very pure product and
solid state of the metals. A movable heater is fitted
is used in the refining of the metals of IA and IIA
around a rod of the metal. The heater is slowly moved
Groups.
across the rod. The metal melts at the point of heating
(v) By fractional distillation : This process is
and as the heater moves on from one end of the rod to
applied for the separation of cadmium from zinc. In
the other end, the pure metal crystallises while the
the metallurgy of zinc, the metal is invariably
associated with cadmium. The impure zinc is mixed impurities pass on the adjacent melted zone.
with powdered coke and heated when the first portion
of the condensate contain cadmium while zinc is
Molten zone
obtained in the subsequent portions.
containing impurity
(vi) By thermal dissociation : In this process the
metal is first converted into some compound which is
then decomposed into pure metal by heating. For
example, impure nickel is heated with carbon
monoxide at 60oC to form nickel carbonyl Ni(CO)4
which is then decomposed at higher temperature, 150-
Pure
180oC to give very pure nickel. Sometimes iron is also metal Moving circular Impure
purified by this method. heater metal
Fig. 16.4. Zone refining of metals
(vii) By Electrolytic refining : Most of the metals
such as copper, silver, gold, zinc, nickel, and
chromium are refined electrolytically. The impure
metal is made the anode and a thin sheet of the pure
metal the cathode in a suitable electrolytic bath. On
passing current the metal from the anode passes in the
solution and pure metal from the electrolyte is
Table 16.1 Summary of the Extraction of Metals
Metal Main Occurrence Main method of Extraction
Sodium Common Salt, NaCl Electrolysis of fused NaCl with CaCl2

Magnesium Carnallite, KCl.MgCl2 .6 H 2 O Magnesite Electrolysis of fused MgCl2 with KCl

MgCO3
 658 General Principles of Extraction of Metals
Calcium Lime stone, CaCO3 Gypsum, CaSO4 .2 H 2 O Electrolysis of fused CaCl2 and CaF2

Aluminium Bauxite, Al2 O3 .2 H 2 O Electrolysis of Al2 O3 in molten Na3 AlF6 (cryolite)

Copper Copper pyrites, CuFeS 2 Cuprite, Cu2 O Partial oxidation of sulphide ore

(2Cu 2 O  Cu 2 S  6 Cu  SO 2 )

Silver Argentite, Ag 2 S Native silver Hydrometallurgy

Ag 2 S  4 NaCN  2 NaAg (CN )2  Na 2 S

2 NaAg (CN )2  Zn  Na 2 Zn (CN )4  2 Ag

Zinc Zinc Blende, ZnS Calamine, ZnCO3 Reduction of ZnO with carbon or electrolysis of
ZnSO 4 ZnO  C  Zn  CO

Lead Galena, PbS Reduction of PbO with carbon

PbO  C  Pb  CO
Tin Cassiterite, SnO 2 Reduction of SnO 2 with carbon

SnO 2  2C  Sn  2CO

Iron Haematite, Fe 2 O 3 Magnetite, Fe 3 O 4 Reduction of oxide with carbon monoxide

Fe 2 O 3  3 CO  2 Fe  3 CO 2

Chromium Chromite, FeO.Cr2 O3 Reduction of Cr2 O3 with Al

Cr2 O3  2 Al   2Cr  Al 2 O3

Nickel Millerite, NiS Reduction of NiO with CO

NiO  5 CO  Ni(CO)4  CO2 ; Ni(CO )4  Ni  4 CO

Mercury Cinnabar, HgS Direct reduction of HgS by heat alone

HgS  O2  Hg  SO 2

Main types of metallurgical processes
Different metallurgical processes can be broadly
divided into three main types
(1) Pyrometallurgy : Extraction is done using
heat energy. The metals like Cu, Fe, Zn, Pb, Sn, Ni, Cr, Hg
etc. Which are found in the nature in the form of
oxides, carbonates, sulphides are extracted by this
process.
(2) Hydrometallurgy : Extraction of metals
involving aqueous solution is known as
hydrometallurgy. Silver, gold etc are extracted by this
process.
(3) Electrometallurgy : Extraction of highly
reactive metals such as Na, K, Ca, Mg, Al etc. by carrying
electrolysis of one of the suitable compound in fused
or molten state.
characteristics. Some principal furnaces have been
described below,
(1) Blast furnace : It is a special type of tall
cylindrical furnace, about 100 feet high with a diameter
of 15-28 feet. It is made of steel sheets lined inside
with fire-proof bricks. The charge is added through a
cup and cone arrangement at the top. At the upper part
of the furnace there is a hole for the escape of the
waste gases of the furnace. There are two outlets in the
hearth of the furnace, one for tapping the molten metal
and the other above it for the slag. The waste gases are
heated and a hot air blast under pressure is blown into
the furnace by means of bellows or fans through water
cooled nozzles ortuyers. The temperature of the
furnace varies from 250oC. to 1500oC. Thus the charge
descends slowly into zone of increasing temperatures.
The blast furnace is used for the extraction of metal
like copper and iron.
Charge

Furnaces
In the extraction of metal different types of
furnaces are used. Each furnace has its own Cup & Cone
arrangement Waste gases
200-250° C
400° C
600° C
700° C Refractory bricks
800-1000° C
 General Principles of Extraction of Metals
(2) Reverberatory Furnace : In this furnace fuel
burns in a separate part and does not mix with the
charge. The furnace may be divided into 3 parts,
(i) Fire Grate : It is on one side where the fuel
burns.
(ii) Flue or Chimney : It is on the other side of
the fire grate. The waste gases escape through it.
(iii) Hearth : It is the middle part of the furnace
where the charge is heated with the flames and hot
gases.
The material to be heated is placed on the hearth
or bed of the furnace and is heated by the hot gases or
flames produced by the burning of fuel. The waste
gases escape out of the chimney. Since the fuel does not
come in contact with the charge, the furnace is very
suitable for calcination and roasting and is employed
for both oxidising and reducing purposes. For oxidation,
the material is heated by the current of hot air while
for reduction the material is mixed with coke and
heated. The furnace find wide application in the
extractive metallurgy.
Charge
hopper
Tie-rod
Hangers
Air and
oil
Furnace charge
Silica Magnesite
Fig. 16.6. Modern reverberatory furnace
(3) Electric Furnace : The fuel burnt furnaces
described in this chapter produce temperature in the
range of 1000-1500oC. Although these furnaces have
the great utility in the extraction of metals yet these
659
are unsuitable where higher temperatures are needed.
One commonly used electric furnace is Heroult’s
furnace shown in fig. It consists of a steel shell lined
inside with dolomite or magnesite. It is provided with
movable water jacketed electrodes suspended from the
roof or from the sides. Heat is generated by striking an
arc between the electrodes, thereby, a temperature of
over 3000oC may be reached. The charge melts and the
impurities e.g., Si, Mn, P and S etc. present in the ore
combine with the basic lining to form slag, which is
free from sulphur or gas bubbles. Steel of very fine
quality is prepared by this method. Electric furnaces
are largely used where,
(i) Cheap power supply is available. (ii) High
temperature are required. (iii) Pure product are
required.
As such they find wide applicability in a
number of industries such as metallurgy, ceramices
plastics chemical and also in the research laboratories.
These furnaces are easily operated and involve the
problem of the storage of fuel and disposal of fuel
waste.
(4) Muffle Furnace : In this furnace the material
to be heated does not come in the contact with the fuel
or flames. A muffle is a chamber made of refractory
material and is surrounded by flames and hot gases on
all sides. The products of combustion are removed
through a door provided in the furnace. Muffle furnace
is used for the extraction of zinc, preparation of red
lead, Pb3O4 and for testing the purity of precious
metals like silver and gold. In an electric muffle
furnace the chamber is surrounded
Flames and hot by resistance coils.
gases
Muffle
Fire
place
Fig. 16.7. Muffle furnace
(5) Bessemer Converter : A Bassemer converter
is a pear–shaped 10 or more feet high, open at the top,
lined with a refractory material such as silica or
magnesia which also acts as a flux. The converter is
mounted on trunnions, so that it can be tilted to collect
the products formed. There is an arrangement of
introducing a hot blast of air from a number of small
openings in the bottom of the furnace. The converter is
used mostly for manufacturing of copper of steel from
 660 General Principles of Extraction of Metals
pig iron. Passing a current of hot air into the molten Alloys
metal taken in the converter, the impurities are
A metallic product containing two or more
oxidised and escaped as gases or from slag. The
metals or sometimes one of the ingredients a non–
Bessemer process is rapid one and does not take more
metal provided that the mixture is homogenous and
than 15 minutes in the production of one bath.
possesses metallic properties, is known as an alloy.
(6) Regenerative Furnace : These are furnaces in Alloys are usually prepared by melting two or more
which the heat of the gases escaping out from the metals together in the proportions and then allowing
chimney is utilized. Most of the furnaces particularly the melting to solidify. If one of the metals is mercury
blast furnaces are fitted up with regenerated system the alloy is known as amalgam.
which means an economy of the fuel. A flowing column Alloys are prepared with a view to impart some
of air is heated by the hot flue gases, it is then brought desirable properties which the individual metals do not
back to the fire and returned to the furnace. This possess. These are,
furnace is largely used in the production of steel.
(1) Change in the chemical reactivity : Sodium
Refractory materials acts vigorously with water, but Na–Hg amalgam reacts
slowly to suit the requirement of a number of chemical
The materials which can withstand very high
reactions.
temperatures without melting or becoming soft are
(2) Hardness : Silver, gold and soft metals but
known as refractory materials. These are not affected
become hard when alloyed with copper.
by slags formed during the extraction of metals. These
(3) Melting Points : Melting points of an alloy
are used in the form of bricks for the internal linings of
may be higher or lower than any of its components.
furnaces. Refractory materials used are of three types, Wood-metal, which is an alloy of Bi, Pb, Sn and Cd fuses
(1) Acid refractories : Silica, quartz, silicious at 60.5oC., while none of these metals fuses at this low
sand stones, etc., are the examples. temperature.
(4) Change of colour : Aluminium bronze is an
(2) Basic refractories : Lime, dolomite,
alloy of aluminium and copper. It is of golden, yellow
magnesite, etc., are the examples.
colour and is used in making decoration articles,
(3) Neutral refractories : Graphite, chromite, jewellery and coins while the colour of aluminium is
bone ash, etc., are the examples. white and that of copper is red.
(5) Corrosion resistance : Iron gets corroded
Silica (92 % SiO2 , 2.7% Al2O3 ) and quartz, can
soon whereas stainless Steel, an alloy of iron and
tolerate temperatures upto about 1750°C, bauxite upto chromium, resists corrosion.
1800°C, alumina upto 2000°C and magnesite, chromite, (6) Casting : An alloy of lead and antimony is
etc., upto 2200°C. Some carbides such as silicon known as type metal is used for casting type required in
carbide is used as refractory for special purposes. printing works.
Table 16.2 Alloys of Al
Alloy Percentage Important Properties Uses
Aluminium Al 95% Light, strong alloy with golden Coins, utensils, jewellary picture frames
bronze Cu 5% lustre, resistant to corrosion etc.
Magnalium Al 95% Light, tough and strong Light instruments, balance beam,
Mg 5% pressure cookers etc.
Duralumin Al 95% Light, tough, ductile, resistant Making aeroplanes automobile parts
Cu 4% to corrosive action pressure cookers etc.
Mg 0.5%
Mn 0.5%

Table 16.3 Alloys of Ag

Alloy Percentage composition Uses
Coinage Ag = 90, Cu = 10 For making silver coins.
silver
Silver solder Ag = 63, Cu = 30, Zn = 7 For soldering and joining metals
Dental alloy Ag = 33, Hg = 52, Sn = 12.5, Cu = 2.0, Zn = 0.5 For filling teeth
 General Principles of Extraction of Metals 661
Silver Ag = 40, Pd = 60 Potentiometers and winding of some
palladium special instruments.

Table 16.4 Alloys of Pb and Sn

Alloy Percentage Composition Uses
Solder Pb = 50, Sn = 50 For soldering.
Pewter Pb = 20, Sn = 80 In making cups, mugs and other utensils.
Type metal Pb = 70, Sb = 20 and Sn = For making printing type.
10
Rose metal Pb = 22, Sn = 28, Bi = 50 For making electric fuses.
Britannia Sn = 90, Sb = 8, Cu = 2 For making table wares.
metals

Table 16.5 Alloys of Copper

Alloy Percentage Composition Uses
Brass Cu = 80, Zn = 20 For making utensils, condenser tubes, wires parts of
machinery etc.
Bronze or Cu = 80, Zn = 10, Sn = 10 For making cooking utensils, statues, coins etc.
Copper
bronze
Aluminium Al = 95, Cu = 5 Coins, picture frames, cheap jewellery
bronze
Gun metal Cu = 90, Sn = 10 For making gun barrels.
Bell metal Cu = 90, Sn = 20 For making bells, gongs etc.
Constantan Cu = 60, Ni = 40 For electrical apparatus
German Cu = 60, Zn = 20, Ni = 20 For making silver wire, resistance wires etc.
silver
Monel metal Cu = 30, Ni = 67, Fe and Mn For making acid pumps and acid containers.
=3
Phosphor Cu = 95, Sn = 4.8, P = 0.2 For making springs, electrical equipment
bronze
Gold-copper Au = 90, Cu = 10 For making gold coins, jewellery, watch cases, spectacle rims
alloy etc.
Table 16.6 Alloys of Iron
Name Percentage Properties Uses
Stainless Fe = 73%, Cr = 18%, Resists corrosion For making utensils, cutlery and
steel Ni = 8% and carbon ornamental pieces.

Manganese Fe = 86%, Mn = 13% and Very hard, resistant to For Making rock drills, safes etc.
steel carbon wear and tear.
Tungsten Fe = 94%, W = 5% and Retains hardness even For making high speed cutting tools.
steel carbon at high temperatures
Invar Fe = 64%, Ni = 36% Practically no For making watches, meter scales,
coefficient of pendulum rods etc.
expansion.
 662 General Principles of Extraction of Metals
Nickel steel Fe = 98–96%, Ni = 2–4% Resistant to corrosion, For making wire cables, gears, drive
hard and elastic. shafts etc.
Permalloy Fe = 21%, Ni = 78% and Strongly magnetised by For making electromagnets, ocean
carbon electric current, loses cables etc.
magnetism when
current is cut off.
Chrome steel Fe = 98–96%, Cr = 2–4% High tensile strength For making axles, ball bearings and
cutting tools such as files.
Alnico Fe = 60%, Al =12%, Highly magnetic For making permanent magnents.
Ni = 20%, Co = 8%
 General Principles of Extraction of Metals 661
2. Naturally occurring substances from which a
metal can be profitably (or economically)
extracted are called
[CPMT 1982; MP PET 1996]
(a) Minerals (b) Ores
(c) Gangue (d) Salts
 Pitch blende is the source of Ra, U and Th. 3. Titanium containing mineral found in our country
 Nitrate is least likely to be found in mineral. is
[NCERT 1984; RPET 1999]
 Oxygen is the most abundant element (45.2%)
(a) Bauxite (b) Dolomite
 Aluminium is the most abundant metal (8.3%) (c) Chalcopyrites (d) Elmanite
 Silicon is the second most common element in 4. Silicon is main constituent of [DPMT 1985]
the universe (27.2%) (a) Alloys (b) Rocks
 First five element comprise al most 92% by (c) Animals (d) Vegetables
weight 5. Ore pitch blende is main source of
[DPMT 1985; RPET 1999]
 First ten elements make up over 99.5% of the
(a) Ra (b) Ce
earth crust.
(c) Th (d) Mg
 Other very abundant element are nitrogen (78%
6. Which of ore is metalloid [MP PMT 1987]
of the atmosphere) and hydrogen which occurs as
(a) As (b) Na
water in the ocean.
(c) Au (d) Fe
 Diamond consist only carbon.
7. A mineral is called an ore if [MP PMT 1990]
 Removal of unwanted earthy and silicious (a) Metal present in mineral is precious
impurity from the ore is called ore dressing or (b) Metal can be extracted from it
concentration. (c) Metal can be extracted profitably from it
 Refractory materials : These are the substances (d) Metal cannot be extracted from it
which can withstand very high temperature 8. The highest quantity present in the atmosphere is
without melting or becoming soft. of
 Noble metal like Au, Ag etc. are obtained by [NCERT 1971, 79; CPMT 1972]
cyanide or amalgamation process. (a) Oxygen (b) Hydrogen
(c) Nitrogen (d) Ozone
 Active metal like Li, Na, K (alkalimetal) Cs, Mg,
Sr, Ba (alkaline earth metal) etc are obtained by 9. Which of the following statement is correct
the electrolysis of their chloride, oxides or (a) Bauxite is an ore of aluminium
hydroxide. (b) Magnetite is an ore of manganese
 Heavy metal like Cu, Zn, Fe, Pb, Sn etc are (c) Haematite is an ore of mercury
obtained by roasting and smelting process. (d) Pyrites is an ore of phosphorus
10. Carnellite is a mineral of
 Gravity separation is employed for the
[CBSE PMT 1988; DPMT 1983; AMU 1999]
concentration of oxide ores.
(a) Ca (b) Na
 Slag is used in road making as well as in the
(c) Mg (d) Zn
manufacture of cement and fertilizers.
11. The salt which is least likely to be found in
minerals is
[DPMT 1984]
(a) Chloride (b) Sulphate
(c) Sulphide (d) Nitrate
12. Metal which can be extracted from all the three
dolomite, magnesite and carnallite is[MP PET 1985]
Occurrence (a) Na (b) K