Physical Chemistry Notes

PHYSICAL CHEMISTRY
NOTES
COMPLETE
THEORY+
ILLUSTRATIONS
CLASS 11th
PAGE. NO
1.MOLE CONCEPT 1-15

2.REDOX 33-50
3.ATOMIC 65-90
STRUCTURE
4.THERMODYNAMICS137-160
5.CHEMICAL 185-199
EQUILIBRIUM
6.IONIC 221- 249
EQUILIBRIUM
Chapter - 1
BASIC CONCEPT OF CHEMISTRY
1.1 Laws of Chemical Combinations
Law of conservation of mass: “In all physical and chemical changes, the total mass of the reactants
is equal to that of the products” or “Matter can neither be created nor destroyed.”
Law of constant composition or definite proportions: “A chemical compound is always found

to be made up of the same elements combined together in the same fixed ratio by weight.”
Law of multiple proportions: “When two elements combine together to form two or more chemical
compounds, then the weights of one of the elements which combine with a fixed weight of the other
bear a simple ratio to one another.”
Law of Reciprocal Proportions: The ratio of the weights of two elements A and B which combine
with a fixed weight of the third element C is either the same or a simple multiple of the ratio of the
weights of A and B which directly combine with each other.
Gay Lussac’s law of gaseous volumes : “When gases react together, they always do so in volumes
which bear a simple ratio to one another and to the volumes of the products, if gaseous, all
measurements are made under the same conditions of temperature and pressure.”
Avogadro’s hypothesis : “Equal volumes of all gases under similar conditions of temperature and
pressure contain equal number of molecules.”
Atom: It is the smallest particle of an element that takes part in a chemical reaction. It may or may
not be capable of free existence.
1
Atomic mass unit (a.m.u) : It is equal to th of the mass of an atom of C-12. It is equal to
12
1.6606 × 10–24 g.
Atomic mass : It is the average relative mass of its atoms as compared with an atom of carbon –
12 isotope taken as 12.
Calculation of average atomic mass : If an element exists in two isotopes having atomic masses
ma  nb
‘a’ and ‘b’ in the ratio m: n, then average atomic mass = .
mn
Gram atomic mass (G.A.M.): The atomic mass of an element expressed in grams is called gram
atomic mass. This amount of the element is called one gram atom. This amount of the element can
also be called one mole atom.
[1]
Basic Concept of Chemistry
Method of determining atomic weight
(i) By application of the relation
At. wt. = Eq. wt. × Valency
Knowing the exact eq. wt. and approximate atomic weight, valency can be calculated (which is
a whole number). Knowing exact eq. wt. and valency, exact atomic weight can be calculated.
(ii) Dulong and Petit’s method: According to Dulong and Petit’s law, for solid elements (except
Be, B, C and Si)
At. wt. × Specific heat = 6.4 (approx.)

6.4
 Approx at. wt. = Sp. heat
Approx. At. wt.
= Eq. wt. = approx. Valency..
The approx. valency is converted to the nearest whole number which is called exact valence.
Eq. wt. × exact valency = exact Atomic Weight.
Cp
(iii) Specific heat/molar heat capacity method: For gases,   is 1.66 for monoatomic, 1.40
Cv
for diatomic and 1.30 for triatomic gases. Thus having known the atomicity of the gas from the
Mol. wt.
value of , Atomic wt. of the gaseous element = Atomicity .
Molecular wt. = 2 × Vapour density.
(iv) Vapour Density method: This method can be used for those elements whose chlorides are
volatile so that their vapour densities can be determined. Then
Mol. wt. of the chloride = 2 × V.D.
If x is the valency of the element (M), then the formula of its chloride will be MClx. Hence
Molecular weight of the Chloride MClx = At. wt. of M + x × 35.5

= Eq. wt. of M × Valency of M + x × 35.5
= E × x + x × 35.5
= x (E + 35.5)
2  V.D.
 x (E + 35.5) = 2 × V.D. or x =
E  35.5
Knowing the eq. wt. E of the element, the valency x can be calculated. Then Atomic weight =
eq. wt. × Valency.
(v) Law of Isomorphism: Compounds having similar molecular formulae and identical crystal
structure are called isomorphs. The method is based upon the fact that elements in isomorphous
compounds have same valencies, e.g.,
(a) K2SO4, K2CrO4 and K2SeO4 are isomorphous. Hence valency of S, Cr and Se = 6.
[2]
(b) ZnSO4.7H2O, FeSO4.7H2O, MgSO4.7H2O are isomorphous. Hence valency of Zn, Fe and
Mg = 2.
(c) Alums, M2SO4.M 2(SO4)3.24H2O in which M is monovalent and M is trivalent are

isomorphous.
Knowing the valency, Atomic wt. = Eq. wt. × Valency
Molecules: It is the smallest particle of an element or a compound that is capable of free existence.
Molecular mass: Molecular mass of a substance is the average relative mass of its molecules as
compared with an atom of C–12 isotope taken as 12.
Gram molecular mass or molar mass (G.M.M.): The molecular mass of a substance expressed
in gram is called gram molecular mass or molar mass. This amount of the substance is called one
gram molecule. This amount of the substance is called one mole of the substance.
Methods of determining molecular weight
(i) Gram Molecular Volume (G.M.V.) method, 22.4 litres of every gas or vapour at STP weigh
equal to molecular weight expressed in grams. This is the principle of Victor Meyer method used
for volatile liquids.
(ii) Vapour density method
Molecular weight = 2 × Vapour Density
Wt. of certain volume of the vapour

where Vapour Density = Wt. of same volume of H under same conditions of temp. and pressure
2
(iii) Diffusion method: According to Graham’s law of diffusion, rates of diffusion of different gases
under similar conditions of temperature and pressure are inversely proportional to the square
root of their densities or molecular weights, i.e.,
r1 d2 2  d2 M2
  
r2 d1 2  d1 M1
Knowing the molecular weight of one gas, that of the other can be calculated.
(iv) Colligative property method: Discussed in the unit of ‘Solutions’.
Moles
The collection of 6.023 × 1023 molecules of an element or ions or compounds constitute one mole of
that element, ion or compound. This number, 6.023 × 1023 is known as Avogadro’s number. This is
called mole-particle relationship.
Mole-Particle Relationship :
e.g.,(i) one mole of Na contains 6.023 × 1023 atoms of Na.
(ii) one mole of oxygen, i.e., one mole of O2 contains 6.023 × 1023 molecules of oxygen.
(iii) one mole of CCl4 carbon tetrachloride contains 6.023 × 1023 molecule of CCl4 (carbon
tetrachloride)
[3]
Mole-Weight Relationship :
(i) one mole of an element weighs equal to gram atomic weight of the element
e.g. one mole of Na weighs 23 gm (Gram atomic wt. of Na = 23)
(ii) one mole of Mg weighs 24 gms (GAM of Mg = 24)
(iii) one mole of substance (molecular state) weighs equal to the gram molecular weight of the
substance.
e.g. one mole of O2 weighs 32 gms (GMM of O2 = 32)

one mole of SO2 weighs 64 gms.
Mole-Volume Relationship:
(i) one mole of every gas at STP occupies 22.4 litres of volume.
e.g. one mole of CO2 at STP occupies 22.4 litres of volume.
(ii) one mole of SO2 at STP occupies 22.4 litres of volume.
Gram Atoms
One gram-atom of an element means collection of 6.023 × 1023 atoms. This concept applies only
to the elements which exists in polyatomic states (e.g., O, Cl, S, P, etc.). It is meaningless for
metals and compounds.
* The number of atoms in w gms of an element whose atomic mass is A is :
w
gm  atom  = mole atom
A
* The number of atoms is given by:

w
No. of atoms =  N0
A
Avogadro’s number: It is the number of atoms present in one gram atom of an element or the
number of molecules present in one gram molecule of the substance. In general, it is the number of
particles present in one mol of the substance. Its value is 6.02 × 1023.
Equivalent weight: The equivalent weight of a substance is the number of parts by weight of the
substance that combine with or displace directly or indirectly 1.008 parts by weight of hydrogen or 8
parts by weight of oxygen or 35.5 parts by weight of chlorine.
Mol. wt. of the acid

Eq. wt. of an acid = Basicity
Mol. wt. of the base

Eq. wt. of a base =
acidity
Gram equivalent weight: The equivalent weight of a substance expressed in grams is called gram
eq. wt. or one gram equivalent.
[4]
Now we can define gram-equivalent (gm eq.) in g gms of a substance whose equivalent weight is
E as follows:
g
No. of eq =
E
* The number of milliequivalents (meq.) in g gms is given by:
g
meq = × 1000
E
Methods of determining equivalent weight:
(i) Hydrogen displacement method: This method is used for metals which react with an acid to
evolve hydrogen gas.
Eq. wt. of the metal is the weight of the metal which displace 1.008 g of H2 or 11200 c.c. of
H2 at STP.
Wt. of metal
Eq. wt. of metal= Wt. of H displaced  1.008
2
Wt. of metal
or = Vol. of H in ml displaced at STP  11200
2
(ii) Oxide formation or reduction of the oxide method: In this method a known weight of the
metal is converted into its oxide directly or indirectly. Knowing the weight of the metal oxide
formed, the weight of oxygen combined can be calculated. Alternatively, a known weight of the
metal oxide may be reduced to metal whose weight is determined.
Wt. of metal
Eq. wt. of metal = Wt. of oxygen combined  8
Wt. of metal
or = Vol. of O displaced / combined in ml at STP  5600
2
weight of metal
Eq. wt. of metal = Wt. of chlorine combined  35.5
Wt. of metal
or  11200
Vol. of Cl 2 combined in ml at STP
(iii) Double decomposition method: For a reaction of the type
AB + CD  AD  + BC
(e.q. AgNO3 + NaCl  AgCl  + NaNO3)
Weight of AB taken Eq. wt. of AB Eq. wt. of A  Eq. wt. of B

Weight of AD formed = Eq. wt. of AD = Eq. wt. of A  Eq. wt. of D
[5]
Knowing the equivalent weights of any two radicals out of A, B and D, that of the third can be
calculated.
(iv) Electrolytic method (based on Faraday’s laws of electrolysis)
1 Faraday (96500 coulombs) deposit one gram equivalent of the substance.
Electrochemical equivalent of a substance is the weight of the substance deposited by one

coulomb.
When the same quantity of electricity flows through solutions of different electrolytes,
Wt. of X deposited Eq. wt. of X

Wt. of Y deposited = Eq. wt. of Y
(v) Neutralization method: This is based on the fact that acids and bases react in equivalent
amounts. Hence equivalent weight of an acid is the weight of the acid which is neutralized by
1000 cc of 1N base solution (which contains 1g eq. of the base) Likewise equivalent weight of
a base can be determined.
(vi) Silver salt method: (for organic acids only) The organic acid is converted into its silver salt
(RCOOAg), a known weight of which is ignited to give residue of Ag which is weighed. Then
Eq. wt. of RCOOAg Wt. of silver salt

Eq. wt. of Ag (108) = Wt. of silver
Eq. wt. of acid (RCOOH) = Eq. wt. of RCOOAg–108.
(vii)Conversion method: When one compound of a metal is converted into another compound of
the same metal (e.g. metal carbonate  metal oxide), then
Weight of compound I Eq. wt. of metal  Eq. wt. of anion of compound I

Weight of compound II = Eq. wt. of metal  Eq. wt. of anion of compound II
Relationship between eq. wt. atomic wt. and valency of an element:

Atomic weight
Eq. wt. =
Valency
Molecular weight of the substance

Equivalent weight of oxidizing/reducing agent = No . of electrons gained/los t by one molecule
Illustration 1: Fe2(SO4)3 is used in water and sewage treatment to aid the removal of suspended impurities.
Calculate the mass percentage of iron, suphur and oxygen in this compound.
Solution: Step - I: Molecular weight of Fe2(SO4)3 = (56 × 2) + (32 × 3) + (16 × 12) = 400
Number of parts by weight of Fe 56  2

Step - II: % of Fe = Molecular weight of Fe (SO ) ×100 =  100 = 28%
2 4 3 400
[6]
Number of parts by weight of S 32  3

% of S= Molecular weight of Fe (SO ) ×100 =  100 = 24%
2 4 3 400
Number of parts by weight of O 16  12
% of O = Molecular weight of Fe (SO ) ×100 =  100 = 48%
2 4 3 400
Illustration 2 : An inorganic salt gave the following percentage composition: Na = 29.11%, S = 40.51% and
O = 30.38%. Calculate the empirical formula of the salt.
Solution : Calculation of empirical formula.
Element Symb % of At. Mass Relative no. of Simplest atomic Simplest
ol element of atoms ratio whole
element = percentage number
atomic mass atomic
ratio
Sodium Na 29.11 23 29.11 1.266 2
 1.266 1
23 1.266
Sulphur S 40.51 32 40.51 1.266 2
 1.266 1
32 1.266
Oxygen O 30.38 16 30.38 1.898 3
 1.898  1.49  1.5
16 1.266
Thus, the empirical formula is Na2S2O3.
SAMPLE PROBLEMS 1.1 (MCQ)

Problem 1: The sodium salt of methyl orange has 7% sodium. What is the minimum molecular weight of
the compound?
(a) 420 (b) 375
(c) 328.57 (d) 294.46
mass of sodium 23
Solution: (c) % of Na =  100  7   100
molecular mass M
23 100
M  326.6 = 328.57
7
Problem 2: 64g of an organic compound has 24g carbon and 8g hydrogen and the rest is oxygen. The
empirical formula of the compound is
(a) CH4O (b) CH2O
(c) C2H4O (d) None of these
Solution: (a) C H O
Mass 24 8 32
24 8 32
Moles
12 1 16
Ratio 2 8 2
Simple inter ratio 2 8 2
Hence empirical formula is CH4O
[7]
Problem 3: How many gram ions of SO24 are present in 1 gram molecule of K2SO4.Al2(SO4)3.24H2O
(a) 2 (b) 3
(c) 1 (d) 4
Solution: (d) 1g molecule is 1 mole
Mole of SO24 4 × 1 = 4 g ion
Problem 4: Common salt obtained from sea-water contains 96% NaCl by mass. The approximate number
of molecules of NaCl present in 10.0g of the common salt is: (Atomic weight Na = 23)
(a) 1021 (b) 1022
(c) 1023 (d) 1024
Solution: (c) Mass of NaCl = 10 × 0.96 = 9.6 g

9.6
Moles of NaCl =
58.5
9.6
No. of molecules =  6.023 1023 1023
58.5
Problem 5: X and Y are two elements which form X2Y3 and X3Y4. If 0.20 mol of X2Y3 weighs 32.0 g
and 0.4 mol X3Y4 weighs 92.8 g, the atomic weights of X and Y are respectively
(a) 16.0 and 56.0 (b) 8.0 and 28.0
(c) 56.0 and 16.0 (d) 28.0 and 8.0
32 92.8
Solution: (c)  0.2;  0.4
2x  3y 3x  4 y
Hence x =56 and y =16
Problem 6: Four 1-1 litre flasks are separately filled with the gases H2, He, O2 and O3 at the same
temperature and pressure. The ratio of total number of atoms of these gases present in
different flask would be:
(a) 1 : 1 : 1 : 1 (b) 1 : 2 : 2 : 3
(c) 2 : 1 : 2 : 3 (d) 3 : 2 : 2 : 3
Solution: (c) No. of atoms = no. of moles × atomicity

H2 He O2 O3
1×2 1×1 1× 2 1×3
2:1:2:3
Problem 7: 16g of an ideal gas SOx occupies 5.6 L at STP. The value of x is
(a) x = 3 (b) x = 2
(c) x = 4 (d) None of these
5.6 1
Solution:
 mole
(b) No. of moles of SOx = 22.4 4
Molar mass of SOx = Wt / Moles = 16 × 4 = 64
x = 2
[8]
Problem 8: The empirical formula of a compound of molecular mass 120 is CH2O. The molecular
formula of the compound is
(a) C2H4O2 (b) C4H8O4
(c) C3H6O2 (d) All of these
molar mass 120

Solution: (b) n   4
Empirical formula mass 30
Molecular formula is C4H8O4
Problem 9: A compound possess 8% sulphur by mass. The least molecular mass is:
(a) 200 (b) 400
(c) 155 (d) 355
Wt.
Solution: (b) % of S = 100
Molar mass
32  100
Molar mass   400
8
Problem 10: 12g of alkaline earth metal gives 14.8 g of its nitride. Atomic weight of metal is
(a) 12 (b) 20
(c) 40 (d) 14.8
Solution: (c) 3M  N 2 
 M3 N 2
12g 2.8g 14.8g
Moles of metal = 3 × moles of N2
12 2.8
 3
Atomic weight 28
120
Atomic weight of metal =  40
3
1.2 Expressing concentration of solutions

Solution is a homogenous mixture of two or more components in which Intermixing particles are of
atomic or molecular dimensions. A solution consists of a dissolved substance known as solute and
the substance in which the solute is dissolved is known as solvent. The concentration of a solution
means the quantity of solute dissolved per unit volume of solution, or per unit quantity of solvent.
quantity of solute
Concentration of solution = quantity of solvent or solution
Note: While discussing various methods for expressing concentration, we have taken solute as B
dissolved in solvent A and WA as grams of solute and WB as grams of solvent.
Mass fraction is the fractional part of a component that is contributed by it to the total mass of
solution.
wB
mass fraction of B = w w
A B
wA
mass fraction of A = w  w
A B
[9]
Mole fraction is the fractional part of the moles that is contributed by each component to the total
number of moles that prepare the solution. In containing nA moles of solvent and nB moles of solute:
nB
mole fraction of B = xB = n  n
A B
nA
mole fraction of A = xA = n  n
A B
Molality (m) is expressed as number of moles of solute dissolved in 1000 gms (1 Kg) of solvent. It
is denoted by m.
nB
m  1000
wA
Molarity (m) is expressed as moles of solute contained in one litre of solution or it is also taken as
millimoles of solute in 1000 cc (ml) of solution. It is denoted by M.
moles of solute millimoles of solute

molarity (M) = litres of solution = millilitre s of solution
nB WB / WB
M  =
Vlt V(lit)
Normality (N) is expressed as the number of gram equivalents (gm eq.) of solute contained in one
litre of solution or it can also be taken as number of milliequivalents (meq) in 1000 cc (ml) of solution.
It is denoted by N.
gm  eq. of solute meq. of solute

normality of solution (N) = litres of solution = millilitres of solution
gm eq.
N= V(lit)
Note: The following results should be remembered and used directly. Molarity (M) and Normality
(N) are temperature dependent but molality (m) and mole fraction are Temperature
independent units.
wB
(1) moles = M Vlt = M
B
wB
milimoles = M Vcc = M  1000
B
wB
(2) gm-eq. = N Vlt = E
B
wB
meq. = N Vcc = E  1000
B
10 x d 10 x d
(3) Molarity (M) = M0 Normality (N) =
E
d : density of solution in g/cc x :% age strength of solution (by weight)
[ 10 ]
(4) N = x × M
1000  xB
(5) m = M  x
A A
x : acidity for base or basicity for acid or electron transfer / mole for O.A. and R.A./n-factor.
Strength of a solution is generally expressed as grams of solute in one litre of solution.

wB
strength = litres of solution
strength = Normality × Eq. wt. = Molarity × Mole wt.
Diluting a solution: Whenever a given solution of known concentration, i.e., normality & molarity
(known as standard solution) is diluted by adding more of solvent, the number of millimoles (or
millequivalents) of solutes remain unchanged. The concentration of solution however changes.
In such cases M1 V1 = M2 V2 (M1 & V1 are molarity and volume of original solution)
(M2 & V2 are molarity and volume of diluted solution)
Stoichiometric Calculations:
(Quantitative analysis of a balance chemical equation)
Consider a balanced chemical reaction of equation:
mA + nB  pC + qD
A and B are reactants; C and D are products; m, n, p, q are the stoichiometric co-efficients.
The above balanced reaction is analysed as:
m moles of A react with n moles of B to produce p moles of C and q moles of D.
This can be represented as:
m moles of A  n moles of B  p moles of C  q moles of D
It is also observed that when a substance takes part in a chemical reaction then the amount of the
substance taking part is proportional to its equivalent weight
i.e. 1 equivalent of every substance combines (displaces, double displaces, oxidises, reduces,
neutralizes) are equivalent of another substance. Hence in a chemical reaction of the type
aA + bB — mC + nD
1 eq. of A combines with 1 eq. of B to form 1 eq. of C and 1 eq of D or
neq of A  neq of B  neq of C  neq of D.
In general, there are two types of stoichiometric reactions (which are most common):
Neutralisation Reactions: The analysis of two types of reactions is generally carried out in the
form of mass of reactants (or products) taking part in a given reaction (gravimetric analysis) or in
terms of concentrations of reactants (or products) taking part in a given reaction
(volumetric analysis).
[ 11 ]
Neutralisation: A reaction in which an acid (or a base) completely reacts with a base (or an acid)
to form salt and water. If HA be the acid, BOH be the base and BA be the salt, then neutralisation
reaction can be represented as follows:
HA + BOH  BA + H2O
As we known that an acid may be monobasic (HCl, HNO3, etc.), dibasic (H2SO4, H2C2O4, etc.) or
tribasic (H3PO4, etc.) and similarly a base may be monoacidic (NaOH, NaHCO3, etc.), diacidic
(Ca(OH)2, Na2CO3, etc.) or triacidic (Al(OH)3, etc.), so it is better to define the neutralisation
reaction in the following manner.
A reaction in which 1 gram equivalent (or 1 meq of an acid (or a base) completely reacts with 1 gram
equivalent (or 1 meq) of a base (or an acid) to form 1 gram equivalent (or 1 meq) of
corresponding salt.
Illustration 1: Oxygen is prepared by catalytic decomposition of potassium chlorate (KClO3). Decomposition

of potassium chlorate gives potassium chloride (KCl) and oxygen (O2). How many moles
and how many grams of KClO 3 are required to produce 2.4 mole O 2 ?
(M KClO3 = 122.5g/ mole)
Solution : Decomposition of KClO3 takes place as

2KClO3(s) 2KCl(s) + 3O2(g)
2 mole KClO3 gives 3 mole of O2
 3 mole O2 is formed by 2 mole of KClO3.
2 
 2.4 mole O2 will be formed by   2.4  mole KClO3 = 1.6 mole KClO3.
3 
Mass of KClO3 = Number of moles × Molar mass = 1.6 × 122.5 = 196 g
Illustration 2: 1 litre mixture of CO and CO2 is taken. This is passed through a tube containing red hot
charcoal. The volume now becomes 1.6 litre. The volumes are measured under the same
conditions. Find the composition of mixture by volume.
Solution : Let there be ‘x’ ml of CO in the mixture. Hence there will be (1000 – x) ml CO2. The
reaction of CO2 with red hot charcoal may be given as,
CO2(g) + C(s) 2CO(g)

1000 – x
– 2000 –2 x
Total volume of the gas becomes = x + 2(1000 – x)
x + 2000 – 2x = 1600
x = 400 ml
 Volume of CO = 400 ml
and volume of CO2 = 600 ml
[ 12 ]
Illustration 3: A solution of oxalic acid C2H2O4. 2H2O is prepared by dissolving 0.63 g of the acid in 250
cm3 of the solution. Calculate molarity of the solution.
Solution : Molar mass of oxalic acid = 126 g/mol.

250
 250 cm3 or L = 0.25 L of the solution contains 0.63 g oxalic acid.
1000
0.63 1
 Molarity of the solution =  = 0.02 M
126 0.25
Problem 1: 2KI  I 2  22HNO3 

 2HIO3  2KIO3  22NO2  10H2 O
If 3 mole of KI and 2 moles I2 are reacted with excess of HNO3. Volume of NO2 gas
evolved at NTP is
(a) 739.2 L (b) 1075.2 L
(c) 44.8 L (d) 67.2 L
Solution: (a) KI is limiting reagent

 3 mole of KI will give 33 mole of NO2 according to stoichiometry.
Problem 2: If 240 g of carbon is taken in a container to convert it completely to CO2 but in industry it has
been found that 280g of CO was also formed along with CO2. Find the mole percentage
1
yield of CO2. The reactions occurring are C  O 2 
 CO 2 ; C  O 2 
 CO
2
(a) 25% (b) 50%
(c) 75% (d) 100
Solution: (b) C  O 2 
 CO2  CO
POAC on ‘C’ atom
1 (mole of C) = 1 (mole of CO2) + 1 (mole of CO)
240 280
 mole of CO 2 
12 28
Mole of CO2 = 20 – 10 = 10
10
Mole % CO2 = 100  50%
20
Problem 3: In the reaction 4A  2B  3C 

 A 4 B2C3 what will be the number of moles of product
formed. Starting from 2 moles of A, 1.2 moles of B and 1.44 moles of C
(a) 0.5 (b) 0.6
(c) 0.48 (d) 4.64
Solution: (c) 4A  2B  3C 
 A 4 B2 C 3
Initial mole 2 1.2 1.44 0
Final mole 0 0.48
C is limiting reagent
 moles of A4B2C3 is 0.48
[ 13 ]
Problem 4: How much NaNO3 must be weighed out to make 50 ml of an aqueous solution containing
70 mg of Na+ per mL?
(a) 12.394 g (b) 1.29 g
(c) 10.934 g (d) 12.934 g
Solution: (d) M wt of NaNO3 = 85

70 mg of Na+ are present in 1 mL
50 ml of solution contains 50 × 70 = 3500 Mg = 3.5 g Na+ ion
23 g of Na+ are present in 85g of NaNO3
85
3.5 g Na+ are present in  3.5  12.934 g of NaNO3
23
Problem 5: The strength of 10 –2 M Na 2 CO 3 solution in terms of molality will be
(density of solution = 1.10 g mL–1) (Molecular weight of Na2CO3 = 106 g mol–1)
(a) 9.00 × 10–3 (b) 1.5 × 10–2
(c) 5.1 × 10–4 (d) 11.2 × 10–3
M 1000
Solution: (a) Explanation: m  where ‘m’ is molarity, M is molarity
(100  d  M  Molecular weight)
102 1000 10 10
    9.00  103
(1000 1.1  102  106) 1100  1.6 1099.4
[Take 1099.4 = 1100]
Problem 6: A solution containing 0.1 mol of a metal chloride MClx requires 500 ml of 0.8 M AgNO3
solution for complete reaction MCl x  xAgNO3 
 xAgCl  M(NO3 ) x . Then the
value of x is
(a) 1 (b) 2
(c) 4 (d) 3
Solution: (c) MCl x  AgNO3 

 xAgCl  M(NO3 ) x
Mole of MCl x Mole of AgNO3

1 x
1
0.1  (0.5  0.8)
x
0.4
x 4
0.1
Problem 7: The temperature at which molarity of pure water is equal to its molality is:
(a) 273 K (b) 298 K
(c) 277 K (d) None of these
Solution: (c) At 4°C i.e. 277 K density of water = 1 g/ml

1 kg water  1000 ml water = 1 lit
Molarity and molarity remains same
[ 14 ]
Problem 8: What is the molarity of H2SO4 solution that has a density 1.84 g/cc at 35°C and contains
98% by weight
(a) 4.18 M (b) 8.14 M
(c) 18.4 M (d) 18 M
(%w / w)  density 10 98  1.84  10

Solution: (c) Molarity    18.4 M
Molar mass of solute 96
Problem 9: 5.85g of NaCl is dissolved in 1 L of pure water. The number of ions in 1 mL of this solution
is
(a) 6.02 × 1019 (b) 1.2 × 1022
(c) 1.2 × 1020 (d) 6.02 × 1020
5.85
Solution: (c) Mole of NaCl =  0.1
58.5
0.1
Molarity =  0.1M
1
Moles in 1 ml of solution = MV = 0.1 × 10–3 = 10–4
Number of ions in 1 ml = 2 × 10–4 × 6.02 × 10–23 = 1.204 × 1020
Problem 10: H3PO4 (98g mol–1) is 98% by mass of solution. If the density is 1.8 g/ml, the molarity is
(a) 18 M (b) 36 M
(c) 54 M (d) 0.18 M
10 1.8  98
Solution: (a) Molarity   18 M
98
[ 15 ]
Chapter - 2
REDOX REACTIONS
2.1 Oxidation-Reduction
(1) Oxidation is a process which involves loss of electrons, i.e., de-electronation. It is an
endothermic process.
(2) Reduction is a process which involves gain of electrons, i.e., electronation. It is an exothermic
process.
Oxidation Reduction
M  M+n + ne– M+n + ne–  M
A–n  A + ne– A + ne–  A– n
M  n1 
 M  n 2  (n 2  n 1 )e M  n1  (n1  n 2 )e 
 M n2
(3) Oxidants are substances which :
(a) oxidize other substances
(b) are reduced themselves
(c) show electronation
(d) show a decrease in oxidation no. during a redox change.
(e) has higher oxidation no. in a conjugate pair redox reaction.
(4) Reductants are substances which
(a) reduce other substances
(b) are oxidized themselves
(c) show de-electronation
(d) show an increase in oxidation no. during a redox reaction
(e) have lower oxidation no. in a conjugate pair of redox reaction
(5) A redox change is one in which a reductant is oxidized to liberate electrons, which are then
used up by an oxidant to get itself reduced.
M1  M 1 n + ne– Oxidation
M 2 n + ne–  M2 Reduction
M1 + M 2 n  M 1 n + M2 Redox reaction
(6) A redox change occurs simultaneously.

Oxidation and Reduction can also be defined in many ways,
(i) Removal of hydrogen atoms is oxidation while addition of hydrogen atoms is reduction. For
example,
H2 + Cl2 2HCl; Cl2 is reduced to HCl

H2S + Cl2 2HCl + S; H2S is oxidised to S
(ii) Addition of oxygen is oxidation, while removal of oxygen is reduction. For example
C + O2 CO2 C is oxidised to CO2

CuO + H2 Cu + H2O CuO is reduced to Cu
[ 33 ]
Redox Reactions
(iii) Increase in positive valency of an element is oxidation, while decrease in positive valency of an
element is reduction.
FeCl2 FeCl3 change in valency of Fe2+  Fe3+
KMnO4 MnO2 change in valency of Mn+7  Mn+4
(iv) Addition of an electronegative element is oxidation while its removal is reduction. For example,
2Na + Cl2 2NaCl (oxidation of Na)
FeCl3 FeCl2 + 1/2 Cl2 (reduction of Fe)
(v) Addition of electropositive element is reduction while its removal is oxidation. For example,
HgCl2 + Hg Hg2Cl2 (reduction of HgCl2)
K4[Fe(CN)6] K3[Fe(CN)6] (oxidation of Fe in K4 [Fe(CN)6])
(vi) According to Franklin, removal or loss of electrons (de-electronation) is oxidation, while addition
or gain of electrons (electronation) is reduction. For example
Na Na+ + e– (oxidation)
–
Cl + e– Cl (reduction)
(vii)Increase in oxidation number is oxidation, while decrease in oxidation number is reduction. For
example,
+2 +4
C CO2 (change in O.N.; + 2  +4, hence oxidation)
+2 +1
CuI2 Cu2I2 (change in O.N.; + 2  + 1, hence reduction
Oxidation Number
(1) Oxidation No. of an element in a particular compound represents the no. of electrons lost or
gained by an element during its change from free state into that compound or Oxidation No. of
an element in a particular compound represent the extent of oxidation or reduction of an element
during its change from free state into that compound.
(2) Oxidation No. is given positive sign if electrons are lost. Oxidation No. is given negative sign if
electrons are gained.
(3) Oxidation No. represents real charge in case of ionic compounds. However, in covalent compounds
it represents imaginary charge.
Rules for Deriving Oxidation Number
Following rules have been arbitrarily adopted to decide oxidation no. of elements on the basis of their
periodic properties:
(1) In uncombined state or free state, oxidation no. of an element is zero.
(2) In combined state oxidation no. of:
[ 34 ]
Redox Reactions
(a) F is always –1.
1
(b) O is –2 in oxides; In peroxides it is –1, in super oxides  . However in OF2 it is +2 and
2
O2F2 it is +1. In ozonides it is –1/3.
(c) H is +1. In ionic hydrides it is –1.
(d) Metals always show +ve. Oxidation number.
(e) Alkali metals (i.e., I A group – Li, Na, K, Rb, Cs and Fr) is always +1.
(f) Alkaline earth metals (i.e., II A group–Be, Mg, Ca, Sr, Ba and Ra) are always +2.
(3) The algebraic sum of all the oxidation no. of all the elements in a compound is equal to zero,
e.g., K2CrO4 (O.N. of K) × 2 + (O.N.of Cr) + (O.N. of O)  4 = 0
(4) The algebraic sum of oxidation no. of all the elements in an ion is equal to the net charge on the
ion, e.g., in SO42– O.N.of S + (O.N. O) × 4 = –2.
(5) Oxidation number can be integer or fraction, (+)ve or (–)ve.
1. Oxidation number of Mn in KMnO4. Let the oxidation number of Mn be x. Now we know

that the oxidation numbers of K is +1 and that of O is –2.
K Mn O4 or K Mn O4
+1 +x +4  –2 +1 +x –8
Now the sum of oxidation numbers of all atoms in the formula of the compound must be zero, i.e.
+1 + x – 8 = 0
Hence the oxidation number of Mn in KMnO4 is +7.
2. Oxidation number of chromium in potassium dichromate. Writing the known oxidation

number of potassium and oxygen
K2 Cr2 O7 or K2 Cr2 O7
+2  1 +2x +7(–2) +2 +2x –14
Since sum of oxidation numbers = 0, i.e.
2 + 2x – 14 = 0
2x = 14 – 2
x = +6
3. Oxidation number of S in S8. Since in S8, sulphur is present in free state, its oxidation number
is zero.
Formal Charge
Formal charge on an atom in a compound can be defined as the calculated charge present on the
atom in a compound. Thus the formal charge present on nitrogen atom in NH4+ ion is +1, and that on
nitrogen and boron atoms in the co-ordination compound H3N  BF3 is +1 an –1 respectively. The
formal charge can be calculated as below.
[ 35 ]
Redox Reactions
1
Formal charge = z – u – s
2
Where z = Number of outer (valence shell) electrons in the atom.

u = Number of unshared electrons
s = Number of shared electrons around the atom in the compound
1
Thus the formal charge on nitrogen atom in NH4+ (z = 5, u = 0, s = 8) = 5 – 0 – 8=1
2
1
Similarly, formal charge on S in SO2 = 6 – 2 – 4=2
2
Balancing of Redox Equations by Oxidation Number Method

This method is based on the fact that the number of electrons gained during reduction must be equal
to the number of electrons lost during oxidation. Following steps must be followed while balancing
redox equations by this method.
(i) Write the skeleton equation (if not given, frame it) representing the chemical change.
(ii) With the help of oxidation number of elements, find out which atom is undergoing oxidation/
reduction, and write separate equations for the atom undergoing oxidation/reduction.
(iii) Add the respective electrons on the right for oxidation and on the left for reduction equation.
Note that the net charge on the left and right sides should be equal.
(iv) Multiply the oxidation and reduction reactions by suitable integers so that total electrons lost in
one reaction is equal to the total electrons gained by other reaction.
(v) Transfer the coefficients of the oxidising and reducing agents and their products as determined
in the above step to the concerned molecule or ion.
(vi) By inspection, supply the proper coefficient for the other formulae of substances not undergoing
oxidation and reduction to balance the equation.
Balancing of Redox equation by Ion-Electron Method

This method involves the following steps:
I Divide the complete equations into two half reactions:
(a) One representing oxidation.
(b) The other representing reduction.
II Balance the atoms in each half reaction separately according to the following steps:
(a) Balance all atoms other than oxygen and hydrogen.
(b) To balance oxygen and hydrogen.
(1) In Acidic Medium:
(i) Add H2O to oxygen deficient side to balance oxygen atoms.
(ii) Add H+ to hydrogen deficient side to balance H atoms.
[ 36 ]
Redox Reactions
(2) In Basic Medium:
(i) For each excess of oxygen, one H2O is added and 2OH– on the other side.
(ii) If H - is not balanced, then for each excess of H, one OH– is added on the same side and
one H2O on the other side.
Balancing of Molecular Reactions by Oxidation Number Method

1. First of all the oxidation number of all those atoms are calculated which are changing during the
reactions.
2. Oxidising and reducing agents are identified.
3. Total number of lost and total number of gained electrons are counted.
4. Now, cross-multiplication is done to find the co-efficients of the reactants and products.
Oxidising agent No. of gained electrons


Reducing agent No. of lost electrons
5. In case of alkaline reactions, balancing should be done from right hand side.
6. If the same atoms are presnt in more than one molecule either on L.H.S. or R.H.S., then
balancing should be done from the side having more molecules having same atom in different
oxidaion number.
Balance the following:
i) KMnO 4  HCl   KCl  MnCl 2  Cl 2  H 2O

ii) K 2 Cr2 O 7  HCl   KCl  CrCl3  Cl 2  H 2 O
iii) Al  NaOH  H 2 O   NaAlO 2  H 2
iv) MnO 4  Fe2   H    Mn 2   Fe3  H 2 O
v) Cr2 O 72   I   H   Cr 3  I 2  H 2 O
vi) MnO 4  C 2 O 42   H   Mn 2   CO 2  H 2 O

OH
vii) Br2   Br   BrO3

viii) Cu  NO3 
H
 Cu 2   NO 2  H 2 O

ix) Cu  NO3 
H
 Cu 2   NO 2  H 2 O
x) FeCl3  SnCl 4 
 FeCl 2  SnCl 4
Illustration 1: Balance the following reaction

NO3– + H2S HSO4– + NH4+ in acidic medium
Solution: Here NO3– is undergoing reduction to NH4 and H2S undergoes oxidation to HSO4–
(i) NO3–  NH4+
(ii) H2S  HSO4–
by balancing each half reaction, we get
(iii) NO3– + 8e– + 10 H+ NH4 + 3H2O
(iv) H2S + 4H2O HSO4– + 8e– + 9H
by combining the equation, we get
NO3– + H2S + H2O + H+ NH4+ + HSO4–
[ 37 ]
Redox Reactions
Illustration 2: Balance the following reaction

NO3– + Al Al3+ + NH4in basic medium
Solution: Here NO3– is undergoing reduction and Al3+ is undergoing oxidation

(i) NO3– NH4+
(ii) Al Al3+
by balancing each half reaction, we get
(iii) NO3– + 7H2O + 8e– NH4++ 10 OH–
(iv) Al Al3+ + 3e–
by multiplying equation (iii) by 3 and equation (iv) by 8, we get
(v) 3NO3– + 7H2O + 24e– 3NH4++ 30 OH–
(vi) 8Al 8Al3+ + 24e–
by combining these equations, we get
8Al + 3NO3– + 21H2O 8Al3+ + 3NH4++ 30 OH–
Illustration 3: Calculate the equivalent weight of each oxidant and reductant in the following reactions.
(a) H3PO2 PH3 + H3PO3
(b) KI + K2Cr2O7 Cr+3 + 3I2
(c) Na2S2O3 + I2  Na2S4O6 + 2NaI
Solution : (a) H3PO2  PH3 + H3PO3

P+ + 4e–  P3–
(P+ P3+ + 2e–) × 2
Net reaction 3P+  P3– + 2P+3
3H3PO2 PH3 + 2H3PO3
n-factor for H3PO2 = 4/3
M 3M
Equivalent weight of H3PO2 = 
4/3 4
(b) 2I– I2 + 2e–
equivalent weight of KI = M/1
= 166/1
= 166
6e– + (Cr+6)2 2Cr+3
equivalent weight of K2Cr2O7
= M/6
= 294/6 = 49
(c) 2(S+2)2  S45/2 + 2e–
M 158
equivalent weight of Na2S2O3 = = = 158
1 1
[ 38 ]
Redox Reactions

Problem 1: Both oxidation and reduction takes place in:
(a) NaBr  HCl 

 NaCl  HBr (b) HBr  AgNO3 
 AgBr  HNO3
(c) H 2  Br2 
 2HBr (c) CaO  H 2SO 4 
 CaSO 4  H 2O
Solution: (c) Both oxidation and reduction are taking place in:
Oxidised (Reducing agent)
0 0 1  1
H 2  Br2 
 2HBr
Reduced (oxidising agent)
O
O O
Problem 2: CrO5 has structure as shown Cr
O O
The oxidation number of chromium in the above compound is
(a) 4 (b) 5
(c) 6 (d) 0
()
(1) O (1)
O O
Solution: (c) Cr
O (+6) O
(1) (1)
Problem 3: In the conversion of Br2 to BrO3 , the oxidation state of bromine changes from
(a) –5 to +5 (b) –5 to 0
(c) 0 to +5 (d) +5 to –5
Solution: (c) BrO3 x + 3 (–2) = –1
x=+5
Problem 4: The sum of the oxidation numbers of the atoms in C6H5CHO is
(a) –1 (b) 0
(c) +1 (d) +2
Solution: (b)
Problem 5: In Ba(H2PO2)2, the oxidation number of phosphorus is

(a) –1 (b) 0
(c) +1 (d) +3
Solution: (c) (H 2 PO2 )  2 (+1) + x + 2 (–2) = –1
x = +1
[ 39 ]
Redox Reactions
Problem 6: Which of the following is not a redox reaction?

(a) KCN  Fe(CN)2 
 K 4 [Fe(CN) 6 ]
(b) Rb  H 2O 
 RbOH  H 2
(c) H 2 O2 
 H2O  O
(d) CuI 2 
 CuI  I 2
Solution: (a) KCN  Fe(CN)2 

 K 4 [Fe(CN) 6 ]
This is not redox reaction
Problem 7: In which of the following oxidation state shows by the iodine?

(a) +1, –1, +3, +5 (b) +1, –1, +3, +5, +7
(c) +1, +3, +5 (d) +1, +3, +7
Solution: (b) Because the oxidation state of I is–1 to +7. So the minimum –1 and maximum + 7
Problem 8: aK 2Cr2O7  bKCl  cH 2SO4 

 xCrO 2 Cl2  yKHSO4  zH 2O
The above equation balances when
(a) a = 2, b = 4, c = 6 and x = 2, y = 6, z = 6
(b) a = 4, b = 2, c = 6 and x = 6, y = 2, z = 3
(c) a = 6, b = 4, c = 2 and x = 6, y = 3, z = 2
(d) a = 1, b = 4, c = 6 and x = 2, y = 6, z = 3
Solution: (d) K 2Cr2O7  4KCl  6H 2SO 4 

 2CrO 2 Cl2  6KHSO4  3H 2O
Problem 9: In the reaction:
As 2S5  xHNO3 
 5H 2SO4  yNO2  2H 2 AsO4  12H 2O
the value of x and y are

(a) 40, 40 (b) 10, 10
(c) 30, 30 (d) 20, 20
Solution: (a) As 2S5  40HNO3 

 5H 2SO4  40NO2  2H3AsO4  12H2 O
Problem 10: Which one of the following reactions involves disproportionation?

(a) 2H 2SO 4  Cu 
 CuSO4  2H2 O  SO 2
(b) As 2O3  3H 2S 
 As2S3  3H 2O
(c) 2KOH  Cl2   KCl  KOCl  H2 O
(d) Ca 3P2  6H 2 O  3Ca(OH) 2  2PH 3
Oxidation
(0) ( 1) ( 1) (0)

2KOH  Cl2 
 K Cl  KO Cl  H 2 O
Solution: (c)
Reduction
[ 40 ]
Redox Reactions
2.2 Volumetric Analysis

The volumetric analysis is an analytical method of determining the concentration of a substance in a
solution by adding exactly same number of equivalents of another substance present in a solution of
known concentration.
This is the basic principle of titration. Volumetric analysis is also known as titrimetric analysis.
The substance whose solution is employed to estimate the concentration of unknown solution is
called titrant and the substance whose concentration is to be estimated is called titrate.
The volumetric analysis is divided into following types:
(a) Simple titrations (Acid-Base or Neutralisation)
(b) Back titrations
(c) Double titrations
Simple Titrations
The aim of simple titration is to find the concentration of an unknown solution with the help of the
known concentration of another solution.
Let us take a solution of a substance ‘A’ of unknown concentration. We are provided with solution of
another substance ‘B’ whose concentration is known (N1). We take a certain known volume (V2
litre) of ‘A’ in a flask and start adding ‘B’ from burette to ‘A’ slowly till all the ‘A’ is consumed by ‘B’.
This can be known with the help of suitable indicator, which shows colour change after the complete
consumption of ‘A’. Let the volume of B consumed is V1 litre. According to the law of equivalents,
the number of equivalents of ‘A’ would be equal to the number of equivalents of ‘B’.
 N1V1 = N2V2, where N2 is the concentration of ‘A’.
Thus using this equation, the volume of N2 can be calculated.
There are four types of simple titrations, namely
(a) Acid-base titrations
(b) Redox titrations
Acid-Base Titrations
In this type of titration, the concentration of an acid in a solution is estimated by adding a solution of
standard base and vice versa. The equivalence point is detected by adding a few drops of a suitable
indicator to the solution whose concentration is to be estimated. An acid-base indicator gives different
colours with acids and bases. The choice of indicator in a particular titration depends on the pH-
range of the indicator and the pH change near the equivalence point. End point is indicated by the
change in colours of indicators, depending upon pH and structure.
[ 41 ]
Redox Reactions
(i) Strong acid-strong base Titration: In the titration of HCl Vs NaOH, the equivalence point
lies in the pH-range of 4-10. Thus, methyl red (pH-range 4.2 to 6.3), methyl orange (pH-range
3.1 to 4.4) and phenolphthalein (pH-range 8.3 - 10) are suitable indicators of such titrations.
(ii) Weak acid-strong base Titration: In the titration of CH3COOH and NaOH, the equivalence
point lies between 7.5 and 10. Thus, phenolphthalein is the suitable indicator.
(iii) Weak base-strong acid Titration: In the titration of NH4OH and HCl, the equivalence point
lies in the pH range of 4 to 6.5. Thus, methyl orange and methyl red are suitable indicators.
(iv) Weak acid-weak base Titration: In the titration of CH3COOH and NH4OH, the equivalence
point lies between 6.5 and 7.5 and the pH change is not sharp at the equivalence point. Thus, no
simple indicator can be employed to detect the equivalence point.
Redox Titrations
In a redox titration, an oxidant is estimated by adding reductant or vice-versa. For example, Fe2+ ions
can be estimated by titration against acidified KMnO4 solution when Fe2+ ions are oxidised to Fe3+
ions and KMnO4 is reduced to Mn2+ in the presence of acidic medium. KMnO4 functions as self-
indicator as its purple colour is discharged at the equivalence point.
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

Fe2+  Fe3+ + e–] × 5
______________________________________
MnO4– + 8H+ + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O
(n = 5)
In addition to acidified KMnO4, acidified K2Cr2O7 can also be employed. Other redox titrations are
iodimetry, iodometry, etc.
(i) Iodimetry: This titration involves free iodine. Such direct estimation of iodine is called iodimetry.
This involves the titration of iodine solution with known sodium thiosulphate solution, whose
normality is N. Let the volume of sodium thiosulphate used be V litre.
I2 + 2Na2S2O3 2NaI + Na2S4O6

(n=2) (n=1)
Equivalents of I2 = Equivalents of Na2S2O3 used = N × V
N× V
Moles of I2 =
2
 N× V 
Mass of free I2 in the solution =   254  g
 2 
(ii) Iodometry: This is an indirect method of estimation of iodine. An oxidising agent is made to
react with excess of solid KI. The oxidising agent oxidises I– to I2. This liberated iodine is then
made to react with Na2S2O3 solution of normality N. Let the volume of thiosulphate solution
required be V litre.
2 Na 2S2 O3
Oxidising Agent (A) + KI  I2   2NaI + Na2S4O6 + reduced form of oxidizing
agent
[ 42 ]
Redox Reactions
Equivalents of ‘A’ = Equivalents of I2 = Equivalents of Na2S2O3 used = N× V

Equivalents of I2 liberated from KI = N × V
Equivalents of ‘A’ = N × V
Let the n-factor of ‘A’ in its reaction with KI be x, then
N× V
Mass of ‘A’ consumed =  M A (where MA is the molar mass of A)
x
Back Titrations
Let us assume that we have an impure solid substance ‘C’, weighing ‘w’ g and we are required to
calculate the percentage purity of ‘C’ in the sample. We are also provided with two solutions ‘A’ and
‘B’, where the concentration of ‘B’ is known (N1) and that of ‘A’ is unknown. For the back titration
to work, following conditions are to be satisfied:
(i) Compounds ‘A’, ‘B’ and ‘C’ should be such that ‘A’ and ‘B’ react with each other.
(ii) ‘A’ and pure ‘C’ also react with each other but the impurity present in ‘C’ does not react
with ‘A’.
(iii) Also the product of ‘A’ and ‘C’ should not react with ‘B’.
Now we take out certain volume of ‘A’ in a flask (the equivalents of ‘A’ taken should be equivalents
of pure ‘C’ in the sample) and perform a simple titration using ‘B’. Let us assume that the volume of
‘B’ used be V1 litre.
Equivalents of ‘B’ reacted with ‘A’ = N1V1
 Equivalents of ‘A’ initially = N1V1
In another flask, we again take same volume of ‘A’ but now ‘C’ is added to this flask. Pure part of
‘C’ reacts with ‘A’ and excess of ‘A’ is back titrated with ‘B’. Let the volume of ‘B’ consumed is V2
litre.
Equivalents of ‘B’ reacted with excess of ‘A’ = N1V2
 Equivalents of ‘A’ in excess = N1V2
Equivalents of ‘A’ reacted with pure ‘C’ = (N1V1 – N1V2)
Equivalents of pure ‘C’ = (N1V1– N1V2)
(N1V1  N1V2 )
Let the n-factor of ‘C’ in its reaction with ‘A’ be x, then the moles of pure ‘C’ =
x
(N1V1  N1V2 )
 Mass of pure ‘C’ = × molar mass of ‘C’
x
(N1V1  N1V2 ) Molar mass of 'C'
 Percentage purity of ‘C’ =  × 100
x w
[ 43 ]
Redox Reactions
Double Titrations
The purpose of double titration is determine the percentage composition of an alkali mixture or an
acid mixture. In the present case, we will find the percentage composition of an alkali mixture. Let us
consider a solid mixture of NaOH, Na2CO3 and some inert impurities, weighing ‘w’ g. We are
required to find the % composition of this alkali mixture. We are also given an acid reagent (HCl) of
known concentration M1 that can react with the alkali sample.
We first dissolve this mixture in water to make an alkaline solution and then we add two indicators,
(Indicators are substances that indicate colour change of solution when a reaction gets completed),
namely phenolphthalein and methyl orange to the solution. Now, we titrate this alkaline solution with
standard HCl.
NaOH is a strong base while Na2CO3 is a weak base. So it is obvious that NaOH reacts first with
HCl completely and Na2CO3 reacts only after complete NaOH is neutralized.
NaOH + HCl NaCl + H2O ...(i)
Once NaOH has reacted completely, then Na2CO3 starts reacting with HCl in two steps, shown as
Na2CO3 + HCl NaHCO3 + NaCl ...(ii)
NaHCO3 + HCl NaCl + CO2 + H2O ...(iii)
It is clear that when we add HCl to the alkaline solution, alkali is neutralized and the pH of the
solution decreases. Initially the pH decrease would be rapid as strong base (NaOH) is neutralized
completely. When Na2CO3 is converted to NaHCO3 completely, the solution is still weakly basic due
to the presence of NaHCO3 (which is weaker as compared to Na2CO3). At this point, phenolphthalein
changes colour since it requires this weakly basic solution to show its colour change. When HCl is
further added, the pH again decreases and when all the NaHCO3 reacts to form NaCl, CO2 and
H2O the solution becomes weakly acidic due to the presence of the weak acid (H2CO3). At this
point, methyl orange changes colour as it requires this weakly acidic solution to show its colour
change.
Thus is general, phenolophthalein shows colour change when the solution contains weakly
basic NaHCO3 along with other neutral substances while methyl orange shows colour change
when solution contains weakly acidic H2CO3 along with other neutral substances.
Illustration 1: 0.56 g of lime stone was treated with oxalic acid to give CaC2O4. The precipitate decolorized
45 ml of 0.2 N KMnO4 in acid medium. Calculate percentage of CaO in lime stone.
Lime stone oxalic acid KMnO

Solution : CaCO3     CaC2O4  4  decolorizes
 Redox changes :
For CaC2O4 C2 3  2C+4 + 2e
For KMnO4 5e + Mn+7  Mn+2

 Meq. of CaCO3 = Meq. of CaC2O4 = Meq. of KMnO4
 Meq. of CaCO3 = Meq. of CaO (since CaO is present in CaCO3)
[ 44 ]
Redox Reactions
 Meq. of CaO = Meq. of KMnO4
w
× 1000 = 45 × 0.2
56 / 2
wt. of CaO = 0.252 g
0.252
 percentage of CaO in lime stone = × 100 = 45%
0.56
Illustration 2: 1 g sample of AgNO3 is dissolved in 50 ml of water. It is titrated with 50 ml of KI solution.

The AgI precipitated is filtered off. Excess of KI in filtrate is titrated with M/10 KlO3 in
presence of 6M HCl till all I– converted into ICl. It requires 50 ml of M/10 KlO3 solution. 20
ml of the same stock solution of KI requires 30 ml of M/10 KIO3 under similar conditions.
Calculate % of AgNO3 in sample. The reaction is :
KIO3 + 2KI + 6HCl  3KCl + 3H2O
Solution : AgNO3 + KI  AgI + KNO3

1. Ag present in AgNO3 is removed as AgI by adding 50 ml KI of which 20 ml requires 30
ml of M/10 KIO3.
2. The solution contains KI unused. The unused KI is converted into ICl by KIO3.
 Meq. of KI in 20 ml = Meq. of KIO3 4e + I+5  I+1
1
= 30 × ×4 I–  I+1 + 2e
10
 Meq. of KI in 50 ml added to AgNO3  Eq. wt. of KI = M
2
30  4  50
= = 30
10  20
1
Now Meq. of KI left unused by AgNO3 = 50 × × 4 = 20
10
 Meq. of KI used for AgNO3 = 30 – 20  Mole ratio of AgNO3 and KI
 Meq. of AgNO3 = 10 reaction is 1 : 1 and thus if Eq.
w
 × 1000 = 10 wt. of KI is M/2, then Eq. wt.
170 / 2
w = 0.85 g of AgNO3 = M/2
0.85 100
 percentage of purity of AgNO3 in sample = = 85%.
1
Illustration 3: A 5.0 cm3 solution of H2O2 liberates 0.508 g of iodine from an acidified KI solution. Calculate
the strength of H2O2 solution in terms of volume strength at STP.
Solution : Meq. of H2O2 = Meq. of I2
(w/17) × 1000 = [0.508/(254/2)] × 1000  w = 0.068 g
H2O2  H2O + (1/2)O2
 34 g H2O2 gives 11.2 litre O2, at STP
 0.068 g gives (11.2 × 0.068)/34 = 22.4 ml O2
 Volume strength of H2O2 = 22.4/5 = 4.48%.
[ 45 ]
Redox Reactions
Illustration 4: A mixture of KMnO4 and K2Cr2O7 weighing 0.24 g on being treated with KI in acid solution
liberates just sufficient l2 to react with 60 ml of 0.1 N Na2S2O3. Find out percentage of Cr
and Mn in mixture.
Solution : The reactions are :

5e + Mn+7  Mn+2 and 2I–  I2 + 2e
6e + Cr2+6  2Cr+3
Let wt. of KMnO4 and K2Cr2O7 be a and b g respectively.
 Meq. of KMnO4 + Meq. of K2Cr2O7 = Meq. of I2 = Meq. of hypo = 60 × 0.1
a b
 × 1000 + × 1000 = 6 .....(1)
158 / 5 294 / 6
Also given a + b = 0.24 .....(2)
 a = 0.098 g i.e. wt. of KMnO4
b = 0.142 g i.e. wt. of K2Cr2O7
55 0.098
Also wt. of Mn in 0.098 g KMnO4 = = 0.034 g
158
52  2  0.142
wt. of Cr in 0.142 g K2Cr2O7 = = 0.050 g
294
0.034  100
 percentage of Mn in sample = = 14.17%
0.24
0.050 100
 percentage of Cr in sample = = 20.92%.
0.24
Illustration 5: 1 g of H2O2 solution containing X% H2O2 by weight requires X ml of KMnO4 for complete
oxidation in acid medium. Calculate normality of KMnO4 solution.
Solution : Redox changes are :

Mn+7 + 5e  Mn2+
O2–1  O20 + 2e
34
 Eq wt. of H2O2 =
2
Now Meq. of KMnO4 = Meq. of H2O2
X
N.(X) = × 1000
100  34/2
 N = 0.588.
Illustration 6: Find out the percentage of oxalate ion in a given sample of oxalate salt of which 0.3 g
dissolved in 100 ml of water required 90 ml of N/20 KMnO4 for complete oxidation.
Solution : Redox changes are :

5e + Mn+7  Mn+2
C2+3  2C+4 + 2e
 Meq. of oxalate ion = Meq. of KMnO4
[ 46 ]
Redox Reactions
w 1 Io n ic w t.
× 1000 = 90 × EC 2 
E 20 2O 4
2
w
88 × 1000 = 9
2 2
 w C O–2 = 0.198 g
2 4
 0.3 g C2O4–2 sample has oxalate ion = 0.198 g

0.198  100
 percentage of C2O4–2 in sample = = 66%.
0. 3
Illustration 7: A 1.1 g sample of copper ore is dissolved and the Cu+2 ion is treated with excess KI. The
liberated I2 requires 12.12 ml of 0.1 M Na2S2O3 solution for titration. What is % of copper
by mass in the ore?
Solution : Cu+2 + e– Cu+

2I–  I2 + 2e–
2S2O32– S4O6– + 2e–
Cu +2
Meq of Cu+2 = Meq. of liberated I2 =Meq of Na2S2O3 ×1000 = 1.212
63.6
WCu+2  0.077g
0.077
%Cu =  100 = 7%
1.10

Problem 1: When 8.3 g copper sulphate reacts with excess of potassium iodide then the amount of
iodine liberated is:
(a) 42.3 g (b) 24.3 g
(c) 4.23 g (d) 2.43 g
Solution: (c) Copper sulphate and potassium iodide react as follows:
2CuSO4  5H2 O  KI 
 2Cu 2 I 2  2K 2SO4  I2  10H2 O
Mass of copper sulphate used = 2(63 +32 + 64 + 5 × 18) = 498g
Mass of I2 liberated = 2 × 127 = 254 g
 496 g of CuSO4 liberate I2 = 254
254
8.3 g of CuSO4 liberate I 2   8.3  4.23g
498
Problem 2: MnO 24 (1 mol) in neutral aqueous medium is disproportionate to:

(a) 2/3 mol of MnO4 and 1/3 mol MnO2
(b) 1/3 mol of MnO4 and 2/3 mol MnO4
(c) 1/3 mol of Mn2O7 and 1/3 mol MnO2
(d) 2./3 mol Mn2O7 and 1/3 mol MnO2
[ 47 ]
Redox Reactions
Solution: (a) The reaction of MnO 24 in aqueous medium takes place as below:
3MnO24  2H 2O 
 MnO2  2MnO4  4OH
Problem 3: Number of moles of K2Cr2O7 reduced by 1 mole of Sn2+ is

(a) 1/6 (b) 1/3
(c) 2/3 (d) 1
Solution: (b) Moles of K2Cr2O7 × n-factor = moles of Sn2+ × n-factor.

1 2 1
Moles of K 2Cr2O7  
6 3
Problem 4: 3.92 g of ferrous ammonium sulphate are dissolved in 100 ml water 20 ml of this solution
requires 16 ml of potassium permanganate during titration for complete oxidation. The weight
of KMnO4 present in one litre of the solution is
(a) 34.75 g (b) 12.38 g
(c) 1.238 g (d) 3.95 g
Solution: (d) Wt. of FeSO4.(NH4)2SO4.6H2O in 20 ml solution = 0.784 g

Molar mass of FeSO4.(NH4)2SO4.6H2O = 392
Molar mass of KMnO4 = 158
Equivalent of FeSO4.(NH4)2SO4.6H2O = Equivalent of KMnO4
Wt. FeSO 4 .(NH 4 ) 2SO 4 .6H 2O Weight of KMnO4


Equivalent weight Equivalent weight of KMnO 4
0.784 Wt. of KMnO 4

 5
392 158
Weight of KMnO4 in 16 ml solution = 0.0632 g

Weight of KMnO4 in 1 lit of solution = 3.95 g
Problem 5: MnO4 ions are reduced in acidic condition of Mn2+ ions whereas they are reduced in neutral
condition to MnO2. The oxidation of 25 ml of solution X containing Fe2+ ions required in
acidic condition 20 ml of a solution Y containing MnO4 ions. What volume of solution Y
would be required to oxidise 25 ml of solution X containing Fe2+ ions in neutral condition?
(a) 11.4 ml (b) 12.0 ml
(c) 33.3 ml (d) 35.0 ml
Solution: (c) In acidic medium n-factor of MnO4 = 5

In neutral medium n-factor of MnO4 = 3
In acidic medium
meq. of MnO4 = meq . of Fe2+
M1 × V1 × n-factor = M2 × V2 × n-factor
M1 × 20 × 5 = M2 × 25 × 1
[ 48 ]
Redox Reactions
M2 = 4 × M1
In neutral medium
meq. of MnO4 = meq . of Fe2+
M1 × V1 × n-factor = M2 × V2 × n-factor
M1 × V1 × 3 = 4 × M1 × 25 × 1
100
V1   33.3 ml
3
Problem 6: Volume V1 mL of 0.1 M K2Cr2O7 is needed for complete oxidation of 0.678 g N2H4 in acidic
medium. The volume of 0.3 M KMnO4 needed for same oxidation in acidic medium will be:
2 5
(a) V1 (b) V1
5 2
(c) 113 V1 (d) cannot be determined
Solution: (a) Equivalent of K2Cr2O7 = equivalent of N2H4

also equivalent of KMnO4 = equivalent of N2H4
So, equivalent of K2Cr2O7 = equivalent of KMnO4
0.1 × 6 × V1 = 0.3 × 5 × V2
so V2 = 2/5 V1
N
Problem 7: 20 mL of H2O2 after acidification with dilute H2SO4 required 30 mL of KMnO4 for
12
complete oxidation. The strength of H2O2 solution is: [Molar mass of H2O2 = 34]
(a) 2 g/L (b) 4 g/L
(c) 8 g/L (d) 6 g/L
Solution: (a) meq. of KMnO4 = meq. of H2O2

1 30 1
30   20  N  N   N
12 12  20 8
1
Strength in gm/litre = N × equivalent mass =  17  2.12 g / L
8
Problem 8: A mixture of 0.02 mole of KBrO3 and 0.01 mole of KBr was treated with excess of KI and
acidified. The volume of 0.1 M Na2S2O3 solution required to consume the liberated iodine
will be:
(a) 1000 mL (b) 1200 mL
(c) 1500 mL (d) 800 mL
Solution: (b) BrO3  6I  

 3I 2  Br 
moles of I2 = 3 × moles of KBrO3

 moles of I2 = 0.03 × 3 = 0.06
0.06 × 2 = 0.1 ×V
V = 1.2 L = 1200 mL
[ 49 ]
Redox Reactions
Problem 9: In the reaction CrO5  H 2SO4 

 Cr2 (SO 4 )3  H 2O  O 2 , one mole of CrO5 will liberate
how many moles of O2:
(a) 5/2 (b) 5/4
(c) 9/2 (d) 7/4
Solution: (d) 4CrO5  6H 2SO4 

 2Cr2 (SO4 )3  6H 2O  7O2
1 mole CrO5 produces 7/4 moles of O2

[ 50 ]
Chapter - 3
ATOMIC STRUCTURE
3.1 Introduction
Matter is constituted by very small particles which can not exist in free state in most of the cases
called atoms. These atoms are constituted further by some fundamental particles called electrons;
protons and neutrons. Present chapter deals with the structure of atom in terms of these fundamental
particles and influence of electronic arrangement on the properties of the molecules.
Nature of cathode rays

(i) They travel in straight lines away from the cathode with very high velocities ranging from
107 – 109 cm per second.
(ii) They produce a green glow when strike the wall beyond anode.
(iii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy.
(iv) They are deflected by the electric and magnetic fields. When the rays are passed between two
electrically charged plates, these are deflected towards the positively charged plate.
(v) When a small pin wheel is placed in their path, the blades of the wheel are set in motion this
indicates cathode rays consists of material particles which have mass and velocity.
(vi) When they fall on material having high atomic mass, new type of penetrating rays of very small
wavelengths are emitted which are called X-rays.
(vii)They affect the photographic plate.
(viii) They can penetrate through thin foils of solid materials and cause ionisation in gases through
which they pass.
(ix) The nature of the cathode rays is independent of:

(a) The nature of the cathode and.
(b) The gas in the discharge tube.
(x) The negatively charged particles which constitute cathode rays are called electrons.
Rest mass of electron: The rest mass of electron is found to be 9.1096 × 10–31 kg.
Mass of moving electron : The mass of moving electron is given by the relation.
rest mass of electron

Mass of moving electron = 2
v
1   
c
Where v is the velocity of the electron and c is the velocity of light. When v becomes equal to c mass
of moving electron becomes infinity.
[ 65 ]
Atomic Structure
Charge on electron : The charge on electron is found to be –1.6022 × 10–19 coulombs. Since the
electron has the smallest charge known, it is designated as unit negative charge.
e/m of electron : Charge to mass ratio of the electron is found to be –1.7588 × 108 C per g.
Nature of Anode Rays

(i) These rays travel in straight lines and cast shadow of the object placed in their path.
(ii) Like cathode rays, they also rotate the wheel placed in their path and also have heating effect.
Thus, the rays possess kinetic energy.
(iii) The rays produce fluorescence on zinc sulphide screen.
(iv) The rays are deflected by electric and magnetic field in the direction opposite to that of cathode
rays. These rays are attracted towards the negatively charged plate showing that they carry
positive charge.
(v) They can pass through thin metal foils.
(vi) They can produce ionisation in gases.
(vii)They are capable of producing physical and chemical changes.
(viii) Positive particles in these rays have e/m values much smaller than that of the electron.
(ix) e/m value is dependent on the nature of the gas taken in the discharge tube. Particles of highest
e/m are obtained when hydrogen is taken in the discharge take. These particles of highest e/m
are called proton.
Mass of proton: Mass of proton is found to be 1.672 × 10–27 kg or 1.0072 amu. (amu = atomic mass
unit)
Charge on proton : Charge on proton is same as charge on electron (i.e., +1.6022 × 10–19 coulombs)
in magnitude but opposite in sign.
e/m of proton: Charge to mass ratio of proton is found to be +9.579 × 104 coulombs per g. Which
is very small as compared to electron.
Rutherford’s -scattering experiment

Rutherford carried out a series of experiments using
-particles. A beam of -particles was directed against a
thin foil of gold, platinum, silver or copper. The foil was
surrounded by a circular fluorescent zinc sulphide screen.
Whenever an -particle struck the screen, it produced a
flash of light.
The following observations were made:
(i) Most of the -particles went straight without suffering any deflection.
(ii) A few of them got deflected through small angles.
(iii) A few of them (about one in 20,000) returned back towards its source.
[ 66 ]
Atomic Structure
Following conclusions were drawn from the above observations:
(i) Since most of the particles went straight through the metal foil undeflected, it indicates most of
space of an atom is empty.
(ii) A few of the -particles were deflected from their original paths through moderate angles, it
was concluded that whole of the positive charge is concentrated and the space called nucleus. It
is supposed to be present in the centre of the atom.
(iii) A very few of the -particles suffered strong deflections or even rebound on their path due to
maximum repulsion and minimum Impact parameter.
Mosley’s Experiment and the concept of Atomic Number : Moseley studied the x-ray spectra
of 38 different elements, starting from aluminium to gold. He measured the frequency of principal
lines of a particular series (the -lines in the k-series) of the spectra. He observed that the frequency
of the particular spectral line was related with the serial number of the element in the periodic table
which he termed as atomic number (Z). He suggested the following relationship.
v  a ( Z  b)
(a) (b)
20 20
v/108 s–1
–1
v/10 s
15 15
8
10 10
5 5
20 40 60 80 100 10 20 30 40
Relative Atomic Mass (A) Atomic Number (Z)
Where v = frequency of X-rays, Z = atomic number, a and b are constants. When the values of
square root of the frequency were plotted against atomic numbers of the elements producing X-rays,
a straight line was obtained.
It was pointed out that the atomic number of an element is equal to the total positive charge contained
in the nucleus.
(i) Atomic number of the element = Serial number of the element in periodic table.
= Charge on the nucleus of the atom of the element
= Number of protons present in the nucleus of the atom of
the element
= Number of extranuclear electrons present in the atom of
the element.
(ii) They produce a green glow when strike the wall beyond anode.
(iii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy.
[ 67 ]
Atomic Structure
Chadwick’s Experiment and discovery of Neutron : Chadwick bombarded beryllium with a

stream of -particles. He observed that penetrating radiations were produced which were not affected
by electric and magnetic fields. These radiations consisted neutral particles, which were called
neutrons.
9 Be  4 He  12 C  1n
4 2 6 0
beryllium α- particle carbon neutron
The mass of the neutron was determined. It was 1.675 × 10–24 g, i.e., nearly equal to the mass of
proton.
Thus, a neutron is a sub-atomic particle which has a mass 1.675 × 10–24 g approximately 1
amu or nearly equal to the mass of proton or hydrogen atom and carrying no electrical
charge. The e/m of neutron is zero.
Rutherford’s Model of Atom : Rutherford proposed a model of the atom which is known as
nuclear atomic model. According to this model.
(i) An atom consists of heavy positively charged nucleus where all the protons and neutrons are
present. The magnitude of the positive charge on the nucleus is different for different atoms.
(ii) The volume of the nucleus is very small and is only a minute fraction of the total volume of the
atoms.
Diameter of atom 108 cm

 13  105.
Diameter of the nucleus 10 cm
Thus, the diameter of an atom is 100,000 times the diameter of the nucleus.
The radius of a nucleus is proportional to the cube root of the mass number.
Radius of the nucleus = 1.33 × 10–13 × A1/3 cm where A is the mass number.
(iii) There is an empty space around nucleus called extranuclear part. In this part electrons are
present. The number of electrons in an atom is always equal to number of protons present in the
nucleus. The volume of the atom is about 1015 times the volume of the nucleus.
Volume of the atom (10 8 ) 3 10 24

   1015
Volume of the nucleus (10 13 ) 3 10 39
(iv) Electrons revolve round the nucleus in closed orbits with high speeds. The centrifugal force
acting on the revolving electrons is being counter balanced by the force of attraction between
electrons and the nucleus.
This model was similar to solar system, the nucleus representing the sun and electrons the
planet. The electrons are, therefore, generally referred as planetary electrons.
[ 68 ]
Atomic Structure
Limitations of Rutherford model

(i) According to wave theory, a charged particle when moves under the influence of attractive
force, it loses energy continuously in the form of electromagnetic radiations. Thus, the electron
which moves in an attractive field (created by protons present in the nucleus), must emit radiations.
As a result the electron should lose energy at every turn and move closer and closer to the
nucleus
Nucleus
following a spiral path and fall into the nucleus, thereby making the
atom unstable. Since atom is quite stable, it means the electrons do not
fall into nucleus, and this model does not explain the stability of the
atom. +
(ii) If the electrons lose energy continuously, the observed spectra should
be continuous but the observed spectra consists of well defined lines of Electron
definite frequencies. Hence, the loss of energy by the electrons is not
continuous in an atom.
Electromagnetic radiations (wave theory): Electromagnetic radiation is generated by oscillations

of a charged body in a magnetic field or of a magnet in an electric field. These radiations or waves
have electric and magnetic fields associated with them and travel at right angle to these fields. The
following are, the important characteristics of electromagnetic radiations.
(i) These consists of electric and magnetic fields that oscillate in directions perpendicular to each
other and perpendicular to the direction in which the wave is travelling.
(ii) All electromagnetic radiations travel with same velocity, i.e., the velocity of light (3 × 108 ms–1 or
3 × 1010 cm s–1).
(iii) The electromagnetic radiations do not require any medium for transmission.
Wave
A wave is always characterised by the following five characteristics :
(i) Wavelength (ii) Frequency (iii) Velocity (iv) Wave number and
(v) Amplitude
(i) Wavelength : The distance between two consecutive crests or troughs is called the wavelength.
It is denoted by .
Crest
Wavelength
Vibrating
source Energy
Trough
(ii) Frequency : It is defined as the number of waves which pass through a point in one second. It
is denoted by the symbol, v and is measured in terms of cycles per second (cps) or Hertz (Hz)
units.
[ 69 ]
Atomic Structure
c
v
λ
or where;  = wavelength
c = velocity of height
v = frequency.
(iii) Velocity : It is defined as the distance covered by wave in one second. It is denoted by the letter
‘c’. All electromagnetic waves travel with same velocity.
Thus, a wave of higher frequency has a shorter wavelength while a wave of lower frequency
has a longer wavelength.
(iv) Wave number: This is reciprocal of wavelength, i.e., It is denoted by the symbol v
1
v Its unit is cm–1 or m–1.
λ
(v) Amplitude: It is defined as the height of the crest of depth of the trough of a wave. It is denoted
by letter ‘a’. It determines the intensity of the radiation.
The arrangement of various types of electromagnetic radiations in the order of increasing or

decreasing wavelengths or frequencies is known as electromagnetic spectrum.
Electromagnetic radiation Wavelength range (Å) Frequency range (Hz)
Cosmic rays 0.01 to zero 3 × 1020 to infinity

Gamma rays 0.1 to 0.01 3 × 1019 to 3 × 1020
X-rays 150 to 0.1 2 × 1016 to 3 × 1019
Ultra-violet radiation (UV) 3800 to 150 7.9 × 1014 to 2 × 1016
Visible radiation 7600 to 3800 3.95 × 1014 to 7.9 × 1014
Infra-red radiation (IR) 6 × 106 to 7600 5 × 1011 to 3.95 × 1014
Micra waves 3 × 109 to 6 × 106 1 × 109 to 5 × 1011
Radio waves 3 × 1013 to 3 × 109 1 × 105 to 1 × 109

Problem 1: Isotopes have
(a) Same number of protons (b) Same number of neutrons
(c) Different number of electrons (d) Different atomic numbers
Solution: (a) Isotopes have same atomic number.
Problem 2: The ratio of mass of an electron to that of the mass of hydrogen atom is:
(a) 1837 : 1 (b) 1 : 2000
(c) 1 : 1837 (d) 1 : 3500
Solution: (c)
[ 70 ]
Atomic Structure
Problem 3: The number of neutrons present in deuterium is:

(a) 3 (b) 0
(c) 2 (d) 1
Solution: (d)
Problem 4: What happens when -rays strike a thin gold foil:

(a) Most of the -rays gets deflected through small angles
(b) Most of the rays do not pass through the foil
(c) Most of the rays passes through without any deviation
(d) Most of the rays gets deflected back
Solution: (c)
Problem 5: Wave number is equal to:

c
(a) (b) λ  ν
λ
1
(c) (d) 
λ
1
Solution: (c) ν 
λ
Problem 6: The frequency of microwaves with wavelength 2 × 106 nm is

(a) 2.5 × 106 s–1 (b) 5 × 108 s–1
(c) 1.5 × 1011 s–1 (d) 3.2 × 107 s–1
c 3  108 ms 1
Solution: (c) ν   3
 1.5 1011 s1
λ 2  10 m
Problem 7: The diameter of an atom is ______times the diameter of the nucleus
(a) 105 (b) 103
(c) 104 (d) 102
diameter of atom
Solution: (a)  105
diameter of nucleus
Problem 8: The unit of frequency is/are

(a) Cycles per second (b) Hertz
(c) Metre per second (d) Both (a) and (b)
Solution: (d) Factual
Problem 9: The limitations of Rutherford’s -ray scattering experiment was

(a) It could not explain the stability of atom
(b) It could not explain the position of nucleus
(c) It could not explain the size of atom
(d) Both (a) and (c)
Solution: (a)
[ 71 ]
Atomic Structure
Problem 10: Unit of wavelength can be

(a) cm (b) nm
(c) pm (d) all of these
Solution: (d) Factual
3.2 Atomic Spectrum of Hydrogen

When an electric discharge is passed through hydrogen gas at low pressure, a bluish light is emitted.
When a ray of this light is passed through a prism, a discontinuous line spectrum of several isolated
sharp lines is obtained. The wavelengths of various lines lie in visible, ultraviolet and infra-red regions.
All these lines observed in the hydrogen spectrum can be classified into five series.
Spectral series Discovered by Appearing in
Lyman series Lyman Ultra-violet region

Balmer series Balmer Visible region
Paschen series Pashcen Infra-red region
Brackett series Brackett Infra-red region
Pfund series Pfund relation Infra-red region
Ritz presented a mathematical relation to find the wave number of various lines of H-spectrum.
1 v 1 1 
v    
λ c  n12 n22 
where R is a universal constant, known as Rydberg constant. It’s value is 109,678 cm –1

(R = 1.097 × 107 m–1) n1 and n2 are integers (such that n2 > n1). For a given spectral series n1 remains
constant while n2 varies from line to line in the same series.
The value of n1 = 1, 2, 3, 4 and 5 for the Lyman, Balmer, Paschen, Brackett and Pfund series
respectively. n2 is greater than n1 by at least 1.
Values of n1 and n2 for various series
Spectral Series Value of n1 Value of n2
Lyman series 1 2, 3, 4, 5,.....

Balmer series 2 3, 4, 5, 6,.....
Pashcen series 3 4, 5, 6, 7,.....
Bracket series 4 5, 6, 7, 8,.....
Pfund series 4 6, 7, 8, 9,.....
(i) They produce a green glow when strike the wall beyond anode.
(ii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy.
[ 72 ]
Atomic Structure
Quantum theory of electromagnetic radiations: The wave theory successfully explains many
phenomenon such as reflection, refraction, diffraction, interference, polarisation etc., but fails to
explain phenomenon like black body radiation, photo-electric effect etc.
In order to explain black body radiation and photo-electric effect a new theory was proposed which
is known as quantum theory of radiation. According to this theory, a hot body emits energy not
continuously but discontinuously in the form of small packets of energy called quantum. The energy
associated with each quantum of a given radiation is proportional to the frequency of the emitted
radiation; E 
or E = hv where h is a constant known as Planck’s constant. It’s numerical value is 6.624 × 10–34 Js.
The energy emitted or absorbed by a body can be either one quantum or any whole number multiple
of hv, i.e., 2hv, 3hv, 4hv,...., nhv quanta of energy.
Thus energy emitted or absorbed = nhv, where n can have values 1, 2, 3, 4,...... Thus, the energy
emitted or absorbed is quantised.
Bohr’s Model of an atom
Postulates:
(i) The atom has a nucleus where all the protons and neutrons are present. It is present at the
centre of the atom.
(ii) Negatively charged electrons are revolving around the nucleus in a same way as the planets are
revolving around the sun. The path of the electron is circular. The force of attraction between
the nucleus and the electron is equal to centrifugal force of the moving electron.
(iii) Out of infinite number of possible circular orbits around the nucleus, the electron can revolve
h h
only in those orbits whose angular momentum is an integral multiple of , i.e., mvr  n
2π 2π
where m = mass of electron, v = velocity of electron, r = radius of orbit and n = 1, 2, 3, .... number
of orbit. Thus the angular momentum is quantized. The specified orbits are called stationary
orbits.
(iv) By the time, the electron remains in any one of the stationary orbits, it does to lose energy. Such
a state is called ground state.
(v) Each stationary orbit is associated with a definite amount of energy. The greater the distance of
the orbit from the nucleus, more shall be the energy associated with it. These orbits are also
called energy levels and are numbered as 1, 2, 3, 4, ..... or K, L, M, N,..... from nucleus outwards.
(vi) The emission or absorption of energy in the form of radiation can only occur when an electron
jumps from one stationary orbit to another.
E = Ehigh –Elow = hv
[ 73 ]
Atomic Structure
Electrons excited
by absorbing energy
(energy absorbed)
+
Nucleus
Energy radiated
when electrons fall
n=1
back
(K) n = 2 n=3
(L) n=4 (Energy emitted)
(M)
(N) n = 0
(O) n = 6
(P)
Energy is absorbed when electron jumps from inner to outer orbit and is emitted when it moves from
outer to an inner orbit.
When the electron moves from inner to outer orbit by absorbing definite amount of energy, the new
state of the electron is said to be excited state.
Radii of various orbits mv2

r Force of
Consider an electron of mass ‘m’ and charge ‘e’ revolving around attraction
v e
the nucleus of charge Ze (Z = atomic number). Let ‘v’ be the
r
tangential velocity of the revolving electron and ‘r’ the radius of the
orbit. The electrostatic force of attraction between the nucleus and + Ze
kZe 2
electron  2 .
r
1
where k is a constant. It is equal to 4πε ,  0 being absolute permittivity of medium. In SI units, the
0
1
numerical value of 4πε is equal to 9 × 109 Nm2/c2.
0
[In C.G.S. units, value of k is equal to 1]

As force of attraction = centrifugal force
kZe 2 mv 2
So, 
r2 r
kZe 2
v2  ...(i)
rm
According to one of the postulates,
h
Angular momentum  mvr  n
2
nh
or v ...(ii)
2mr
Putting the value of ‘v’ in eq. (i)
n 2h 2 kZe 2

4 2 m 2 r 2 mr
[ 74 ]
Atomic Structure
n 2h 2
or  kZe 2
4 2 mr
n 2h 2
or r ...(iii)
4 2 mkZe 2
n 2h 2
For hydrogen atom Z = 1, so, r 
4 2 mke 2
Now putting the values of h, p, m, e and k
r = 0.529 × 10–8 × n2 cm.
n2
and rn  0.529  Å for hydrogen like species.
Z
Velocity
We know
KZe 2
v2 = .....(i)
r.m
also we know
nh
v = 2r m .....(ii)
Dividing (i) by (ii) we get
v2 KZe 2 2   m
= .m . nh
v
2 KZe 2
v=
nh
2 Ke 2
v=
h
Z
v = 2.18 × 106 . m/sec.
n
Energy of an electron: Let the total energy of the electron be E. It is sum of kinetic energy and
potential energy.
E = kinetic energy + potential energy

1 kZe 2
 mv 2 
2 r
Putting the value of mv2 from eq. (i)
kZe 2 kZe 2 kZe 2

E  
2r r 2r
Putting the value of r from eq. (iii)
2 2 Z 2 k 2 me 4
E ...(iv)
n 2h 2
[ 75 ]
Atomic Structure
For hydrogen atom, Z = 1
2 2 k 2 me 4
so, E
n2h2
Putting the values of p, k, m, e and h
13.6
E  eV / atom
n2
313.6
E kcal/mole
n2
1313
E kJ / mole
n2
E1
En  for hydrogen atom
n2
Z2
and E n  E1  for hydrogen like species.
n2
Interpretation of hydrogen spectrum

P
The electron in the hydrogen atom O
resides in the first orbit. When energy N Pashcen
is supplied, the electron moves to series
M
higher energy shells depending on the L
amount of energy absorbed. When this Balmer K Brackett
series series
electron returns to any of the lower
energy level, it emits energy. Lyman
series is obtained when the electron Pfund
returns to the lowest energy state while series
Balmer series is obtained when the
electron returns to second energy shell. Lyman
series
Similarly, Pashcen, Brackett and Pfund
series are obtained when electron returns to the third, fourth and fifth energy shell from higher
energy shells respectively.
Maximum number of lines produced when an electron jumps from nth level to ground level. It is equal
n ( n  1)
to . If the electron comes back from energy level having energy E2 to energy level having
2
energy E1, then the difference may be expressed in terms of energy of photon as :
E2 – E1 = E = h
s or The frequency of the emitted photon is given by
E

h
[ 76 ]
Atomic Structure
Since, E can have only definite values depending on the energies of E2 and E1, v will have only fixed
values in an atom.
c E
or V  
 h
hc
or  
E
Since h and c are constants, E corresponds to definite energy, thus, each transition from one energy
level to another will produce a light of definite wavelength. This is actually observed as a line in the
spectrum of hydrogen atom.
Thus, the different spectral lines in the spectra of atoms correspond to different transitions of electrons
from higher energy levels to lower energy levels.
Let n1 and n2 be the two energy shells in hydrogen atom (n1 < n2).
2 2 me 4 k 2
Energy associated with n1 shell (E1)   n12 h 2
2 2 me 4 k 2
Energy associated with n2 shell (E2)  
n 22 h 2
2 2 me 4 k 2  2 2 me 4 k 2 
E 2  E1    
n 22 h 2  n12 h 2 
2 2 me 4 k 2  1 1
E  2  2
 2
h  n1 n 2 
c
E  hv  h.

c 2 2 me 4 k 2  1 1
h.   n2  n2 
 h2  1 2
1 2 me k  1
2 4 2 1
or   n2  n2 
 h 3c  1 2
1 1 1
   RH  2  2 
  n1 n2 
1 1
or   RH c  2  2 
 n1 n2 
where, RH is Rydberg constant for hydrogen. Its value is 109, 679 cm–1. (RH = 1.098 × 107 m–1) for
H like atoms (Li2+, He+, etc.)
1 1
v  Z 2 RH  1  2 
 n1 n2 
1 1
v  Z 2 RH c  1  2 
 n1 n2 
[ 77 ]
Atomic Structure
The following points support Bohr’s theory:
(i) The frequencies of the spectral lines calculated from Bohr’s equation are in the agreement with
the frequencies observed experimentally in hydrogen spectrum.
(ii) The value of Rydberg constant calculated from Bohr’s equation tallies with the determined
experimentally.
(iii) The spectra of hydrogen like species such as
He+, Li+2, Be3+, can be explained with the help of Bohr’s theory.
Limitations of Bohr’s theory

(i) It does not explain the spectra of multi-electron species (due to inter electronic repulsion)
(ii) When a high resolving power spectroscope is used, it is observed that a spectral line in the
hydrogen spectrum is a collection of several lines which are very close to one another. Bohr’s
theory does not explain the fine spectra of even hydrogen atom.
(iii) It does not explain the splitting of spectral lines into a group of lines under the influence of
magnetic field (Zeeman effect) and electric field (Stark effect).
(iv) It is not in agreement with Heisenberg’s uncertainty principle.
Photoelectric Effect: The emission of electrons from the surface of a metal when illuminated by
electromagnetic radiation of suitable wavelength of frequency is called photoelectric effect. For a
given material, there exists a minimum frequency or incident radiation which emits photoelectrons. If
the frequency is less than that no electron can be emitted from the metal surface, no matter how
intense the radiation may be. This minimum value of frequency is called threshold frequency. The
energy of the photoelectrons is proportional to the frequency of the incident radiation and the number
of photoelectrons emitted per second is proportional to the intensity of the incident radiation.
Accepting to Planck’s idea that radiation consists of photons, Einstein suggest that photon’s energy
is used in two ways:
(i) A part of energy is used to free the electron from the atom. This energy is known as photoelectric
work function. This is denoted by .
(ii) Rest of the energy is used in giving kinetic energy to the electron. Thus, energy of the photon,
hv    12 mv2 ...(i)
where, v is the velocity of the emitted electron .

When photon’s energy is equal to  the kinetic energy becomes zero. Under this condition, eq. (i)
reduces to
hv0 = 
where, v0 is the threshold frequency, from eq. (i)
1
2 mv2  hv 
Putting the value of 0,
[ 78 ]
Atomic Structure
1 mv 2  hv  hv 0
2
1 mv 2  h (v  v0 )
2
For a definite metal, the value of hv0 is constant
So, 1 mv 2  hv
2
or v2  v
Thus, increase of frequency of the incident radiation causes an increase in the velocity of electron
provided intensity of incident light is constant.
Wave nature of electrons (deBroglie’s hypothesis): de-Broglie proposed that electrons like
light, behaves both as material particle and as a wave.
de-Broglie derived an expression for calculating the wavelength of the wave associated with the
electron. According to Planck’s equation
c
E  h  h. .....(i)

The energy of a photon on the basis of Einstein’s mass energy relationship is
E = mc2 .....(ii)
where c is the velocity of electron
Equating both the equations
c
h.  mc 2

h
or  .....(iii)
mc
The wavelength decreases if the value of mass (m) increases, de-Broglie equation is applicable in
the case of smaller particles like electron and has no significance for large particles.

Problem 1: Bohr’s theory is not applicable to:
(a) Be2+ (b) H
(c) He + (d) Li2+
Solution: (a) Bohr’s theory is applicable only to hydrogen and H-like species.
Problem 2: n1 for Balmer series of hydrogen spectrum where e– falls is:

(a) 3 (b) 2
(c) 4 (d) 1
Solution: (b) For Balmer series n1 = 2, n2 > 2
Problem 3: Radius of Bohr’s orbit of H-atom is

(a) 0.53Å (b) 0.26Å
(c) 1.25Å (d) 2.57Å
n2
Solution: (a) rn  0.53 
Z
[ 79 ]
Atomic Structure
Problem 4: Which of the following transitions in the H-atom will emit most energetic photon as per
Bohr’s theory.
(a) n = 5 to n = 3 (b) n = 6 to n = 5
(c) n = 2 to n = 1 (d) n = 6 to n = 1
Solution: (d) Difference of energy is maximum between orbit 6 and 1
Problem 5: The number of spectral lines observed when an electron falls from n = 5 to n = 1 in visible
region is
(a) 5 (b) 3
(c) 2 (d) 4
Solution: (b) 5  2, 4  2, 3  2 (3 lines)
Problem 6: The energy of the 3rd orbit of H-atom is

(a) –0.342 × 10–19J (b) –0.726 × 10–18 J
(c) –2.18 × 10–18 J (d) –2.42 × 10–19 J
Solution: (d) E n  R H  Z2 / n 2
Problem 7: The K.E. of photoelectrons depends upon:

(a) Intensity of incident rays (b) Frequency of incident rays
(c) Number of photons striking (d) Number of photoelectrons ejected
Solution: (b) Factual
Problem 8: The work function () of a metal having threshold frequency (0) 5.2 × 1014 s–1 is:
(a) 2.19 × 10–10 J (b) 1.23 × 10–22 J
(c) 3.44 × 10–19 J (d) 7.64 × 10–15 J
Solution: (c) Work function () = h0
Problem 9: The ratio of the radii of the three Bohr’s orbit is:
(a) 1 : 5 : 3 (b) 1 : 4 : 9
(c) 1 : 8 : 27 (d) 1 : 3 : 9
n2
Solution: (b) rn  0.529 
Z
Problem 10: A certain metal irradiated to light of frequency 3.2 × 1016 Hz emits photoelectrons with
twice K.E. as did photoelectrons when the same metal is irradiated by light of frequency
2 × 1016 Hz. The threshold frequency of metal is
(a) 1.2 × 1016 Hz (b) 4 × 1015 Hz
(c) 8 × 1015 Hz (d) 9 × 1014 Hz
Solution: (c) Threshold frequency (0) = h0
[ 80 ]
Atomic Structure
3.3 Bohr’s theory versus de-Broglie Equation

One of the postulates of Bohr’s theory is that angular momentum of an electron is an integral
h
multiple of . This postulate can be derived with the help of de-Broglie concept of wave nature of
2
electron.
Consider an electron moving in a circular orbit around nucleus. The wave would be associated with
the circular orbit. If the two ends of the electron wave meet to give regular series of crests and
troughs, the electron wave is said to be in phase, i.e., the circumference of Bohr’s orbit is equal to
whole number multiple of the wavelength of the electron wave.
so, 2r = n
2r
or  .....(i)
n
From de-Broglie Equation (In phase) (Out of phase)
h
 .....(ii)
mv
h 2r
Thus, 
mv n
h
or mvr  n. [v = velocity of electron and r = Radius of the orbit]
2
h
i.e., Angular momentum  n. ...(iii)
2
This proves that de-Broglie and Bohr-concepts are in perfect agreement with each other.
Heisenberg Uncertainty Principle: Werner Heisenberg presented a principle known as

Heisenberg uncertainty principle which states: “It is impossible to measure simultaneously the
exact position and exact momentum of a body as small as electron.”
The uncertainty of measurement in position, x, and the uncertainty of momentum, p or mv, are
related by Heisenberg’s relationship as
x.p  h/4
or x.mv  h/4 where, h is Planck’s constant.
For an electron of mass m (9.10 × 10–28 g), the product of uncertainty is quite large.
In the case of bigger particle (having a considerable mass), the value of the product of uncertainty is
negligible.
If the position is known quite accurately i.e., is very small, v becomes large and vice-versa. Thus,
uncertainty principle is important only in the case of smaller moving particles like electrons.
[ 81 ]
Atomic Structure
Quantum Numbers
The four quantum numbers are :
(i) Principal quantum number (ii) Azimuthal quantum number
(iii) Magnetic quantum number (iv) Spin quantum number
Each quantum number refers to a particular character of the electron in an atom. First three quantum
numbers have been deduced from Schrodinger wave equation.
Quantum or Wave mechanical model of atom: This new model of atom was put forward by
Schrodinger in 1920 by taking into account the de Broglie concept of dual nature of matter and
Heisenberg’s uncertainty principle. He described the motion of the electron in three dimensional
space in terms of a mathematical equation called Schrodinger wave equation viz.
 2  2  2 8 2 m
   (E – V)  = 0
x 2 y 2 z 2 h2
where  is the amplitude of the electron wave at a point with coordinates x, y, z, E = total energy and
V = potential energy of the electron y is also called wave function.  2 gives the probability of finding
the electron at (x, y, z). The acceptable solutions of the above equation for the energy E are called
eigen values and the corresponding wave function  are called eigen functions.
Schrodinger wave equation can be written as

 2 2  2  8 2 m
    
 x 2 y 2 z 2  (E – V)  = 0
  h2
2 8 2 m
or    (E – V) = 0
h2
2 2 2 2
where   2  2  2 is called Laplacian operator
x y z
The above equation can be rewritten as
8 2 m
 2  – (E – V) 
h2
 2 
 – h 2  V 
or  8 m
2  =E
 
or H = E
h2
where H  – 2
 2  V is called Hamiltonian operator..
8 m
In this operator, first term represents kinetic energy operator (T) and second term represents potential
energy operator (V). Hence Schrodinger wave equation can also be written as
(T + V)  = E 
[ 82 ]
Atomic Structure
Application of Schrodinger wave equation to hydrogen atom: For hydrogen atom, potential
e2
energy, V = – . Replacing mass m of the electron by reduced mass (µ) of hydrogen atom (1/µ)
r
= 1/me + 1/mp), Schrodinger wave equation for hydrogen atom is obtained. As µ = mp me /(mp + me)
and me << mp therefore, µ ~
 me. On solving of E, we get
2 2 me e 4
En = 
n2 h2
1 2 2 me e 4 me e 4
or in S.I. units. En = –   , where 0 is permittivity of vacuum.
(4 0 ) 2 n 2 h 2 8 20 n 2 h 2
Schrodinger wave equation in terms of

spherical polar co-ordinates: Putting x = r sin Z
 cos , y = r sin  sin , z = r cos , Schrodinger P(x, y, z) or (r, )

wave equation in terms of spherical polar co-
ordinates is obtained, i.e., it now consists of three r
variables, r,  and . Hence, the complete wave

function can be expressed in the form
X

(r, ) = R(r). O
H ().  ()
90°
R (r) which is a function of radical Y

H (q). ()
distance r is called O
which depends upon angle  and
 is called Angular wave
function.
Dependence of Radial and Angular wave functions on quantum numbers:
 n, l, m(r, ) = Rn, l (r). O

H l, m (). m ()
where n, l and m represent principal, azimuthal and magnetic quantum numbers respectively.
Plots of Radial Wave Function (R), Radial Probability Density (R2) and Radial Probability
Function (4  r2R2): The probability of funding the electron in a spherical shell of thickness dr at
a distance r from the nucleus is equal to the product of the volume of shell of thickness dr at distance
r from the nucleus (4 r2dr) and the radial probability density (R2) per unit volume, i.e., equal to
4r2 dr R2 = P dr where P = 4r2R2 is called radial probability function.
2p
1s 2s
R R
R
(a) NODE
+
r r – r
[ 83 ]
Atomic Structure
2p
1s NODE 2s
R2 R
2
R
2
(b)
r r r
14
12 2p
10 1s 5 5
2s
4r2R2
4r2R2
4r2R2
4 4
6 3 3
4 2 2
(c) 2 1 1 2.1 Å
2.7 Å
0 0 0
2 4 6 8 2 4 6 8 2 4 6 8
r(Å) r(Å) r(Å)
0.529 Å
In the plots of radial probability versus distance from the nucleus, number of peaks, i.e. region of
maximum probability = n – l, e.g., 2s has two peaks 3s will have 3 peaks, 2p has one peak, 3p has
two peaks and so on.
Note that the nodal surface of 2s orbital exists at a distance of 2a0 from the nucleus where a0 is the
Bohr radius, i.e., 0.529 Å.
H )|2: For any ns

H ) and angular probability density | O
Plots of angular wave function ( O
H  = (1/4)1/2 i.e., it is independent of angles  and . Hence, the plots of O
orbital, O H  as well as
H |2 are circular in two dimensions or spherical in three dimensions. The plots of O
|O H  for pz
orbital involves angle  while those for px and py orbitals involve both  and . Hence, in their case,
two tangent spheres are obtained.
Principle quantum number: It describes the average distance of the electron from the nucleus. It
is designated as ‘n’. The energy of the electron and the volume of the electron cloud are dependent
on this quantum number. Theoretically it may have all integral values from 1 to  but only values
from 1 to 7 have been established in the atoms of known elements so far,
Higher the value of ‘n’:
(i) Greater is the distance of the shell from nucleus,

(ii) Greater is the magnitude of energy.
The maximum number of electron which can be present in a principal energy shell is equal to 2n2.
No energy shell in the atoms of known elements possess more than 32 electrons.
Azimuthal quantum number : This quantum number is also called secondary or subsidiary quantum
number. It is designated by symbol ‘l’. It describes spatial distribution of electron cloud and the
angular momentum of the electron. It actually tells about the shape of orbital occupied by the electron.
For any given value of principal quantum number ‘n’, the azimuthal quantum number ‘l’ can have all
integral values from 0 to (n – 1). Each value corresponds to an energy sub-shell or sublevel. The total
number of sublevels in each principal shell is numerically equal to the value of ‘n’.
[ 84 ]
Atomic Structure
The sub shells are designated by the letters s, p, d and f.
l=0 s-sub-shell; l=2 d-sub-shell

l=1 p-sub-shell; l=3 f-sub-shell
s, p, d and f are spectral terms and signify sharp, principal, diffuse and fundamental respectively.
The energies of the various sub-shells in the same shell are in order of s < p < d < f. Sub-shells
having equal l values but with different n values have similar shapes but their sizes increase as the
value of ‘n’ increases.
Magnetic quantum number: This quantum number is designated by the symbol ‘m’. To explain
splitting of spectral line into a number of closely spaced lines in the presence of magnetic field
(Zeeman effect), electron producing a single line has several possible space orientations for the
same angular momentum vector in a magnetic field, i.e., under the influence of magnetic field each
sub-shell is further sub-divided into orbitals. Magnetic quantum number describes the orientation or
distribution of electron cloud. For each value of ‘l’, the magnetic quantum number ‘m’ may assume
2l + 1 values ranging from –l to +l including zero. Each value of “m” represent on ORBITAL, which
contains maximum of two elements, with opposite spins, m for pz is zero.
Characteristics of orbitals
(i) All orbitals of the same shell in the absence of magnetic field possess same energy, i.e., they are
degenerate.
(ii) All orbitals of the same sub-shell differ in the direction of their space orientation.
(iii) Total number of orbitals in a main energy shell is equal to n2.
Spin quantum number: When spectral lines were observed by instruments of high resolving power,
each line was found consisting of a pair of lines. To account for these doublets, it was suggested that
electron while moving around the nucleus in an orbit, is also spinning about its own axis either in
clockwise or in anti-clockwise direction. There are two possible values either. These spins are also
shown by arrows; upwards () or downwards ().
Spin  12 clockwise
Spin  12 ¯ anti-clockwise
The electrons with the same sign of spin quantum numbers are said to have parallel spins while those
having opposite signs of spin quantum numbers are said to have opposite spins or paired up spins.
N Magnetic field S
+1/2 –1/2
S N
[ 85 ]
Atomic Structure
Since, a spinning charge is associated with a magnetic field, an electron must have a magnetic
moment associated with it.
Pauli’s Exclusion Principle: The principle states that no two electrons in an atom can have
the same set of all the four quantum numbers. In other words, an orbital cannot have more than
two electrons.
Conclusion :
(i) The maximum capacity of a main energy shell is equal to 2n2 electrons.
(ii) The maximum capacity of a sub-shell is equal to 2(2l + 1) electrons.
(iii) Number of sub-shells in a main energy shell is equal to the value of n.
(iv) Number of orbitals in a main energy shell is equal to n2.
(v) One orbital cannot have more than two electrons. If two electrons are present, their spins should
be in opposite directions.
Aufbau’s Principle: This principle gives us a sequence in which various sub-shells are filled with
electrons. The sequence in which various sub-shells are filled up depends on the relative order of the
energy of sub-shells. The sub-shell with minimum energy is filled up first and when this
attains maximum quota of electrons, then next sub-shell of higher energy starts filling.
The sequence in which the various sub-shells are filled is the following:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
1s 2s 3s 4s 5s 7s
2p 3p 4p 5p 7p
3d 4d 5d
4f
The sequence in which various sub-shells are filled up can also be determined with the help of (n +
1) value for a given sub-shell. The sub-shell with lowest (n + l) value is filled up first. When
two or more sub-shells have same (n + l) value, the sub-shell with lowest value of ‘n’ is
filled up first.
Hund’s Rule of Maximum Multiplicity (Orbital Diagrams): It states that electrons are
distributed among the orbitals of a sub-shell in such a way as to give the maximum number
of unpaired electrons with parallel spins. Thus, the orbitals available in a sub-shell are first filled
singly before they begin to pair. This means that pairing of electrons occurs with the introduction of
[ 86 ]
Atomic Structure
second electron in s-orbital, the fourth electron in p-orbitals, sixth electron in d-orbitals and eighth
electron in f-orbitals.
The rule is based on the fact that electrons being of the same charge repel each other and hence try
to keep farther apart from each other as much as possible. The electrons thus, occupy different
orbitals of the sub-shell as to minimise the inter-electronic repulsion and increase the stability of the
atom. Orbitals tend to become half filled or completely filled since such an arrangement will be more
stable on account of symmetry.
All those atoms which consist of at least one of the orbitals singly occupied behave as paramagnetic
materials because these are weakly attracted to a magnetic field, while all those atoms in which all
the orbitals are doubly occupied behave as diamagnetic materials because they have no attraction
for magnetic field. However, these are slightly repelled by magnetic field due to induction.

Problem 1: In which of the following orbitals, the sum of (n + l) value is lowest?
(a) 4s (b) 4p
(c) 5s (d) 3d
Solution: (a)
Problem 2: The maximum number of electrons that can be accommodated in d x 2  y 2 orbital is
(a) 5 (b) 2
(c) 1 (d) 3
Solution: (b) An orbital can accommodate only 2 electrons.
Problem 3: The maximum value of ‘m’ for a 3p orbital is

(a) +1 (b) +2
(c) +3 (d) +4
Solution: (a) For a p-orbital m = +1, 0, –1
Problem 4: The correct sequence of energy of orbitals in a multielectron species is:

(a) 4s < 4p < 3d (b) 4s < 3d < 4p
(c) 3d < 4s < 4p (d) 4p < 3d < 4s
Solution: (b) Use (n + l) to calculate the energy.
Problem 5: The number of electrons present in ‘L’ shell of phosphorus (Atomic number = 15) is
(a) 2 (b) 6
(c) 10 (d) 8
Solution: (d) K shell = 2 electrons

L shell = 8 electrons
M shell = 5 electrons
[ 87 ]
Atomic Structure
Problem 6: Which of the following ions contains maximum number of unpaired electrons?
(a) Fe2+ (b) Zn+
(c) Cu+ (d) Ti2+
Solution: (a) Write the electronic configuration of each ion.
Problem 7: In which of the following orbital the four lobes are present along the axis?
(a) d xy (b) d x 2  y 2
(C) d yz (d) d xz
Solution: (b)
Problem 8: The four quantum numbers of an electron present in valence shell of potassium atom are:
1 1
(a) 4,1,0, (b) 4,1,1,
2 2
1 1
(c) 4,0,0, (d) 4,0,1,
2 2
Solution: (c) Last electron of potassium is present in 4s orbital.
Problem 9: Maximum number of unpaired electrons present in a f-subshell is

(a) 3 (b) 5
(c) 9 (d) 7
Solution: (d) f-subshell has 7-orbitals.
Problem 10: Which of the following atom cannot have electrons in d-subshell?
(a) Si (b) Ca
(c) Cu (d) C
Solution: (d)
SOLVED EXAMPLES
Example 1 : Calculate the radius of the first Bohr orbit of a hydrogen atom. Given that h = 6.63 × 10–27 erg.
sec; m = 9 × 10–28 g and charge of an electron = 4.8 × 10 –10 esu.
Solution: We have, for hydrogen Z = 1, n = 1

h2
r1 
4 2 me 2
27 2
(6.63 10 )
 2 28 10 2
4  (3.14)  9  10  ( 4.8 10 )
= 0.53 × 10–8 cm = 0.53 Å.
Example 2 : Calculate the ionisation energy in eV of a hydrogen atom in the ground state.
Solution : Since ionisation energy is defined as the energy required to remove an electron from outermost
orbit of atom, we can mathematically say that since the hydrogen atom is in ground state,
[ 88 ]
Atomic Structure
ionisation energy will be the energy required to remove the electron from the first orbit to 
orbit (i.e., r1 to r).
Thus,
Ionisation energy = E – E1
= 0 – (2.18 × 10–11) erg.
We know that E1 = – 2.18 × 10–11 erg.
11
2.18  10
 Ionisation energy = 2.18 × 10 –11
erg.  12
 13.60 eV
1.602  10
Example 3 : Calculate the wavelength in angstrom of the photon that is emitted when an electron in Bohr
orbit n = 2 returns to the orbit n = 1 in the hydrogen atom. The ionisation potential of the
ground state of hydrogen atom is 2.17 × 10–11 erg per atom.
Solution : Since the hydrogen atom has only one orbit containing only one electron, the ionisation
potential of the ground state of the, hydrogen atom is the energy of the electron of the first
orbit, i.e.,
E1 = –2.17 × 10–11 erg.
E
Thus, E2  2
.....(Eqn. 5)
n
2.17  10 11
= – 2
(n = 2)
2
 Energy of the radiation emitted,
E = E2 – E1
2.17 1011
= 2
 (2.17 1011 )
2
= 1.627 × 10–11 erg
hc
We know E = h 

hc 11
Thus,  1.627 10

27 10
6.62  10  3  10 5
 11
 1.22  10 cm
1.627  10
= 1220Å (1 Å = 10–8 cm)
Example 4 : The vapour of Hg absorbs some electrons accelerated by a potential difference of 4.5 volt
as a result of which light is emitted. If the full energy of a single incident electron is supposed
to be converted into light emitted by single Hg atom, find the wave number (1/) of the light.
Solution: We know that electron volts = charge in coulombs × potential difference in volts
 Charge of an electron   Potential difference 

4.5 eV =   
 in coulomb   in volt 
= (1.6022 × 10–19) (4.5) joule
[ 89 ]
Atomic Structure
Now,
1 E
wave number = 
 h.c
19
(1.6022  10 ) (4.5)
= 34 8
(6.626  10 ) ( 2.998 10 )
= 3.63 × 106 metres–1.
Example 5 : 13.6 eV is needed for ionisation of a hydrogen atom. An electron in a hydrogen atom in its
ground state absorbs 1.50 times as much energy as the minimum required for it to escape
from the atom. What is the wavelength of the emitted electron? (me = 9.109 × 10–31 kg, e =
1.602 × 10–19 coulomb, h = 6.63 × 10–34 J.s.)
Solution : 1.5 times of 13.6 eV, i.e., 20.4 eV is absorbed by the hydrogen atom out of which 6.8 eV
(20.4 – 13.6) is converted to kinetic energy.
KE = 6.8 eV = 6.8 (1.602 × 10–19 coulomb) (1 volt) = 1.09 × 10–18 J
1 2
Now, KE  mv
2
KE 2(1.09 10 18 J)

or, v  2 
m (9.109 10 31 kg )
= 1.55 × 106 metres.
34
h 6.63 10
   = 37 6 = 4.70 × 10–10 meters.
mv (9.109 10 ) (1.55 10 )
[ 90 ]
Chapter - 4
CHEMICAL THERMODYNAMICS
Introduction
Thermodynamics, the branch of chemistry, is concerned with heat effects accompanying chemical reactions.
Much of this chapter deals with determining quantities of heat by measurements and by calculation. It is not
only important but necessary to know the interconvertibility of various forms of energy into one another and
their quantitative estimation during the course of a reaction. The concepts included here in deal with all such
problems and also answer a host of practical questions such as :
Why natural gas is a better fuel than coal?
What drives a chemical reaction, etc.
Given below are some basic terms used in mathematical formulations of various thermodynamic laws.
4.1 A] These are: System, Surroundings, Extensive and Intensive properties, thermodynamic processes,
Internal energy and work, etc.
1. System : That part of the universe which is used for thermodynamic considerations is
called system.
2. Surrounding : The remaining portion of the universe which is not used for thermodynamic
considerations is called surrounding.
3. Boundary : The imaginary line which separates the system from the surrounding is called
boundary.
4. Types of Systems :
(i) Open System : A system is said to be an open system if it can exchange both matter and
energy with the surroundings.
(ii) Closed System : If a system can exchange only energy with the surrounding but not
matter is called closed system.
(iii) Isolated System : If a system can neither exchange matter nor energy with the
surrounding is called an isolated system.
5. State of a System and State Variable
(i) The existence of a system under a given set of conditions is called state of a system.
(ii) The properties which change with change in the state of system are called state variables,
e.g., pressures, volume, and temperature, etc. The first and last state of a system are
called initial state and final state respectively.
6. State Function and Path Function : A physical quantity is said to be state function if its
value depends only upon the state of the system and does not depend upon the path by which
[ 137 ]
Chemical Thermodynamics
this state has been attained. For example, a person standing on the roof of a five storeyed
building has a fixed potential energy, irrespective of the fact whether he reached there by
stairs or by lift. Thus the potential energy of the person is a state function. On the other hand,
the work done by the legs of the person to reach the same height, is not same in the two
cases, i.e., whether he went by lift or by stairs. Hence, work is a ‘path function’.
Extensive And Intensive Properties: An extensive property of a system is that which depends
upon the amount of the substance or substances present in the system. e.g., mass, volume,
energy, etc.
An intensive property of a system is that which is independent of the amount of the substance
present in the system. e.g., temperature, pressure, density, velocity, etc.
Thermodynamic Processes: The operation by which a thermodynamic system changes from one
state to another is called a thermodynamic process.
(i) Isothermal process : A process in which although heat enters or leaves the system yet
temperature of the system is maintained constant throughout the process is called an isothermal
process. For an isothermal process, change in temperature (T) = 0.
(ii) Adiabatic process : A process during which no heat enters or leaves the system during any
step of the process is known as adiabatic process. For an adiabatic process, change in heat
(q) = 0 or q remain constant.
(iii) Isobaric process : A process during which pressure of the system remains constant throughout
the reaction is called isobaric process, i.e., P = 0.
(iv) Isochoric process : A process during which volume of the system remains constant throughout
the reaction is known as isochoric process, i.e., V = 0 .
(v) Cyclic process : A process during which system comes to its initial state through a number of
different processes is called a cyclic process. For a cyclic process, E = 0, H = 0.
Internal energy (E): The total energy stored in a substance by virtue of its chemical nature and
state is called internal energy, i.e., it is the sum of its translational, vibrational, rotational, chemical
bond energy, electronic energy, nuclear energy of constituent atoms and potential energy due to
interaction with neighbouring molecules. It is also called intrinsic energy.
E = Et + Er + Ev + Ee + En + EPE
Internal energy is a state property and its absolute value can’t be determined. However, change in
internal energy (difference between the internal energies of the products and that of reactants) can
be determined experimentally using a bomb calorimeter. Internal energy of a system depends upon
(a) the quantity of substance, (b) its chemical nature, and (c) temperature, pressure and volume.
(i) For a given system, E is directly proportional to its absolute temperature.
(ii) At constant volume, the quantity of heat supplied to a system (isochoric process) is equal to the
increase in its internal energy, i.e.
Qv = E
[ 138 ]
(iii) In the adiabatic expansion of a gas, it gets cooled because of decrease in internal energy.
(iv) In cyclic process the change in internal energy is zero (E = 0) since E is a state function.
(v) For exothermic reactions, sign of E is negative.
(vi) For endothermic reactions, sign of E is positive.
Work: Work is expressed as the product of two factors, i.e.
W = Intensity factor × Capacity factor
where, Intensity factor is a measure of force responsible for work and Capacity factor is a measure
of extent to which the work is done Thus,
(a) Mechanical work = Force × Displacement = F × d
(b) Expansion work = Pressure × Change in volume = P × V
Pressure - Volume Work
It is a kind of mechanical work. The expression for such a work may be dl

a
derived as follows
Consider a gas enclosed in a cylinder fitted with a weightless and frictionless

piston.
Suppose area of cross section of a cylinder = a sq cm.
Pressure on piston = P which is less than the internal pressure such that the gas expands.
Let dl be the distance covered by the piston when the gas expands. Work done is given by
dW = – Fdl.
= – Force × distance
 Force = Pressure × area
 dW = – P.a.dl
= – PdV.
Let the volume limits be V1 and V2. Hence, integrating the equation dW = –PdV
v2
 dW =  Pd v
v1
W = – PV
W = – P(V2 – V1)
 When expansion takes places
V2 > V1  W = –ve
Hence work is done by the system
 When compression of gas takes place then V2 < V1, W = +ve. Hence work is done on the
system.
[ 139 ]
Work Done During Isothermal Reversible Expansion of an Ideal Gas.
we know that,
v2
 Pdv
dW = – PdV  dW = v
1
For an ideal gas PV = nRT,
nRT
P 
V
v2
nRT
 W  dV
v1
V
v2
dV
 W  nRT 
v1
V
V2
W  2.303nRT log
V1
Also,
P1
 W  2.303nRTlog P
2
P
W  2.303nRT log 2
P1
(i) Work is not a state function because amount of work performed depends upon the path followed.
(ii) Positive value of work signifies that the work has been done on the system by the surroundings
and it leads to an increase in the internal energy of the system. On the other hand, negative value
of work indicates that work has been done by the system and it leads to decrease in the internal
energy of the system.
4.2 B] Laws of Thermodynamics, Enthalpy and Heat Capacity

. Zeroth Law: It states that “Two system in thermal equilibrium separately with the third system
are said to be in thermal equilibrium with each other”, i.e., If system A and B separately are in
thermal equilibrium with another system, then system A and B are also in thermal equilibrium.
. Ist Law of Thermodynamics: The first law of thermodynamics states that “Energy can neither
be created nor destroyed.
It can be converted from one form to another”:
Let a system be at state I with internal energy E1,
Let it be changed to state-II with internal energy E2,
This can be achieved in the ways:
(i) By heat transfer
(ii) By doing work (either on system or by system)
[ 140 ]
Let the heat change taking place during the change of state of system from state-I to state-II
be ‘q’ and work done be W.
Then according to I law of thermodynamics.
E2 = E1 + q + W
E2–E1 = q + W
E = q + W (If it is work of expansion)
Then, E = q – PV or q = E + PV. Note that the internal energy, E of an ideal gas is a
function of temperature. Hence, for an ideal gas undergoing an isothermal change E = 0. Then
q = – W, i.e., heat absorbed by the system is equal to workdone by the system.
(a) Adiabatic process (compression)
(i) E = W.  E = + PV
(ii) Adiabatic (expansion)
E = –W  E = – PV
Enthalpy (Important features): Internal energy changes are usually measured at constant
volume. But in actual practice, most of the processes are carried out at constant pressure rather
than at constant volume. Hence volume changes which occur cause changes in internal energy.
To account for these changes, a new thermodynamic property called as Enthalpy is introduced.
It is defined as sum of internal energy and product of pressure volume work.
It is denoted by the letter H.
H = E + PV.
Characteristics:
(a) It is a state functions.
(b) It is an extensive property.
Let a system at state-I be transformed to state-II at constant pressure condition.
State - I State - II
Enthalpy H1 H2
Internal energy E1 E2
Pressure P P
Volume V1 V2
H1 = E1 + PV1
H2 = E2 + PV2
H2 – H1 = H = (E2 + PV2) – (E1 + PV1)

= (E2 – E1) + P (V2 – V1)
ΔH  ΔE  PΔV
[ 141 ]
Also for an ideal gas PV = nRT
 PV1 = n1 RT and PV2 = n2RT
 P(V2  V1 )  Δn g RT
Where, ng = n2 – n1 = difference between the number of moles of gaseous products and of
gaseous reactants.
When ng = 0  H = E
When ng > 1  H > E
When ng < 1  H < E
Also we can write H = E + PV
or qP = qv + PV
Heat Capacity: It is the amount of heat required to raise the temperature of a system
through 1ºC. Also called as Heat capacity of the system. For one mole of a substance it is called
molar heat capacity. It’s for one gram of substance we call it heat capacity or
specific heat.
If ‘q’ is the amount of heat supplied to a system and as a result let the temperature rise from
T1 to T2 ºC.
Then,
q q
Heat capacity = C = T  T  T
2 1
When heat capacity varies with temperature then the value of C has to be considered over a
very narrow range of temperature.
q
Then, C =
dT
Thus, the quantity of heat capacity (q) required to change the temperature of a substance
depends on:
 How much temperature is to be changed
 Quantity of substance
 Nature of the substance
So q = m × specific heat × T
Molar Heat Capacity at Constant Volume

It is the amount of heat required to raise the temperature of 1 gm of a gas through 1º C at constant
volume.
[ 142 ]
Molar heat capacity : It is the amount of heat required to raise the temperature of one mole of a gas
through 1º C.
 dE   E 
 Cv    =  T 
 dT  V   V
or dE  C v dT
This is also a mathematical expression for the first law of thermodynamics at constant volume.
Similarly heat capacity at constant pressure.
 H 
CP =  T  or ΔH  C p dT. This is an expression of first law at constant pressure.
 P
Cp
Also, C p  C v  R and r
Cv
Calculation of w, E, H, for Isothermal Expansion of Ideal Gas
(A) (i) For an ideal gas E depends on temperature. Since temperature is constant, i.e., T = 0
E = 0.
(ii) According to I law.

dE = dq + dw
since dE = 0
 dq = – dw
 q = – w.
 Heat absorbed is equal to work done by the system during isothermal expansion of
ideal gas
(iii) Enthalpy change

H = E + PV
 H = E + PV
= E + (nRT)
H = E + nRT (T = 0, process is isothermal)
H = 0 + 0
Hence, H = 0
(B) Adiabatic Reversible Expansion of Ideal Gas
(a) Calculation of E
E = f (T, V)
 E   E 
dE =  T   T    T dV .
 V  V 
 E 
But  T = 0
 V 
 E 
 dE =  T  dT or dE  C vdT
 V
[ 143 ]
Also, dE = n CvdT for n moles

But q = 0
 E = – w = Cv (T2 – T1) [Because expansion of gas takes place]
or, w = –Cv (T2–T1)
or, w = –n Cv (T2–T1) = –nCvT (for n moles)
SAMPLE PROBLEMS 4.1 and 4.2 (MCQ)

Keep the following points in mind :
 Any energy enterring the system carries a positive sign. Thus, if heat is absorbed by the system, q > 0.
If work is done on the system w > 0.
 Any energy leaving the system carries a negative sign. Thus, if heat is given off by the system q < 0. If
work is done by the system w < 0.
 In general internal energy of a system changes as a result of energy entering or leaving the system as
heat or work. If more energy enters the system than leaves E is positive. If more energy leaves than
enters E is negative.
Problem 1: How much heat is required to raise the temperature of 7.35 g of water from 210. to 98.0ºC.
[Sp heat of water = 4.18 Jg-1ºC-1].
Solution: The heat needed to change the Tr. of 7.35 g of water is = 7.35 times as great as needed to
change the Tr. of 1 g of water. Heat required to change the Tr. by 77.0ºC is 77 times as
great as that needed to raise the Tr. by 1ºC.
So, ? J = 7.35  (98 - 21.0)= 2.37  103J. Answer
Problem 2: Which of the following is an extensive property?

(a) Enthalpy (b) Concentration
(c) Density (d) Viscosity
Solution: (a) Enthalpy depends on the quantity of substance.
Problem 3: Which one of the following is a state function?

(a) Heat (b) Work
(c) Internal energy (d) Potential energy
Solution: (c) Internal energy change does not depend on the path followed during the process.
Problem 4 : A gas while expanding absorbs 25 J of heat and does 243 J of work. What is E
for the gas?
(a) +218 J (b) - 218 J
(c) +268 J (d) - 268 J
Solution: (b) Key to problems of this type lies in assigning the correct signs to the quantities of heat
and work. Since heat is absorbed q is +ve. Work is done by the system represents
energy leaving the system. So w is negative.
Therefore E = (+25 J) + (- 243 J) = -218 J
[ 144 ]
Problem 5: Temperature of an ideal gas increases in :

(a) Adiabatic expansion (b) Adiabatic compression
(c) Isothermal expansion (d) Isobaric expansion
Solution: (b) In adiabatic compression work is done on the system. Internal energy and temperature
increase (b).
Problem 6 : A liquid is stirred in thermally insulated container for 2h. Which of the following is correct?
(a) w > 0, q = 0, U>0 (b) w < 0, q = 0, U = 0
(c) w > 0, q > 0, U=0 (d) w < 0, q < 0, U = 0
Solution: (a) Work is done on the system. Internal energy will increases.
Problem 7: Two moles of an ideal gas are expanded isothermally and reversibly from 1 litre to 10 litres
at 300 K. Enthalpy change (H) for the process is
(a) 11.4 KJ (b) - 11.4 KJ
(c) 0 KJ (d) 4.8 KJ
Solution: (c) H = nCpT. Since T = 0, H is also = zero.
Problem 8: Work done when 1.0 mol of water at 373 k vaporises against an atmospheric pressure of
1.0 atm. (Assume ideal gas behaviour).
(a) + 310.0 (b) - 310.0
(c) + 314.03 (d) - 314.03
Solution: (d) Volume occupied by water is neglected in comparision to vapour. Now volume V
1.0  0.0821  373

occupied by 1 gm mol of water vapour =  31.0L
1.0
Work done = Pext  V   1   3.10  Latm.

or w = -3.10  101.3J=-314.03 J
Example 9 : An ideal gas (consider H2) whose weight was 10.0g undergoes a reversible reduction in
pressure from 20 to 1.0 atm. at a constant Tr. of 273 K. The value of E and q are :
[Take R = 2 cal K-1 mol-1]
(a) 810 and 242 cal (b) - 810 and -242 cal
(c) zero and -248 cal (d) zero and -8180 cal
Solution: (d) Tr. constant so E=0

10 20
w  2.303   2  273 log  8180 cal
2 1
q  E  w  0  8180  8180 cal
Problem 10 : In the given P-V diagram an ideal gas is taken around in the cycle ABCA. Network done
by the gas during the cycle is :
(a) 12P1V1 (b) 6 P1V1
(c) 3 P1V1 (d) P1V1
[ 145 ]
B
4P1
P
C
P1 A
V1 3V1
V
1
Solution: (c) w   4P1  P1  3V1  V1   3P1V1  Area of  ABC.
2
Example 11: For the reaction N 2  g   3H 2  g   2NH 3  g  which of the following is correct?
(a) H=E (b) 
(c) H < E (d) H = E
Solution: (c) ΔH  ΔE  ΔnRT Now Δn  2

So, ΔH  ΔE  2RT or ΔE  ΔH  2RT
ΔE  ΔH
Example 12: Magnitude of enthalpy change for reversible adiabatic expansion of a gas from volume
V1 to V2 (in L) is H1 and for irreverisible adiabatic expansion for the same expansion is
H2. Then,
(a) H1  H 2 (b) H1  H 2
(c) H1  H 2 (d) H1  U1 and H 2  U 2
Where U1 and U 2 are the changes in magnitude for internal energy of gas in the two
expansions.
Solution : (a) The work done in a reversible expansion process is always greater than in an irreversible
expansion process. From Ist law q = 0 = U + (- w). So decrease in U will be larger
in Rev, Adiabatic, and less in irrev, adiabatic change.
4.3 Thermochemistry and Kirchoff’s Equation

Thermochemistry
Thermochemistry is the branch of chemistry which deals with the heat changes accompanying a
chemical reaction.
Thermochemical equations : A chemical reaction which tells about the amount of heat evolved or
absorbed during the reaction is called a thermochemical equation. A complete thermochemical equation
supplies the following informations.
(i) It tells about the physical state of the reactants and products. This is done by inserting symbols
(s), (l) and (g) for solid, liquid and gaseous state respectively with the chemical formulae.
(ii) The aqueous solution of the substance is indicated by the word aq.
[ 146 ]
(iii) It tells whether a reaction proceeds with the evolution of heat or with the absorption of heat,
i.e. heat change involved in the system. Heat changes of the system, heat of reactants and
products are represented by H, HR and HP respectively. Mathematically,
H = HP – HR
For exothermic reactions, HR > HP or H (enthalpy change) is negative
For endothermic reactions, Hp > HR or H (enthalpy change) is positive
Heat of Reactions
Heat of reaction is defined as the amount of heat evolved or absorbed (i.e., the change in enthalpy)
when quantities of the substances indicated by the chemical equation have completely reacted. For
example,
C(s) + 2S   CS2 (l), H = 22.0 kcal

 2NH3 (g), H = – 22 kcal
N2(g) + 3H2 (g) 
Heat of reaction at constant volume (qv) is equal to change in internal energy (E), i.e.,
qv = E
while heat of reaction at constant pressure (qp) is equal to change in enthalpy (H), i.e.,
qP = H
Relation between H and E:

ΔH  ΔE  PΔV ΔH  ΔE  Δn g RT
where, n(g) = Number of moles of gaseous products – number of moles of gaseous reactants
Thus, if n(g) = 0, H = E ;n(g) > 1, H > E ; n(g) < 1, H < E
For reactions involving only solids and liquids H = E.
Factors affecting heat of reaction : Among the various factors affecting heat of reaction, viz.
amount of reactants, physical state of reactants and products, pressure and temperature, temperature
is most important. The variation of heat of reaction with temperature is given by
Kirchoff’s equations:
(i) For heat of reactions at constant pressure
H2 – H1 = CP (T2 – T1)
(ii) For heat of reactions at constant volume
E2 – E1 = Cv (T2 – T1)
where,
H2 = Heat of reaction at temperature T2 at constant pressure

H1 = Heat of reaction at temperature T1 at constant pressure
E2 = Heat of reaction at temperature T2 at constant volume
E1 = Heat of reaction at temperature T1 at constant volume
Cp = Difference of heat capacities of products and reactants at constant pressure
Cv = Difference of heat capacities of products and reactants at constant volume.
[ 147 ]
Various Types of Reactions

(i) Enthalpy 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 Hf.
Normally the temperature and pressure are chosen as 25ºC and 1 atmospheric pressure. This is
called standard state. The heat of formation under these conditions is called standard heat of
formation which may be defined as the heat change accompanying the formation of 1 mole of
the substance in the standard state from its elements also taken in the standard state (i.e. 25ºC
and 1 atmospheric pressure).
C (s) + O2 (g)  CO2 (g); Hf = – 94 kcal
H2 (g) + 1/2 O2 (g)  H2O (l) ; Hf = – 68 kcal
It is important to note that,
(a) Since, the enthalpy of the elements in the natural state is zero, the standard heat of
formation (heat of formation at 1 atmospheric pressure and 25ºC) of a substance will be the
same as its enthalpy.
(b) Higher the negative value of enthalpy of formation, greater is the stability of the compound.
(ii) Heat of combustion : It is the amount of heat evolved (i.e., change in enthalpy) when one
mole of the substance is completely burnt in air or oxygen. For example,
CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l) ; H = –192 kcal
C2H6 (g) + 3.5 O2 (g)  2CO2 (g) + 3H2O (l); H = – 372.8 kcal
(Heat of combustion is always negative.)
(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.,
HCl (aq.) + NaOH (aq.)  NaCl (aq.) + H2O; H = – 13.7 kcal
It has been observed that the heat of neutralisation of a strong acid against a strong
base is always constant (13.7 kcal or 57 kJ mole–1). 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–  H2O; H = – 13.7 kcal
In case of neutralisation of a weak acid or a weak base against a strong base or acid
respectively, a part of the evolved heat is used up in ionising the weak acid or base and so the
value is always less than 13.7 kcal mole–1 (57 kJ mole–1). For example, heat of neutralisation
of HCN (a weak acid) and NaOH (a strong alkali) is – 2.9 kcal because 10.8 kcal of heat is
absorbed for the ionisation of HCN (i.e., the heat of dissociation or ionisation of HCN
is 10.8 kcal).
[ 148 ]
HCN (aq.) + NaOH (aq.)  NaCN (aq.) + H2O; H = – 2.9 kcal
HCN (aq.) H+ + CN– ; H = 10.8 kcal
(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,
NH4Cl(s) + H2O (l)  NH4Cl(aq.) ; H = + 3.90 kcal
BaCl2 (s) + H2O(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 one mole of an anhydrous salt combines with the required number of moles of water
to form a specific hydrate. For example,
CuSO4 (s) + 5H2O (l)  CuSO4 . 5H2O (s); H = – 18.69 kcal
Laws of Thermochemistry
1. Lavoisier 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’, e.g.
C(s) + O2 (g)  CO2 (g); H = – 94.3 kcal
CO2 (g)  C(s) + O2 (g); H = +94.3 kcal
2. Hess’s law of constant heat summation : The law states that the total heat change (H)
accompanying a chemical reaction is the same whether the reaction takes place in one or more
steps. It means that the heat of a reaction depends only on the initial reactant and final products
and not on intermediate products that may be formed.
Hess’s law has been tested experimentally and found to be true. For example, carbon can be
converted into carbon dioxide either directly or via the formation of carbon monoxide. The heat
change involved in both the process are indicated below :
Formation of CO2 directly :
1. C(s) + O2(g)  CO2(g) Here, Hº (CO2) = –94 kcal
1
2. C(s) + O (g)  CO(g) Here, Hºf (CO) = –26.4 kcal
2 2
1
3. CO(g) + O (g)  CO2(g) H3 = –67.6 kcal
2 2
Now, equation (1) = equation (2) + equation (3)

Hf(CO2) = Hºf (CO) + H3
–94 = –26.4 + (–67.6)
–94 = –94
Hence, Hess’s Law is followed
[ 149 ]
Bond Energy: When a bond is formed between two free atoms in a gaseous state to form a
molecular product in a gaseous state, some heat is always evolved which is known as the bond
formation energy or the bond energy. The bond energy may be referred to as heat of formation of
the bond.
Alternatively, bond energy may be defined as the average amount of energy required to dissociate
(i.e., break bonds) of that type present in one molecule of the compound. Thus, bond energy of C–H
in methane (CH4) is the average value of the dissociation energies of the four C–H bonds.
Bond energy data used for formation  Bond energy data used for dissociati on 
Hreaction = of bond (to be taken as ve)  + of bond (to be taken as ve) 
   
HReaction = BE(R) – B.E(P) taking Bond Energies as +ve values.
Important features about Thermochemical Calculations

1. The co-efficients of various substances involved in chemical equation represent their respective
moles.
2. The value of H in a thermochemical equation represent the enthalpy change for the specified
number of mole of reactants and products involved in reaction.
3. If the co-efficients involved in equation are multiplied or divided by some integer then H value
is also multiplied or divided by same integer.
4. When an equation is reversed the sign of corresponding H is also reversed.
Probem 1: H f for CO 2  g   393.5 KJ mol1 ; CO  g   110.5 KJ mol1 ;

H 2 O  g   241.8 KJ mol 1.
Standard enthalpy change for the reaction CO2  g   H 2  g   CO  g   H 2 O  g  in KJ is

(a) 524.1 (b) 41.2
(c) - 262.5 (d) - 41.2
Solution: H  Hf  CO   H f  H 2 O   H f  CO 2 
  110.5    241.8   393.5   41.2 KJ.
Problem 2: One mole of soda ash dissolves in water with evaluation of 25 KJ of heat. Dissolution of 1
mole of hydrated crystals in water result in absorption of 67 KJ of heat. Heat of hydration
of soda ash is :
(a) + 92 KJ (b) + 42 KJ
(c) - 42 KJ (d) - 92 KJ
Solution: According to Hess’s law H so ln .  Anhydrous salt)   H Hydr.  H So ln .  Hydrated salt 

So, H Hydr.   25    67   92KJ
[ 150 ]
Problem 3: The value of H soln. of anhydrous CuSO 4 is - 66.11 KJ. Dissolution of 1 mole of blue vitriol
[Copper (II) Sulphate pentahydrate] is followed by absorption of 11.5 KJ of heat. The heat
of dehydration of Blue vitriol is
(a) - 77.61 KJ (b) + 77.61 KJ
(c) - 54.61 KJ (d) + 54.61 KJ
Solution: H Hydr.  CuSO 4  

 CuSO 4 .5H 2 O
= (- 66.11) - (+ 11.5) = - 77.61 KJ
So, H dehydr.  77.61 KJ
Problem 4: The heat produced by the neutralisation of 100 ml HNO3 with - KOH solution is 1.713 KJ.
Molarity of HNO3 solution is
(a) 0.1 (b) 1.0
(c) 0.3 (d) 0.5
Solution: Let molarity of HNO3 be M. Then moles of HNO3 = 100  103  M  0.1M
Heat produced by 0.1 mole of HNO3 = 1.713 KJ
1.713
Heat produced by 1.0 mole of HNO3 =  57.1 since both acid base are strong.
0.1M
1.713
M  molarity    0.3
0.1 57.1
Problem 5: Use the following data to calculate the heat of formation of acetic acid.
(i) CH3COOH  l   202  g   2CO2  g   2H 2O  l  Hº  200.00 Kcal
(ii) C  s   O 2  g   CO 2  g  Hº  94.4 K cal
1
(iii) H 2  g   O 2 (g)  H 2 O  l  Hº  68.0 K cal
2
(a) –124.0 kcal (b) +124.0 kcal
(c) –63.0 kcal (d) +63.0 kcal
Solution: The required equation is :

2C  s   2H 2  g   O 2  g   CH 3COOH  l  H ? This can be obtained by multiplying
(b) and (c) by 2, than add them and subtract (a). We get
2C  2O 2  2H 2  O2  CH 3COOH  l   2O 2  2CO 2  2H 2 O  2CO 2  2H 2O

Or, H CH3 cOOH   2  94    2  68    200 
= - 124.0 K cal
Problem 6: Bond energy for C-H bond is 400 KJ and C – Cl bond is 320 KJ H of the reaction :
CH 2 Cl 2  g   C  s   2H  g   2Cl  g  is
(a) - 1440 KJ (b) + 1440 KJ
(c) - 720 KJ (d) + 720 KJ
Solution: Hº = sum of B.E. of reactants - sum of B.E. of products.

= [2  C – H + 2 (C - Cl) - O]
= [2 ] = 1440 KJ
[ 151 ]
Problem 7: Following are some combustion reactions.

1
(i) H 2  g   O 2  g   H 2 O H1  241 KJ mol1
2
17 1
(ii) C6 H10  O2  6CO 2  5H 2 O H 2  3800 KJ mol
2
(iii) C6 H12  902  6CO2  6H2O H3  3920 KJ mol1
Enthalphy of hydrogenation of cyclohexene is
(a) + 121 KJ mol1 (b) - 121 KJ mol1
(c) + 242 KJ mol1 (d) - 242 KJ mol1
Solution: We need C6 H10  H2  C6H12 , H  ?

For this add (i) + (ii) and Subtact (iii) i.e.,  H1  H 2   H 3  121 KJ mol 1
Problem 8: The standard molar heat of formation of ethane, carbondioxide, and H 2 O  l  are
– 21.1, – 94.1 and –68.3 K cal. Standard molar heat of combustion of ethane is
(a) - 372 K cal (b) - 240 K cal
(c) + 162 K cal (d) + 183.5 K cal
7
Solution: C2 H 6  g   O2  g   2CO 2  g   3H 2 O  l 
2
H Comb.  2  94.1  3  68.3   21.1  372 K cal
Problem .9: The enthalpies of atomisation of CH 4  g  and C 2 H 6  g  are respecitvely 400 KJ mol1 and
670 KJ mol–1. The value of H C  C is :
(a) 270 KJ mol1 (b) 70 KJ mol1
(c) 200 KJ mol1 (d) 240 KJ mol1
Solution: CH 4  g   C  g   4H  g  H  400KJ So,  C  H  100 KJ mol 1

CH3  CH 3  g   2C  g   6H  g  H  670 KJ
670 KJ  H C  C  H C  H
= H C C  6  100 or H C C  70 KJ mol1
Problem 10: XY, X2 and Y2 are diatomic molecules. H X  X , H Y  Y and H X  Y are in the ratio of
2 : 1 : 2 and enthalpy of formation of XY from X2 and Y2 is, - 100 KJ mol1 . The value of
H X  X in KJ mol1 is :
(a) 200 (b) 400
(c) 250 (d) 500
1 1
Solution: X 2  Y2  X  Y H  100 KJ mol1
2 2
1 1
or - 100 KJ = H X X  H Y Y  H X  Y
2 2
Let H Y  Y be  a
1 1
 - 100 KJ = 2a  a  2a or a = 200 KJ
2 2
So, H X  X  2  200  400 KJ mol1
[ 152 ]
Problem 11: Vapour pressures of Benzene at 300 K and 330 K are r espectively
0.13  105 Nm 2 and 0.52  105 Nm 2 . The approximate value of  H vap of benzene is
(log 4 = 0.6020):
(a) 40.02 KJ (b) 50.4 KJ
(c) 20.03 KJ (d) 38.03 KJ
Solution: Use clapeyron’s eqn.

2.303RT1T2 P 2.303  8.314  300  330 0.52  105
H V  log 2  log
T2  T1 P1  330  300  0.13  105
= 38037.7 J or 38.03 KJ
4.4 Spontaneity, Entropy and Second Law of Thermodynamics, Gibbs Free

Energy and Equilibrium
Limitations of First Law of Thermodynamics: Though the first law of thermodynamics gives us
the equivalence of heat and work, whenever there is a change of heat into work or vice versa, but it
suffers from the following limitations :
(i) No indication is available as regards the direction in which the change will proceed.
(ii) It gives no idea about the extent to which the change takes place.
These limitations can be understood from the following examples :-
(i) This law can easily explain the heating of a bullet when it strikes a block due to the conversion of
kinetic energy into heat, but it fails to explain as to why heat in the block cannot be changed into
kinetic energy of bullet and make it fly back from inside of the block.
(ii) When a vessel of water is placed over fire, heat flows into the vessel. What prevents the heat
from flowing from water into the fire, and thereby cooling the water and ultimately converting it
into ice. Thus direction of (flow) change is not known from first law.
(iii) It is practically found that whole of heat can never be converted into work. The first law has no
answer to this observation. Thus, first law fails to tell the extent to which the interchange of heat
into work and vice versa is possible.
Spontaneous and Non-Spontaneous Processes

1. Spontaneous Processes : In our daily life, we come across a large number of physical and
chemical processes which occur in a widely varying conditions. For example,
(i) Some processes proceed on their own, e.g., Water always flows down a hill, heat flows
from a body at higher temperature to a body at lower temperature.
(ii) Some processes require proper initiation but once properly initiated they continue on their
own, e.g., Kerosene oil once ignited continues to burn till whole of it has been consumed or
exhausted.
[ 153 ]
(iii) Some processes proceed only so long as the external energy is available. e.g., Electrolysis of
water continues so long as current is passed and stops as soon as current is cut off. “The
process which can take place by itself or after proper initiation, under the given set of
conditions, is called a spontaneous processes.” The term “Spontaneous” simply means that
given process is feasible or possible. Therefore, spontaneous processes are also called as
feasible or probable processes. Spontaneous process may or may not be instantaneous. But
all instantaneous process are spontaneous.
It may be pointed out that the term ‘Spontaneous’ should not mean that the process occurs
“instantaneously”. It simply implies that process has an urge to proceed or it is practically possible.
e.g., (i) Processes which occur on their own without proper initiation:
(a) HCl (g) + NH3 (g)  NH4Cl(s)
(b) H2O(l)  H2O(g)
Water keeps on evaporating from ponds and rivers, etc.
(c) Sugar dissolves in water and forms a solution
(d) 2NO(g) + O2 (g)  2NO2 (g)
(ii) Processes which require initiation:
(a) In domestic oven, once coal (carbon) is ignited it keeps on burning
C(s) + O2 (g)  CO2 (g)

(b) CH4(g) + 2O2 (g)  CO2(g) + 2H2O(l)
From the above discussion we conclude that spontaneous process is the one which has natural
tendency to occur. The process is spontaneous due to the presence of driving force. The Driving
force depends upon two factors:
(i) Minimum energy factor (ii) Entropy
2. Non-Spontaneous Process : A process which has no tendency to occur or which is made to

occur only if energy from outside is continuously supplied. e.g.,
(i) Decomposition of water into H2 and O2 is non-spontaneous. However, water can be

decomposed by passing an electric current through it, in a process called electrolysis.
Electricit y
2H2O (l)    2H2 (g) + O2(g)
The process will continue as long as electric current is supplied, and as soon as the supply of
electricity is cut off the decomposition stops.
(ii) Water cannot be made to flow up the hill, without the help of a machine.
(iii) Gold ornaments do not get tarnish in air even after a number of years. This shows that gold
does not combine with oxygen in the air.
[ 154 ]
Entropy
It may be defined as the measure of degree of randomness in a system. It is represented by the
symbol S.
Characteristic of Entropy
The exact value of entropy may be determined by applying the III law of thermodynamics.
The change in entropy during a process when a system undergoes change from one state to another
is represented as S.
Thus, S = Sfinal – Sinitial
and for chemical reaction S = Sproduct – SReactant
Calculation of Changes in Entropy

(a) Reversible Process at Equilibrium,
q Rev
S = T
(i) In a reversible reaction heat gained in the forward reaction is equal to heat lost in the reverse
reaction.
Hence in a reversible cyclic process the net change in entropy is zero. This is called Clausius
Theorem
(ii) Suniverse = Ssystem + SSurrounding
q Rev(system) q Rev(surrou nding)

Ssystem = Ssurrounding =
T T
Heat gained by system = heat lost by surrounding

 qRev(system) = qRev(surrounding)
q Rev(system) q Rev(surrou nding)

 Sunivers = +
T T
q Rev(system) q Rev(system)
= –
T T
= 0
Hence, Suniverse (Rev) = 0
(iii) Suniv > 0 for irreversible process (spontaneous process)
(iv) Entropy change for an isothermal process
E = q + w
E = 0 (Isothermal process)
 q = –w
[ 155 ]
V2
But , w = –2.303 nRT log V
1
V2
 q = 2.303 nRT log V
1
or, for a reversible process
V2
qrev = 2.303 nRT log V
1
q Rev 1 V2
S = = (2.303 nRT log V )
T T 1
V2
ΔS  2.303  nR log
V1
1
Also, V 
P
P1
 ΔS  2.303nR log
P2
(v) Entropy change in an isobaric process
dq Rev(P)
dS = also dqRev(P) = dH
T
But dH = CpdT
 dS = CpdT/T
Integrating both sides
T2
S2 dT
 S1
ds = Cp  T
T1
T
S = C p ln T  T12 = Cp ln T
T 2
1
T2
ΔS  2.303C P log
T1
(vi)Entropy change for Isochoric process

dq Rev(v)
ds = Also, dq(Rev)(v) = dE
T
But, dE = CvdT
 dqv = CvdT
 Integrating both sides one get
T
S = C v ln T T12 = Cv ln T
T 2
1
T2
ΔS  2.303C V log
T1
(vii) Entropy changes during phase transformation
q Rev
S =
T
[ 156 ]
(a) Entropy of fusion : The entropy change taking place when 1 mole of a solid substance
changes into liquid form, at the melting temperature,
ΔH fusion
Sfusion = T
fusion
(b) Entropy of vapourization is the entropy change when one mole of a liquid changes into
vapours at boiling point
H vapourisat ion
Svap = Svap – Sliquid = Tboiling point
(c) Entropy of sublimation is the entropy change when one mole of a solid changes into
vapours at sublimation temperature.
ΔH sub
Ssub = T
sub
(d) Hence for any physical transformation,

ΔH transition
Stransition = T
transition
Second Law of Thermodynamics

It can be defined in number of ways as follows:
1. All spontaneous processes (or naturally occurring processes) are thermodynamically irreversible.
2. Without the help of an external agency, a spontaneous process cannot be reversed e.g. heat
cannot by itself flow from a colder to hotter body.
3. The complete conversion of heat into work is impossible without leaving some effect elsewhere.
4. All spontaneous processes are accompanied by a net increase of entropy.
5. The entropy of the universe is increasing.
Gibb’s Free Energy: It is defined as, the energy available in the system for conversion into
useful work. It is that thermodynamic quantity of a system, the decrease in whose value during a
process is equal to the useful work done by the system.
G = H – TS
where, H is the heat content, T is the absolute temperature and S is the entropy of the system. As
before, for the isothermal processes, we have
G = H – TS
H = H2 – H1 is the enthalpy change of the system
Deriving the criteria for spontaneity.
The equation G = H – TS combines in itself both the factors which decide the spontaneity of a
process, namely
(i) the energy factor, H (ii) the entropy factor, TS
[ 157 ]
Depending upon the signs of H and TS and their relative magnitudes, the following different
possibilities arise.
1. When both H and TS are negative i.e. energy factor favours the process but randomness
factor opposes it, Then
(i) If H > TS, the process is spontaneous and G is negative
(ii) If H < TS, the process is non-spontaneous and G is positive.
(iii) If H = TS, the process is in equilibrium and G is zero.
2. When both H and TS are positive, i.e., energy factor opposes the process but randomness
factor favours it. Then
(i) If H > TS, the process is non-spontaneous and G is positive
(ii) If H < TS, the process is spontaneous and G is negative
(iii) If H = TS, the process is in equilibrium and G is zero
3. When H is negative but TS is positive i.e., energy factor as well as the randomness factor
favour the process. The process will be highly spontaneous and G will be highly negative.
4. When H is positive but TS is negative i.e., energy factor as well as the randomness factor
oppose the process. The process will be highly non-spontaneous and G will be highly positive :
An important advantage of free energy criteria over the entropy criteria lies in the fact that the
former requires free energy change of the system only whereas the latter requires the total
entropy change for the system and the surroundings.
Relationship between G and Equilibrium constant
G° = –2.303 RT log K.
Where K = equilibrium constant
Relationship between G and standard cell potential
G° = –nFEº
Problem 1: Which of the following is true for the process CO 2 (g) 

 Dry Ice
(a) H as well as S is less than zero (b) H is positive while S is negative
(c) Both H and S are positive (d) H < 0 but S > 0
Solution: (a) This is condensation of gas into solid. In this H = –ve and also S = –ve.
Problem 2: In a chemical process both H and S have values greater than zero. Under which conditions,
the reaction would not be spontanoeus?
(a) H < TS (b) TS – H < 0

(c) H = TS (d) G < 0
Solution: (b) Factual consider the expn G = H – TS
[ 158 ]
Problem 3: Which of the following processes proceed with increase in entropy?

(I) solid changing into liquid (II) Liquefaction of a gas
(III) Dissolution of solid in liquid (IV) Polymerisation
(a) (I), (III) (b) (II), (III)
(c) (II), (IV) (d) (I), (IV)
Solution: (a) Only process at (I) and (III) result in an increase in entropy.
Problem 4: Which of the following process shows negative values of S?

(a) Occlusion of H2 on Palladium (b) 2O3 (g) 
 3O 2 (g)
Δ
(c) H 2 O(l ) 
 H 2 O(g) (d) CaCO3   CaO  CO2
Solution: (a) By definition of entropy
Problem 5: Solubility of product of AgCl is 1.6 × 10–10 and log Ksp is –9.80. The values of G0 for the
process AgCl(s)  aq. Ag (aq)  Cl (aq) at 298 K is
(a) –55.9 kJ (b) +55.9 kJ
(c) +100.8 kJ (d) –100.8 kJ
0 2.303  298  (9.80)  8.314

Solution: (b) ΔG  2.303 RT log K   55.9kJ
1000
Problem 6: S0 and H0 for combustion of methane are 186 JK–1 and –74.8 kJ mol–1 respectively. the
value of U0 for the process is:
(a) Unpredictable (b) (74.8 – R)JK–1
(c) 74.78 kJ (d) (596 R – 74.8) kJ
Solution: (c) ΔU 0  ΔH 0  ΔnRT
CH 4  2O 2 
 CO 2  2H 2O(l ) Δn  (1  3)  2
ΔU 0  ( 74.8)  (2)R  298
ΔU 0  (596R  74.8)kJ
Problem 7: If Hlattice and HHydration of NaCl are repsectively 778 and –774.3 kJ mol–1 S dissolution
of NaCl at 298 K is 43 J mol–1. G0 for dissolution of 1 mole of NaCl is
(a) – 9.114 kJ (b) – 11.14 kJ
(c) – 7.14 kJ (d) + 9.114 kJ
Solution: (a) ΔH dissolution  ΔH lattice  ΔH hydration  778  774.3  3.7 kJ
ΔG  ΔHdissolution  TΔSdiss.  3.7  298103  9.114 kJ
Problem 8: Hvap of pure water is 40.617 kJ mol–1 at 100°C. Value of Svap is:
(a) 108.91 kJ mol–1 (b) 108.91 JK–1 mol–1
(c) 606.27 JK–1 mol–1 (d) 808.27JK–1 mol–1
40.627  1000
Solution: (b) ΔSvap  ΔH vap/T   108.91 JK 1 mol1
373
[ 159 ]
Problem 9: One mole of monoatomic gas (ideal gas) at TK undergoes reversible adiabatic change
under a constant external pressure of 1 atm. Its volume changes from 1 litre to 2 litre. Final
temperature would be
T 2
(a) (b) T 
(2)2/3 3 0.081
3
(c) T (d) T 
2  0.081
Solution: (a) TVr – 1 = K
T1 T
 T1V12/3  T2 V22/3 or T1 (1) 2/3  T2 (2) 2/3 or T2  2/3

(2) (2) 2/3
Problem 10: For the reaction H 2 Ol (1 bar, 373K) 

 H 2 O (g) (1 bar, 373K) the correct set of
thermodynamic parametres is:

(a) G = 0, S = +ve (b) G = 0, S = –ve
(c) G = + ve, S = 0 (d) G = – ve, S = +ve
Solution: (a) Sg > Sl. At 100° the process is spontaneous and is in equilibrium. So G = 0.
[ 160 ]
Chapter - 5
CHEMICAL EQUILIBRIUM
Introduction
A system in equilibrium is defined as the state when measurable properties such as concentration, temperature,
position, speed of the system do not change with time. Most of the chemical reactions are reversible in
nature. At the start of a reversible process containing only reactants, the reaction proceeds towards the
formation of products. As soon as some products molecules are formed, theoretically the reverse process
also begins to take place and the reactant molecules are formed from product molecules.
Chemical equilibrium is achieved when the rate of the forward and reverse reactions is equal and the
concentrations of the product and reactants remain constant. Chemical equilibria are stable and dynamic in
nature.
5.1 Reversible and Irreversible Reactions

On the basis of extent of reactions, chemical reactions can be classified in two categories reversible
and irreversible reactions. Irreversible reactions goes for completion whereas in reversible reactions,
we are left with some quantity of reactants even after sufficient period of time.
Examples of Reversible and irreversible reactions:
Reversible Irreversible
PCl5(g) PCl3(g) + Cl2(g) NaCl + AgNO3  AgCl(s) + NaNO3


2HI(g) H2(g) + I2(g) 2KClO3 2KCl + 3O2 

RCOOH + ROH RCOOR + H2O 2Pb(NO3)2 2PbO + NO2+ O2
N2 + 3H2 2NH3
Certain reactions are reversible in closed vessel and irreversible under open conditions.

eg., CaCO3(s) CaO(s) + CO2(g) (closed vessel)

CaCO3(s)  CaO(s) + CO2(g) (open vessel)
Chemical equilibrium is study of reversible reactions, there extent of completion and factors
affecting it.
Law of Mass Action
The law of mass action states that under a given set of conditions, rate of chemical reactions is
directly proportional to the active masses of the reacting substances.
e.g., Consider the reaction:
A + 2 B  Products
[ 185 ]
Chemical Equilibrium
Rate  [A]
Rate  [B]
Rate  [B]
Thus Rate  [A] [B]2 or Rate = k [A] [B]2
Here, k is termed as rate constant or velocity constant.
Active Mass
Active mass is represented by [ ] and expressed as
Active Mass = activity co-efficient × Concentration.
For dilute liquid solution and gases behaving ideally activity co-efficient is taken as unity. Thus,.
active mass is equal to concentration for dilute liquid solutions and ideal gases. Active mass of liquids
and solids is taken as unity.
Chemical equilibrium
As reaction proceeds concentration of reactants decrease and concentration of products increase,

thus rate of forward reaction decreases and rate of backward reaction increases with time and after
some time rate of forward reaction equals to rate of backward reaction.
Rateforward = Ratebackward
that means that amount of products formed by forward reaction is equal to amount of products
consumed in backward reaction, similarly amount of reactants consumed in forward reaction is
equal to amount of it formed by backward reaction, thus net concentration of reaction species remain
constant and rate of two reactions also get constant. Thus is termed as state of chemical equilibrium.
Characteristics of chemical equilibrium:
1. It is a dynamic equilibrium state.
2. It can be approached from both the sides.
3. At equilibrium the concentrations of the reactants and products remain constant.
4. Catalyst does not affect the equilibrium state but hastens the approach of equilibrium state.
5. At equilibrium the change in free energy, G = 0.
6. Equilibrium conditions can be affected by change in external variables such as change in

concentration, temperature pressure, etc.
Equilibrium constant
Let us consider a general reversible reactions

aA + bB mC + nD.
Rate (forward) = Kf CAa CBb
Rate (backward) = Kb Ccm CDn
[ 186 ]
At equilibrium
Rate (f) = Rate (b)
Kf CAa CBb = Kb Ccm CDn
m n
Kf C C
 C a Dn
Kb C A CB
Where, CA CB CC CD are concentrations under equilibrium conditions.
Kf
The ratio K = K = Equilibrium constant
b
Reaction Quotient (Q)
for a given equilibrium
aA + bB cC + dD.
[C]c [D]d
Kc =
[A]a [B]b
[C]c [D]d
But at any stage of the reaction the expression is called Q.
[A]a [B]b
(i) Q = KC the reaction is in equilibrium.
(ii) Q > KC the reaction will go in backward direction.
(iii) Q < KC the reaction will go in forward direction.
Kc and KP
When Active masses are taken in terms of concentration (moles per litre), equilibrium constant is
termed as concentration equilibrium constant Kc. In case of gas phase reactions, the terms active
masses may be replaced by partial pressure of each gas at equilibrium, corresponding equilibrium
constant is termed as pressure equilibrium constant Kp.
m n
pC pD
Hence, Kp =
p Aa pBb
Where, pA, pB, pC and pD are partial pressure of each component at equilibrium.
Relationship between Kc and KP
PV = nRT where, V = volume (litre)
n n
 P= RT ; P = cRT [ C = = moles/litre]
V V
 pA = CA RT and thus
[ 187 ]
m n
(C RT ) m (C RT ) n
c D C C
D C
Kp = (C RT ) a (C RT ) b  × (RT)ng
A B C Aa CB b
Kp = Kc RT ng where ng = (m + n) – (a + b)

= ng (P) – ng(R)
Characteristics of Equilibrium constant
(1) Its value is independent of :
(a) Original concentrations of reactants

(b) Volume
(c) Presence of catalyst
(d) Presence of inert material
(e) Nature and number of steps in the reactions as long as the stoichiometry is not changed.
(2) Its value depends upon temperature:
Effect of temperature is represented as,
K2 H  T2 T1 
log K1  2.303R  T1 T2  at constant pressure
 
K2 E  T T 
log K1  2.303R  2 1  at constant volume
 T1 T2 
(a) For endothermic reactions K increases with increase in temperature.
(b) For exothermic reactions K decreases with increase in temperature.
(3) Larger the value of equilibrium constant, higher will be the yield of the reaction.
(4) The value of K depends on stoichiometry of reactants and products.

K1
e.g. A2 + B2 2AB
[ AB]2
K 1 = [ A ][ B ]
2 2
If we multiply it with integer m. then equation become
mA2 + mB2 2 mAB
[ AB]2 m
K2 = [ A ]m [ B ]m = (K)m
2 2
Hence, K2 = (K1)m
(5) If the final equation at equilibrium is written as the sum of two different equation then the final
equilibrium constant is the product of the equilibrium constants of each individual steps.
[ 188 ]
K
e.g. N2 + 2O2 2NO2
[ NO 2 ]2
K=
[ N 2 ][O 2 ] 2
Suppose this equation takes place in two steps

K1
Step - I N2 + O2 2NO
[ NO]2
K 1 = [ N ][O ]
2 2
K2
Step - II 2NO + O2 2NO2
[ NO 2 ]2
K2 =
[ NO]2 [O 2 ]
Then, K = K1 × K2
Also when equations are subtracted then the equilibrium constant obtained will be the equilibrium
constant of one reaction divided by the equilibrium constant of the other.
Illustration 1: If concentration are expressed in moles L–1 and pressure in atmospheres, what is the ratio of
Kp to Kc for the reaction.
2SO2(g) + O2(g) 2SO3(g) at 25ºC ?
Solution: ng = –1
Hence, Kp = Kc (RT)–1
1
or, Kp /Kc = 1/RT = 0.0821  298 = 0.04.
Illustration 2: What two changes on the equilibrium N2(g) + 3H2(g) 2NH3(g), H = –92.5 kJ can
keep its state undisturbed ?
Solution : Increase of temperature alongwith suitable increase of pressure or increase of pressure

alongwith suitable increase of temperature.

Problem 1: Which oxide of nitrogen is the most stable?
(a) 2NO 2 (g) N 2 (g)  2O 2 (g); K = 6.7 × 1016 mol litre–1
(b) 2NO(g) 2N 2 (g)  O 2 ; K = 2.2 × 1030 mol litre–1
(c) 2N 2O 5 (g) 2N 2 (g)  5O 2 (g); K = 1.2 × 1034 mol–5 lire–5
(d) 2N 2 O(g) 2N 2 (g)  O 2 (g); K = 3.5 × 1033 mol litre–1
Solution: (a) Lower is the value of K, lesser will be the tendency to show forward reaction.
[ 189 ]
Problem 2: If K1 and K2 are equilibrium constants for reaction (I) and (II) respectively for,
N 2  O2 2NO ...(i)
1 1
N2  O2 NO ...(ii)
2 2
Then:
(a) K2 = K1 (b) K 2  K 1
1
(c) K2 = 2K2 (d) K1  K 2
2
[NO]2 [NO]
Solution: (b) K1  ; K2 
[N 2 ][O 2 ] [N 2 ]1/2 [O 2 ]1/2
 K1  K 22
Problem 3: The equilibrium PCl5 (g) PCl 3 (g)  Cl 2 (g) shows that Kp is 24.63 times the value of
Kc at a particular temperature T. Then T (in K) is

(a) 200 (b) 100
(c) 300 (d) 400
Kp
Solution: (c)  (RT)Δn
Kc
24.63 = (0.0821 × T)2

T = 300 K
Problem 4: For the reaction, N 2  3H 2 2NH 3 in a vessel, after the addition of equal number of
mole of N2 and H2, equilibrium state is formed. Which of the following is correct?
(a) [H2] = [N2] (b) [H2] > [N2]
(c) [H2] < [N2] (d) [H2] > [NH3]
Solution: (b) 1 mole of N2 reacts with 3 mole H2 thus, for
N 2  3H 2 2NH3 ;(a  x )  (a  3 x)
α α
( a x ) ( a 3 x ) 2x
Problem 5: A higher value for equilibrium constant, K shows that:

(a) The reaction has gone to near completion towards right.
(b) The reaction has not yet started
(c) The reaction has gone to near completion towards left
(d) None of these
Solution: (a) Higher is the value of Kc or Kp more is feasibility for reaction to show forward reaction.
[ 190 ]
Problem 6: Which reaction has n = 2?
(a) CaCO 3 (g) CaO(s)  CO 2 (g)
(b) 3Fe(s)  4H 2 O(g) Fe 3O 4 (s)  4H 2 (g)
(c) NH 4 Cl(g) NH 3 (g)  HCl(g)
(d) CuSO 4  5H 2O(s) CuSO 4  3H 2 O(s)  2H 2 O(g)
Solution: (d) n + Mole of product – Mole of reactant; count only gaseous phase reactants.
Problem 7: Which is reversible reaction?

(a) H 2  I2 
 2HI
(b) H 2SO 4  Ba(OH) 2 

 BaSO4  2H 2O
(c) NaCl  AgNO3 

 NaNO3  AgCl 
(d) 2KClO3 
 2KCl  3O2 
Solution: (a) An irreversible reaction is one in which either of the product is separated out as solid or
escapes out as gas.
Problem 8: For a hypothetical equilibrium:
4A  5B 4 x  6 y , the equilibrium constant Kc has the unit

(a) mol2litre–2 (b) litre mol–1
(c) litre2mol–2 (d) mol litre–1
Solution: (d) Unit of Kc = [ ]dn .n = +1
Problem 9: Kp/Kc for the reaction,
1
CO(g)  O 2 (g) CO 2 (g) is
2
(a) RT (b) 1/ RT
(c) RT (d) 1
Solution: (b) Kp = Kc/(RT)–1/2

 Δn   1 / 2
Problem 10: Chemical equilibrium is dynamic in nature because:

(a) The equilibrium is maintained rapidly
(b) The concentration of reactants and products become same at equilibrium
(c) The concentration of reactants and products decrease with time
(d) Both forward and backward reactions occur at all times with same speed
Solution: (d) The reaction does not cease up but goes in both directions with same speed.
[ 191 ]
5.2 Le Chatelier’s Principle

When a system at equilibrium is subjected to stress or strain in the form of temperature, pressure,
volume, concentration, etc., then system moves in that direction in which the stress or strain is nullified.
(1) Effect of change in concentration:
(a) When concentration of products is raised system moves in backward direction to attain
equilibrium.
(b) When product concentration decreases system moves in forward direction to attain equilibrium
(2) Effect of pressure: The change in pressure depends upon the sign. of ng.
A. When ng = – ve
(a) Increasing pressure system will move in forward direction to attain equilibrium.
(b) Decreasing pressure system moves in backward direction to attain equilibrium.
B. When ng = +ve
(a) Increasing pressure system moves in backward direction to attain equilibrium.
(b) Decreasing pressure system moves in the forward direction.
(3) Effect of temperature:
Kc changes with temperature according to the equation,
k2 H  T2 T1 
log 
k1 2.303 R  T1T2  (at constant pressure)
k2 E  T2 T1 
log 
k1 2.303 R  T1T2  (at constant volume)
(a) For Exothermic reaction:
(i) When temperature increases Kc value decreases so system moves in backward direction.
(ii) When temperature is lowered Kc increases and hence, system moves in forward direction.
(b) For endothermic reaction:
(i) Increasing the temperature will increase Kc value so that the system moves in forward
direction.
(ii) Decreasing the temperature will decrease K c value so that the system moves in
backward direction.
(4) Adding Inert gas at constant volume: Addition of inert gas to a system at equilibrium at
constant volume does not change equilibrium state.
(5) Adding Inert gas at constant pressure
(a) Adding inert gas to a system at equilibrium at constant pressure will increase the volume and
hence if ng = –ve the system moves in backward direction attain equilibrium.
[ 192 ]
(b) Adding inert gas to a system at equilibrium at constant pressure will increase the volume and
if ng = +ve then system moves in forward direction attain the equilibrium.
(6) Adding catalyst : Addition of catalyst to a system at equilibrium does not shift equilibrium
because rate of forward and rate of backward direction both are increased.
Degree of Dissociation
Degree of dissociation si the fraction of a mole of the reactant that underwent dissociation. It is
represented by ‘’.
no. of moles of the reactant dissociated

α=
no. of moles of the reactant present initially
For example: Let the equilibrium reaction is the dissociation equilibrium of HI into H2 and I2.
1 1
HI(g) H 2(g)  I2(g)
2 2
Let initial moles of HI taken by ‘a’ and the moles of HI dissociated at equilibrium be ‘x’ then
1 1
HI(g) H 2(g)  I2(g)
2 2
Moles initially a 0 0
Moles at equilibrium a–x x/2 x/2
then, the degree of dissociation of HI will be
x
α
a
The degree of dissociation is defined only for those equilibrium in which dissociation takes place.
Degree of dissociation by vapour density measurements
for PCl5 PCl3 + Cl2
or N2O4 2NO2
D
1 
d
where D =Density of pure PCl5
Density of Pure N2O4
d =Density of mixture of PCl5 + PCl3 + Cl2 or N2O4 + NO2
Illustration 1: Calculate the percent dissociation of H2S(g) if 0.1 mole of H2S is kept in 0.4 litre vessel at
1,000 K. For the reaction 2H2S(g) = 2H2(g) + S2(g) the value of Kc is 1.0 × 10–6.
Solution : 2H2S(g) 2H2(g) + S2(g)

At equb. 0.1 – x x x/2
0.1 – x x x
Molar conc. at equb.
V V 2V
[ 193 ]
( x /V ) 2 ( x / 2V )
 Kc = 2
 0.1 x 
 
 V 
–6
x3
1.0 × 10 = 2
2V (0.1)
x 3 = 2 × 0.4 × 0.1 × 10–6
x = 2 × 10–3
2  10 –3  100
 % dissociation = = 2%.
0.1
Illustration 2: What happens to the equilibrium PCl5(g) PCl3(g) + Cl2(g), if nitrogen gas is added to
it (i) at constant volume (ii) at constant pressure ?
Solution : (i) The state of equilibrium remains unaffected.

(ii) Dissociation increases (i.e., equilibrium shifts forward).
Illustration 3: Ammonia under a pressure of 15 atm at 27ºC is heated to 347ºC in a closed vessel in the
presence of a catalyst. Under the conditions, NH3 is partially decomposed according to the
equation, 2NH3 N2 + 3H2. The vessel is such that the volume remains effectively
constant whereas pressure increases to 50 atm. Calculate the percentage of NH3 actually
decomposed.
Solution : Let the degree of decomposition = x
1 3
NH3 N (g) + H [Total number of moles]
2 2 2 2
Initial No. of moles 1 0 0 1
At equilibrium 1 – x x/2 3x/2 1+x
Applying gas equation PV = nRT
At constant V, P = nRT
nT n1 T1 n2 T2
or = constant or P1 = P2
P
1 300 (1  x )620
=
15 50
300 50
1+x = 62  3 =
31
19
x == 0.613
31
Percentage decomposition = 0.613 × 100 = 61.3%.
Illustration 4: At temperature, T compound AB2(g) dissociates according to the reaction

2AB2(g) 2AB(g) + B2(g)
with a degree of dissociation, x, which is small compared with unity. Deduce the expressure
for x in terms of the equilibrium constant, Kp and the total pressure, P
[ 194 ]
Solution : 2AB2(g) 2AB(g) + B2(g)

Initial moles 1 0 0
x
Moles of equb. 1–x x
2
x 2 x
Total moles at equilibrium =1–x+x+ =
2 2
2
 2x   x 
2  P   P 
( p AB ) ( p B ) 2 x  2 x  x3P
2
 Kp = 2 =  2(1  x )  = 2
( p AB ) ( 2  x )(1  x)
2  ( 2  x) P 
 
1/ 3
3  2K p 
Kp  x P or x=  P 
2  
Illustration 5: The pressure of iodine gas at 1273 K is found to be 0.112 atm. whereas the expected
pressure is 0.074 atm. The increased pressure is due to dissociation I2 2I.
Calculate Kp
Solution : I2 2I
Initial conc. 1 0
Eqbm. conc. 1–x 2x
Total moles of equilibrium = 1 – x + 2x = 1 + x
Since, the pressure is proportional to the number of moles.
Experiment al value of pressure 1 x
 Expected value of pressure = 1
0.112 1 x
or =
0.074 1
0.112 = 0.074 + 0.074x
0.038
x = = 0.51
0.074
PI 2
Now Kp = P
I2
2
 2x 
  P
 1 x  4x 2
 Kp = 2 = 2 P
 1 x  1 x
  P
1 x
Putting x  = 0.51, P
 = 0.112 atm
We get Kp = 0.1575.
Illustration 6: A saturated solution of iodine in water contains 0.330 g I2 / litre. More than this can dissolve
in a KI solution because of the following equilibrium.
I2(g) + I– I3–
A 0.100 M KI solution (0.100 MI–) actually dissolves 12.5 g of Iodine/litre, most of which is
converted into I3–. Assuming that the concentration of I2 in all saturated solutions is same,
calculate the equilibrium constant for the above reaction.
[ 195 ]
Solution : No. of mole of I2 in saturated solution of iodine
m 0.330
n= = = 1.30 × 10–3
M 254
Moles of I2 in 0.100 M KI solution
12.5
= 254 = 0.0492
I2 + I– I3–
[I 3  ]
 K = 
[I 2 ][I ]
At equilibrium, I2 = 1.30 × 10–3 M.

[I3–] = 0.0492 – 0.0013 = 0.00479 M
–
and, [I ] = 0.100 – 0.0479 = 0.0521 M.
0.00479
K = 1.3  10 3  0.0521 = 70.72
Illustration 7: When PCl5 is heated it gasifies and dissociates into PCl3 and Cl2. The vapour density of the
gas mixture at 200ºC and 250ºC is 70.2 and 57.9 respectively. Find the percentage dissociation
of PCl5 at 200ºC and 250ºC.
Solution: If no dissociation were to occur,
Mol. wt 31  177.5
the vapour density (D) of PCl5 = = = 104.25
2 2
However, observed vapour density (d) at 200ºC = 70.2
D d 104.25  70.2
Hence, degree of dissociation  = = = 0.485
d 70.2
Percentage dissociation at 200ºC = 0.485 × 100 = 48.5 %
D d 104.25  57.9
Similarly, degree of dissociation () at 250ºC,  = = = 0.800
d 57.9
% dissociation = 0.800 × 100 = 80%

It is important to note that the above relation between degree of dissociation and densities
is applicable only when the reaction is accompanied by change in total number of moles.
This relation is not applicable to reactions in which number of moles of the reactants and
products are equal as in the formation or decomposition of HI.
H2 + I2 2HI
[ 196 ]

Problem 1: For the gaseous phase reaction,
–1
2NO N 2  O 2 ,ΔH 0  43.5 kcal mol , which statement is correct for,,
N 2 (g)  O 2 (g) 2NO(g)?

(a) K is independent of temperature
(b) K increases as temperature decreases
(c) K decreases as temperature decreases
(d) K varies with addition of NO
K 2 ΔH [T2  T1 ]
Solution: (c) 2.303log K  R T T
1 1 2
H = +ve for the reaction, N 2  O 2 2NO
Problem 2: For the reaction,
CH 4 (g)  2O 2 (g) CO 2 (g)  2H 2 O(g)
Δ r H  170.8 kJ mol1
Which of the following statements is not true?
(a) Addition of CH4(g) or O2(g) at equilibrium will cause a shift to the right
(b) The raction is exothermic
(c) At equilibrium, the concentrations of CO2(g) and H2O (l) are not equal
[CO2 ]
(d) The equilibrium for the reaction is given by K p  [CH ][O ]
4 2
P  CO 2
Solution: (d) Kp of the reaction is K p 
 P  P 
CH 4 O2
Problem 3: N2O4 is dissociated to 33% and 40% at total pressure P1 and P2 atm respectively. Then the
ratio of P1/P2 is
(a) 7/4 (b) 7/3
(c) 8/3 (d) 8/5
N 2O 4 2NO 2
Solution: (d) 0 0
1α 2α
(n NO2 ) 2  P 1
Kp   
n N 2O 4   n 
(2  0.33) 2  P 
For 33% dissociation: K p  
0.67 1.33 
(2  0.40) 2  P 
For 40% dissociation: K p  
0.60 1.40 
P1 8
  1.56 1.60 
P2 5
[ 197 ]
Problem 4: Which can be explained at applications of Le-Chatelier’s principle?

(a) Transport of oxygen by haemoglobin in blood
(b) Removal of CO2 from tissues by blood
(c) Tooth decay due to use of sweet substances
(d) All of the above
Solution: (d) (i) The haemoglobin of RBC combines with oxygen in lungs following equilibrium,
H b (s)  O 2 (g) H b O 2 (s)

When these are at lungs, the partial pressure of O2 being appreciable to show forward
reaction, however, when they pass to tissues, the partial pressure of O2 decreases
to favour backward reaction releasing O2.
(ii) Removal of CO2 from blood is based on the equilibrium,
CO 2 (g)  H 2 O H  (aq)  HCO 3 (aq)

In tissues CO2 gas dissolved in H2O due to high pressure whereas in lungs, the CO2
is released out because of low pressure of CO2.
(iii) Tooth enamel substance (hydroxyapatite) Ca 5(PO4)3OH shows the following
equilibrium.
Demineralisation
Ca 5 (PO4 )3 OH Re min eralisatiion
5Ca 2 (aq)  3PO34 (aq)  OH _ (aq)
Problem 5: For the equilibrium, PCl5 PCl3  Cl 2

Kc = 2 / (1 – )V, temperature remaining constant:
(a) KC will increase with the increase in volume
(b) KC will increase with the decrease in volume
(c) KC will not change with the change in volume
(d) KC may increase or decrease with the change in volume depending upon its numerical
value
Solution: (c) Kc is characteristic constant for a given reaction at a temperature.
Problem 6: For the liquefaction of gas, the favourable conditions are:

(a) low T and high P (b) low T and low P
(c) low T and high P and a catalyst (d) low T and catalyst
Solution: (a) Gas Liquid, ΔH   ve
Apply Le-Chatelier’s principle
Problem 7: In the thermal decomposition of potassium chlorate in a closed container given as,
2KClO3 (s) 
 2KCl(s)  3O2 (g),
law of mass action:
(a) cannot be applied
(b) can be applied
(c) can be applied at low temperature
(d) can be applied at high temperature and pressure
3
Solution: (b) K p  (R O2 )
[ 198 ]
Problem 8: Favourable conditions for manufacture of ammonia by the reaction,
N 2  3H 2 2NH 3 ; ΔH  21.9 kcal are:

(a) low temperature, low pressure and catalyst
(b) low temperature, high pressure and catalyst
(c) high temperature, low pressure and catalyst
(d) high temperature, high pressure and catalyst
Solution: (b) Follow Le-Chatelier’s principle.
Problem 9: On applying pressure to the equilibrium

ice water
Which phenomenon will happen?
(a) More ice will be formed (b) More water will be formed
(c) Equilibrium will not be disturbed (d) Water will evaporate
Solution: (b) Volume of ice > volume of water and thus, increase in pressure favours forward reaction
showing decrease in volume.
Problem 10: In the dissociation of 2HI H 2  I 2 , the degree of dissociation will be influenced by the
(a) addition of inert gas at constant volume
(b) addition of inert gas at constant pressure
(c) increase of temperature
(d) increase of pressure
Solution: (c) n = –1 and Kp = Kc = (RT)n
[ 199 ]
Chapter - 6
IONIC EQUILIBRIUM
6.1 Acids and Bases
Different workers gave different definitions for acids and bases from time to time.
(i) Arrhenius Theory : Arrhenius defined acids as those compounds which give hydrogen ions in
aqueous solution, and bases as those compounds which give hydroxide ions in solutions.
e.g., H2SO4 (aq) 2H+ (aq) + SO42– (aq)
The strength of an acid or base depends upon its tendency to furnish H+ or OH– ions in solution.
This definition can be applied only for those reactions which take place in aqueous solutions.
Further, this theory does not include substances that do not contain H+ and OH– ions but
still can neutralize acids and bases.
Basicity or protonicity of acids: It is the number of H+ ions furnished by a molecule of an acid.
Monobasic acid : An acid furnishing one H+ ions e.g., HCl, HNO3, etc.
Dibasic acid : An acid furnishing two H+ ions e.g., H2SO4, H3PO3, etc.
Tribasic acid : An acid furnishing there H+ ions e.g., H3PO4.
Acidity or Hydroxicity of base : It may be defined as the number of OH– ions furnished by a
molecule of a base.
Monoacidic base : e.g., NaOH, KOH
Diacidic base : e.g., Ca(OH)2, Ba(OH)2
(ii) Bronsted Lowry Theory : According to this theory acids are defined as substances which
give up proton and bases as a substance which accepts proton.
HCl + H2O H3O+ + Cl–

e.g.. A1 B2 A2 B1 Equation .....1
NH3 + H2O NH4+ + OH–

B1 A1 B2 Equation .....2
A2
From the above observations we may conclude that every acid has a conjugate base and every
base has a conjugate acid.
In above equation 1 the conjugate base of acid HCl is Cl–. The conjugate acid of water is H3O+
(hydroxonium ion).
In the above equation 2 the conjugate acid of base NH3 is NH4 and the conjugate base of H2O
is OH–.
Thus, according to this theory the following conclusions can be drawn.
[ 221 ]
Ionic Equilibrium
(a) A substance can act as an acid/base when another substance capable of accepting a proton/
capable of donating a proton exists.
(b) In aqueous solutions H ions exist as hydrated ions or H3O+ (H+. H2O) ions.
(c) Even ions may act as acids or bases.
(d) Water, can act both as an acid or base because it can give off a proton as well as can accept
a proton.
H2 O + H2 O H3O+ + OH–
i.e., A-1 B-2
B-1 A-2
(e) The strength of acids (or bases) depends on the medium which acts as base (or acids)
e.g., HCl + H2O  H3O + Cl–

HCl + NH3  NH4 + Cl–
HCl + Benzene  No reaction
Acidic nature of HCl is greatest in ammonia and least in benzene.
Lewis Concept of Acids And Bases
According to Lewis, an acid is any species which is capable of accepting a pair of electrons and a
base is a species that is having a lone pair of electrons for donations.
This, statement covers a wide range of acids and bases.
Thus, all Bronsted-Lowry bases are Lewis bases while all Bronsted-Lowry acids are not Lewis
acids.
Hence this theory includes acids which do not donate proton or liberate H+ (aprotic)
 
e.g., NH3 + BF3 H3N  BF3
R-Cl + AlCl3 R+ — AlCl4–
Lewis acids:
(i) Compounds where the central atom has incomplete octet. This means all electron deficient
molecules can act as Lewis acids, e.g.
BF3, BBr3, AlCl3, FeCl3, GaCl3, etc.
(ii) Compounds in which the central atom has available vacant orbitals. e.g., SnF4, SnCl2, SnCl4,
PF3, PF4, SF4, TiCl4, etc.
(iii) Simple cations like Ag+, Cu2+, Al3+, etc., e.g., Cu2+ + 4NH3 [Cu (NH3)4]2+.
The strength of the Lewis acid depends upon
(i) Nuclear charge on central atoms : More the nuclear charge on central atom more the Lewis
acidic strength.
[ 222 ]
Ionic Equilibrium
(ii) Number of electronegative atom attached to central atoms. More the number of electronegative
atoms attached more is the acidic strength. e.g., SO3 is more stronger a acid than SO2.
(iii) Increase in positive charge on ion makes it a strong acid.
e.g., Sn4+ > Sn2+ acidic strength
Fe3+ > Fe2+ acidic strength
(iv) When charge is same on the cation then decrease in the radii of cation increase acidic
strength. e.g., Li+ > Na+ > K+ acidic strength
(v) With the increase in the nuclear charge the acidic strength increase
Li+ < Be2+ < B3+
Lewis Bases:
(i) All simple anions are Lewis bases e.g., Cl–, NO3–, OH–.
(ii) Molecules containing one or more unshared pairs of electrons (Lone pairs) e.g. H2O, NH3,
ROH, NX3, R2S, etc. are Lewis bases.
(iii) Multiple bonded compounds which can donate the pair of electrons. e.g. C  O, N  O,
CH2 = CH2, CH  CH.
Hard And Soft Acids and Bases
Lewis acids and bases are further classified as Hard acids, Hard bases and soft acids soft bases:
(a) Cations (electron accepting atom) having high charge, and small sizes are termed as hard
acids. While cations (electron accepting atoms) have less charge and large size are termed
as soft acids.
(b) A Lewis base where the electrons can be easily polarized or where the base holds its electrons
weakly is called soft base while a lewis base where the electron are not easily polarized or
where the base holds its electrons strongly are called hard bases.
Some examples of Hard Acids and Hard Bases, Soft Acids and Soft Bases
Hard Acids Hard Bases Soft Acids Soft Bases
Li+, K+, Na+, Ca2+ H2O, OH–, F– Pb2+, PF2+ R2S, R–, CN–
Sr2+, Al3+ Cl–, CO32–, CrO4– Cd2+, Hg2+ R3P, I–, RS
Fe2+ NO3–, NH3, NH2– GaCl3, I2, Br2 RNS, C2H4, CH  CH
Ce3+, As3+, BF3, SO3
Salt
A substance which ionizes in water to produce ions other than H+ and OH– is called a salt.
[ 223 ]
Ionic Equilibrium
Types of Salts
Neutral Salts : Those salts whose aqueous solutions neither turn blue litmus red nor red litmus blue
are called neutral salts. These are prepared by the neutralization of strong acid and strong base. e.g.
NaCl, K2SO4, KNO3, etc.
Basic Salts : Those salts whose aqueous solution turn red litmus blue are called basic salts. These
are formed by the neutralization of strong bases with weak acids. e.g. Na2CO3, CH3COONa
Mixed Salts : Salts formed by the neutralization of one acid by two bases or one base by two acids
are called mixed salts, e.g., CaOCl2
Double Salts : A compound of two salts whose aqueous solution shows the tests for all constituent
ions is called double salt e.g.
Mohr Salt FeSO4. (NH4)2 SO4. 6H2O
Potash Alum K2SO4. Al2 (SO4)3. 24H2O.
Complex Salts : A compound whose solutions does not give tests for the constituent ions is called
a complex salt. e.g.
K4 [Fe(CN)6]
Li (AlH4)
Ionic Dissociation
The process in which molecules (acids, bases, and salts) when dissolved in water or when melted
break into ions is called ionic dissociation.
Such solutions conduct electricity and are therefore known as electrolytes.
Hence substances which dissociate into ions in aqueous solutions are called electrolytes, e.g., NaCl,
NaNO3, HCl, K2SO4, etc.
Molecules of the substances which do not dissociate into ions in aqueous solutions are called non-
electrolytes, e.g., sugar, urea, etc.
Strong Electrolyte and Weak Electrolyte

Those electrolytes which dissociate almost completely into ions are known as strong electrolytes.
e.g. HCl, HBr, HI, HClO4, NaCl, Na2SO4, KNO3 etc.
Those electrolytes which dissociate partially are called weak electrolytes, e.g., H3PO4, HF, H2CO3,
HCN, CH3COOH, NH4OH,, etc.
Dissociation of Weak Acids in Water
Dissociation of Weak acids : Consider the dissociation of a weak acid HA in water, represented by
the equation.
HA + H2O H3O + A–
[ 224 ]
Ionic Equilibrium
Applying the laws of chemical equilibrium, the equilibrium constant Kc is given by the expression.
C H 3O  C A 
Kc = C C
HA H 2O
C H3O  or C A  are concentrations expressed in moles per litre. Since, water is present in large
excess in dilute solutions, its concentrations may be taken as constant, say K. The above equations
may therefore, be expressed as
CH CA
Kc = C HA K
=
C H  C A
 Kc K = Ka = C HA
The constant Ka is characteristic of the acid concerned, and is known as the dissociation constant of
the acid.
Greater the value of dissociation constant greater will be the H+ ions concentration, in the solutions
of HA and hence, more strong the acid would be.
If C is the concentration in moles per litre (molarity of the acid HA) and - is the degree of dissociation
then,
Number of moles of HA dissociating = C.

Number of moles of H+ formed = C.
Number of moles of A– formed = C.
Hence at equilibrium.
Number of moles of HA left = (C – C)

Number of moles of H+ = C
Number of moles of A– = C
C O O
Initial conc. moles/litre
HA H+ + A–
Final concentration (C – C) C C in moles/lit.
C α2
 Ka = 1  α
This equation is referred to as Ostwald dilution law.
In case of weak acids the degree of dissociation  is very small, therefore, (1 – ) may be taken to
be equal to unity.
Hence,
Ka = C2
Ka
 α
C
[ 225 ]
Ionic Equilibrium
Since,
Ka
(H  )  C  C   Ka C
C
Also as,
Ka
α  VK a
C
This shows that degree of dissociation is inversely proportional to square root of concentration and
directly proportional to square root of dilution of the solution.
For polybasic acids of the type H2A, H3A, etc. The acids undergo complete ionization in several
steps. The number of steps is equal to the number of replaceable hydrogen atoms in the molecule.
Hence, there will be as many ionization constants as the number of replaceable hydrogen atoms.
K1
e.g,. H2 A H+ + HA–
K2
HA– H+ + A2–
The relative values of dissociation constants would be K1 > K2 .
The overall dissociation constant is given by the relationship K = K1 × K2

K1
e.g., H2 S H + HS–
K2
HS– H+ + S2–
Here, K1 > K2 and K = K1 × K2.
Dissociation of Weak Base in Water

The dissociation of a weak base can be represented in the same manner as a weak acid.
e.g.,
C O O
(initial) B + OH–
BOH
Final concentration in moles/lit. C - C C C.
Where, C = Initial conc in moles/litre
 = Degree of dissociation
CB C OH C 2 α 2 C α 2
 Kb =  
C BOH C (1 α) 1 α
Because base is weak
  1  1 –  = 1.
 Kb = C2
  = Kb / c
[ 226 ]
Ionic Equilibrium
Kb
Hence, [OH–] = C = C ×
C
[OH–] = Kb C
Strengths of Acids and Bases
(i) The strength of an acid/base depend upon the number H+/OH– present in solution.
(ii) Since,  = V  K a or  = V  Kb
  increases when V increase.
 Ionization increases with dilution, hence number of H+ /OH– increases.
(iii) At infinite dilution the ionization of all acids and bases tends to become almost equal and all
acids and bases behave equally strong at infinite dilution.
(iv) All mineral acids or bases which ionize fully at all dilutions are considered as strong acids. While
acids/bases like CH3COOH/NH4OH respectively which ionize to a less extent are called weak
acids/bases. The relative strengths is generally compared in terms of their dissociation constants.
We known that
Ka = C1 12 1  1
1
Ka = C2 22 2  1
2
K a1
C1 K a1 C 2 α1
 =  When two acids with different concentration are taken.
K a2 K a2 C1 α2
C2
However, when both acids taken are of equal concentrations C1 = C2.
K a1 α1
 
K a2 α2
Similarly for bases,
K b1 C 1 α 12
 when C1  C2
K b2 C 2 α 22
α1 K b1 C2
  when C1  C2
α2 K b2 C1
α1 K b1
 when C1  C2
α2 K b2
(v) Strength of all strong acids/bases in water is same. This is called levelling effect.
[ 227 ]
Ionic Equilibrium
Self Ionization of Water
Water can behave both as an acid as well as a base. This behaviour of water is due to ionization of
water to form protons and hydroxyl ions.
H2O H+ + OH–
C H C OH –
Hence, K = CH 2O
 K CH = CH+ COH–
2O
K CH = Kw = CH+ COH–
2O
Kw is the Ionic Product of water and may be defined as the product of concentration of ions
[(H+) and (OH–)] ions. Its value depends only on temperature and is found to be 1 × 10–14 at 25ºC.
At, OºC Kw = 0.11 × 10–14 mol2/lit2
10ºC Kw = 0.30 × 10–14 mol2/lit2
25ºC Kw = 1 × 10–14 mol2/lit2
100ºC Kw = 7.5 × 10–14 mol2/lit2
For pure water CH+ = COH– = 10–7 mol/lit at 25ºC.
Degree of dissociation of pure water at 25ºC
For pure water CH+ = COH–.
Also at room temperature CH+ COH– = 10–14 mol2/lit2.
 CH+ = 10–7 mol/lit
 C = 10–7 mol/lit
10 7 10 7
=  = 1.8 × 10–9
C 55.6
Hence, degree of dissociation = 1.8 × 10–9
 % degree of dissociation = 1.8 × 10–7
Hydrogen ion / Hydroxyl ion conc. of acid / base
(i) In case of strong acids (or bases) concentration in water solution is taken as equal to normality
of the acid/base since they ionize completely.
[H+] = Normality of acid = Molarity × Basicity
[OH–] = Normality of base = Molarity × Acidity
[ 228 ]
Ionic Equilibrium
(ii) In case of weak acids/Bases, the H+/OH– concentration is less than normal and may be calculated
by using Oswalds dilution law.
[H+] = K a C = C = N × 
[OH–] = K bC = C = N × 
pH Scale:
It may be defined in number of ways.
(i) The pH value of a solution is equal to the negative power to which 10 must be raised in order to
express [H+] concentration [H+] = 10–PH.
(ii) It can also be defined as the negative logarithm of its [H+] ion concentrations,
pH = –log[H+]
pH values do not give instantaneous idea above the relative strengths of the solution.
pOH Scale:
It may be defined as the negative logarithms of hydroxyl ions concentration,
pOH = –log (OH–).
Also, it is known that [H+] [OH–] = 10–14 = Kw
–log[H+] (+) –log[OH–] = 14 = PKw
 pH + pOH = pKw = 14.
Illustration 1: A solution contains 0.10 M H2S and 0.3 M HCl. Calculate the concentration of S2– and HS–
ions in the solution. For H2S,
Ka1 = 1.0 × 10–7 Ka2 = 1.3 × 10–13
Solution : Dissociation of H2S can be represented as:

(a) H2S H+ + HS–
(b) HS– H+ + S2–
 
[H ] [HS ]
From the first ionisation of H2S = [H 2S] = K a1
Since H2S is weakly ionised and its ionisation is further decreased in presence of highly
ionised HCl, concentration of H+ in solution will be mainly due to HCl. Thus, [H+] = 0.3
Substituting the values in the above equation
0.3 [HS ]
= 1 × 10–7
0.1
[HS–] = 3.33 × 10–8 M
From the second ionisation of H2S,
 2– 2
[H ] [S ] 0.3  [S ]
– = Ka2 or 8 = 1.3 × 10–13
[HS ] 3.33  10
[S2–] = 1.44 × 10–20 M
[ 229 ]
Ionic Equilibrium
Illustration 2: Nicotinic acid (Ka = 1.4 × 10–5) is represented by the formula HNic. Calculate its percent
dissociation in a solution which contains 0.10 mol. of nicotinic acid per 2.0 litre of solution.
Solution : HNic Nic– + H+

(1 – )c c c
where,  is the dissociation of the acid and c is the concentration of nicotinic acid.
[H  ][Nic – ] c  c 
 c
Ka = = (1– )c or
[HNic ] 1– 
0.1 mol
c = = 0.05 mol/litre
2.0 litre

  0.05
1.4 × 10–5 =
1– 
 = 0.016594
 Percent dissociation = 0.016594 × 100 ~ 1.66%.
Illustration 3: How many moles of calcium hydroxide must be dissolved to produce 250 ml of an aqueous
solution of pH 10.65 ? Assume complete dissociation.
Solution : pH + pOH = 14
pOH = 14 – 10.65 = 3.35
[OH–] = 4.47 × 10–4 mol/litre
4
4.47  10
No. of OH– moles in 250 ml = = 1.12 × 10–4
4
1
No. of moles of Ca(OH)2 dissolved = × 1.12 × 10–4 = 0.56 × 10–4
2
Illustration 4: Saccharin (Ka = 2 × 10–12) is a weak acid represented by formula HSac. A 4 × 10–4 mole
amount of saccharin is dissolved in 200 cm3 water of pH 3. Assuming no change in volume,
calculate the concentration of Sac– ions in the resulting solution at equilibrium.
Solution : Calculation of [H+] and [HSac] at start

We know that [H+] = 10–pH = 10–3 = 0.001 M
4
4  10  1000
[Hsac] = = 0.002 M
200
The dissociation of HSac is as below
HSac. H + + Sac–
At start 0.002 0.001 0
At equb 0.002 – x 0.001 + x x
[H  ][Sac – ] (0.01 x) x
 Ka = = = 2 × 10–12
[Hsac] 0.002 – x
x = 4 × 10–12 M
 [Sac–]equb = 4 × 10–12 M
Illustration 5: Calculate the pH value of the mixture containing 50 c.c. of N HCl and 30 c.c. of N NaOH
solution both to be completely dissociated in normal solution.
Solution : Since, we know 30 c.c. of N NaOH will neutralise 30 c.c. of N HCl.

 Amount of N HCl left un-neutralised = 50 – 30 = 20 c.c.
Total volume after mixing = 50 + 30 = 80 c.c.
[ 230 ]
Ionic Equilibrium
In other words 20 c.c of N HCl has been diluted to 80 c.c.

Now, since 1000 c.c. of N HCl contain = 1 g eq of HCl
20 1
20 c.c. of N HCl contain = 1 × = geq.
1000 50
 1 
This  50 geq.  is the amount of HCl present in 80 c.c. of the mixture.
 
1
Thus, 80 c.c. of the mixture contain = g eq. of HCl
50
1 1000
1000 c.c of the mixture contain = × g eq. = 0.25 geq.
50 80
 [H+] = 0.25 g eq. per litre
We know that pH = –log [H+] = –log [0.25] = 0.6021
Illustration 6: The pH of a 0.10 M hydrocyanic acid solution is 5.2. What is the value of Ka for hydrocyanic
acid ?
Solution : HCN + H2O H3O+ + CN–

(0.1 – x) x x
+
–5.2 = log[H3O ]
[H3O ] = 6.3 × 10–6
+
or x = [H3O+] = 6.3 × 10–6 M/l
[H3O  ][CN – ] x x
Ka = = 0.1  x
[HCN]
6 6
6.3  10  6.3  10
= 6 = 39.6 × 10–11
0.1  6.3  10

Problem 1: The pH of a 0.005 M aqueous solution of sulphuric acid is approximately:
(a) 0.005 (b) 2
(c) 1 (d) 0.01
Solution: (b) 0.005 M H2SO4  2 × 0.005 N H2SO4

= 0.01 N H2SO4
Thus, [H+] = 10–2 M
pH = 2
Problem 2: The pH of the solution obtained by mixing 10 mL of 10–1 N HCl and 10 mL of 10–1 N
NaOH is:
(a) 8 (b) 2
(c) 7 (d) None of these
Solution: (c) Meq. HCl = 10 × 10–1 = 1

Meq. of NaOH = 10 × 10–1 = 1
Thus, both are neutralized and 1 Meq. of NaCl (a salt of strong acid and strong base)
which does not hydrolyse and thus, pH = 7.
[ 231 ]
Ionic Equilibrium
Problem 3: When 10–8 mole of HCl is dissolved in one litre of water, the pH of the solution will be:
(a) 8 (b) 7
(c) above 8 (d) below 7
Solution: (d) [HCl] = 10–8 M, Being very dilute pH < 7.
Problem 4: 1 M solution of an acid has a pH of 5. Which of the following is the most reasonable
explanation for this acid?
(a) The acid is too dilute
(b) It is a strong acid
(c) It reacts with water to produce a high concentration of hydronium ions
(d) It is a weak acid
Solution: (d) 1 M solution of strong acid must have pH = 1. Since, pH =5 which is possible only when
acid is weak, [H+] = C.
Problem 5: The gastric juice in our stomach contains enough hydrochloride acid to make the hydrogen
ion concentration about 0.01 mol/litre. The pH of the gastric juice is
(a) 0.01 (b) 1
(c) 2 (d) 14
Solution: (c) [H+] = 10–2 M

pH = 2
Problem 6: 10–6 M HCl is diluted to 100 times. Its pH is

(a) 6.0 (b) 8.0
(c) 6.95 (d) 9.5
Solution: (c) New concentration of
106
HCl   108 M
100
[H  ]  108  107 = 1.1 × 10–7 M
 pH  7
Problem 7: The ionic product of water at 60°C is 9.61 × 10–14. The pH of water at 60°C is
(a) 6.51 (b) 6.70
(c) 9.61 (d) 4.8
Solution: (a) pH   log[H ] and [H  ]  9.611014
 pH  6.51
Problem 8: pH of 0.05 M Mg(OH)2 is

(a) 13 (b) 10
(c) 1 (d) Zero
Solution: (a) [OH–] = 2 × 0.05 = 0.1

pOH  1 and pH = 13
[ 232 ]
Ionic Equilibrium
Problem 9: The number of mole of hydroxide [OH–] ion in 0.3 litre of 0.005 M solution of Ba(OH)2 is
(a) 0.0075 (b) 0.0015
(c) 0.0030 (d) 0.0050
Solution: (c) Mole OH– = M × Vin litre
No. of OH– 0.3 × 0.005 × 2 = 0.0030
Problem 10: At 25°C, Kb for a base BOH is 1.0 × 10–12. The [OH–] in 0.01 M aqueous solution of
base is:
(a) 1.0 × 10–6 M (b) 1.0 × 10–7 M
(c) 1.0 × 10–5 M (d) 2.0 × 10–6 M
Solution: (b) BOH B  OH 

(1α) cα cα
 
[B ][OH ]
Kb   [OH  ]2
BOH
[OH  ]2  K b  [BOH]
[OH  ]2  1 1012  0.01 = 1× 10–14
6.2 Hydrolysis of Salt

It is the process involving action of water on a salt to form a mixture of acid and alkali.
The hydrolysis of a salt is reverse of neutrilization.
Let there be a salt BA. The hydrolysis of such a salt can be represented as
H2O + AB HA + BOH
water salt acid base
[HA] [BOH] [HA] [BOH]

K = [AB][H O]  K[H2O] = [AB]
2
[HA] [BOH]
 Kh = [AB] where Kh = hydrolysis constant.
The hydrolysis constant is dependent on nature of acid or base which is formed as a result of
hydrolysis.
Degree of hydrolysis
Let C moles/lit. of salt be taken then C moles/lit. of cation and anion will be formed respectively.
C
BA B+ + A–
C mole/lit. C mole/L.
Let ‘h’ be the degree of hydrolysis of A–
 Ch moles/lit. of A– will take part in hydrolysis and Ch moles/lit. of HA and Ch moles/lit. of [OH]
will be formed.
C O O O
A– + H2O HA + OH–
[ 233 ]
Ionic Equilibrium
At equilibrium (C – Ch) Ch Ch
conc. in moles/L.

[HA][OH ] 2
 Kh = – = Ch
[A ] 1– h
When h <<<< 1  Kh  Ch2
Kh
 h= = K hV .
C
This shows degree of hydrolysis increases with dilution.
Degree of hydrolysis is directly proportional to the square root of volume of solution in litres containing
one mole of salt.
1
Also h C
Degree of hydrolysis in inversely proportional to the square root of concentration of salt in moles/lit.
pH of solution
Kh
[OH–] = Ch = C × C
Kw
(OH–) = K hC = C
Ka
1 1 1 1
pOH = pKw – logC – log K
2 2 2 a
1 1 1 1
= pKw – logC – log K
2 2 2 a
1 1 1
pOH = pKw – logC – pKa
2 2 2
1 1 1
= × 14 – logC – pKa
2 2 2
1 1
pOH =7– logC – pKa
2 2
1 1
 pH = 14 – pOH = 7 + pKa + logC
2 2
Anionic Hydrolysis : It is the Hydrolysis of salts of Weak acids and Strong Base, e.g.
CH3COONa, Na2CO3, K2CO3, KCN, Na2S, etc.
Let the salt hydrolysis be represented as
BA + H2O BOH + HA
BA B+ + A–
[ 234 ]
Ionic Equilibrium
Since A– is a strong base is under hydrolysis according to the equation
A– + H2O HA + OH–
This is called anionic hydrolysis
[HA] [OH – ]
Kh = [A – ]
Multiplying and dividing RHS by H+ we get

   
[HA] [OH – ][H  ] K w
  K w  [H  ][OH  ] K a  [H ][A ] 
Kh = [A – ][H  ] Ka  [HA] 
 
Kw
Hence, hydrolysis constant = Kh = K
a
1
 Kh  K i.e., hydrolysis constant varies inversely with dissociation constant of acid.
a
Cationic Hydrolysis
It involves the hydrolysis of a salt of strong acid with a weak base e.g. NH4Cl, (NH4)2SO4, NH4NO3,
BaSO4, FeCl3, etc.
These solutions are acidic solution,
BA + H2O HA + BOH
salt stong acid weak acid
Here the salt dissociates to form the cation and the anion. Let C moles of salt be taken in one litre
solution and ‘h’ be the degree of hydrolysis.
BA B+ + A–
Initial conc. (mole/lit.) C 0 0
B+ + H2O BOH + H+
Final conc. (mole/lit.) (C – Ch) Ch Ch

[H ][BOH] 2
Kh =  = Ch
[B ] 1– h
 –  –
Kw [H ][OH ] [H ][OH ]
Kh = K = = 
b [B ][OH – ] [B ]
[BOH]
1
Kh  K
b
Since, h <<< 1  Ch2 = Kh
 h= K h /C = K hV
1
h C and h  V
[ 235 ]
Ionic Equilibrium
pH of solution
Kw
[H+] = Ch = K hC = C
Kb
1 1 1 1
pH = – log Kw – log K – logC
2 2 b 2
1 1 1
= pKw – pKb – logC
2 2 2
1
pH = 7 – [pKb + logC]
2
Cationic and Anionic Hydrolysis

Salts of Weak Acids and Weak Bases
Here both cation and anion undergo hydrolysis.
BA + H2O HA + BOH
weak acid weak base
Let C moles per litre of salt solution be taken.
Let the degree of hydrolysis be ‘h’
BA B+ + A–
C moles/lit. C moles/lit
Cationic Hydrolysis Anionic Hydrolysis
conc. of B+ + H2O BOH + H conc. of A– + H2O HA + OH–
equilibrium (C – Ch) Ch Ch equilibrium (C – Ch) Ch Ch
BA B+ + A–
B+ + A– + H2O BOH + HA
weak base weak acid
 –
[BOH][HA] [H ][OH ][HA][BOH]
Kh =  – = –  – 
[B ][A ] [OH ][B ][A ][H ]
Kw [BOH][HA]
Kh = K K =  –
a b [B ][A ]
2
Ch Ch h
Kh = C(1– h) C(1– h) = 2
(1 h)
 When h <<< 1
h2 = Kh or h = Kh
So degree of hydrolysis is independent of the concentration of salt taken.
[ 236 ]
Ionic Equilibrium
1
Also, pH = ( pKw + pKa – pKb )
2
When pKa > pKb then solutions alkaline and anionic hydrolysis takes place more than cationic hydrolysis
when pKa < pKb then solution acidic and cationic hydrolysis takes place more than anionic hydrolysis.
When pKa = pKb solution neutral and extent of anionic and cationic hydrolysis are equal.
Common Ion Effect

When a solution of weak electrolyte is mixed with another electrolyte which provides one or more
ion common with the weak electrolyte the dissociation of weak electrolyte is suppressed. This
suppression of dissociation of weak electrolyte on addition of a common ion is called common ion
effect.
For example, if we consider dissociation of CH3COOH in the presence of CH3COONa we get

following situation :
CH3COOH CH3COO– + H+
CH3COONa CH3COO– + Na+
In this case the CH3COO– ion contributed by CH3COONa suppresses the dissociation of CH3COOH.
This suppression of dissociation of CH3COOH is called common ion effect.
Buffer Solutions
A buffer is a solution which resists any change in its pH value on either (a) dilution or (b) addition of
acid/base. The process by which the added H+/OH– are removed to maintain the pH of solution, is
known as buffer action.
Types of Buffer :
1. Simple buffers : - A salt of weak acid and weak base in water, e.g.
(a) NH4CN or CH3COONH4.
(b) Proteins and amino acids.
(c) A mixture of an acid salt and normal salt of a poly basic acid.e.g.,
NaHCO3 + Na2CO3
Na2 HPO4 + Na3PO4
2. Mixed Buffer : These are of two types:
Acid Buffer Solution : An acidic buffer solution of a weak acid and its salt with strong base.
e.g., CH3COOH + CH3COONa

CH3COOH CH3COO– + H+ (Weakly ionized)
CH3COONa CH3COO– + Na+ (Highly ionized)
[ 237 ]
Ionic Equilibrium
The sodium acetate, being a salt ionizes completely to form CH3COO– and Na+ ion. But acetic
acid being a weak acid is ionized to a less extent. Also its ionizations is further suppressed by the
acetate ion from sodium acetate.
Let C moles/litre be the concentration of CH3COOH taken and C1 be the concentration of

CH3COONa.
The degree of dissociation of CH3COOH is a in the presence of sodium acetate
 Initial conc. (mol/lit.) C 0 0

CH3COOH CH3COO + H+
Final conc. (mol/lit.) (C – C) C C
Initial conc.(mol/lit.) C1 0 0
CH3COONa CH3COO– + Na+
Final conc.(mol/lit.) 0 C1 C1
Hence, in the solution:
CH3COOH concentration = (C – C)
CH3COO– concentration = C + C1
H+ concentration = CH+ = C
But since  is very small [CH3COOH] = (C – C)  C. [CH3COONa] = C + C1  C1
C CH – CH  C
3COO
Ka= C CH 3COOH = CH+ = Ka × C
1
C1
 pH = – log CH+ = PKa + log
C
 pH = pKa + log [Salt]
[Acid]
This equation is called Henderson’s equations.
Buffer Action
When a few drops of acid is added then the H+ ions from the acid combines with excess of CH3COO–
ions to form CH3COOH. Hence, there is no rise in [H+] ion concentrations but due to the consumptions
of CH3COO– the concentration of CH3COO– decreases and the concentration of CH 3COOH
[Salt]
increases hence the ratio of [Acid] decreases slightly. Thus, the pH change is minimal, meaning the
solution has resisted the change in pH.
In other words one can say the pH change which is very minimal is not due to change in concentration
of [H+] but due to change in buffer capacity of solution.
On the other hand when NaOH is added, the [OH–] ions of the base reacts with the unionized
CH3COOH to form acetate ion and water. OH– + CH3COOH  CH3COO– + H2O
[ 238 ]
Ionic Equilibrium
Basic Buffers: A basic buffer solution consists of a mixture of a weak base and its salt with a
strong acid.
e.g., mixture of NH4OH and NH4Cl.
NH4OH NH4+ + OH– Weakly ionized
NH4Cl NH4+ + Cl– Highly ionized
The NH4+ ions of NH4Cl suppress the ionization of NH4OH due to common ion effect.
Let the concentrations of NH4OH taken be C moles/lit. and -be the degree of ionization after
adding NH4Cl. Let C1 be the concentration of NH4Cl taken.
Initial conc. (mol/lit.) C 0 0
NH4OH NH4 OH–

+
Final conc. (mol/lit.) (C – C) C C

Initial conc.(mol/lit.) C1 0 0
NH4Cl NH4 + Cl–
+
Final conc.(mol/lit.) 0 C1 C1
The concentration of
[NH4+] = C1 + C  C1 [  1]
[NH4OH] = C – C  C [  1]
[OH–] = C.
C NH  C OH – C NH 4 OH
4
Kb = C NH 4OH  COH– = Kb C NH 
4
C NH 
4 C
 pOH = pKb + log C = pKb + log 1
NH 4 OH C
[Salt]
 pOH = pKb + log [Base]
Buffer Action: When few drops of base say NaOH is added then the OH– ions added react with
NH4+ to form NH4OH and thus the concentration of [OH–] remains unchanged. But the ratio of
[NH 4  ]
changes.
[NH 4OH]
Thus, the change in pH is very small and that too due to change in buffer capacity.
On the other hand when a few drops of acid (Say HCl) is added, then the [H+] ions of acid combine
with excess of NH4OH to form H2O and NH4+ ions,. i.e., NH4OH + H+ NH4+ + H2O.
Thus, the addition of acid does not increase the H+ ions but since the concentration of NH4OH

+ [NH 4 ]
decreases and [NH4 ] ion conc. increases, the ratio increases and thus pH changes
[NH 4 OH]
infinitively.
Also, the pH of buffer changes with temperature because Kw of water changes with temperature.
[ 239 ]
Ionic Equilibrium
Buffer Capacity : It is defined as the number of moles of the acid/base added to the buffer solution
to produce a change in pH by one unit.
number of moles of acid/base added

Buffer Capacity = change in pH
In general Buffer Capacity would be maximum when both components are present in equimolar
proportions.
A given acid must have a pH ranging between pKa + 1 to pKa – 1 if it is to be used in buffer solution.
The best buffer will have the acid with pH = pKa.
Illustration 1: An aqueous solution contains 10% ammonia by mass and has a density of 0.99 g cm–3.
Calculate hydroxyl and hydrogen ion concentration in this solution.
+ –10
(Ka for NH4 = 5.0 × 10 M)
Solution : [OH–] in aqueous solution of NH4OH can be determined from the following relation.
[OH–] = Kb  c
(a) Determination of the value of Kb

14
Kw 1  10 –5
Kb = K = 10 = 2 × 10
a 5.0  10
(b) Determination of concentration (molarity) c of NH4OH solution

Wt. of NH3 in 100 ml of NH4OH solution = 10 gm
100
Vol. of 100 g of NH4OH solution =
0.99
w 1000 10  1000  0.99 99

Molarity = m V = 17  100 =
17
(c) Determination of [OH–]
[OH–] = Kb C
5 99 19.8
= 2  10 
17 = 10–2 17
= 10–2 1.16
[OH–] = 10–2 × 1.077 mol l–1 = 1.077 × 10–2 mol l–1
14
+
10 –13
[H ] = 2 = 9.28 × 10 mol l–1
1.077  10
Illustration 2: How many grams of NH4Cl should be dissolved in 500 ml of water to have solution of pH
4.5? Kb for ammonium hydroxide is 1.8 × 10–5.
Solution : pH = –log[H+]
log[H+] = log 1 – 4.5 = 5 .5
[ 240 ]
Ionic Equilibrium
 [H+] = Antilog [5.5] = 3.162 × 10–5 mole per litre

Kw  c
[H+] = hc = Kb
 2
Kw  c [H ]  K b
+ 2
or [H ] = K  Kw
b
5 5 5
3.162  10  3.162  10  1.8  10
c= 14 = 1.8 mole/litre
1  10
1000 ml contains 1.8 moles
1 .8
500 ml contains = 0.9 moles
2
Weight of gms. = Numbers of moles × Mol. wt. of NH4Cl

= 0.90 × 53.5 = 48.150 gm
Illustration 3:: Calculate the pH at the equivalence point when a solution of 0.10 M acetic acid is titrated
with a solution of 0.10 M sodium hydroxide. Ka for acetic acid is 1.9 × 10–5.
Solution : We know that pH of a mixture of solution containing weak acid and strong base can be
calculated as below.
1 1
pH =7+ pKa + log c
2 2
1 1
=7+ × 4.7212 + log 0.05
2 2
= 7 + 2.3606 – 0.65 = 8.71
Illustration 4: Calcium lactate is a salt of a weak organic acid and represented as Ca (Lac)2. A saturated
solution of Ca (Lac)2 contains 0.13 mol of this salt in 0.50 litre solution. The pOH of this
solution is 5.60. Assuming a complete dissociation of the salt, calculate Ka of lactic acid.
Solution : Ca (Lac)2 Ca 2+ + 2 Lac–

0.13 × 2 M 2 × 0.26 M
 Concentration of the lactate ion (c) = 0.52

Also, we are given pOH = 5.6  pH = 14 – 5.6 = 8.4
K w = 10–14 or log Kw = –14
Substituting the values in the following equation for the salt of a weak acid and strong alkali.
1
pH = (log Kw + log Ka – log c)
2
1
8.4 = – (–14 + log Ka – log 0.52)
2
Ka = 8.26 × 10–4
[ 241 ]
Ionic Equilibrium

Problem 1: What is [H+] mol/L of a solution that is 0.20 M in CH3COONa and 0.1 M in CH3COOH? Ka
for CH3COOH is 1.8 × 10–5
(a) 3.5 × 10–4 (b) 1.1 × 10–5
(c) 1.8 × 10–5 (d) 9.0 × 10–6
[Conjugate base]
Solution: (d) pH  pK a  log
[Acid]
0.2
  log1.8  105  log = 5.045
0.1
 [H  ]  9.0  106
Problem 2: A buffer solution is prepared in which the concentration of NH3 is 0.30 M and the concentration
of NH 4 is 0.20 M. If the equilibrium constant Kb for NH3 equals 1.8 × 10–5 what is the pH
of this solution? (log 2.7 =–0.43)
(a) 8.73 (b) 9.08
(c) 9.43 (d) 11.72
 Conjugate acid 
Solution: (c) pOH = pK b + log
 base
0.2
= -1og 1.8  105  log
0.3
= -log1.8×10-5 + log0.66
= 4.744 - 0.176 = 4.567
pH=14 - 4.567 = 9.423
Problem 3: The ionization constant of ammonium hydroxide is 1.77 × 10–5 at 298 K. Hydrolysis constant
of ammonium chloride is:
(a) 5.65 × 10–12 (b) 5.65 × 10–10
(c) 6.50 × 1012 (d) 5.65 × 10–13
Kw 10-14
Solution: (b) K H = = = 5.65×10-10
K b 1.77 ×10-5
Problem 4: A weak acid HA after treatment with 12 mL of 0.1M strong base BOH has a pH of 5. At the
end point, the volume of same base required is 26.6 ml. Ka of acid is
(a) 1.8 × 10–5 (b) 8.12 × 10–6
(c) 1.8 × 10–6 (d) 8.2 × 10–5
Solution: (b) For neutralisation,

Total Meq. of acid = Meq. of base = 26.6  0.1 = 2.66
Now, for partial neutralisation of acid
[ 242 ]
Ionic Equilibrium
HA  BOH 
 BA  H 2 O
Meq. before reaction 2.66 1.2 0 0
Meq. after reaction 1.46 0 1.2 1.2
The result mixture acts as a buffer and [HA] and [BA] may be placed in terms of
Meq. since volume of mixture is constant.
Conjugate base
 pH   log K a  log
 Acid 
1.2
or, 5   log a  log 1.46
 
 K a  8.129  106
Problem 5: Solution prepared by dissolving equal number of mole of HOCl (Ka = 3.2 × 10–8) and NaOCl
is a buffer of pH:
(a) 8.0 (b) 3.2
(c) 7.5 (d) 4.8
Solution: (c) pH  pK a , if  Conjugate base    Acid 
Problem 6: What volume of 1.0 M sodium formate solution should be added to 50 ml of 0.05M formic
acid to produce a buffer solution of pH = 4.0 (pKa of formic acid = 3.80)?
(a) 1.21 × 10–6 ml (b) 39.62 ml
(c) 40 ml (d) 40.62 ml
Solution: (b) Let V mL of 0.1M HCOONa be mixed to 50 mL of 0.05 M HCOOH.
 Total millim ole 

 
Total volume 

0.1  V
 In mixture [HCOONa] =  V  50 
50  0.05
  HCOOH  
V  50
Conjugate base
 pH   log K a  log  Acid 
 0.1  V  V  50 
 4.0  3.80  log 2.5 /  V  50 
 V = 39.62 mL
Problem 7: Buffering action of a mixture of CH3COOH and CH3COONa is maximum when the ratio
of salt to acid is equal to
(a) 1.0 (b) 100.0
(c) 10.0 (d) 0.1
Solution: (a) The buffer action of a buffer mixture is effective in the pH range pK a  1. It is
maximum when pH  pK a .
[ 243 ]
Ionic Equilibrium
Problem 8: 0.1 M acetic acid solution is titrated against 0.1 M NaOH solution. What would be the
difference in pH between 1/4 an d 3/4 stages of neutralization of acid?
(a) 2 log 3/4 (b) 2 log 1/4
(c) log 1/3 (d) 2 log 3
Solution: (d) CH 3COOH  NaOH 

 CH 3COONa  H 2O
0.3 0.1
 1 / 4 neutralisation 
4 4
1
 pH1  pK a  log
3
CH3 COOH  NaOH 
 CH3COONH 4  H 2 O
0.1 0.3
4 4
 pH 2  pK a  log 3
1
 pH1  pΗ 2  log  log 3  2log3
3
Problem 9: For preparing a buffer solution of pH 6 by mixing sodium acetate and acid, the ratio of
concentration of salt and acid (Ka =10–5) should be
(a) 1 : 10 (b) 10 : 1
(c) 100 : 1 (d) 6.85
[salt]
Solution: (b) pH  pK a  log
[acid]
10 [salt]
 5  log if  10 :1, Then
1 [acid]
pH = 6
Problem 10: If 50 ml of 0.2 M KOH is added to 40 ml of 0.5 M HCOOH, the pH of the resulting is
(Ka = 1.8 × 10–4).
(a) 3.75 (b) 5.6
(c) 7.6 (d) 3.4
Solution: (a) Meq. KOH =50 × 0.2 = 10
Meq. of HCOOH =40 × 0.5 = 20
Thus, Meq. of HCOOH left = 10
Meq. of HCOOK formed = 10
[Conjugate base]
 pH   log K a  log
[Acid]
6.3 Solubility
It is the amount of the solute in gram that can be dissolved in 100 gm of a solvent to obtain a saturated
solutions at a particular temperature.
However, solubility can also be expressed in moles/litre.
Solubility in gms/lit.
Solubility of solution in moles/litre = Molecular weight of solute
[ 244 ]
Ionic Equilibrium
The factors affecting solubility are:
(a) Nature of solvent

(b) Nature of solute
(c) Temperature
(d) Pressure
Solubility Product: If a sparingly soluble salt is added in water, very little amount of it dissolves in
water, and thus solution becomes saturated, but for a highly soluble salt saturation is reached on
dissolving more of salt.
For all salts at saturation an equilibrium is achieved between the undissolved salt and the ions in
solutions.
BA(s) B+(aq)+ + A–(aq)
Applying law of mass action we get
[A – ] [B  ]
K= [BA]
 K[BA] = [B+] [A–]
Since, only little of salt dissolves so, the concentration of salt remains constant,
 K[AB] = K × Constant = Ksp = [B+] [A–]
For any salt,
BxAy xB y +(a q) + yAx– (aq)
Ksp = [By+]x [Ax–]y
Ksp = Kc This expression shows that in a saturated solution of a sparingly soluble salt the ionic
product is equal to the solubility product.
Ksp = Solubility Product
It is defined as the product of the molar concentrations of its ion raised to the power equal to its
number of ions present at equilibrium representing the ionization of one molecule of salt at a given
temperature.
Points to Remember :
(1) When Ksp = Ki solution saturated.
(2) When Ki < Ksp unsaturated solution.
(3) When Ki > Ksp super saturated solution.
Hence, precipitation occurs to keep Ki = Ksp
[ 245 ]
Ionic Equilibrium
Relationships Between Solubility and Solubility Product

Let the solubility of a salt.
Bx Ay in water be s moles/lit.
Thus at equilibrium,
–
BxAy xB y +(a q) + yAx (aq)
At equilibrium xs mol/lit ys moles/lit.

–
 Ksp = [By+]x [Ax ]y
= (xs)x (ys)y
Ksp = xx y y sx + y
Hence, for salts of type MA (AgCl, BaSO4, etc.)
Ksp = s2  s = K sp
For M2A type of salts
Ksp = 4 s3  s= 3 K sp / 4
For MA3
Ksp = 27 s4  s = 4 K sp / 27
Illustration 1: The solubility of BaSO4 and BaCrO4 at 25°C are 1 × 10–10 and 2.4 × 10–10 respectively.
Calculate the simultaneous solubilities of BaSO4 and BaCrO4.
Solution: Let the solubility of BaSO4 be x and that of BaCrO4 be y mole litre–1 in the presence of each
other
BaSO 4 (s) Ba 2  SO 42 ; BaCrO 4 (s) Ba 2  CrO 24
(x + y) x (x + y) y
[Ba 2 ][SO24 ]  1 1010  ( x  y) ...(i)
[Ba 2 ][CrO24 ]  2.4 1010  ( x  y ) y

Dividing (i) by (ii) we get
y
 2.4;  y  2.4 x
x
Substituting the value of y in (ii), we get
3.4x × x = 1 × 10–10
x = 5.42 × 10–4 M
y = 2.4 × 5.42 × 10–6 = 1.3 × 10–5 M
[ 246 ]
Ionic Equilibrium
Illustration 2: The solubility product of calcium oxalate is 2 × 10–4 at 25°C. Calculate the solubility of
calcium oxalate at this temperature. What will be its solubility in a 0.1 M solution at ammonium
oxalate? Assume that ammonium oxalate is completely ionized in solution. Name the effect,
which operates on addition of ammonium oxalate to calcium oxalate.
Solution: The solubility product, Ksp of calcium oxalate is given by
K sp  [Ca 2 ][C3O 24 ]  2 10 9
Let ‘s’ be the solubility of calcium oxalate in mole litre–1.

s2 = 2 × 10–9
s  2  10 4  4.472 10 3 mole/l.

Let the solubility of CaC2O4 be s in the presence of 0.1 M ammonium oxalate solution.
CaC2 O 4 Ca 2  C 2O 34
 2NH 4  C 2O 42
(NH 4 ) 2 C 2O 4 
0.1 M
Since, CaC2O4 is sparingly soluble, the concentration of C2O 42 derived from CaC2O4 is
negligible in comparison to 0.1
K sp  [Ca 2 ][C 2O 42 ]  s  0.1  2  10 4
2  104
s   2 108 mole/l
0.1
In the presence of ammonium oxalate, the solubility of CaC2O4 drops from 4.472 × 10–5
to 2 × 10–8 mole/l. This effect is called common ion effect.

Problem 1: A student wants to prepare a saturated solution of Ag+ ion. He has got three samples
AgCl (Ksp = 10-12 ), AgBr (Ksp = 10-13 ) and Ag2 CrO4 (Ksp = 10-12 ).
Which of the above compound will be used by him using minimum weight to prepare
the saturated solution?
(a) AgCl (b) AgBr
(c) Ag2 CrO 4 (d) All of these
Solution: (b) (S) or mole of AgCl needed = K sp  105
(S) or mole of AgBr needed = K sp  3.16  107

K sp
(S) or mole of Ag 2 CrO 4 needed = 3  0.62  104
4
5 3
 Weight of AgCl = 10  143.5  1.435  10 g
7 5
 Weight of AgBr = 3.16  10  188  5.94  10 g
5 2
 Weight of Ag 2 C rO 4 = 6.2  10  332  2.058  10 g
[ 247 ]
Ionic Equilibrium
Problem 2: Ksp for sodium chloride is 36 mol2 /litre2 . The solubility of sodium chloride is :
1 1
(a) M (b) M
36 6
(c) 6M (d) 3600 M
Solution: (c) s  K sp  36  6M
Problem 3: The solubility product of a sparingly soluble salt AB at room temperature is 1.21  106 .
Its molar solubility is :
(a) 1.21  106 (b) 1.21  103
(c) 1.1  104 (d) 1.1  103
6
Solution: (d) s  K sp  1.21 10  1.1  103 M
Problem 4: The concentration of hydroxyl ion in a solution left after mixing 100 mL of 0.1M Mg Cl 2
11
and 100 mL of 0.2M NaOH  K sp of Mg  OH  2  1.2  10  is :
(a) 2.8  103 (b) 2.8  102

(c) 2.8  104 (d) 2.8  105
Solution: (c)  Mg  OH 2  2NaCl

MgCl 2  2NaOH 
milli mole before reaction 10 20 0 0

milli mole after reaction 0 0 10 20
2
Thus, 10m mole of Mg  OH 2 are formed. The product of  Mg 2    OH   is there-
2
 10   20  4
fore     5  10 which is more than K sp of Mg  OH 2 . Now, solubil-
 200   200 
ity (s) of
Mg  OH 2 can be derived by K sp  4s 3
23 4
Problem 5: The solubility products of Al  OH 3 and Zn  OH 2 are 8.5  10 and 1.8  10 respec-
tively. If NH 4 OH is added to a solution containing Al3 and Zn 2  ions, then substance
precipitated first is :
(a) Al  OH 3 (b) Zn  OH 2
(c) Both together (d) None at all
Solution: (a) Solubility of Al  OH 3 is lesser than Zn  OH 2 .
Problem 6: The pH at which Mg  OH 2 begins to precipitate from a solution containing 0.10M Mg 2 

11
ions  K sp of Mg  OH 2  1  10  is :
(a) 5 (b) 9
(c) 4 (d) 10
[ 248 ]
Ionic Equilibrium
Solution: (b) I.P. = [Mg2+] [OH– ]2

When I.P. = Ksp – precipitation starts
1 × 10–11 = [0.1] [OH– ]2
[OH– ] = 10–5 , pH = 9
Problem 7: Zn salt is mixed with  NH 4 2 S of molarity 0.021M. The amount of Zn 2 remains
unprecipitated in 12 mL of this solution  K sp of ZnS  4.51  10  which is :

24
(a) 1.677  1022 g (b) 1.767  1022 g

(c) 2.01 1023 g (d) None of these
Solution: (a)   NH 4 2 S  0.021M

2
 S   0.021M
2
 At equilibrium  Zn  S2   K sp of ZnS
24  
2 4.51  10
  Zn    2.15  1022 M
1000
2
  Zn  left in solution = 2.15  10  65g / litre
22
2.15  1022  65  12
 g / 12 mL  1.677  1022 g / 12 mL
1000
Problem 8: A saturated solution of Mg  OH 2 in water at 25ºC contains 0.11 g Mg  OH 2 per litre
of solution. The solubility product of Mg  OH 2 is :

2 3
(a)  0.11 (b)  0.11
3 3 3
(c) 4   0.11 (d) 4   0.11 /  58
3
Solution: (d) K sp  4s
0.11
Also, s  mol 3litre 1
58
 0.11 
 K sp  4   
 58 
Problem 9: If the solubility of Ca  OH 2 is 3. The solubility product of Ca  OH  2 is :
(a) 3 (b) 27
(c) 3 (d) 12 3
3
Solution:
3
(d) K sp  4s  4   3  12 3
Problem 10: The 100 mL of 0.1M AgNO3 solution solid K 2SO 4 is added. The concentration of
K 2SO 4 that shows the precipitation is,  K sp for Ag 2SO4  6.4  10 M  :
5
(a) 0.1M (b) 6.4  103 M

(c) 6.4  107 M (d) 6.4  105 M
 2 2
Solution: (b)  Ag  SO 4   K sp
6.4  105
SO24    2
 6.4  103 M
 
0.1
[ 249 ]
CLASS 12th
PAGE. NO
1.SOLUTIONS 1-48
2.ELECTROCHEMISTRY 117-150
3.CHEMICAL ADDED IN
LAST
KINETICS
Chapter - 1
SOLUTIONS
1.1 Introduction
When several non reacting substances are mixed, then there are three possible types of mixtures :
(a) Coarse mixture (Sand + Salt and Sugar + Salt)
(b) Colloidal dispersion (Gum + water and fine clay + water)
(c) True Solution (Salt + water)
In the coarse mixture there exists heterogeneity where as in true solutions there is complete
homogeneity, In colloidal dispersions the heterogeneity is not readily apparent and it is not homogeneous.
Distinction between Solute and Solvent

I. Phase Method: Let there be a substance ‘A’ in solid phase and ‘B’ in liquid phase then if the
phase of the resulting mixture is
(a) Solid, then Solute = B and Solvent = A.

(b) Liquid, then Solute = A and Solvent = B.
II. Amount Method: According to this method, the substance which is in larger proportion by mass
is solvent while the one in lesser proportion is solute.
Example: a solid mixture of A and B. If WA > WB then solute is B and solvent is A.
In the solutions of solids in liquids, where the liquid is usually present in large excess over the
solid, there is no ambiguity, here liquid is solvent and solid is solute.
However, when we deal with solubility of liquid.
Example: Acetone + water, here the one which is in larger quantity is solvent.
Saturated, Unsaturated And Super Saturated Solutions

Saturated Solution: A solution, which contains as much solute as it can hold at a given temperature
is said to be a saturated solution.
Unsaturated Solution: A solution which contains less solute than the amount of solute it can hold
then it is called unsaturated solution.
Super Saturated: A solution which contains more solute than the amount it can hold at a particular
temperature is called a super saturated solution.
Factors Influencing Solubility

The extent to which a substance will dissolve in another varies greatly with the substance, and
depends on nature of solute, solvent, temperature, and pressure.
[1]
Solutions
1. The effect of pressure on solubility is small unless gases are involved.

2. The effect of temperature however is very pronounced. The direction in which the solubility of
a substance in a solvent, changes with temperature depends on heat of solution.
(a) If the dissolution is exothermic then the solubility decreases with increase in temperature.
(b) If the dissolution is endothermic then the solubility increases with increase in temperature.
3. In general, the compounds with similar character are more readily soluble in each other. While
those with entirely different chemical characteristics will be very much insoluble.
Hence with these two extreme ends, a considerable number of intermediate stages are possible,
which we call as mutual solubilities, e.g.
(i) When ethyl alcohol and water are mixed, the two dissolve in each other in all proportions and
hence there is no saturation limit. Such substances are completely miscible.
(ii) When water and mercury are mixed they do not dissolve in each other at all and hence are
called completely immiscible.
(iii) Between these two extreme pairs we have liquid pairs as ether + water, phenol + water
which dissolve in each other to a limited extent only. Liquid pairs of these kinds are called
partially miscible.
Types of Binary Solutions (Table-1)
S.No. Solute Solvent Example of solution

1. Solid Solid Alloy (Brass)
2. Liquid Solid Hydrated salts butter
3. Gas Solid H2/Ni adsorption
4. Solid Liquid Sugar in water
5. Liquid Liquid Alcohol in water
6. Gas Liquid Cold Drinks
7. Solid Gas Dust, Smoke
8. Liquid Gas Fog
9. Gas Gas Air
Expressing concentration of Solutions

Concentration of a solution is defined as the amount of solute dissolved in a known amount of the
solvent or the solution.
The concentration of a solution can be expressed in various ways as follows:
1. Percentage of Solution:
[2]
Solutions
The formula for calculating percentage concentration is:
Mass of the component in the solution

Mass % of a compound (w/w %) =  100
Total mass of solution
Mass of the component in the solution
Mass / volume % of a component (w/v %) = 100
Total volume of the solution (in ml)
Volume of the component
Volume percentage of a component (v/v %) = 100
Total volume of the solution
2. Strength: Strength of a solution is defined as the amount of solute present in one litre of solution.
So, it is expressed in gm L–1.
Mass of solute (in gm)

 Strength of a solution =
Volume of the solution in litres
3. Molarity (M): Molarity of a solution is defined as the no. of moles of solute dissolved in one litre
of solution.
No. of moles of solute

 Molarity of a solution (M) =
Volume of solution in litres
Mass of solute (w)
No. of moles of solute (n) =
Molar mass of solute
Also, M1V2 = M2V2 Dilution formula
4. Molality (m): Molality of a solution is defined as the no. of moles of solute dissolved in 1 kg of
solvent.
No. of moles of solute

 Molality of a solution (m) =
Mass of solvent in kg
5. Mole Fraction (x): Mole fraction is being calculator for both solute and solvent in a solution.
It is defined as the no. of moles of a component upon total no. of moles of all the components
present in the solution.
n2
 Mole fraction of solute (n2 ) 
n1  n2
n1
and mole fraction of solvent (n1 )  n  n
1 2
Where, n2 and n2 are the no. of molar of solvent and solute respectively.
Also, n1  n2  1
 n1  1  n 2 and n2  1  n1
6. Normality (N): Normality of a solution is defined as no. of gram equivalent of solute per litre of
solution.
[3]
Solutions
No. of gm. equivalents of solute

  Normality of a solution (N) =
Mass of solute
 No. of gram equivalents of solute =
Equivalent mass (or wt.) of solute
Molar mass of solute
 Equivalent mass (or wt.) of solute =
n - factor
 n - factor = basicity of an acid or acidity of a base or No. of electrons involved during the
reaction by a salt or an oxidising agent or a reducing agent.
 Basicity of an acid = No. of H+ ions liberated by an acid during reactions.
Example: HCl (nf = 1), H2SO4 (nf = 2), H3PO4 (nf = 3), CH3COOH (nf = 1), etc.
Acidity of a Base = No. of OH– ions liberated by a base during the reaction.
Example: NaOH (nf = 1), Ca(OH)2 (nf = 2), Al(OH)3, (n = 3), etc.
No. of electrons involved during the reaction by a salt
Example: NaCl (nf = 1), CaCl2 (nf = 2), Al2(SO4)3 (nf = 6), Fe2O3 (nf = 6), SnCl4 (nf = 4), etc.
 Normality equation: N1V1  N 2 V2
 Normality (N) = Molarity (M) × nf

N
 N  M  n f and M 
nf
 Milliequivalent (meq.) = N × V ml
meq. of an acid = meq. of a base
N1 V1  N 2 V2
Also, N 3  (V1  V2 ) (here V1 + V2 = V3)
Illustration 1: A solution contains 25% water, 25% ethanol and 50% acetic acid by weight. Find out the
mole fraction of each component.
Solution: Let us consider that total mass of the solution is 100 g

Mass of water = 25 g
Mass of ethanol = 25 g
Mass of acetic acid = 50 g
25
Moles of water = = 1.388
18
25
Moles of ethanol = = 0.543
46
50
Moles of acetic acid = = 0.833
60
[4]
Solutions
1.388
Mole fraction of water = 1.388  0.543  0.833 = 0.502
0.543
Mole fraction of ethanol = 1.388  0.543  0.833 = 0.196
0.833
Mole fraction of acetic acid = 1.388  0.543  0.833 = 0.301
Illustration 2: Find out the mass of sodium bromate and molarity of solution necessary to prepare 85.5 ml
of 0.672 N solution where the half cell reaction are
(i) BrO3– + 6H+ + 6e– — Br– + 3H2O
(ii) BrO3– + 12H+ 10e– — Br2 + 6H2O
Solution: For equation (i)
Molecular weight 151

Equivalent weight of NaBrO3 = = = 25.167
6 6
Mass of NaBrO3 is solution = N  V in litre  Equivalent weight

85.5
= 0.672   25.167 = 1.446 g
1000
Normality 0.672
Molarity = No. of electrons accepted = = 0.112
12
6
For equation (ii)

Mol. wt. 151
Equivalent weight of NaBrO3 =  = 15.1
10 10
85.5
Mass of NaBrO3 in solution = 0.672  15.1 = 0.867 g
1000
Normality 0.672
Molarity = No. of electrons accepted  10 = 0.0672

Problem 1: The volume of 95% H2SO4 (density = 1.85 g cm–3) needed to prepare 100 cm3 of 15%
solution of H2SO4 (density = 1.10 g cm–3) will be
(a) 5 cc (b) 7.5 cc
(c) 9.4 cc (d) 12.4 cc
95 1
Solution: (c) Molarity of 95% H2SO4    1000  17.93M
98 100 / 1.85
Molarity of 15%
15 1
H2SO4   1000  1.68 M
98 100 /1.10
M1V1  M 2 V2
(95% H2SO4 ) (15% H2SO4 )
17.93  V1  1.68  100 or V1  9.4 cm3
[5]
Solutions
Problem 2: An X molal solution of a compound in benzene has mole fraction of solute equal to 0.2. The
value of X is
(a) 14 (b) 3.2
(c) 1.4 (d) 2.0
Solution: (b) x1 =0.2,  x2 = 0.8

n2 n1
i.e., n  n  0.2 and n  n  0.8
1 2 1 2
n2 0.2 1
Dividing n  0.8  4
1
If n1 =1000 g = 1000/78 mol = 12.8 mol,
12.8
n2   3.2, i.e., molality = 3.2
4
Alternatively, mole fraction of solute = 0.2

moles of solute = 0.2 mole, solvent = 1 – 0.2 = 0.8 mole
Mass of solvent = 0.8 × 78 g = 62.4 g.
0.2
Hence, moles of solute in 1000 g of solvent  1000 = 3.2
62.4
Problem 3: The normality of mixture obtained by mixing 100 ml of 0.2 M H2SO4 with 100 ml of 0.2 M
NaOH is
(a) 0.2 (b) 0.01
(c) 0.1 (d) 0.3
Solution: (c) 100 ml of 0.2 M H2SO4 = 100 × 0.2 millimoles

= 20 millimoles = 40 milli eq.
100 ml of 0.2 M NaOH = 100 × 0.2 millimoles
= 20 millimoles = 20 milli eq.
20 milli eq. NaOH neutralize 20 milli eq. of H2SO4
H2SO4 left = 20 milli eq.
Volume after mixing = 200 ml
20
 Normality =  0.1N
200
Problem 4: A 500 mL sample of the effluent from a water softener required 6 drops of standard soap
solution to produce a permanent lather. The soap solution had been calibrated against an
artificial hard water solution containing 0.136 g of CaCl2 per litre. On the average it required
28 drops of standard soap solution to lather 500 mL of the artificial sample. Then the hardness
of effluent sample in terms of ppm of CaCO3 is
(a) 123 ppm (b) 26 ppm
(c) 0.123 ppm (d) 38 ppm
[6]
Solutions
6
Solution: (b) Harness of effluent sample is th of the hardness of CaCl2 solution
28
Hardness of CaCl2 solution can be calculated as follows:
111 parts of CaCl 2 = 100 parts of CaCO 3 (Mol. wt. of CaCl 2 = 111,
Mol.wt. of CaCO3 = 100)
100
0.136 parts of CaCl2 =  0.136  0.123 parts of CaCO3
111
0.136g of CaCl2 in 1000 g of water = 0.123 g of CaCO3
 In 106 parts it will be = 123
i.e., Hardness of CaCl2 in terms of CaCO3 = 123 ppm
6
Hardness of effluent sample =  123  26 ppm
28
Problem 5: 250 mL of 6 M HCl and 630 mL of 3 M HCl were mixed together. The volume of water to
be added so that the molarity of the final solution is 3 M will be
(a) 250 mL (b) 1150 mL
(c) 500 mL (d) 975 mL
Solution: (a) M1V1 + M2V2 = M3(V1 + V2)

6 × 250 + 3 × 650 = M3 (250 + 650)
or 1500 + 1950 = 900 M3 or M3 = 3450/900 M
i.e., Molarity of solution after mixing = 3450/900 M
M1V1  M2 V2
Again applying (Before dilution ) (Before dilution )
3450
 900  3  V2  1150 mL
900
Volume of water to be added = 1150 – 900 = 250 mL
Problem 6: The molality and molarity of a sulphuric acid solution are 94.5 and 11.5 respectively. The
density of the solution is
(a) 1.15 g L–1 (b) 1.25 g L–1
(c) 1.35 g L–1 (d) 1.45 g L–1
Solution: (b) Molarity 11.5 means 11.5 moles of H2SO4 are present in 1 L of the solution. Suppose the
density of the solution is d g mL –1, then 1 L, i.e., 1000 mL of solution has
mass = 1000 d g. Thus, 1000 d of the solution contain H2SO4 = 11.5 moles = 11.5 × 98
g = 1127 g
1000 M
M
1000d  MM1
1000  11.5
94.5 
1000d  (11.5  98)
1248.7
d  1.2487 gL1
1000
[7]
Solutions
Problem 7: One litre of N/2 HCl solution is heated in a beaker. When volume of the solution was
reduced to 600 mL, 3.25 g of HCl was found to have been lost. The normality of the new
solution is
(a) 0.585 N (b) 0.685 N
(c) 0.785 N (d) 0.883 N
N 1
Solution: (b) 1 L of HCl contains HCl = × 36.5 g = 18.25 g
2 2
HCl now present = 18.25 – 3.25 = 15 g
Now volume = 600 ml = 0.600 L
15 1
Normality = mol   0.685N
36.5 0.600L
M
Problem 8: 5 g of NaOH is added to 250 mL of NaOH solution (density = 1.05 g/cm3). The density
4
of the new solution is formed to be 1.06 g/cm3. The molarity of the new solution will be
(a) 0.46 M (b) 0.56 M
(c) 0.66 M (d) 0.76 M
M
Solution: (d) 250 ml of NaOH  2.5 g NaOH
4
WNaOH = 5.25 + 2.5 = 7.5 g
Mass of solution = 250 × 1.05 = 262.5 g
262.5
Volume of solution = ml
1.06
7.5  1000  1.06
M  0.76 M
40  262.5
Problem 9: 250 mL of 0.10 M K2SO4 solution is mixed with 250 mL of 0.20 M KCl solution. The
concentration of K+ ions in the resulting solution is
(a) 0.30 M (b) 0.15 M
(c) 0.20 M (d) 0.40 M
Solution: (c) No. of moles of K+ in 250 ml of 0.1 M K2SO4

0.1 2
  250  0.05 mole
1000
No. of moles of K+ in 250 ml of 0.2 M KCl
0.2
  250  0.05 mole
1000
Total volume of the solution after mixing = 500 ml = 0.5 L
0.1 mole
Molar conc. of K+ in the final solution =  0.2 M
0.500 L
Problem 10: You are given one litre each of 0.5 M HCl and 0.2 M HCl. The ratio in which they should be
mixed so as to give maximum volume of 0.4 M HCl should be
(a) 3 : 2 (b) 2 : 3
(c) 2 : 1 (d) 3 : 1
[8]
Solutions
Solution: (c) Suppose V lire of 0.5 HCl is mixed with 1 litre of 0.2 M HCl to prepare 0.4 M HCl. Then
M1V1 + M2V2 = M3 (V1 +V2) gives
0.5 × V + 0.2 × 1 = 0.4 (V + 1)
or 0.5V + 0.2 = 0.4V + 0.4 or 0.1 V = 0.2
or V = 2 L
Thus, 2 L of 0.5 HCl is needed which is not available.
Again, suppose V litre of 0.2 M HCl is mixed with 1 litre of 0.5 M HCl to prepare 0.4 M
HCl. Then
M1V1 = M2V2 = M4 (V1 + V2)
0.2 × v = 0.5 × 1 = 0.4 (V +1)
or 0.2 V +0.5 = 0.4 V + 0.4 or 0.2V = 0.1
or V = 0.5 L
Thus, 0.5 L of 0.2 M HCl should be added to 1 litre of 0.5 M HCl to obtain 0.4 M HCl.
Volume of the 0.4 M HCl solution obtained =1.5 L
Then, ratio in which 0.5 HCl and 0.2 M HCl should be mixed = 1 L : 0.5 L = 2 : 1
Alternatively, suppose x L of 0.5 M HCl are mixed with y L of 0.2 M HCl to make
0.4 M HCl. Then,
M1V1 + M2V2 = M3(V1 + V2)
i.e., 0.5 x + 0.2 y =0.4 (x + y)
x 2
or 0.1 x +0.2 y or 
y 1
Thus, 0.5 M HCl and 0.2 M HCl should be mixed in the ratio of 2 : 1. As maximum
amount available is 1 L of each, thus means 1 L of 0.5 M HCl should be mixed with 0.5
L of 0.2 M HCl. Volume of 0.4 M HCl obtained = 1.5 L.
1.2 Solubility of Gases In Liquids

Gases dissolve in liquids to form true solutions, the degree of solubility depends on the nature of the
gas, the nature of the solvent, the pressure and the temperature. Gases like nitrogen, hydrogen and
helium dissolve to a slight extent, while gases like hydrogen chloride and ammonia are very soluble.
The large solubility of HCl and ammonia is accounted by the chemical reaction of these gases with
the solvent to form hydrochloric acid, and ammonium hydroxide respectively.
Under the same pressure and temperature:
(a) N2, CO2 are more soluble in CH3OH than in H2O.
(b) H2S and NH3, are more soluble in H2O than in C2H5OH.
From this it is quite clear that chemical similarity between solute and solvent leads to higher solubility.
e.g., Hydrocarbons vapours (non polar) are more soluble in other hydrocarbons (non polar) and
other organic solvents than they do in water. HCl vapours (polar) more soluble in H2O (polar) than in
CS2 (non polar).
[9]
Solutions
Factors Influencing Solubility of Gases in Liquids

The solubility depends upon
(i) Nature of solute or solvent (ii) Temperature (iii) Pressure (In case of gases)
1. Nature of Gas and Nature of Solvent: The solubility of gas in a given solvent varies considerably
with nature of the gas. Generally speaking, the gases which are easily liquified, are more soluble
in common solvents.
Thus, CO2 is more soluble than H2 and O2 in water or in any other solvent.
The gases which are capable of forming ions in aqueous solutions, are much more soluble in
water than in other solvents, e.g., Hydrogen chloride is highly soluble in water but not in benzene,
because HCl dissociates into H+ +Cl– in water: Similarly NH3 is highly soluble in H2O than in
benzene.
The solubility of gases is generally expressed in terms of absorption co-efficient (a). This is
defined as the volume of the gas reduced to STP dissolved by a unit volume of a solvent at the
temperature of the experiment and under a pressure of one atmosphere of the gas.
The absorption co-efficient of few gases at 20ºC in different solvents.
H2 N2 O2 CO 2
Solvent
H2O 0.017 0.015 0.028 0.88
C2H5OH 0.080 0.130 0.130 3.00
C 6H 6 0.066 0.104 0.105 —
2. Effects of Temperature: It has been found that under constant pressure the solubility of a gas
diminishes with rise in temperature. The absorption coefficient of a few gases at different
temperatures are
Temperature CO 2 O2 N2
0 1.713 0.0484 0.0239

10 1.194 0.0380 0.0196
20 0.878 0.0380 0.0196
30 0.665 0.0260 0.0138
40 0.530 0.0231 0.0118
3. Effects of Pressure on solubility of gases in liquids: The effect of pressure on the solubility
of a given gas in a particular liquid at constant temperature can be obtained by carefully observing
the process in reverse direction, viz., the gas as a solute which vapourizes to establish a vapour
pressure above the solution.
Henry’s Law: It states that at constant temperature the solubility of a gas in a liquid is directly
proportional to the pressure of the gas above it.
[ 10 ]
Solutions
When several gases are dissolved simultaneously in a solvent, the solubility of each gas from a
mixture of gases is directly proportional to the partial pressure of the gas mixture. The proportionality
constant will however be different for each gas.
The strict applicability of Henry’s law is limited to the lower pressure and at high pressures the law
becomes less exact.
Generally, higher the temperature and lower the pressure, the more closely is the law obeyed. This
law is not valid when the gas reacts with the solvent, or when the dissolved gas ionizes.
Solubility of Partially Miscible Liquids
These are pairs of liquids which dissolve in each other to a limited extent only.
There are four types of such partially miscible liquid -liquid systems.
Case-1: Those in which partial miscibility increases with increase in temperature
Example: C6H5OH + H2O, C6H5NH2 + H2O

C6H5NH2 + hexane, CH3OH + CS2
cyclohexane + CH3OH
Case-2: Those in which partial miscibility decreases with increase in temperature
Example: (C2H5)2NH + H2O, (C2H5)3N + H2O
Case-3 : Those in which partial miscibility increase both on increasing the temperature as well as
decreasing the temperature, in certain ranges
Example: H2O + Nicotine, and H2O + -picoline
Case-4: Those in which complete miscibility cannot be attained.
Example: ether + H2O
Nernst Distribution Law
H3BO3 is soluble in both water and amyl alcohol. But when a solution of H3BO3 in amylalcohol is
shaken with water, it is found that H3BO3 distributes itself in such a way that the ratio of the
concentration of H3BO3 in water and alcohol is a constant at a particular temperature.
Similarly iodine is soluble in H2O and CCl4 and the distribution of iodine in H2O and CCl4 remains
constant at a particular temperature.
This is also one of the direct consequences of thermodynamic requirement for equilibrium.
Let a substance ‘X’ be miscible in two immiscible pairs of solvents A and B. Then
aA
 Cons tan t  K
aB
aA
This equation a = Constant = K is a mathematical representation of Nernst distribution law..
B
[ 11 ]
Solutions
It states that a substance will distribute itself between two solvents until at equilibrium the ratio of the
activities of the substances in two layers is a constant at any given temperature.
Assuming the solution to be dilute or when solute behaves ideally the activity becomes equal to
concentration C and hence, we have
cB
K
cA
where K = distribution or partition co-efficient of solute between two solvents.
K depends upon:
(i) Nature of solute.
(ii) Nature of liquids involved.
(iii) The temperature at which the liquids are maintained.
(iv) The magnitude depends upon the manner in which the constant is represented CA/CB or CB/CA.

Problem 1: If N2 gas is bubbled through water a 293 K, how many millimoles of N2 gas would dissolve
in 1 L of water. Assume that N2 exerts a partial pressure of 0.987 bar. Given that Henry’s
law constant for N2 at 293 is 76.48 K bar.
(a) 0.716 (b) 716
(c) 7.16 (d) 71.6
Solution: (a) The solubility of gas is related to its mole fraction in a aqueous solution. The mole
fraction of the gas in its solution is calculated by applying Henry’s law. Thus,
pN 0.987 bar
χ N2  2   1.29  105
K H 76480 bar
As 1 L water contains 55.5 mol of it, therefore,
n mol n
χ N2    1.29  105
n mol  55.5 mol 55.5
Thus, n = 1.29 × 10–5 × 55.5 ml
= 7.16 × 10–4 mol
4 1000 mmol
= 7.16 10 mol  =0.716 mmol
1 mol
Problem 2: Henry’s law constant for oxygen dissolve in water is 4.34 × 104 atm at 25°C. If the partial
pressure of oxygen to air is 0.4 atm. Calculate the concentration (in mole per litre) of the
dissolved oxygen in water in equilibrium with air at 25°C.
(a) 5.11 × 10–3 M (b) 5.11 × 10–4 M
(c) 5.11 × 10–2 M (d) 5.11 × 10–1 M
[ 12 ]
Solutions
Solution: (b) Given:

Henry’s law constant KH = 4.34 × 104 atm
According to Henry’s law,
p  KHχ
n O2
pO2  K H 
n O2  n H2 O
n O2
0.4  4.34  104 
55.56  n O2
 n O  n H2 O
2
55.56  0.4
 n O2   5.1110 4
4.34  104
Since 5.11 × 10–4 mol are present in 1000 ml of solution, therefore, molarity is
5.11 × 10–4 M
Problem 3: Henry’s law constant for the solubility of N2 gas to water at 298 K is 1.0 × 105 atm. The
mole fraction of N2 in air is 0.6. The number of moles of N2 from air dissolved in 10 moles
of water at 298 K and 5 atm pressure is
(a) 3 × 10–1 (b) 3 × 10–2
(c) 3 × 10–4 (d) 3 × 10–3
Solution:  
(c) Partial pressure of N2 in air pN 2  Ptotal  χ N2 (in air) = 5 × 0.6
pN2 (in air)  K H  χ N2 (in H2O)
5 × 0.6 =1.0 × 105 × χ N2 (in H2 O)
n N2
3  105 
n N2  10
 n N2  n H 2 O
n N2
  3 105
10
 nN2  3  10 4
Problem 4: For a solution of acetone in chloroform, Henry’s law constant is 150 torr at a temperature of
300 K. (a) Calculate the vapour pressure of acetone when the mole fraction is 0.12. (b)
Assuming that Henry’s law is applicable over sufficient range of composition to make the
calculation valid, calculate the composition at which Henry’s law pressure of chloroform is
equal to Henry’s law pressure of acetone at 300 K. (Henry’s law constant for
chloroform is 175 torr).
(a) 18, 0.103 (b) 10, 0.103
(c) 14, 0.103 (d) 15, 0.403
[ 13 ]
Solutions
Solution: (a) The given values are

K H  150 torr; χ acetone  0.12
Using Henry’s law equation
P  K H χ , on substituting all values
P = (150 torr) (0.12) = 18.0 torr
(b) Here P = 18.0 torr, and KH = 175.0 torr
P 18.0 torr
 χ acetone    0.103
K H 175.0 torr
Problem 5: Henry’s law constant for oxygen and nitrogen dissolved in water at 298 K are 2.0 × 109 Pa
and 5.0 × 109 Pa, respectively. A sample of water at a temperature just above 273 K was
equilibrated with air (20% oxygen and 80% nitrogen) at 1 atm. The dissolved gas was
separated from a sample of this water and then dried. Determine the composition
of this gas.
(a) Percentage of O2 is 38.27, Percentage of N2 is 61.73
(b) Percentage of O2 is 36.27, Percentage of N2 is 60.73
(c) Percentage of O2 is 35.27, Percentage of N2 is 59.73
(d) Percentage of O2 is 30.27, Percentage of N2 is 55.73
Solution: (a) The given values are:
K H(O2 )  2  109 Pa; K H( N2 )  5  109 Pa
Partial pressure of oxygen
pO2 = 0.2 atm = 20265 Pa
Partial pressure of nitrogen; [1 atm = 101325 Pa]
pN2 =0.8 atm = 81080 Pa
Using Henry’s law equation
p
χ
KH
 Amount fraction of O2 in water
pO 2 20265
χ O2   9
 10.13 104
K H (O2 ) 2  10
Amount fraction of N2 in water
pO 2 81060
χ N2    16.212  10 6
K H( N 2 ) 5  109
Amount of dissolved oxygen 10.13  106
   0.62
Amount of dissolved nitrogen 16.212  106
0.62
Hence, percent of O2 = 100  38.27%
1.62
Percent of N2 = 100 – 38.27 = 61.73%
Problem 6: Which of the following gases are highly soluble in water

(a) HCl (b) SO2
(c) NH3 (d) H2
Solution: (c) Conceptual
[ 14 ]
Solutions
Problem 7: Henry’s law can be applied for which of the following gases for solubility in water
(a) H2 (b) HCl
(c) SO2 (d) NH3
Solution: (d) As it is highly soluble.
Problem 8: It takes larger time to cook food on hills than in plains. This is because
(a) high pressure on hills
(b) low pressure on hills
(c) boiling point decreases on going up the hills
(d) none of these
Solution: (c) At hills atm pressure is low so boiling point is also low.
Problem 9: Which of the following will have maximum intermolecular hydrogen bonding?
(a) H2O (b) CH3OH
(c) H2S (d) PH 3
Solution: (a) 1 molecule of H2O forms H-bond with 4 other H2O molecule.
Problem 10: The melting points of most of the solid substances increase with an increase of pressure
acting on them. However, ice melts at lower temperature than its usual melting point when
the pressure increases. This is because
(a) ice is less dense than H2O (b) pressure generates heat
(c) the bonds break on pressure (d) ice is not a true solid
Solution: (a) Conceptual
1.3 The Vapour Pressure of Binary Ideal solution Containing Volatile liquids
In a liquid, the molecules are always in the state of random motion, due to collision of molecules with
each other and with walls of container. This leads to the molecules acquiring certain kinetic energy. The
molecules of the liquid which possess high kinetic energy have a tendency to change to vapour state.
The minimum energy which the molecules of a liquid should acquire to transform from liquid state to
vapour state is termed as escape energy. Lesser the escape energy, greater is the volatility of
a liquid from liquid surface.
When a liquid is placed in a closed container then due to evaporation, vapours of liquid are produced
which ultimately leads to an equilibrium state due to the tendency of the vapours to convert back to
liquid.
Vapour Pressure
A(g)
The pressure exerted by the vapours of the liquid which are in
equilibrium with the liquid phase at the given temperature is called A(l) A(g)
equilibrium
vapour pressure. A(l)
A(l) A(g) (Rate of evaporation = Rate of condensation)
The vapour pressure of liquid depends upon

(i) Nature of the liquid
(ii) Temperature
[ 15 ]
Solutions
Nature of Liquid: When the intermolecular forces of attractions are stronger then the vapour
pressure will be low because less number of molecules can leave the liquid
Temperature: Higher the temperature, greater would be the vapour pressure. This is because
when temperature is raised, kinetic energy of the molecules increase and therefore, the number of
molecules leaving surface of liquid, is large.
Vapour Pressure
A(l) A(g)
The Clausius Clapeyron equation gives the relationship for

vapour pressure of liquid with temperature
P2 H  T2 – T1 
i.e. log P  2.303 R  T T  . Temperature
1  1 2 
Vapour Pressure of Solution
Let two volatile liquids A and B dissolve in each other to form an ideal A(g) B(g)
solution. Then the vapours above the solution will contain the vapours of A
and B. A (l) B (l)
An ideal solution is one in which the activity of each constituent is equal to its mole fraction throughout
complete range of concentration.
Hence, applying Dalton’s law of partial pressure the vapour pressure of the solution will be
vapour pressure of solution =Psolution = PA + PB
Where, PA and PB are the partial vapour pressures of A and B.
Solution being dilute (Condition for ideality) Raoult’s law can be applied.
Raoult’s law for binary solutions state that “the vapour pressure of any volatile constituent of
a binary solution at any given temperature is equal to the product of the vapour pressure of
pure constituent and its mole fraction.”
PA = PA0  A PBº
ºB
+ PB
A
PB = PA0  B = P Aº
PS
B
º
0 0
PA and PB are vapour pressure of pure A and B respectively P Aº
B
P
=
A and B are mole fraction of A and B respectively.

PB
Hence,
Vapour
Ps = PA0  A  PB0  B Pressure P
A =
Hence, P
A º

Ps = PA0 (1 χ B )  PB0 χ B [A + B = 1]
A = 1 B A = 0
Ps = PA0  ( PB0  PA0 ) χ B
B = 0 B = 1
Increasing
This equation is of the form y = mx + c Mole fraction
Where y = Ps, c = PA0 , x = B, and m = ( PB0  PA0 )
[ 16 ]
Solutions
The value of m (slope) may be (+ve) or (–ve).

Depending upon whether PB0  PA0 (m = +ve) or PB0  PA0 (m = –ve).
Hence a plot of a graph of Ps vs B will be a straight line with an intercept on y-axis.
Note: Formation of a true ideal solution is rare and largely exceptional. However, a large number of
solution are obtained which are found to be nearly ideal.
Ideal Solution
A few binary miscible liquid systems which obey Raoult’s law throughout the complete range of
concentration, are:
(1) Ethylene dibromide and Propylene dibromide.
(2) Chlorobenzene and Bromobenzene.
(3) Benzene and Ethylene dichloride.
(4) CCl4 + SnCl4.
(5) CH3OH + C2H5OH.
(6) n-Hexane + n-Heptane.
(7) Benzene + Toluene.
Such systems are called nearly ideal or ideal solutions.
Such solutions obey Raoult’s law and comply to the equation Ps = PA0 . χ A  PB0 . χ B .
To comply to this condition for ideality the two liquids A and B should fulfill the under mentioned
conditions:
1. The attractive forces between the particles A and B (i.e., A–B interactions) should be equal to
the attractive forces between A and A (i.e., A–A interaction) and between B and B (i.e., B–B
interaction)
2. Such an interaction can be equal if the structure and polarity are almost same. e.g., CH3–OH and
C2H5–O–H.
In such solutions:
(i) Vmix = 0 (ii) S mix > 0 (iii) H mix = 0.
Non Ideal Solutions

There are certain liquid pair systems which deviate from the Raoult’s law to a greater or lesser
extent depending upon the nature of the liquids and the temperature.
Set-A Set-B
(i) Ether + Acetone (i) CH3 OH + CH3COOH

(ii) CCl4 + CH3OH (ii) H2O + HNO3
(iii) C6H6 + acetone (iii) H2O + HCl
(iv) H2O + C2H5OH (iv) H2O + H2SO4
(v) n-Hexane + Ethyl alcohols (v) CHCl3 + CH3COOCH3
Set A exhibits positive deviation while set B exemplify negative deviation.
[ 17 ]
Solutions
Positive Deviation Solution

Here the A Sets of solution show a relationship where the vapour pressure of the solution observed
is greater than the vapour pressure of solution under ideal conditions
Ps PBº
i.e., Ps (obs) > Ps(ideal)
or Pi
Ps > Pi where Pi = PA0 χ A  PB0 χ B
B
P
i.e., Ps > PA0 χ A  PB0 χ B PAº
(i) B
P
Such solutions are said to have a +ve deviation from
Vapour
ideality. The graph obtained resembles as given below Pressure P
A
The reasons for such a +ve deviation could be linked PB

(i )
to the fact that after mixing the interactions between
the liquid A and B is less than the interaction between
A–A particle and B–B particles. A = 1 B A = 0
B = 0 B = 1
This leads to a less escape energy for the molecules of Increasing
A and B liquids in the solution. Molefraction of B
This also some times leads to an increase in volume of solution after mixing,
Vmix > 0. Vmix = Vobs – Vactual Smix > 0
Negative Deviation
The B set of solutions show a relationship where the vapour pressure of solution observed is lesser
than the vapour pressure of the solution under ideal conditions, i.e.
Ps(obs) < Psolution (ideal)

Ps < Pi.
 Ps < PA0 χ A  PB0 χ B
Here this equation is due to the fact that when interactions increase the escape kinetic energy
required, increases, leading to a lowering of vapour pressures such that PA < PA0 χ A and PB < PB0 χ B
Hence the sum.
PB º
PA + PB < PA0 χ A  PB0 χB ide a
l)
Ps ( )
obs
 Ps < Pi Ps (
P Aº
When the interactions between liquid A particles and
(i )
B
P
liquid B particles increases

P
Vapour
Pressure
A–B interaction > A–A interaction and B–B interactions.
P
Hmix < 0  Hmix = –ve. and also P A (i)
A
Vmix < 0  Vmix = –ve

A = 1 B A = 0
Smix > 0. B = 0 B = 1
Increasing
The graph corresponds to the one given. Molefraction of B
[ 18 ]
Solutions
Vapour Phase Composition

To obtain the relationship between the composition of solutions and the composition of
the vapour above it.
Let A and B be the mole fraction of components A and B in the vapour phase above the liquid
solution consisting of A and B mole fractions of A and B respectively.
Then according to gas law
PB A P PA 
n A 
P(s)
 B and P   A  P  n  n   A  ,
(s)  S A B 
0 0
PB χ B P χ
   B  0 B B0 = Vapour phase composition of B.
P(s) PA χ A  PB χ B
PA0 χ A PA0 χ A
and A  = Vapour phase composition of A.
P(s) PA0 χ A  PB0 χ B
Generally the distillate composition is the vapour phase composition.
Azeotropic Mixtures
The study of the vapour pressure curves of completely miscible liquid mixture is of great help in
separating the constituents of the liquid mixtures by distillation.
Azeotropic mixture are those completely miscible liquid mixtures which distil over unchanged in
composition and boil at constant temperature.
The separation by fractional distillation is possible only when the vapour phase has a composition
different from that of the boiling mixture. Thus azeotropes can not be separated by frictional distillation.
When a plot of the boiling point temperature versus composition of solution is done then we get.
I For Ideal Solution
TAº Vap
our nA  nB
A B
T Tb(a)
Liq u
id
Vapour Phase
Vapour TBº
Pressure
Liquid Phase
a n n
A A B B
(b) (a) (a)
B = 1
A = 1 Molefraction Distillate
richer in B
Residue from
distillation Mixture composition
of a a richer in A
Graph for boiling point vs composition for ideal solution:

Point 1: Mixture composition (a) taken richer in a component (A).
Point 2: Mixture composition (a) boils at Tb(a) temperature.
Point 3: Distillate (a) of (a) is the mixture composition richer in component B.
Point 4: ‘b’ is residue during distillation of mixture composition ‘a’.
Hence, such solution can be successfully separated into pure A and pure B.
Successive distillation of a’ give a” and then finally pure B. as distillate.
[ 19 ]
Solutions
II For non Ideal Solutions

A) +Deviation solution or (–ve boiling azeotropes)
When temperature versus composition graphs are drawn for +ve deviation solution we get
TAº Vap
ou r
Liquid
V TBº
T Tb(a)
Vapour L
Pressure e)
D
es i du
e (R
b a a
c c B = 1
A = 1 d
Molefraction
(Graph for boiling point vs composition for non-ideal solution showing +ve deviation)
Point 1: Here when mixture composition ‘a’ is boiled, then the distillate (a) becomes
more rich in ‘B’ but, successive distillation of a will finally lead to compositions
(‘d’) where vapour phase and liquid phase compositions are same. Hence d(D)
is a solution which cannot be separated into pure A and B. Hence, it is a –ve
boiling azeotropic mixture. But the residue ‘b’ becomes richer in ‘A’.
Point 2: When mixture composition ‘c’ is boiled then distillate is (c) richer in ‘A’ but
successive distillation makes it to composition d(D), i.e., –ve boiling azeotropic
mixture.
The distillate is ‘e’ richer in (B) component:
Table for Minimum Boiling Azeotropic Mixtures
Component A B.pt Component B B.P. B. pt of % of B
Azeoropic mixture
H2O 100ºC CHCl3 61.2ºC 56.12 97%
H2O 100ºC C2H5OH 78.3º 78.13 96%
H2O 100ºC C 6H 6 80.2ºC 69.25 91%
H2O 100ºC C3H7OH 97.2ºC 87.7 97%
Chloroform 61.2ºC CH3OH 64.7ºC 53.43 13.6%
B) –ve Deviation solutions (+ve Boiling azeotropic)
When temperature versus composition are drawn for the solutions showing –ve deviation the
graph obtained is
D
V V
TB º
L
T Aº L
a a b c c
A = 1 d e B = 1
Molefraction
(Graph of Boiling point VS composition for non-ideal solutions –ve deviation)
[ 20 ]
Solutions
Point 1: When mixture composition ‘a’ is taken, then on boiling:
(i) Distillate a is obtained which is richer in component A.

(ii) Residue is ‘b’
Successive distillation of ‘b’ leads to azeotropic solution D. (+ve boiling azeotropic
mixture).
(iii) Successive distillation of a will lead to pure (A)
Point 2: When mixture composition c is taken and boiled:
(i) Distillate is c which is richer in component B and successive distillation of

distillates lead to solution becoming pure ‘B’.
(ii) The residue of ‘c’ is ‘e’ successive distillation of ‘e’ makes the residue richer in
‘D’ which is +ve boiling azeotropic mixtures.
Table for Maximum Boiling Azeotropic Mixture

A B.pt of A B B.pt B B. pt of % of B
in ºC in ºC Azeoropic mix
HCl –20º H2O 100 108.5 79.96
HNO3 86º H2O 100 120.5 32
CHCl3 61.2 Acetone 56.5 64.7ºC 20
CHCl3 61.2 CH3COOC 2H5 57 64.8 23
Ratio of Distillate to Residue Compositions

The relative proportions of the two liquids in the distillate can be calculated on the basis that the
number of moles of each component present in the vapour phase is proportional to its vapour pressure.
If nA and nB are the number of moles of the components A and B in the vapour phase, then
nA/nB = p ºA / p Bº (1)
If wA and wB represent the actual masses of the two components in the distillate and MA and MB
their respective molecular masses, then Eq. (1) may be written as,
wA n A M A po M wA po M
  Ao A   Ao A
wB n B M B pB M B wB pB M B
Thus, the masses of the liquids in the distillate will be in the ratio of their vapour pressures and molar
masses.
Illustration 1: 4.45 g of pure sulphuric acid is added to 82.20 g water. The density of the solution was found
to be 1.029 g/ml. Calculate (a) weight percent (b) mole fraction (c) mole percent (d) molality
(e) molarity and (f) normality of sulphuric acid solution.
[ 21 ]
Solutions
Solution: Mass of H2SO4 = 4.450 g

Mass of water = 82.20 g
Mass of solution = 86.65 g
Density of solution = 1.029 g/ml
4.45
(a) Weight percent of H2SO4 in solution = 100 = 5.14
86.65
4.45
(b) Moles of H2SO4 = = 0.0454
98
82.20
Moles of H2O = = 5.566
18
Total no. of moles = 0.0454 + 4.566 = 4.6114
0.0454
Mole fraction of H2SO4 = = 0.0098
4.6114
Mole fraction of water = 1 – 0.0098 = 0.9902
(c) Mole percent
Moles of solute
Mole percent of solute =  100
Total moles in solution
= Mole fraction of solute  100 = 0.0098  100 = 0.98
Mole percent of solvent = Mole fraction of solvent  100
= 0.9902  100 = 99.02
(d) Molality
Moles of solute
Molality = Mass of solvent in g  1000
0.0454
= 1000 = 0.552.
82.2 ´
(e) Molarity
Moles of solute
Molarity =
Mass of solution in g 86.65

Volume of Solution = Density of solution = 1.029  1000 litre
0.0454  1000  1.029

Molarity = = 0.539
86.65
(f) Normality
No. of equivalent s of solute dissolved
Normality =
No. of litres of solution made
4.45
Equivalent of H2SO4 =
49
86.65
Volume of solution = 1.029  1000
4.45  1000  1.029

Normality = 49  86.65 = 1.078
[ 22 ]
Solutions
Illustration 2: The vapour pressures of ethanol and methanol are 44.6 mm and 88.0 Hg, respectively. An
ideal solution is formed at the same temperature by mixing 60 g of eathanal with 40 g of
methanol. Calculate the total vapour pressure of the solution and the mole fraction of methanol
in the vapour.
Solution: Mol. mass of ethyl alcohol (C2H3OH) = 46

60
Number of moles of ethyl alcohol =  1.304
46
Mol. mass of methyl alcohol (CH3OH) = 32
40
Number of moles of methyl alcohol =  1.25
32
1.304
Mole fraction of ethyl alcohol, χ A   0.5107 mm Hg
1.304  1.25
1.25
Mole fraction of methyl alcohol, χ B   0.4893 mm Hg
1.304  1.25
Partial pressure of ethyl alcohol = χ A PA0  0.5107  44.0  22.46 mm Hg
Partial pressure of ethyl alcohol = χ B PB0  0.4893  88.0  43.05 mm Hg

Total vapour pressure of solution = 22.47 +43.05 = 65.52 mm Hg
43.05
Mole fraction of CH3OH in vapour phase =  0.6870
65.52
Illustration 3: Two liquids A and B form ideal solution, A 300 K, the vapour pressure of a solution containing
1 mol of A and 3 mol of B is 500 mm of Hg. At the same temperature, if one more mole of
B is added to the solution, the vapour pressure of the solution increases by 10 mm of Hg.
Determine vapour pressures of A and B in their pure states.
Solution: Let the vapour pressure of pure A be = pA0 , and the vapour pressure of pure B be = pB0
Total vapour pressure of solution (1 mol A = 3 mol B)
= χ B pB0  χ B pB0 [ χ A is mole fraction of A and χ B is mole fraction of B],
1 0 3 0
500  pA  pB
4 4
or 2000  pA0  3 pB0 ...(i)
Total vapour pressure of solution (1 mol A + 4 mol B),
1 4
 p 0A  pB0
5 5
2250  pA0  4 pB0 ...(ii)
Solving equations (i) and (ii), we get:
pB0 = 550 mm of Hg = Vapour pressure of pure B
p 0A = 330 mm of Hg = Vapour pressure of pure A
[ 23 ]
Solutions
Illustration 4: Heptane and octane form an ideal solution. At 373 K, the vapour pressure of the two liquids
are 105.0 kPa and 46.0kPa, respectively. What will be the vapour pressure, of the mixture of
25 g of heptane and 35 g of octane?
Solution: Mw of heptane, C7H10, MwA = 100

Mw of octane, C9H18, MwB = 114
W 25 35
nA  A   0.25; nB   0.3
MwA 100 114
0.25 0.3
χA   0.45; χB   0.55
0.25  0.30 0.25  0.30
P = pA0 χ A  pBχ B
= 105.0 × 0.45 + 46.0 × 0.55 = 47.25 + 25.30

= 72.55 kPa
Illustration 5: Two liquids A and B form an ideal solution such that p 0A  700 mm and pB0  300 mm . A
small amount of solution is vapourized and the vapour condensed (at equilibrium). The
condensate has equilibrium vapour pressure of 500 mm (at same temperature). Find the
composition of the original solution.
Solution: Pt  PA  PB
Pt  PA0 χ A  PB0 χ B  700χ A  300(1  χ A ) ...(i)

P 700χ A 7χ A
χ 0A  A  
Pt 300  400χ A 3  4χ A
P 300χ B 300(1  χ A ) 3  3χ A
χ 0B  B   
Pt 300  400χ A 300  400χ A 3  4χ A
Putting value in equation (i),
 7χ A   3  3χ A 
500  700    300  
 3  4χ A   3  4χ A 
 χ A  0.3, χ B  0.7
Illustration 6: Assuming ideal behaviour, calculate the pressure 1.0 molal solution of a non-volatile molecular
solute in water at 30°C. the vapour pressure of water at 30°C is 0.222 atm.
m
Solution: solute 
m  55.56
1
  0.0177
1  55.56
 Psolution  PA0 χ A  0.222  0.0177  0.218 atm
Illustration 7: 100 g of water contains 1.0 g urea and 2.0 g sucrose at 298 K. The vapour pressure of water
at 298 is 0.3 atm. Calculate the vapour pressure of the solution. (Molecular weight of urea =
60; Molecular weight of sucrose = 342).
[ 24 ]
Solutions
Solution: The given values are:

WH2O  100 g ; M H2O  18 g mol 1
Wurea  10 g ; Mwurea  60 g mol1
Wsucrose  2 ; Mwsucrose  342 g mol1

PH02O  0.3 atm
n solvent
solvent 
n solvent  n solute
100 5.556
   0.97
18 5.729
 100   2 10 
   
 18   342 60 
According to Raoult’s law,
pA  pA0 χ A
Vapour pressure of solution = 0.3 × 0.97 = 0.29 atm
Illustration 8: Benzene and toluene form nearly ideal solution. At 298K, the vapour pressure of pure benzene
is 150 torr and of pure toluene is 50 torr. Calculate the vapour pressure of the solution,
containing equal weights of two substances at this temperature?
Solution: Let the weights of benzene and toluene in the solution is = W g

W
χ  78  0.541
Mole fraction of benzene, b W W

78 92
Mole fraction of toluene χ t  1  0.541  0.459
According to Raoult’s law pA  pA0 χ A
Partial pressure of benzene pB  Pb0  χ b  150  0.541  81.15 torr
 Partial pressure of toluene, pt  Pt 0  χ t  50  0.459  22.95 torr
Total vapour pressure of solution = pb  pt
= 81.15 +22.95 =104.1 torr
Illustration 9: An aqueous solution containing 28% by weight of a liquid A (molecular mass = 140) has a
vapour pressure of 0.200 bar at 37°C. Calculate the vapour pressure of pure liquid (vapour
pressure of water at 37°C = 0.100 bar).
Solution: The given values are

Wliquid = 28g, Mw1 = 140
WH2 O  72g; MwH2 O  18
pH0 2O  0.10 bar; p total  0.2 bar

28
χ  140  0.048
Mole fraction of liquid, t 28 72

140 18
Mole fraction of water, χ H2 O  1  0.048  0.952
[ 25 ]
Solutions
According to Raoult’s law
p total  pl0 χ l  pH2O χ H2O
0.2  pl0  0.048  0.1 0.952
0 0.2  0.1 0.952

or pl   2.18 bar
0.048
Therefore, the vapour pressure of pure liquid is 2.18 bar.
Illustration 10:The vapour pressure of chloroform CHCl3, and dichloromethane (CH2Cl2) at 298 K is 200
mm Hg and 415 mm Hg, respectively. Calculate
(a) The vapour pressure of the solution prepared by mixing 25.5 g of CHCl3 and 40 g of
CH2Cl2 at 298 K.
(b) Mole fractions of each component in vapour phase.
Solution: Molar mass of CH2Cl2 = 85 g mol–1

Molar mass of CHCl3 = 119.5 g mol–1
40 g
Moles of CH2Cl2 = 85g mol-1  0.47 mol
25.5 g
Moles of CHCl3 = 119.5 mol-1  0.213 mol
Total number of moles = 0.47 + 0.213 = 0.683 mol
0.47 mol
χ CH2Cl2   0.688
0.683 mol
χ CHCl3  1.00  0.688  0.312
0 0 0
ptotal  pCHCl 3
 ( pCH 2Cl 2
 pCHCl 3
)χ CH2 Cl2
= 200 + (415 – 200) × 0.688
= 347.9 mm Hg
To calculate the mole fraction of component in vapour phase.
p
χ vi  i
pT
 pCH 2Cl2  0.688  415 mm Hg = 285.5 mm Hg
285.5
χ CH2Cl2V   0.82
347.9
62.4
χ CHCl3V   0.18
347.9
Illustration 11:Certain liquid X boils at 33.5º C at 1 atm. At what temperature will it boil at 750 mm. Latent
heat of vaporization is 88.4 cal/g, R = 1.987 cal. and Mol. wt. of X is 74.
Solution: We known,
P
2  Hv  T  T 
2 1
log P  2.302 R  T T 
1  1 2 
P1 = 760 mm
[ 26 ]
Solutions
P2 = 750 mm
Hv = 88.4  74
T1 = 33.5 + 273 = 306.5
T2 = ?
750 88.4  74  T2  306.5 

log 760  2.303  1.987  306.5  T 
 2 
T2 = 305.9 K
= (305.9 – 273)º C = 32.9ºC
Illustration 12: Solutions of two volatile liquids A and B obey Raoult’s law. At certain temperature T, it is
found that when the total pressure above a given solution is 400 mm Hg the mole fraction of
A in the vapour phase is 0.45 and in the liquid it is 0.65. Find out the vapour pressure of two
pure liquids at temp. T.
Solution Total Pressure = 400 mm

xA = 0.65 YA = 0.45 PºA = ?
xB = 0.35 YB = 0.55 PºB = ?
We know P = PºA xA + PºB.xB
400 = PºA × 0.65 + PºB × 0.35
Also we know
PA Pº A .x A
YA = 
P P
0.65 PA0
0.45 =
400
400 0.45
PºA = = 277 mm
0.65
Now,
400 = 277  0.65 + PºB  0.35
400  180
PºB = = 630 mm
0.35
Illustration 13: At 30ºC A and B have vapour pressures of 119.6 and 36.7 mm respectively. What are the
partial pressures of each of these components and the total pressure over a solution consisting
of equal weights of these two components at 30ºC. What is the composition of the vapour in
equilibrium with the solution at this temperature. Comment on the results. [mol. wt. of A = 78
and mol. wt. of B = 92].
Solution: Say the amount taken is 92 g for each liquid.

92
Moles of A = = 1.18
78
92
Moles of B = =1
92
[ 27 ]
Solutions
1.18
xA = = 0.541
2.18
1
xB = = 0.459
2.18
PA = 0.541  119.5 = 64.7 mm
PB = 0.459  36.7 = 16.8 mm
Total pressure = 64.8 + 16.8 = 81.5
Composition of vapour
64.7
xA in vapour phase = = 0.793
81.5
xB in vapour phase = 1 – 0.793 = 0.207.
This indicates that the vapour is always richer in the more volatile liquid.
Illustration 14: Aniline-water mixture boils at 98ºC at a pressure of 1 atm. At this temperature the vapour
pressure of water is 707 mm. If the system is distilled in steam what fraction of total weight
of the distillate will be aniline
Solution: MA = 93 P 0A = ? WA = ?
MW = 18 P0W = 707 mm WW = ?
We know
P = P 0A + P 0W
760 = P0A + 707
P0A = 53 mm
We know
WA PA0 . M A 53  93 4929
WW = 0
PW . M W = 707  18 = 12726
WA 4929
xA = W  W = 4929  12726 = 0.279
A W
% of A = 0.279  100 = 27.9 %.
Illustration 15: The vapour pressure of 2.1% aqueous solution of a non-electrolyte is 755 mm at 100ºC.
Find out the mol. wt. of solute.
Solution: Vapour pressure of pure water at 100ºC = 760 mm

Vapour pressure of solution at 100ºC = 755 mm
Mass of solute = 2.1 g
Mass of water = 100 – 2.1 = 97.9 g
2 .1
Moles of solute = (m = mol. wt. of solute)
m
97.9
Moles of water =
18
We know
P0  Ps Wsolute  M solvent

Ps M solute  Wsolvent
[ 28 ]
Solutions
760  755 2.1 18


755 M solute  97.9
2.1 18  755
M solute   58.3
97.9  5
Illustration16: A very small amount of a non-volatile solute (non-electrolyte) is dissolved in 56.8 ml of
benzene (density 0.889 g cm–3). At room temperature, vapour pressure of this solution is
98.88 mm Hg while that of benzene is 100 mm Hg. Find the molality of this solution. If the
freezing temperature of this solution is 0.73 degree lower than that of benzene what is the
value of cryoscopic constant of benzene.
Solution: We know for a very dilute solution.

P0  Ps Wsolute  M solvent

P0 M solute  Wsolvent
P0  Ps m  78

P0 1000
1000  (P0  Ps )
m
78  P0
1000  (100  98.88)
  0.1435
78  100
Further we know,
Tf = Kf  m
T f 0.73
Kf = = = 5.087 K kg. mol–1.
m 0.1435
Illustration 17: Dry air was passed through a solution (obtained by dissolving 50 g of solute in 100 g water)
and then through pure water. The loss in weight of pure water is found to be 0.05 g. The wet
air was then passed through concentrated H2SO4. In the process H2SO4 gained 2 g. Find out
the molecular weight of the solute.
Solution: Loss in weight from pure water = 0.05 g

Loss in weight from solution = 2 – 0.05 = 1.95 g
Total loss in weight = 2.0 g
We know,
Loss in weight from solution  Ps
Total loss in weight P
Also we know,
w 50
P  PS m 2.0  1.95 m
= w W; = 50 100
P  2.0 
m M m 18
1 50  18
=
40 900  100m
m = 351
[ 29 ]
Solutions

Problem 1: The vapour pressure of water at 293 K is 17.51 mm. The lowering of vapour pressure of
sugar is 0.0614 mm. The relative lowering of vapour pressure will be
(a) 0.00351 (b) 0.00311
(c) 0.00355 (d) 0.00358
Solution: (a) Here we are given that

Vapour pressure of water (P0) = 17.51 mm
Lowering of vapour pressure (P0 – Ps) = 0.0614
Relative lowering of vapour pressure
P 0  Ps 0.0614
  0.00351
P0 17.51
Problem 2: The vapour pressure of a 5% aqueous solution of a non-volatile organic substance at 373 K
is 745 mm. Calculate the molecular mass of the solute.
(a) 48 (b) 47
(c) 58 (d) 57
Solution: (a) 5% aqueous solution of the solute implies that 5 g of the solute are present in 100 g of the
solution, i.e.,
Weight of solute (W2) = 5 g
Weight of solute = 100 g
Weight of solvent (W1) =100 – 5 = 95 g
Further as the solution is aqueous, it means that the solvent is water and we know that
vapour pressure of pure water at 373 K = 760 mm.
Vapour pressure of the solution at 373 K (Ps) = 745 mm (given)
Molecular mass of solvent (water), Mw1 = 18
Molecular mass of solute Mw2 = To be calculated
Using the formula for dilute solution, viz
P 0  Ps n2 W2 / Mw2
 
P0 n1 W1 / Mw1
760  745 5 / Mw2 5  18

We get,  
760 95 /18 95  Mw2
5  18  760
or Mw2   48
15  95
Problem 3: Two liquids A and B an ideal solution. What will be the vapour pressure at 27°C of a solution
having 1.5 mol of A and 4.5 mol of B? The vapour pressure of A and B at 27°C is 0.116 atm
and 0.140 atm, respectively. Then total vapour pressure at this condition will be
(a) 0.132 (b) 0.133
(c) 0.029 (d) 0.134
[ 30 ]
Solutions
Solution: (d) nA = 1.5 nB = 4.5

1.5 1.5 1
χA   
1.5  4.5 6.0 4
1 3
χ B  1 
4 4
1 3
P  PA0 χ A  PB0 χ B  0.116   0.14 
4 4
P = 0.029 + 0.105 = 0.134 atm
Problem 4: At 298 K, the vapour pressure of water is 23.75 mm Hg. Calculate the vapour pressure at
the same temperature over 5% aqueous solution of urea, [CO(NH2)2].
(a) 23.375 (b) 20.375
(c) 22.375 (d) 21.375
Solution: (a) Applying raoult’s law
P 0  Ps n1 W1  M 2
 
P0 n2 M 1  W2
Substituting the values, we get

23.75  Ps 5 18
 
23.75 60 95
5 18
23.75  Ps    23.75
60 95
or 23.75  Ps  0.375  Ps  23.375 mm
Problem 5: Liquids A and B form an ideal mixture, in which the mole fraction of A is 0.25. At temperature
T, a small quantity of the vapour in equilibrium with the liquid is collected and condensed.
This process is repeated for a second time with the first condensed. This process is repeated
for a second time with the first condensate. The second condensate now contains 0.645
mole fraction of A. Calculate the ratio ( PA0 PB0 ) . What will be the mole fraction of B in the
third condensate?
(a) 0.101 (b) 0.104
(c) 0.102 (d) 0.103
Solution: (a) Mole fraction of A (χ A )  0.25
Mole fraction of B (χ B )  0.75
After the condensation

Partial pressure of A ( pA )  PA0 χ A  PA0  0.25
Partial pressure of B ( pB )  PB0  0.75
PA PA0 0.25
  
PB PB0 0.75
After second condensation
Mole fraction of A (χ A )  0.645
[ 31 ]
Solutions
Mole fraction of B ( (χ B )  1  0.645  0.355

Ratio of partial pressures
PA0  P 0  0.25 0.645
  A0   
PA  PB  0.75 0.345
 P 0  0.645 0.75
 A0   
 PB  0.345 0.25
PA0
  2.33
PB0
After third condensation
PA00  PA0  0.25 0.25
 00
  0   (2.33)3   4.242
PB  PB  0.75 0.75
 Mole fraction of B
PA00 1
 00 00
  0.101 = Mole fraction of B
PB  PB 3.42
Example 6: The boiling points of bromine (Br2) and iodine monochloride (IC1) are 58.8ºC and 97.4ºC
respectively. The boiling point of IC1 is higher than that of Br2 because
(a) IC1 is polar and Br2 is non-polar.
(b) the vapour pressure of IC1 is higher than of Br2 at room temperature.
(c) IC1 is ionic, while Br2 is molecular compound.
(d) both (a) and (c).
Example 7. The correct relationship between the boiling points of very dilute solutions of AlCl3 (t1) and
CaCl2 (t2) having the same molar concentrations
(a) t1 = t2 (b) t2 > t1
(c) t1 > t2 (d) t2  t1

Problem 8. If a thin slice of sugar beet is placed in concentrated solution of NaCl then
(a) sugar beet loses water from its cell
(b) sugar beet will absorb water from solutions
(c) sugar beet will neither absorb nor lose water
(d) sugar beet will dissolve in water

Problem 9: 2N HCl solution will have same molar concentration as a
(a) 4.0 N H2SO4 (b) 0.5 N H2SO4
(c) 1N N2SO4 (d) 2N H2SO4
Problem 10. The solution having lower osmotic pressure when compared to another is called
(a) Isotonic solution (b) Hypertonic
(c) Hypotonic (d) None of these
Solution:. (c) Conceptual
[ 32 ]
Solutions
1.4 Colligative Properties of Solution

Solutions of Non Volatile Solute and Volatile Solvent
Colligative Properties
The properties which depend entirely upon the number of particles of solute in a given volume of
solvent and not on the chemical nature of the solute molecule are defined as Colligative properties.
Here, we shall consider four properties of solution containing non volatile solutes.
(i) Lowering in vapour pressure.

(ii) Elevation in boiling point.
(iii) Depression in freezing point.
(iv) Osmotic pressure.
It is convenient to subdivide the solutions in the
A. Solutions of non electrolytes
B. Solutions of electrolytes
A. Solutions of Non Electrolyte

Lowering in Vapour pressure: When a non volatile solute is present in the solution, the vapour
pressure of the solution will be less than vapour pressure of pure solvent.
Let there be a solution of solute B. in solvent A Only 'A' Particles
Since ‘B’ is non volatile it won’t go to the vapour phase Solvent (A)
hence, the vapours above solution will be only due to
Solute (non volatile) (B)
volatile solvent ‘A’. Since,
PA  PA0A
 PA < PA0 so, vapour pressure is lowered.
For a binary system A +B = 1.
Substituting the value of A
 PA = PA0 (1–B)
PA = PA0 – PA0 B
 PA0 B = PA0 – P = P (Lowering in vapour pressure)
P = PA0 B
 P B
 Lowering in vapour pressure is directly proportional to the mole fraction of solute.
The relative lowering in vapour pressure is equal to the mole fraction of solute.
ΔP
= B
PA0
[ 33 ]
Solutions
Hence,
(a) Lowering in vapour pressure is directly proportional to the mole fraction of solute in the
solution.
(b) Relative lowering in vapour pressure is equal to the mole fraction of solute.
1. Calculation of molecular mass of solute (B) in solvent (A)

nB
P = PA0 B = PA0
nA  nB
 
 W /M 
B B
= PA0  W WB


A

 M A M B 
WB WA WB
But when the solution is dilute then M <<< M and hence, M can be neglected in the
B A B
denominator
 0   W M 
0 WB  M A  P   B A
 P = PA  or MB =  P   WA 
WA  M B    
2. The relative lowering in vapour pressure is determined by Ostwald And Walker Method. In
this method a stream of dry air is passed successively through a set of weighed bulbs containing
the solution and then through a set of merged bulbs containing pure solvent and finally
through weighed U-shaped tubes containing anhydrous CaCl2.
(a) Let the loss in weight of solution bulbs be = w1 gm.

(b) Loss in weight of solvent bulbs = w2 gm.
(c) Loss in weight of solution bulbs (w1)  vapour pressure of solution.
(d) Loss in weight of solvent bulbs (w2)  vapour pressure of solvent – vapour pressure of
solution.
 Ps  w1 and (P0 – Ps)  w2
P 0  Ps w2
 0

P w1  w 2
Loss in weight of solvent bulbs

= Total loss in weight of solution bulbs and solvent bulbs
= XB, i.e., mole fraction of solute
Elevation in Boiling Point

When a liquid is heated then due to rise in temperature the liquid vapourises and the vapour pressure
increases. When the vapour pressure of the liquid becomes equal to the atmospheric pressure, the
liquid begins to boil. The temperature at which the equilibrium vapour pressure of the liquid becomes
equal to the atmospheric pressure is called boiling point.
[ 34 ]
Solutions
When a non volatile solute is added to the solvent the vapour pressure of the solvent in the solution
decreases. Consequently the solution has to be heated to a higher temperature to have its vapour
pressure equal to atmospheric pressure.
Relationship for elevation in Boiling points
Consider the graph of vapour pressure

1 atm A D E
versus temperature in Kelvin scale. Pº
Vapour
Pressure
Here, Triangle ADB and ACE are similar P1 T Bº = Boiling point
nt B temperature
l ve 1
So tion- 2
Hence, P2 lu -
i on C
So lu t
AD AB So

AE AC TBº T1 T2
TB
T1 – T 0 P 0 – P1 Temperature

T2 – T 0 P 0 – P2
 T 1 – T 0  P0 – P1
 TB  P
Also,
P  B
 TB  B
nB
TB 
nA  nB
nB
TB  [Dilute solutions]
nA
B W
A M
TB  M  W
B A
WB
  TB  Kb
MB WA
WB
When, M = 1 mole and WA = mass of solvent in kilogram (kg)
B
  TB  K b  m m = molality of solution KB = Ebullioscopic constant
 TB  K B [when concentration is kept constant]. Hence, elevation in boiling point depends
upon
KB, i.e., nature of solvent
ΔTB  m [When solvent taken is same]
KB is defined as the elevation in boiling point of a solvent when 1-gm mole of a non-volatile solute is
dissolved in 1000 gm of solvent.
2
RTb
Kb = lv = latent heat of vapourization per gram of the solvent.
1000 lv
[ 35 ]
Solutions
RTb2 M 0
Also Kb = where M0 = molecular weight of solvent.
1000H v
Kb W solute Kb WB
ΔTB   1000 ΔTB   1000
M soluteW solvent MB  WA
WB = Wsolute = Mass of solute taken

MB = Msolute = Molecular weight of solute
WA = Wsolvent = Mass of solvent taken in grams
Kb WB
 Msolute   1000
TB  WA
TB (1) K B (1)
Also TB ( 2) = K B ( 2 ) when concentration is same but solvent different
TB (1) m1
TB ( 2) = m2 when solvent is same but concentration different
TB (1) Mo(2) 1

TB ( 2) = Mo(1)  TB  Mo when solvent same and amount of solute is same
(1)
Depression in Freezing Point

When a solvent is cooled, a temperature is eventually reached at which solid begins to separate from
the solution. The temperature at which this separation begins is called freezing point of solvent.
At freezing point liquid and solid are in equilibrium.

F.P.
Liquid Solid
At the freezing point, the vapour pressure of liquid and solid will be same.
Addition of a non-volatile solute, decreases the vapour pressure of pure liquid. Therefore, for a solid
to have the same vapour pressure as the solution, the temperature would lower down. This phenomenon
is called depression in freezing point.
Relationship for Depression in Freezing Point.
Here again.
Tf p Tf  P
p  molality or P  XB
Tf  molality Tf  XB
nB
 Tf  n for dilute solutions
A
WB
 Tf = Kf M W when WA is in kilogram
B A
[ 36 ]
Solutions
 T f  K f m
K f = molal depression constant
K f is defined as the depression in freezing point of a solvent when 1-gm mole of a non-volatile
solute is dissolved in 1000 gm of solvent, i.e.
RT f2 RT f2 M 0
Kf  also Kf 
1000 l f 1000 H f
where T f = freezing point
T f = latent heat of fusion per gram
Also
RT f  w solute
T f  1000
M solute  W solvent
Hence molecular weight of solute
K f  W solute
M solvent  1000
T f  W solvent
Since, T f = Kf m  T f  Kf [When concentration is same but different solvents are taken]
T f  m [when solvent is same but different concentration are taken]
Osmotic Pressure
Osmosis
1. The phenomenon of osmosis, first observed by Abbe Nollet, may be defined as a process in
which pure solvent molecules pass through a semipermeable membrane from a solution of low
concentration to a solution of higher concentration.
(a) Exosmosis is the outward flow of water from a cell containing an aqueous solution through
a semipermeable membrane, e.g., grape in NaCl solution.
(b) Endosmosis is the inward flow of water into a cell containing an aqueous solution through a
semipermeable membrane, e.g., grape in water.
2. The most frequently used semipermeable membrane in laboratory is that of copper ferrocyanide,
Cu2[Fe(CN)6] because it is very strong and can withstand very high pressure. Remember that
semipermeable membrane of Cu2[Fe(CN)6] does not work in non-aqueous solution because it
gets dissolved in non-aqueous solvents. Other synthetic semipermeable membrane is that of
calcium phosphate. Natural semipermeable membranes are parchment paper, cell walls, pig’s
bladder, skin surrounding white of an egg, membrane surrounding RBCs, etc.
When a solution (say of sugar) is separated from the pure solvent (water in present case) by
means of a semipermeable membrane (a membrane which allows only the solvent molecules but
not the solute molecules to pass through it), the pure solvent passes through the membrane and
goes to solution (osmosis) till the hydrostatic pressure of the liquid column exactly balances the
[ 37 ]
Solutions
tendency of water to pass inward through the semipermeable membrane. The hydrostatic pressure
set up as a result of osmosis is a measure of the osmotic pressure of the solution. For instance,
if the solution of density d rises to height h, then osmotic pressure is expressed as
 = h × d × g, where, g is the acceleration due to gravity.
The osmotic pressure may be defined as the excess pressure which must be applied to a solution
in order to prevent flow of solvent into the solution through the semipermeable membrane.
Osmotic pressure may also be defined in several other ways.
(i) Osmotic pressure is the excess pressure which must be applied to a given solution in order
to increase its vapour pressure until it becomes equal to that of the solution.
(ii) Osmotic pressure is the negative pressure produced when a solution is separated from the
solvent by a semipermeable membrane.
(iii) Osmotic pressure is the hydrostatic pressure produced when a solution is separated from
the solvent by a semipermeable membrane.
Laws of Osmotic Pressure

The different laws of osmotic pressure are:
1. Boyle-Vant Hoff law 2. Charles-Vant Hoff law
3. Avogadro-Vant Hoff law 4. Vant Hoff theory of osmotic pressure
Vant Hoff Theory of Dilute solution:
Vant Hoff gave an idea that dilute solution behave like ideal gases and gas laws obeyed by ideal gas
are also obeyed by dilute solution .
We know that
1
V (Boyle - van’t Hoff Law)

VT (Charles Van’t Hoff law)
Vn (Avogadro - Van’t Hoff law)
n T
 V

nRT
 V= R = solution constant (0.0821 it atm K–1 mol–1)

n
 = RT
T
V
 = CRT
Hence, at a given temperature
C
Important relations concerning osmotic pressure, P or 

n
(i) V = n RT or V = n ST or = ST or = CST
V
where = Osmotic pressure in atmospheres
n = Number of moles of the solute present in V litres of the solution
C = Concentration of the solution in moles per litre
T = Temperature in K
R or S = 0.0821 l atm deg–1 mole–1
[ 38 ]
Solutions
w  w 
(ii) V = M ST  n  M 
0  0 
wST
M0 = (M0 = Molecular weight of solute)
V
where w = Wt. of solute in g dissolved in V l of solution
m = Molecular wt. of the solute
(iii)  = h d g
where h = Height, d = density, g = Gravitational acceleration.
(iv) In isotonic solutions, since osmotic pressure, p is equal, their concentration (C) must also
be equal, i.e.
n1 n2 w1 w
 ;  2
V1 V2 m1V1 m2 V2
(v) If a number of solutes are present in the solutions and 1, 2, 3, etc., are their individual osmotic
pressures, then
Total osmotic pressure = 1 + 2 + 3 + .....
Reverse osmosis
If a pressure higher than osmotic pressure is applied on the solution, the solvent will flow from the
solution into the pure solvent through the semipermeable membrane. Since, here the flow of solvent
is in the reverse direction to that observed in the usual osmosis, the process is called reverse osmosis.
It is used in the desalination of sea water to obtain pure water.
Isotonic Solutions
A pair of solutions having the same osmotic pressure are known as isosmotic or isotonic solutions.
Isotonic solutions have the same concentration. 0.85% NaCl solutions is found to be isotonic with
blood, while 0.9% NaCl solution isotonic with human RBCs. A solution having lower or higher osmotic
pressure than the other is to be hypotonic or hypertonic respectively in respect to other solution.
(i) When placed in water or hypotonic solutions, cell swell and burst (haemolysis).
(ii) When placed in hypertonic solutions, the fluid from the plant cells comes out and thus the cells
contract in size (plasmolysis). When excess of fertilizers (like urea) are applied, plasmolysis
takes place and plants dry up (wilt).
Osmolarity
Osmolarity is the term used by physiologists to discuss the osmotic behaviour of solutes which either
dissociate or associate in solution. Mathematically,
Osmolarity = Molarity × No. of particles produced per formula unit of the solute
B. Solution of Electrolytes
Abnormal Behaviour of Solutions: Since the colligative properties of solutions, viz. lowering
of vapour pressure, elevation in boiling point, depression in freezing point and osmotic pressure,
[ 39 ]
Solutions
depend solely on the number of solute particles present in solution and not on their nature,
colligative properties of the solutes which undergo dissociation (electrolytes) in solution would be
higher than expected for the normal substances (non-electrolytes). For example, one mole of a
solute like glucose, cane sugar, urea, etc. when dissolved in 1000 g of water depresses the
freezing point of water by 1.86ºC. However, solution of one mole of NaCl or BaCl2 in 1000 g of
water depress the freezing point of water by 3.72ºC (2 × 1.86) and 5.58ºC
(3 × 1.86) respectively because each molecule of NaCl and BaCl2 dissociates to give 2 (Na+ &
Cl–) and three (Ba2+ and 2Cl–) ions respectively and each ion behaves as a particle in itself.
Thus, among the 0.1 M solution of the various substances like can sugar, NaCl, BaCl2, Al2(SO4)3,
etc. the colligative effect will be maximum in Al2(SO4)3 solution giving 5 ions per molecule.
Similarly, there are certain substances which associate when dissolved in a particular solvent.
Hence, the molecular weight of such substances as determined with the help of colligative
properties will be more than the theoretically calculated value from the molecular formula. For
example, the observed molecular weight of acetic acid when dissolved in benzene is found to be
118 which is nearly double the value (60) calculated from its molecular formula, CH3COOH.
This is due to the fact that acetic acid, in benzene, does not exist as CH3COOH but as a dimer,
i.e., (CH3COOH)2.
Vant’f Hoff Factor, i.

To account for the above anomalies, Van’t Hoff introduced a factor ‘i’ in the Van’t Hoff equation
( V = RT) of osmotic pressure. The modified equation may thus be written as V = iRT
The factor ‘i’ was defined by the expression:

Observed osmotic pressure
i = Normal osmotic pressure
The experimental value of i can be obtained by dividing the observed osmotic pressure of the
solution under study with that of the solution of a normal substance (say sucrose) of the same
concentration (molarity) as that of the substance under study.
Now since osmotic pressure behaves like other colligative properties, the factor i can also be
applied to other colligative properties. Thus, in general,
Actual number of particles

i = No. of particles when no ionisation /associati on
Observed colligativ e property (experimen tal)

i= Normal colligativ e property (calculate d)
Now, since molecular weight of a solute is inversely proportional to the colligative property, the
factor i may also be defined in the following way
Normal molecular wt. (calculated value)

i = Observed molecular wt. (experimental value)
Evidently for a normal substance (which neither dissociates nor associates in solution), the factor
i is always unity.
[ 40 ]
Solutions
When the Van’t Hoff factor is included then the colligative properties get modified as follows
(a) Relative Lowering in Vapour Pressure

0
P  PS P0  Ps inB
0 = i  XB  0

P P inB  nA
Where i = van’t Hoff factor
XB = mole fraction of solute for dilute solution
P 0  PS nB
0 =i n
P A
nB = number of moles of solute
nA = number of mole of solvent
P 0  PS B W A M
 0 =i M W
P B A
Where, WB = Amount of solute dissolved
WA = Amount of solvent taken
MB = Molecular mass of solute
MA = Molecular mass of solvent
(b) Elevation in Boiling point
TB = iKb m
WB
TB = iKb  M  W ( gms) 1000
B A
(c) Depression in Freezing Point
Tf = iKf m.
WB
Tf = iKf  M  W ( gms) 1000
B A
(d) Osmotic Pressure
v = inRT
 = iCRT
Relationship between Van’t Hoff factor for Dissociation and

association
1. Dissociation: Degree of dissociations : It is defined as the number of moles dissociated
over the initial concentration taken.
Total number of particles at equilibriu m
Van’t Hoff Factor :
Initial concentrat ion
[ 41 ]
Solutions
Let c moles per litre of an electrolyte AxBy be taken and let it dissociate as
AxBy xAY+ + yBx–
Initial conc c o o
.. yC moles of Bcx– is formed
c o o
 Ax By xAy+ + yBx–
(C – C) xC yC
(C  C )  x C   y C 
i=
C
1    x  y
 i= = 1 + [(x + y)–1]
1
Let x + y = n = number of particles formed after dissociation
 i = 1 + (n – 1)
i 1
=
n 1
2. Association: Degree of Association : It may be defined as the number of molecules associated

over initial concentration
number of moles associated

=
Total number of moles of particles at equilibriu m

i=
Let n molecules of an electrolyte A undergo association

nA An
Let the initial concentration of A = C
The degree of association = 
C
when C moles of A associate then moles of An are formed
n
C
C  C 
C n
number of moles of equilibrium (C – C) i=
n C
If C = 1

1  
n
i= 1
1  i 1
i = 1 +  n 1  = 1
  1
n
[ 42 ]
Solutions
Illustration 1: Calculate the freezing point of an aqueous solution of non-electrolyte having an osmotic
pressure of 2.0 atmosphere at 300 K. [Given Kf = 1.86 K kg mole–1 and S = 0.0821 litre atm
K–1mol–1]
Solution: We know
 = CST
Given
 = 2.0 atm
T = 300 K
S = 0.0821 litre atm K–1 mol–1
C=?
2.0 = C  0.0821  300
2.0
C= = 0.0812 mol litre–1
0.0821 300
Since solution is very dilute molality may be taken as equal to molarity
Tf = Kf  m
Tf = 1.86  0.0812
= 0.151
F.P. = –0.151ºC
Illustration 2: A tube of uniform bore (a = 1 cm2) is closed at one end with semipermeable membrane. A 5%
(w/v) solution of glucose is filled in the tube and it is dipped in pure water at 27ºC, so that
equilibrium is attained. Find out
(a) Osmotic pressure of the solution
(b) Height developed in vertical column
[Given density of the final sucrose solution is 2g/cc]
Solution: We know,
v = nRT
w
v = . RT
T
M
w = 5g, v = 100 ml or 0.1 litre, M = 180, R = 0.0821, T = 300 K
5
0.1  =  0.0821  300
180
5  0.0821 300
= = 6.84 atm.
180  0.1
Further,
 = 6.84 atm = 6.84  1.01  105 Nm–2
d = 2 g/ml = 2  103 kg m–3
g = 9.81 m sec–2
we know
 = hdg
 6.84  1.01105
h = dg =
2  103  9.81
= 35.22 meters
[ 43 ]
Solutions
Illustration 3: Boiling point of an aqueous solution is found to be 100.5ºC. Find out the osmotic pressure of
this solution. [Given K b = 0.5 K kg mol–1]
Solution: B.P. of water = 100ºC

Tb = 100.5 – 100 = 0.5
We know
Tb = Kb  m
0.5 = 0.5  m
m =1
Since, solution is dilute molality = molarity
We know,
 = CRT
 = 1  0.0821  300
= 24.63 atm
Illustration 4: The boiling point of pure benzene is 80ºC. The boiling point of a solution containing 1g of a
substance dissolved in 83.4 g of benzene is 80.175ºC. If the latent heat of vaporization of
benzene is 94 cal per g. Calculate the mol.wt., of solute.
Solution: Latent heat of vaporization = 94 cal per g

Boiling point of benzene = 80ºC = 353 K
We know,
R.Tb 2 1.98  353  353
Kb = = = 2.624 K Kg mol–1
1000lv 1000  94
Further we know,
1000Kb  w
Msolute =
Tb  W
Tb = (80.175 – 80) = 0.175ºC
1000  2.624  1
Msolute = = 179.78
0.175  83.4
Illustration 5: 100 g of Sucrose solution in water is cooled to 272.5 K. Find out the weight of ice that will
separate at this temperature. Assume that the solution started freezing at –38ºC.
[K f = 1.86 K Kg mol–1]
Solution: Mass of solution = 100 g

Say mass of solute is w g and mass of solvent Wg
w = 100 – W
Tf = 38º
Molecular weight of sucrose = 342
1000 1.86 100 w

m=  W
38
W = 93.47 g
[ 44 ]
Solutions
When the solution is cooled to –0.5ºC let the mass of water left unfrozen = W1g
Tf = 0.5
1000  K f  w
m = ΔTf  w
[w = 100 – 93.47 = 6.53 g]
1000  1.86  6.53

342 = 0.5  W1
W1 = 71.028 g
Hence, amount of water separated out = 22.43 g.

Problem 1: A solution containing 6 g of a solute dissolved in 250 cm3 of water gave an osmotic pressure
of 4.5 atm at 27°C. Calculate the boiling point of the solution. The molal elevation constant
of water is 0.52°C per 1000 g.
(a) 100.095 (b) 0.095
(c) 0.094 (d) 0.092
Solution: (a) Van’t Hoff equation for osmotic pressure is

πV  nRT
4.5 × 0.25 = n × 0.0821 × 300
4.5  0.25
or n   0.0457 mol
0.0821 300
i.e., 0.0457 mol of the solute is present in 250 ml of solution.
0.0457
Molality of the solution m   1000 = 0.1128
250
ΔTb  K b m  0.52  0.1128  0.095C
Boiling point of solution
Tb s  Tb0  Δ Tb  1 0 0  0 .0 9 5  1 0 0.0 9 5  C
Problem 2: A mixture which contains 0.550 of camphor and 0.090 g of an organic solute melts at 161°C.
The solute contains 93.75% C and 6.25% H by weight. What is the molecular formula of
compound? Kf for camphor is 37.5°C mol–1 kg. The melting point of camphor is 209°C.
(a) C10H8 (b) C10H10
(c) C10H12 (d) C10H22
Solution: (a) Given,

ΔT  209  161  48C
W2 = 0.09 g (organic solute)
W1 = 0.55 g (camphor)
Kf = 37.5°C mol–1 kg
1000  K f  W2
ΔT 
Mw2  W1
[ 45 ]
Solutions
1000  37.5  0.09

48 
Mw2  0.55
 Mw2  127.84
% No. of moles Mole ratio
93.75 7.8125
C = 93.75  7.8125  1.25
12 6.25
6.25 6.25
H = 6.25  6.25 1
1 6.25
 Empirical formula is C5H4 and empirical formula weight = 64
127.84
 Molecular formula is (C5H4)n and n  2
64
 Molecular formula of solute is (C5H4)2= C10H8
Problem 3: If the boiling point of an aqueous solution 100.1°C, what is its freezing point? Given Lf = 80,.
Lv = 540 cal g–1 respectively for H2O.
(a) 0.36°C (b) 0.46°C
(c) 0.56° (d) 0.76°
Solution: ΔT f  K f  m
ΔTb Kb RTb2 1000 L f

  
ΔT f K f 1000Lv RT f2
2
ΔTb Tb  L f
 2
ΔT f Tf  Lv
Tbs  100  273  373K
Tb0  273 K
ΔTb  100.1 100  0.1C
0.1 (373)2  80

ΔT f (273) 2  540
ΔT f  0.36C
Tf  0.36C
Problem 4: 0.5 g KCl was dissolved in 100 g water, and in solution, originally at 20°C, freezes at
– 0.24°C. Calculate the percentage dissociation of salt. (Kf for water is 1.84 K kg mol–1).
(a) 92% (b) 90%
(c) 85% (d) 80%
Solution: (a) Calculate the (theoretical) molecular mass of KCl

= 39 + 35.5 = 74.5
ΔTf  K f  m
1.84  0.5
0.24  i   1000
74.5  100
[ 46 ]
Solutions
i = 1.92
Now, KCl dissociates as KCl K  Cl
Total moles 1 0 0
Mole after dissociation 1–  
Total number of moles after dissociation = 1 –  +  +  = 1 + 
1 α
i
1
or  + i – 1 = 1.92 – 1 = 0.92
Percentage dissociation = 0.92 × 100 = 92%
Problem 5: Calculate the Van’t Hoff factor when 0.1 mole NH4Cl dissolved in 1 L of water. The degree
of dissociation of NH4Cl is 0.8 and its degree of hydrolysis is 0.1.
(a) 7.68 (b) 2.68
(c) 1.68 (d) 0.68
Solution: (b) Given,

Degree of dissociation () = 0.8
Degree of hydrolysis (h) = 0.1
Considering, ionsiation of NH4Cl;
NH 4 Cl NH 4  Cl 
Initial 0.1 0 0
At equilibrium – 0.08 + 0.08 + 0.08
–––––––––––––––––––––––––––––––
0.02 0.08 0.08
Considering hydrolysis of NH 4 ion
NH 4  H2O NH 4OH + H
Initial 0.08 0 0
– 0.008 + 0.008 + 0.008
––––––––––––––––––––––––––––––––––––––––––––––––
At equilibrium 0.072 0.008 0.008
Total number at equilibrium
i
Initial moles
n NH4 Cl  n NH  n Cl  n NH 4 OH  H 
i  4
0.1
0.02  0.072  0.08  0.008  0.008 0.188

   1.88
0.1 0.1
Problem 6: Each salt undergoes 90% dissociation which of the following will have the highest building
point?
(a) Decinormal Al2(SO4)3
(b) Decinormal BaCl2
(c) Decinormal Na2SO4
(d) A solution obtained by mixing equal volume of (b) and (c) and filtering
[ 47 ]
Solutions
Solution: (a) Al2(SO4)3 can furnish maximum no. of ions.

Problem 7: The ratio of the value of any colligative property for KCl solution to that of sugar solution is:
(a) 1 (b) 2
(c) 0.5 (d) 4
obs. C.P. 1    x  y (KCl) 2

Solution: (b) i   
cal. C.P. 1 1
Problem 8:. Which of the following aqueous solution will have highest boiling point?
(a) 1 g NaCl solution (b) 1 g KCl solution
(c) 1 g urea solution (d) all will have same boiling point
Solution (a) Elevation in boiling point depends upon number of solute particle only.
Problem 9:. When HgI2 is added to an aqueous solution of KI there will be

(a) increase in boiling point (b) decrease in freezing point
(c) increase in vapour pressure (d) both (a) and (b)
Problem 10:. That solvent is better to be used during ebullioscopic measurements where the solvent has
(a) high Kb value
(b) low Kb value
(c) where K b and Kf values are equal for solvent
(d) none of these
[ 48 ]
Chapter - 3
ELECTRO CHEMISTRY
Electrochemistry is that particular section by physical chemistry which deals with the interaction between
electrical energy and chemical energy. Both are interconvertible. Electrical energy can be produced at the
cost of chemical energy and chemical energy can be produced at cost of electrical energy. The instrumental
devices within which such kind of interconversion is possible are called as “Cells”. Cells of two types:
1. Electrolytic Cell: In such cells, chemical energy is produced at the cost of electrical energy. No
salt bridge is used.
2. Electrochemical Cell: An electrochemical cell is that in which chemical energy is used to produce
electrical energy by using Salt Bridge.
Salt Bridge is U-shaped glass tube containing solution of a particular salt, used in Electrochemical
cells (Galvanic cells) in order to:
(a) maintain electrical contact between two different electrolyte solution.

(b) minimise the formation of liquid junction potential conditiosn for Salt Bridge.
(c) Salt should be chemically inert.
(d) The ionic speed of cation and anion should almost be same.
3.1 Electrical Conductors

Substances which allow the flow of current are called electrical conductors. The conductors are of
two types.
(i) Metallic Conductors. (ii) Electrolytic Conductors.
(i) Metallic Conductors: In these conductors conduction of electricity is due to the movement of
free electrons from a higher negative potential to a lower one without producing chemical
change.
e.g., Metals, alloys, graphite, certain solid salts like CuS, CdS, etc.
(ii) Electrolytic Conductors : Current flows due to the migration of ions towards oppositely charged
electrodes and is accompanied by chemical changes at electrodes. e.g. Molten Salts, aqueous
salt solutions, acids and basesm, etc.
[ 117 ]
Electro Chemistry
Difference Between Metallic and Electrolytic Conduction
Electronic or Metallic Conduction Electrolytic Conduction
1 Passage of current due to flow of electrons. 1. Passage of current due to movement

of ions.
2. Only physical change take place. 2. Physical and chemical changes both
take place.
3. No transfer of matter takes place. 3. Transfer of matter takes place.
4. Metallic conduction decreases 4. Electrolytic conduction increases with

with temperature due to increases in resistance increasing temperature.
(Decrease in viscosity takes place)
Electrolysis
The phenomenon in which passage of current through an electrolyte brings chemical changes involving
electronation (reduction) as well as de-electronation (oxidation) of ions is known as
electrolysis.
Chemical Changes During Electrolysis
The products formed during electrolysis depends upon:
(1) Nature of electrodes (reacting or non-reacting electrode).
(2) Nature of electrolyte (molten or aqueous).
(3) Concentration of solution used
Case A : Electrolysis of Molten NaCl.

Using Pt electrode [when electrode does not react, (inert electrode)]
NaCl Na+ + Cl–
1
at anode: Cl– Cl + e– Oxidation
2 2
at Cathode: Na+ + e– Na Reduction
Case B: Electrolysis of Molten NaCl (using Hg electrode)

NaCl Na+ + Cl–
1
at anode : Cl– Cl + e– de-electronation
2 2
at cathode: Na+ + e– Na electronation
2Na + Hg 2Na – Hg (amalgam)
Case C : Electrolysis of aqueous NaCl. Using Pt electrode

NaCl Na+ + Cl–
2H2O H3O+ + OH–
[ 118 ]
Electro Chemistry
Sub Case (i) Concentrated NaCl Solution

1
At anode: Cl– Cl + e– O.P. of Cl– < O.P. of OH–
2 2
1 1
At cathode: H3O+ + e– H2O + H or H+ + e– H
2 2 2 2
O.P. of H3O+ or H+  O.P. of Na+
Sub Case (ii) Very Dilute Solution of NaCl

1
At anode: Cl– 
 2 Cl2 + e
–
1
2OH–  – –
 H2O + 2 O2 + 2e (But only oxidation of OH takes place)
At cathode: 2H3O+ + 2e– 
 2H2O + H2
Case D : Electrolysis of aqueous NaCl using Ag electrode

Here the reactions are very similar to that using Pt electrode, i.e.
At cathode : 2H+ + 2e– H2
At anode: Ag + Cl– AgCl + e–
Here the O.P. of H+  O.P. of Na+
Case E : Electrolysis of aqueous solution of NaOH

NaOH Na+ + OH–
H2O H+ + OH–
Here sodium hydroxide provides the conducting medium. However, the main
reactions are
At cathode : 2H+ + 2e– H2
At anode : 2OH– 2OH + 2e–
1
2OH H2O + O
2 2
overall anodic reaction
1
2OH– H2O + O + 2e–
2 2
Note 1. The phenomenon of electrolysis occurs only at the electrodes.
2. In case of two are more similar ions to be discharged, the higher is the discharge
potential of an ion, lesser is its tendency to get itself discharged at the electrodes.
3. The discharge of ions at different electrodes takes place only for the time electricity
is passed.
4. If electrodes which can be attacked are used, the anode metal gets dissolved whereas
deposition of metal occurs at cathode and thus no change in concentration of a
solution is noticed.
5. The electrolytic solution remains electrically neutral during electrolysis since same
equivalents of charge are neutralized at opposite electrodes.
6. A minimum emf is required for the electrolysis of a solution, e.g., in the case of
formation of H2 and Cl2 from a brine solution under standard condition, a minimum
emf of 2.19 V is required.
[ 119 ]
Electro Chemistry
Application of Electrolysis
1. In electrometallurgy.
2. Preparation of Chemicals : e.g., NaOH, Cl2, H2O2, F2, KMnO4.
3. In Galvanisation.
4. In Electroplating.
5. In electrorefining of metals (impure).
Faraday’s Law
Faraday owrked on electrolysis and established a mathematical relationship between weight of
deposited substance and the electricity passed. According to him
First Law: The amount (w) of an ion oxidised or reduced at either electrode during the passage of
current (i.e., during electrolysis) is directly proportional to the quantity of electricity passed through
electrolytic solution
W  Q.  Q=Ct
WCt  W = ZCt
C = current strength in amperes
t = time in seconds
Where, Q is total charge (electricity) passed through solution in coulombs and Z is electrochemical
equivalent of the substance
Unit of Z = g C–1
Points to Remember
(a) One equivalent of substance (weighing equal to g eq. wt.) is deposited when 96500 C of
electricity is passed through an electrolyte
(b) 96500 C = 1 Faraday = charge on 1 mole of electrons i.e. charge on electron

= 1.602  10–19 C
(c) 96500 C deposits E g (E = Eq. wt)

E
 1 coulomb deposits = Z (electrochemical equivalent)
96500
(d) Number of equivalent deposited = number of Faradays electricity passed
W Q (coulombs) Q
= =
E 96500 F
Second Law of Electrolysis : It states that the ratio of the weights of the substances deposited at
any electrode is in the ratio of their chemical equivalents, provided same amount of electricity is
passed through the electrolytes.
E1 W1 W1 W2
E2 = W or E = E2
2 1
Thus the number of equivalents of substances deposited at various electrodes are equal provided
same quantity of electricity is passed through different electrolytes.
[ 120 ]
Electro Chemistry
E1 Z1
Also, E2 = Z2
W1 Z1
W2 = Z2
This implies that the ratio of the weights of substances deposited will be in the ratio of their
electrochemical equivalents.
The weight of deposited substance on the respective electrodes depend upon the following factors;
(a) Atomic weight, equivalent weight of the deposited ions/substances.

(b) Valency / charge on deposited ion / substances.
(c) Strength of current passed.
(d) Surface area of the electrode surface.
(e) Density of deposited substances
(f) Discharge potential
(g) Time of electricity passed on combining Ist and 2nd laws of Faraday,
A E EQ
(i) W  Ct  Ct 
nF F F
W = Wt. deposited
A = Atomic weight
E = Equivalent weight
C = Strength of current
t = Time
Q = Charge
E W Q
(ii) W  Ct or 
F E F
W Ct Q
or No. of equivalence =   = N × V (litre) = M × n-factor × V (litre)
E F F

Problem 1: A 250 ml sample of 0.2 M Cr3+ is electrolysed with a current of 96.5 amp, if the remaining
concentration of Cr3+ ion is 0.14, then duration of electrolysis is
(a) 75 sec. (b) 150 sec.
(c) 200 sec. (d) 25 sec.
Solution: (a) No. of moles of Cr3+ before electrolysis = 0.05

No. of moles of Cr3+ after electrolysis = 0.025
 No. of moles of Cr3+ electrolysed = 0.05 – 0.025 = 0.025
Mass Cr electrolysed = 0.025 × 52gm = 1.3 gm.
52
E Cr   17.33
3
A E 96.5  t 13.3
W  C t  C t   1.3
nF F 96500
t = 75 seconds
[ 121 ]
Electro Chemistry
Problem 2: Element A (Atomic weight = 112) and Element B (Atomic weight = 27) form chlorides.
Solution of there chlorides are electrolysed separately and it is found that when same quality
of electricity is passed 5.6 gm A and 0.9 gm B has deposited. What is the ratio of valency
of A and B?
(a) 2 : 3 (b) 3 : 2
(c) 1 : 1 (d) 3 : 1
A 112
Solution: (a) W  nF C  t 5.6 =
nAF
Ct ...(i)
27
0.9  C t ...(ii)
nBF
(i)
; nA : nB  2 : 3
(ii)
Problem 3: In the electrolysis of an aqueous solution of Cr2(SO4)3 solution using a current of 2 ampere,
the mass of cathode increased by 8 gm. How long was electrolysis conducted? (Cr =52).
(a) 6. 19 hr (b) 5.6 hr
(c) 2.4 hr (d) 2.6 hr
A 52
Solution: (a) W  I t 8  I t  t  6.19 hr
nF 3  96500
Problem 4: Silver is electrodeposited on a metallic vessel of surface area 800 cm2 by passing a current
of 0.2 amp for 3 hours. Calculate thickness of Ag deposited of density of Ag is 10.47 gm/cc?
(Ag = 108)
(a) 10–4 cm (b) 2.88 × 10–4 cm
(c) 25.8 × 10–4 cm (d) 2.8 cm
A
Solution: (b) W  C t n  d  A  thickness
nF
108
WAg   0.2  3  3600 ...(i)
1 96500
m Ag  10.47  800  x
108  0.2  3  3600
  10.47  800  x
96500
 x  2.88 104 cm
Problem 5: 3 amp of current was passed through an aqueous solution of an unknown salt of Pd
for 1 hour 2.977 gm of Pd+n was deposited at cathode then find the value of n (Pd = 106.4)?
(a) 4 (b) 2
(c) 3 (d) 5
A 106.4 106.4  3  36
Solution: (a) W  C t  2.977   3  1  3600 
nF n  96500 965  n
106.4  3  36
n 4
2.977  965
[ 122 ]
Electro Chemistry
3.2 Conductance of Solution

Electrolytic solutions behave just like metallic conductors and obey ohm’s law, which relates EMF,
applied to a conductor and the strength of the current flowing through it.
According to ohm’s law I = V/R,
The resistance of any uniform conductor varies directly as its length (l meter) and inversely to its
area of cross reaction (A meter2),
l l
i.e., R   R=
A A
 (rho) = Sp. resistance or resistivity units = ohm meter–1
Specific conduction or conductivity of any conductor is defined as the reciprocal of specific resistance,
l 1 A
=  l
R
l 1
where, = conductance and  = specific conductance
R
A l
 Conductance = Specific conductance  or conductance  = specific conductance
l A
Conductance  cell constant = specific conductance or conductivity
Specific conductance is defined as conductance of a material of a unit length and unit area of cross
section.
Alternatively specific conductance is conductance of one cubic metre of material or solution.
Conductanc e
Hence, specific conductance =
Volume of solution
or Conductance = Specific conductance × Volume
Equivalent Conductance:
The conductance observed when a given volume(V) of an electrolyte solution contains one equivalent
of the substance.
i.e. eq = K  V
KV
However, if (Ceq are present in V ml of solutions then eq = C
eq
However, if Ceq equivalents are present in 1 litre of solutions then,
1000 K  1000
eq = K  =
C N
(Because number of equivalent in 1L of solution = normality)
Molar Conductance:
It is the conducting power of all the ions present in a solution having one mole of electrolyte, in a
given volume (V) of electrolytic solution.
[ 123 ]
Electro Chemistry
If one mole of electrolyte is present in V ml of solution then,
m = KV
If Cmoles of electrolytes are present in V ml of solutions then,

KV
m = C
moles
If Cmoles of electrolyte are present in one litre of solution then

K  100C K  1000
m = C mole = M
Factors Which Effect the Electrolytic Conductance:
1. The inter ionic attraction (depends upon solute-solute interaction).
2. The solvation of ions (depends upon solute - solvent interaction).
3. The viscosity of the solvent (depends upon solvent - solvent interaction).
4. Concentration of the solutions.
5. Temperature.
6. Effect of high voltage.
(1) Interionic Attraction: If the interionic forces of attraction are stronger then electrolytic
conductance is less. because ionic mobility is reduced.
(2) Effect of Solvent: In solvents with low dielectric constant having small ionization effect on
electrolytes the electrostatic forces of attraction between oppositively charged ions would be
appreciable and there by decrease the electrolytic conductions. However solvents with high
dielectric constants increase conducting capacity of the solution. Also if solvations of ions is high
then electrolytic conductance decreases or becomes low.
(3) Viscosity of Medium: The dependence of conductance on viscosity of medium is given by

Walden’s rule, which says. Electrolytic conductance (equivalent conductance) is inversely
proportional to the viscosity of the medium
(4) Concentration of Solutions: If the concentration of the solution increases then:
(i) Conductance increases.
(ii) Molar and equivalent conductance decreases.
(iii) Specific conductance increases.
(5) Effect of Temperature: The conductance of all electrolytes increase with increasing temperature.
The rise in conductance with increases in temperature is due to:
(a) decrease in viscosity of solutions.

(b) increase in the speed of the ion.
(c) increase in degree of dissociation in case of weak electrolyte.
[ 124 ]
Electro Chemistry
Variation of Conductance with Dilution
1. The conductance of solution increases with increase in dilution due to increase in number of ions
as well as increase in ionic mobility. The term ionic mobility refers to the speed of ion under unit
potential gradient.
distance travelled by ions

Speed of ion = (units = cm sec–1)
time taken
Speed of ion
Ionic mobility = Potential gradient (units = cm3 volt–1 sec–1)
2. The specific conductivity decreases with dilution because number of ions per ml. decreases.
3. The molar conductance and the equivalent conductance increases with dilution because the
volume of the electrolyte solution containing one mole of electrolyte or one equivalent of electrolyte
increases.
4. The increase in molar/equivalent conductance for strong electrolytes is very small even at infinite
dilution because degree of dissociation for strong electrolytes do not increase appreciably. It is
only that the interionic forces are broken.
5. The increase in the molar/equivalent conductance for weak electrolyte is very large and at
infinite dilution the value shoots up. This could be attributed to the fact that upon dilution the
degree of dissociation of weak electrolyte increases largely and the interionic forces of attractions
also decreases. Kohlrausch suggested that,
°m
m =  om – b C POTASSIUM CHLORIDE
MOLAR CONDUCTANCE
SO DIU M CH LO
RIDE
where,  om = molar conductance at infinite
dilution.
C OP PER
SU LPHA
TE
From this it is possible to determine the molar
conductance at infinite dilutions for strong
electrolytes by extrapolating the graph. For ACETIC ACID
most electrolytes it is not possible to determine
CONCENTRATION
the molar conductance at infinite dilution. There
are indirect methods for determining the molar conductance at infinite dilution for
most electrolytes.
Kohlrausch Law of Independent migration of Ions

The law states that at infinite dilution where ionization of all electrolytes is complete and where
all interionic effects are absent, each ion migrates independently of its counter ion, and contributes
a definite share to the total conductance of the electrolyte,
i.e., o = Λ o + Λ o
e.g., Λ oKCl =  oK  +  oCl 
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Electro Chemistry
Calculation of o of weak electrolyte, e.g., CH3COOH

 oCH
3 COOH
=  oCH 3COO – +  oH 
Hence, we can get the  oCH 3COOH from the  om of strong electrolytes such as HCl, NaCl and
CH3COONa
 oCH =  oCH 3COONa +  oHCl –  oNaCl
3 COOH
=  0H  +  0CH 3COO 
Applications of Conductance Measurements

(1) Degree of Ionization or dissociation : We know that at infinite dilution electrolytes are
completely dissociated and at any other concentration it is partially ionized. Thus
 m  eq
 = degree of dissociation =     
m eq
(2) Determination of solubility of sparingly soluble salt.
Consider a salt,
MX (s) M+(aq) + X–(aq)
Here Ksp = [M+] [X–]
Let KB = Specific conductance of saturated solution of salt
KH2O = Specific conductance of pure water
 Ksalt = Specific conductance of salt only
Ksalt = KB – K H 2O
The equivalent conductance or molar conductance is given by
K salt  1000 K salt  1000 K 1000

 m  or m = or eq = salt or m =
K  1000
Ceq C moles N M
This solution can be regarded as infinitely dilute
K salt 1000 K salt  1000

 0m = C moles = Solubility
 m      
K salt  1000
 0
  0  = Concentration in moles /L = solubility

By knowing the solubility in moles/L we can calculate Ksp of salt

The above principle can also be used for determining the:
(a) ionic product of water
(b) degree of hydrolysis of salts
Ionic Mobilities and Conductance

The ionic conductance depends upon the charge and velocity of ions:
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Electro Chemistry
 0  +   0 = +  F
 0  –   0 = –  F
 0 =  0 +  0
= F(+ + –)
Fall around anode 
= 
Fall around cathode 
Transport Number : The fraction of total current carried by each ion is called transport number,
current carried by cation
t+ =
Total current
Also quantity of current carried is proportional to ionic mobilities,

  
 t+ =    =     
   
  
t– =    =     
   

Problem 1: The equivalent conductivity of 1 M H 2 SO 4 solution having conductivity
26 × 10–2 Ohm–1 cm–1
(a) 13 Ohm–1 cm2 eq–1 (b) 130 Ohm–1 cm2 eq–1
(c) 4.9 Ohm–1 cm2 eq–1 (d) 49 Ohm–1 cm2 eq–1
k 1000 26 102  1000

Solution: (b) λ eq    130 Ohm 1cm 2 eq 1
N 2 1
Problem 2: If m NH4OH = 9.33 Ohm–1 cm2 mol–1, λm NH4OH  238.3 Ohm1cm2mol1. Then degree of
dissociation of NH4OH is:
(a) 0.0392% (b) 0.392 %
(c) 3.92 % (d) 39.2 %
λ m 9.33
Solution: (c) α  λ  238.3  0.0392  3.92%
m
N
Problem 3: The sp conductance of KCl solution at 20°C is 2.12 × 10–2 Ohm–1 cm–1 and resistance
10
of this cell is 55 Ohm. The cell constant of the cell is
(a) 4.61 cm–1 (b) 3.32 cm–1
–1
(c) 2.17 cm (d) 1.16 cm–1
ρ 1  2 1 l l 1
Solution: (d) We know, R  a  ρ  R  a  2.12 10     1.16cm
55 a a
Problem 4: The resistance of 0.5 (N) KCl solution is 25 Ohm. The distance between two electrodes of
the cell is 1.2 cm and area of cross-section of electrode is 2.2 cm2. Then value of eq
for KCl is
(a) 4.35 Ohm–1 cm2 eq–1 (b) 43.6 Ohm–1 cm2 eq–1
(c) 21.8 Ohm–1 cm2 eq–1 (d) 2.18 Ohm–1 cm2 eq–1
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Electro Chemistry
k 1000 k 1000 1 1 1 1.2

Solution: (b) λ eq   k    0.0218
0.5 0.5 ρ R  a 25 3.2
k 1000 0.0218  103

λ eq    43.6 Ohm 1 cm 2 eq 1
0.5 0.5
Problem 5: Ionic conductances at infinite dilution of Al3+ and SO24 ion are 189 Ohm–1 cm2 eq–1 and 160
Ohm–1 cm2 eq–1 respectively, calculate the molar conductances of Al2(SO3)3 at infinite
dilution?
(a) 858 (b) 8.58
(c) 452 (d) 4.52
 3
Solution: (a) Molar conductance of Al3(SO4)3 at infinite dilution = No. of Al3+ × λ eq Al
 2
+ No. of SO24 + λ eqSO 4
= 2 × 189 + 3 × 160
= 858 Ohm–1 cm2 eq–1
Redox Reactions in Aqueous Solutions
Redox reactions in aqueous solutions are of two types :
(1) Direct Redox Reaction: A Redox reaction in which both oxidation and reduction takes place
in the same beaker (or container) is called a direct redox reaction.
For example, when a zinc rod is dipped in an aq. solution of CuSO4 in a beaker a spontaneous
reaction takes place and the following observations are made.
(i) Zinc rod starts dissolving and loses its weight gradually.
(ii) The blue colour of the solution slowly fades away.
(iii) The reddish brown ppt. of copper settles down at the bottom of the beaker.
(iv) The reaction is exothermic i.e., takes place with the evolution of heat.
(v) The solution remains electrically neutral.
(vi) The reaction stops after some time.
The above reaction may be written as two half reactions which takes place simultaneously.
Zn(s) — Zn2+(aq) + 2e– Oxidation
Cu2+(aq) + 2e– — Cu(s) Reduction
The overall reaction may be represented as
Zn(s) + Cu2+(aq) + SO42–(aq) — Zn2+(aq) + SO42–(aq) + Cu(s)
and cancelling the common sulphate ions from both sides, we get
Zn(s) + Cu2+(aq) — Zn2+(aq) + Cu(s)

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Electro Chemistry
It is also observed that during the reaction Chemical energy is converted into heat energy.
Now, if we place copper rod in a ZnSO4 solution no chemical reaction takes place. This means
that reverse reaction does not take place.
Cu(s) + Zn2+(aq) — No Reaction
It is thus evident that Zn has more tendency to lose electrons than Cu.
(2) Indirect Redox Reactions: The redox reactions in which oxidation and reduction takes place
in two separate containers, are called indirect redox reactions.
Electro-chemical Cell
Redox reactions, which occur in the same beaker, chemical energy in form of heat is produced.
By suitable means, it is possible to convert this chemical energy into electrical energy. A device used
to convert chemical energy produced in a redox reaction into electrical energy is called an Electro-
chemical Cell or simply a Chemical Cell. In such cells two half-cells are coupled together with the
help of a Salt-Bridge.
Construction of an Electro-chemical Cell
The main requirements of such cells are :
(i) The redox reaction should be separable into two partial reactions so that electrons are lost by
one reactant and are simultaneously gained by another.
(ii) The substance that loses electrons and the one that accepts the electrons should not be in direct
contact with each other, so that electron transfer occurs through an external circuit.
The following is the observations made when the two compartment are joined :
(i) The galvanometer shows deflection indicating that the electricity is produced in this experiment.
The deflection of the needle indicates that electrons are flowing from zinc towards copper.
(ii) With passage of time Zn rod goes on dissolving in one beaker. In second beaker copper metal is
precipitated, and get attached to copper rod. Thus, Zn rod loses weight and copper rod gains
weight.
(iii) The weight of zinc dissolved and the weight of copper precipitated are in the ratio of their
equivalent weights,
Weight of Zn  dissolved Eq. wt. of Zn 65.4
Weight of Cu precipitated = Eq. wt. of Cu = 63.5
(iv) The concentration of ZnSO4 solution increases in the zinc half cell and concentration of copper
sulphate decreases in copper half cell (i.e., blue colour of solution fades away).
(v) The solutions in both the beakers remain electrically neutral.
(vi) The temperature of solutions remain constant. Thus, no evolution of heat is observed during the
reaction.
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Electro Chemistry
(vii)The cell stops working after some time.
The above observations can be explained on the basis of the following reaction.
Zn(s) + CuSO4(aq) — ZnSO4(aq) + Cu(s)
Zn(s) + Cu2+(aq) — Zn2+(aq) + Cu(s)
Each Zn atom in the zinc rod loses two electrons to form Zn2+ ions,
Zn(s) — Zn2+(aq) + 2e–
The Zn2+ ions migrate from the rod into the solution while the electrons move from the rod into
the copper wire, and through copper wire, ultimately reaches the copper rod.
On reaching the copper rod, they come at the surface of the copper rod and combines with
Cu2+(aq.) ions present in the solution to form neutral copper atoms, which in turn get
deposited on the copper rod.
Cu2+(aq) + 2e– — Cu(s)
(viii) As the Zn2+ ion concentration increases the solution becomes +vely charged at anode and as
Cu2+ ion concentration decreases the solution at cathode becomes –vely charged . Hence cell
stops functions.
(ix) To have a continuous supply of electricity a salt bridge is used. A salt bridge contains a semi-solid
paste obtained by adding gelatin or agar-agar to the solution of a strong electrolyte (such as
K2SO4, NaNO3, NH4NO3, KNO3 etc.) which does not react during the process.
Functions of Salt Bridge

The main functions of the salt bridge are :
(i) To Complete the Electrical Circuit : The electrons flow in the outer circuit through the wire,
while the inner circuit is complete by flow of ions from one solution to the other. Hence
current flows.
(ii) To Maintain the Solutions Electrically Neutral :The main function of the salt bridge is to
provide a path for the migration of positive and negative ions so as to keep the solutions in both
the beakers electrically neutral and thus, maintain the flow of electric current through the circuit.
Electrode Potential
The potential associated with an electrode potential is developed due to formation of electrical double
layer in between the metallic surface and solution.
Formation of electrical double layer depends upon:
(a) Electrolytic solution pressure (P)
(b) Osmotic Pressure ()
P > , then metallic surface acquires –ve charge w.r.t. solution. But, in case of > P, then metallic
surface acquires +ve charge w.r.t. solution.
Potential is the work done in bringing a particular charge from a particular point to a point of interest.
[ 130 ]
Electro Chemistry
For the same element,

E 0OX  E 0Re d  0 i.e., E OX
0
  E 0Re d
Zn   Zn 2   2e, E 0OX  0.76 Volts
Zn 2  2e   Zn 0 , E 0Red  0.76 Volts
Cu 2   2e   Cu 0 , E 0Re d   0.34 Volts
Cu 0   Cu 2  2e, E0OX  0.34 Volts
Nerst Equation: At 25°C
0.059 [Product]
E  E0  log
n [Reactant]
where, E 0  E 0Re d (R)  E Red
0
(L)
E 0  E 0Re d (Cathode)  E Re
0
d (Anode)
n = No. of lost or gained electron

G 0   nFE 0
(a) if E0 = +ve, G0 = –ve, spontaneous
(b) if E0 = –ve, G0 = +ve, non-spontaneous
(c) if E0 = 0, G0 = 0, Equilibirum attained
G0 = –nFE0
G0 = –2.303 RTlogK
 2.303 RTlogK = nFE0
nFE 0
 log K 
2.303RT
To understand the concept of electrode potential, consider a metal rod (M) placed in contact with its
own ions (Mn+). Then there is one of the following three possibilities.
(i) Mn+ ions may collide with the metal rod and deflected back without undergoing any change.
(ii) Mn+ ions, on collision with the metal rod may gain electrons and change into metal atoms,
i.e., Mn+ ions are reduced.
Mn+ + ne– — M .....(i)
(iii) Metal atoms of the metal rod may lose electrons and change into Mn+ ions, i.e., metal atoms get
oxidised.
M — Mn+ + ne– .....(ii)
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Electro Chemistry
If metal has relatively higher tendency to get oxidized, reaction (ii) will occur, the electrons will
accumulate on the metal rod which will, therefore, develop a negative charge. This in turn may
attract some metal ions from the solution which may change into metal atoms. Ultimately, an equilibrium
is reached as follows :
M Mn+ + ne–
If metal ions have relatively higher tendency to get reduced, reaction (i) will occur. Metal ions (Mn+)
will gain electrons from the metal rod. As a result metal rod will develop a positive charge with
respect to the solution and ultimately the following equilibrium will be attained.
Mn+ + ne– M
Hence, the potential difference set up between the metal and its ions in the solution is called electrode
potential or the electrode potential may be simply defined as the tendency of an electrode to lose or
gain electrons when it is in contact with solution of its own ions.
Electrode Potential
(i) Electrode Potential : The potential difference arising when the metal is put inside its metallic
salt solution is called Electrode Potential.
(ii) Standard Electrode Potential : The potential difference arising when a pure metal strip is put
inside its metallic salt solution of 1M concentration at 25ºC is called standard
electrode potential Eº.
(iii) Oxidation Potential : Potential generated due to the process of oxidation.
(iv) Reduction Potential : Potential generated due to the process of reduction.
Electro-Chemical Series
The arrangement of elements in the order of increasing reduction potential values is called an
electrochemical series or activity series.
Standard Reduction Electrode Potentials (at 298 K)
Electrode Electrode Reaction (Reduction) EºMn+/M (volts)
Li Li+ (aq) + e– Li(s) –3.05

+ –
K K (aq) + e K(s) –2.93
2+ –
Ba Ba (aq) + 2e Ba(s) –2.90
Ca Ca2+ (aq) + 2e– Ca(s) –2.87
Na Na+ (aq) + e– Na(s) –2.71
2+ –
Mg Mg (aq) + 2e Mg(s) –2.37
3+ –
Al Al (aq) + 3e Al(s) –1.66
Zn Zn2+ (aq) + 2e– Zn(s) –0.76
Cr Cr3+ (aq) + 3e– Cr(s) –0.74
2+ –
Fe Fe (aq) + 2e Fe(s) – 0.44
2+ –
Cd Cd (aq) + 2e Cd(s) –0.40
[ 132 ]
Electro Chemistry
Electrode Electrode Reaction (Reduction) EºMn+/M (volts)
Co Co2+ (aq) + 2e– Co(s) –0.28
Ni Ni2+ (aq) + 2e– Ni(s) –0.25
Sn Sn2+ (aq) + 2e– Sn(s) –0.14
Pb Pb2+ (aq) + 2e– Pb(s) –0.13
H 2H+ (aq) + 2e– H2(g) –0.00
Cu Cu2+ (aq) + 2e– Cu(s) +0.34
Hg Hg22+ (aq) + 2e– Hg(l) +0.79
Ag Ag+ (aq) + e– Ag(s) + 0.80
Au Au3+ (aq) + 3e– Au(s) + 1.42
F F2 + 2e– 2F– + 2.87
Reference Electrodes
The electrode which has an accurately known potential at 298K and is used to find single electrode
potential of other electrodes are called reference electrodes.
(a) Primary Reference Electrode (b) Secondary Reference Electrode
(a) Primary Reference Electrode: Standard hydrogen electrode is employed as primary reference
electrode.
Standard Hydrogen Electrode: It has been observed that:
(i) A half cell reaction can not take place independently.
(ii) For purpose of measurement, as soon as another metal conductor is put into the solution, it
will set up its own potential.
In view of these difficulties, the electrode potential has to be measured against some reference
electrode. It is called Standard Hydrogen Electrode (SHE) or Normal Hydrogen Electrode (NHE).
It consists of a platinum wire sealed in a glass tube

and has a platinum foil attached to it. The foil is
coated with finely divided platinum black. It is Pt. H2 (atom)
wire
dipped in an acid solution containing H+ ions in 1M
concentration (1M HCl). Pure Hydrogen gas at
1 atm pressure is constantly bubbled into solution
at constant temperature at 298K. The surface of
Pt. foil 1 M HCl
the foil gets surrounded by hydrogen gas. The
following reactions occur in this half cell depending Standard Hydrogen
electrode
upon whether it act as an anode or cathode.
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Electro Chemistry
(i) If SHE acts as anode H2(g) 2H+ + 2e–
This electrode is usually represented as,
Pt, H2 (1atm) | H+ (1M)
(ii) If SHE acts as cathode
2H+ + 2e– H2(g)
This electrode is usually represented as H+ (1M) | Pt, H2 (1atm).
The standard hydrogen electrode is regarded as reversible electrode.
H2(g) 2H+ + 2e–
The electrode potential of the standard hydrogen electrode is taken as zero.
In using SHE, many difficulties arise, such as,
(i) It is very difficult to maintain a pressure at 1 atm of H2 gas. Purity of H2 gas is another
problem.
(ii) It is difficult to use liquid junctions.
(iii) It can not be used in presence of reducible ions.
(b) Secondary Reference Electrodes: Some other secondary reference electrodes are used.
Such as,
(1) Calomel electrode (2) Quinhydrone electrode

(3) Glass electrode (4) Ag - AgCl electrode
We will discuss here only Calomel electrode.
Calomel Electrode: Calomel electrode consists of Hg in contact with a paste of insoluble or

sparingly soluble mercurous chloride (Hg2Cl2). The solution of KCl of definite concentration is
taken above the paste and is added from the side tube on RHS. The electrode potential depends
upon the concentration of Cl– ions.
The electrode may be represented as,
Hg – Hg2Cl2 (s) | Cl– (aq)
When the electrode reaction involves oxidation, electrons are liberated and Hg22+ ions enter
the solution where, these combine with Cl– ions to form sparingly soluble Hg2Cl2. As a result
there is a decrease in the concentration of Cl– ions.
Oxidation: 2Hg(l) Hg22+ (aq) + 2e–
Hg22+ (aq) + 2Cl– Hg2Cl2(s)
This reaction may be represented as,
2Hg (l) + 2Cl– Hg2Cl2(s) + 2e–
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Electro Chemistry
Reduction: Hg2Cl2(s) Hg22+ (aq) + 2Cl– (aq)
Hg22+ + 2e– 2Hg(l)
Hg2Cl2(s) + 2e– 2Hg (l) + 2Cl– (aq)

 electrode is reversible w.r. t. Cl– ions.
Cell Potential or EMF of A cell
The force which causes flow of electrons from an electrode at higher potential to the electrode at
lower potential, due to their potential difference is called electromotive force (EMF) of a cell or Cell
Potential or Cell Voltage or simply, the difference between the electrode potentials of the two half
cell is known as EMF of a cell.
It depends upon:
(i) nature of reaction.

(ii) concentration of solutions in the two half cells.
(iii) temperature.
It is expressed in Volts.
Differentiate EMF and Potential Difference
EMF Potential Difference
1 EMF is the potential difference between the Potential difference is the difference
two electrodes of the cell when no current between the electrode potential of the two
is flowing in the circuit (i.e., in open circuit) electrodes under any conditions, i.e., closed
circuit.
2. It is determined by means of a potentiometer. It is determined by means of simple

voltmeter.
3. It is the maximum obtainable voltage from the It is less than the maximum obtainable
cell. voltage from the cell
4. It is maximum obtainable work from the cell. It is less than maximum obtainable work
from the cell.
5. EMF is responsible for the flow of steady Potential difference is not responsible for
current in the circuit. the flow of steady current in the circuit.
Applications of Electrode potential

1. To compare the relative oxidising and reducing powers.
Elements with high reduction potentials are strong oxidising agents while those with high oxidation
potentials are strong reducing agents.
2. To compare the relative activities of metals.
Greater the negative value of reduction potential of an element, greater is its power to reduce the
other element.
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Electro Chemistry
3. In predicting anode and cathode. Electrons always move from lower reduction potential (LRP)
to higher reduction potential (HRP) and oxidation occurs at LRP, i.e., Anode, whereas reduction
occurs at HRP, i.e., cathode. Thus, electrode having lower reduction potential act as anode and
the electrode having higher reduction potential acts as cathode.
4. To calculate the standard EMF of any electrochemical cell,
EºCell = Eºcathode – Eºanode
Example: Calculate the standard EMF of a cell which involves the following cell reaction
Zn + 2Ag+ Zn2+ + 2Ag
Given that Eº Zn2+ | Zn = – 0.76 volt and EºAg+ | Ag = + 0.80 volt
Solution: (a) The cell reaction be split into two half reactions as:
Zn Zn2+ + 2e– (Oxidation half reaction)
2Ag+ + 2e– 2Ag (Reduction half reaction)
Alternatively, as oxidation takes place at the zinc electrode and reduction at the
silver electrode by convention the cell may be represented as
Zn | Zn2+ | |Ag+ | Ag
Eºcell = Eº cathode – Eº anode = 0.80 – (–0.76) = 1.56 volts.
5. To predict whether a metal reacts with acid to evolve hydrogen gas : In order that a metal M
(assuming it to be monovalent) may react with an acid to give H2 gas, following reactions should
take place :
M + H+ M+ + 1/2H2
which can be split into half reactions as:
M M+ + e– (Oxidation half reaction)

+ –
H +e 1/2H2 (Reduction half reaction)
If the E.M.F. of a cell having above reaction is +ve metal will react with acid to evolve H2
6. To Predict spontaneity of a reaction:
Example: Knowing that,

Cu2+ (aq) + 2e– Cu(s) ; Eº = 0.34 V
2Ag+ + 2e– 2Ag ; Eº = 0.80 V
Again if the E.M.F. of the cell having above reaction as cell reaction is +ve metal will react with
acid to evolve hydrogen.
Find out whether 1 M silver nitrate solution can be stored in copper vessel or 1 M copper
sulphate solution can be stored in silver vessel.
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Electro Chemistry
7. To know the Eº of other reactions
e.g., E1 value for the reaction Cu+ Cu = + 0.15 ... (1)
E2 value for the reaction Cu2+ Cu = +0.34 ... (2)
Calculate the E3 value for the reaction Cu2+ Cu+ ... (3)
The electrode potentials are path functions so they are non-additive. But G = –nFE. Hence, we
calculate G for eq. 3 and then get the value for E3.
Eq-3 can be obtained by subtracting Eq-1 from Eq-2

 G3 = G2 – G1
 – n3FEº3 = –n2FEº2 – (–n1FEº1)
 n3Eº3 = n2Eº2 – n1Eº1
n2 E 2o  n1 E1o
Eº3 = n3
 Eº3 = –0.34 – 0.15 = –0.49 v.
Nernst Equation for Electrode Potential

The quantitative relationship between the concentration of ions and electrode potentials is given by
Nernst equation. For a general electrode reaction:
Nernst equation can be written as
0 RT [M n  ]
E (M n  / M)  E (M n
/ M)
 In
nF [M]
0 2.303RT [M n  ]
E M n  / M  E (M n
/ M)
 log ... (1)
nF [M]
where E M n  / M  Electrode potential
E 0M n  / M  Standard electrode potential with reference to SHE when concentration of Mn+ is 1 mol
L–1 and temperature is 298 K.

Substituting these values in equation (1) we get
0 2.303  8.314  298 [M n  ] 0.059 [M n  ]

E M n  / M  E (M n
/ M)
 log  E 0(M n  / M)  log
n  96500 [M] n [M]
In general, for any electrode,
0 0.0591 [Oxidised state]

E red  E red  log
n [Reducedstate]
The concentration of solids, i.e., [solid] is taken to be unity while concentration of gases is expessed
in terms of their respectively partial pressures.
[ 137 ]
Electro Chemistry
Calculation of Cell Potential using Nernst Equation

1. Zn/Zn2+(aq)||Cu2+(aq)/Cu
Cell potential = Ecathode – Eanode

0 0.0591 [Cu 2  ]
Using Nernst equation for copper electrode E Cu 2  / Cu  E Cu 2
/ Cu
 log
2 [Cu]
Similarly, for zinc electrode
0.0591 [Zn 2  ]
E Zn 2  / Zn  E 0Zn 2  / Zn  log
2 [Zn]
0.0591 [Cu 2 ] 0.059 [Zn 2 ]

Cell Potential  E 0Cu 2  / Cu  log 0
 E Zn 2
/ Zn
 log
2 [Cu] 2 [Zn]
0.0591 [Cu 2 ][Zn]

 E 0Cu 2  / Cu  E zn
0
log
2
/ Zn

2 [Cu]  Zn 2 
Since concentration of solids is taken to be unity
 [Zn] = [Cu] = 1
0.0591 [Cu 2 ]
Cell potential = E 0Cell  log
2 [Zn 2 ]
In general, for a redox cell reaction involving the transference of n electrons
aA + bB 
 cC + dD
RT [A]a [B]b
E cell  E 0cell  In
nF [C]c [D]d
0 0.0591 [A]a [B]b

E cell  E cell  log
n [C]c [D]d
While using equation, the following points must be kept in mind :
(i) Concentration of solids (metals) is taken to be unity.
(ii) Concentration of ionic species are taken in mol L–1.
(iii) Concentration of gases are expressed in terms of their respective partial pressures in bar.
The values of n, a, b, c, d are obtained from the balanced cell reaction. For example, let us consider
the cell,
Zn/Zn2+ || Ag+/Ag
The balanced cell reaction is
2Ag  (aq)  Zn(s) 

 2Ag(s)  Zn 2 (aq)
Here, n = 2
2
0.0591 Ag    Zn 
E cell 0
 E cell  log  
2  Zn   Ag 2
2 
 
[ 138 ]
Electro Chemistry
[Ag] = [Zn] = 1
Similarly, for the cell,
Al / Al3 | | Ni2  / Ni, the cell reaction is
2Al (s) + 3Ni2+(aq) 

 3Ni(s) + 2Al3+ (aq)
Here n = 6
0 0.0591 [Ni 2 ]3 [Al]2

E cell  E cell  log
6 [Al3 ][Ni]3
[Ni] = [Al] = 1
Nernst Equation and Equilibrium Constant
Galvanic cell does not continue working indefinitely and stops working after some time. In fact, as
the cell reaction progresses, there is a fall in the concentration of cations around cathode due to
reduction and at the same time there is an increase in the concentration of metal cations around
anode due to oxidation. Consequently, electrode potential of cathode decreases and that of anode
increases with the passage of time. Ultimately, a stage reaches when the potential difference (Ecathode
– Eanode) becomes zero and the flow of electrons stops.
For example :
In a cell, Zn/Zn2+(aq)||Cu2+(aq)/Cu, the flow of electrons from zinc to copper stops when E Zn 2 / Zn
becomes equal to E Cu 2 / Cu .
In this stage the concentration of Zn2+ (aq) and that of Cu2+(aq) will be equilibrium concentration
because the cell reaction attains equilibrium.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Considering the concentrations of Zn(s) and Cu(s) to be unity, the equilibrium constant for the above
reaction, KC is given by the expression.
 Zn 2 
K C   2 
 Cu 
Applying the Nernst equation for cell potential
2.303RT  Cu 2 
E cell  E 0cell  log  2 
nF  Zn 
2.303RT  Zn 2  
E cell  E 0cell  log  2 
nF  Cu 
Since Ecell at equilibrium is zero
2.303RT
 0 = E0cell – log K c
nF
2.303 RT
or E 0cell  log K C
nF
[ 139 ]
Electro Chemistry
2.303 8.314  298 0.0591

 E0cell  log K C or E 0cell  log K C
n  96500 n
The value of KC gives the extent of the cell reaction. For example, the value of KC for the Zn–CuSO4
cell reaction at 298 K is 2 × 1037 , which shows that the reaction has proceeded almost to completion
before attainment of equilibrium conditions.
Electrochemical Cell and Gibb’s Energy
A galvanic cell is a source of electrical energy which can be used for different kinds of work. Unlike
heat energy, the electrical energy can be quantitatively converted into work. The electrical work or
the electrical energy is equal to the product of EMF of the cell and the electrical charge that flows
through the external wire.
WElec = (EMF) × (Electrical charge flowing through the wire)
If Ecell is the EMF of the cell, then WElec = nF × Ecell where n is the mole of electron
transferred.
In case of electro-chemical cell, the driving force for the cell reaction is provided by decreasing free
energy. In other words, the decrease of Gibb’s energy ( G ) of cell reaction provides a measure of
electrical work (Wele.).
Thus G  Wcell = nFEcell
or G  nFE cell
Standard Gibb’s energy change is given as G   nFEcell
For cell reaction to be spontaneous, G must be negative, and for G to be negative, the value of
E must be positive.
Relationship between Standard EMF and equilibrium constant
We know that standard free energy change is related to equilibrium constant as

G   RT In K C
also G    nFE 
 nFE   RT In K C  2.303 RT log K C
RT
or E  2.303 log K C
nF
Concentration Cells
In the electrochemical cells discussed so far, the cell consisted of two different electrodes and the
emf produced was due to the chemical reaction taking place in the cell. For example Daniel cell.
However, it is possible to prepare a cell in which the two electrodes are of the same type and they
differ only in the concentration of the electrolytes with which they are in contact. EMF produced in
such cells is only due to the difference in concentration and there is no net Chemical Reaction.
[ 140 ]
Electro Chemistry
Such cells in which the EMF is produced only due to the difference in the concentration of the
solution of the electrolytes with which they are in contact are called concentration cells.
Concentration cells are of following types:
The two electrodes are immersed in the same solution of the electrolyte and thus, there is no
transference of electrolyte involved. Hence, these cells are called concentration cells without transfer.
Examples: Pt ; H2(P1) | H+, HCl | H2 (P2) Pt.
(i) In which the two electrodes are same, having different concentration of electrolytes and connected
by a salt bridge.
e.g. H2 (1 atm) | H+ (a1) | | H+ (a2) | H2 (1 atm)

2 2
Zn | Zn (a1)
| | Zn (a 2)
| Zn
0.0591 Zn(a  )1
E = Eº – log Zn(a )
2  2
(ii) In which the two electrodes are same having different concentration of electrolytes but the two
solutions are in direct contact with each other.
e.g. H2 (1 atm) | HCl(a1)  HCl(a2) | H2 (1 atm)

Zn | ZnSO4(a1)  ZnSO4(a2) | Zn
The junction at which the two solutions meet is called as liquid junction.
(iii) Cells obtained by combination of chemical cells:
In electrolyte concentration cells of type (i) and (iii) there is no direct transfer of electrolyte,
therefore, they also constitute concentration cells without transfer, while type (ii) constitutes
concentration cells with transfer.
Liquid Junction Potential

In a chemical cell or in a concentration cell, when the two solutions are in direct contact (i.e., in a cell
with transfer) there is a diffusion of ions across the boundary between the two solutions. If the ions
move with equal speed to the two sides through the boundary there would be no separation of
charge. However, usually as the ions move across the boundary with different speed, a separation of
charge results. This produces a potential at the boundary, i.e., at the junction. Thus, the potential set
up at the junction of the two solutions because of the difference in the speeds of the ions moving
across the boundary is called as Liquid Junction Potential (LJP).
However, the type of junction employed most commonly is the salt bridge containing an electrolyte
such as KCl. It is believed that K+ and Cl– ions move with almost equal speed and the junction
potential is almost reduced to zero.
Thus, LJP in normal electrochemical cells, can be eliminated by choosing a suitable electrolyte.
[ 141 ]
Electro Chemistry
Applications of EMF Measurement

(1) In the determination of Valency of Ions
This determination is based upon the fact that the EMF of concentration cell without transference
is given by
RT a2 RT c
E = nF ln a ~ ln 2
1 nF c1
In this expression n is the valency of ion involved. Thus knowing all other quantities, n can be
calculated
(2) In the determination of the Solubility and Solubility Product
Principle: The EMF of a concentration cell is given by
RT c2
E = nF ln c
1
Thus, knowing EMF of the cell and concentration of the ions in one of the solutions, that in the
other can be calculated. If the second solution is that of the sparingly soluble salt, its ionic
concentration is equal to its solubility assuming that the substance is completely dissociated.
(3) Determination of H+ ion concentration or pH of a solution.
One of the most important application of EMF measurement is in the determination of H+ ion
concentration and hence, pH of solution (pH = – log [H+]).
1
E H  H  0  0.0591 log 
2
[H ]
E H  H  0.0591 pH
2
3.3 Cells
There are three main types of commercial cells:
(1) Primary Cells: are those in which redox reactions occurs only once and cell becomes dead
after some time and can not be used again. e.g., Dry Cell, Mercury Cell.
(2) Secondary Cells : are those which can be recharged again by passing an electric current, and
can be used over and again e.g., Lead storage battery and Nickel-Cadmium storage Cell.
(3) Fuel Cells: are those in which the energy produced from the combustion of fuels (such as H2,
CO, CH4, etc.) is directly converted to electrical energy - Such a conversion is possible because
combustion reactions are also redox reactions.
(1) Primary Cells:
(a) Structure of a dry cell : A dry cell consists of zinc container as anode and cathode is
graphite rod surrounded by a powdered MnO2 and carbon. The space between the two
electrodes is filled with a moist paste of NH4Cl and ZnCl2 which act as electrolyte. The
electrode reactions are quite complex, but they can be approximately written as
Anode : Zn (s) Zn2+ + 2e–
Cathode : MnO2 (s) + 2NH4 +(aq) + 2e– Mn2O3 (s) + 2NH3 (g) + H2O
[ 142 ]
Electro Chemistry
(b) Mercury Cell : Another dry cell which is commonly used in hearing aids, watches and
camera Zinc-Mercury cell. In this cell, Zn-Hg (Zinc amalgam) act as anode and a paste
of Mercury (II) oxide HgO and carbon act as cathode.
The electrolyte is the paste of KOH and ZnO.
Anode : Zn + 2OH– ZnO (s) + H2O + 2e–
Cathode : HgO (s) + H2O + 2e– Hg(l) + 2OH–
Overall : Zn + HgO(s) ZnO (s) + Hg (l)
(2) Secondary Cells :
(a) Lead storage battery : This is one of the most commonly used batteries in the automobiles.
A 12 V lead storage battery is generally used which consists of 6 cells each producing 2 V.
Each cell consists of a lead anode (or a grid of lead filled with finely divided spongy lead as
the anode) and a grid of lead packed with lead dioxide as the cathode. These electrodes are
arranged alternately, separated by thin wooden or fibre glass sheets and suspended in dilute
sulphuric acid (38% by mass or having a density of 1.30 g cm–3) which acts as the electrolyte.
The electrode reactions that occur during discharge (i.e., when the external circuit is closed)
are as follows :
At anode : Pb (s) + SO42– (aq) PbSO4 (s) + 2e–
At cathode : PbO2(s) + SO42– (aq) + 4H+(aq) + 2e– PbSO4(s) + 2H2O
Overall reaction : Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42–(aq) 2PbSO4(s) + 2H2O
From the above equations, it is obvious that H2SO4 is used up during the discharge. As a
result, the density of H2SO4 falls. When it falls below 1.20 g cm–3, the battery needs
recharging.
During recharging, the cell is operated like a electrolytic cell i.e., now electrical energy is
supplied to it from an external source. The electrode reactions are the reverse of those that
occur during discharge.
PbSO4 (s) + 2e– Pb (s) + SO42– (aq)
PbSO4 (s) + 2H2O PbO2 (s) + SO42– (aq) + 4H+ (aq) + 2e–
2PbSO4 (s) + 2H2O Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42– (aq)
(3) Fuel Cells :
It is an electrochemical device for continuous conversion of the portion of free energy change
into electrical energy. Such cell converts 74% of chemical energy into electrical energy. The fuel
used is in the gaseous state, H2 – O2 fuel cell is a common example.
It consists of porous carbon electrodes containing catalyst (Pt, Ag) incorporated in them; conc.
NaOH or KOH solution is placed between electrodes and act as electrolyte. Following electrode
reactions take place.
At anode : 2H2 (g) + 4OH– (aq) 4H2O (l) + 4e–
At cathode : O2 (g) + 2H2O (l) + 4e– 4OH– (l)
Overall reaction : 2H2 (g) + O2 (g) 2H2O (l)
[ 143 ]
Electro Chemistry
These fuel cells are more efficient than conventionally used methods of generating electricity on
a large scale by burning hydrogen, carbon fuels.
Advantages of fuel cells over ordinary batteries
1. The fuel cells convert the energy of the fuel directly into electricity, while the conventional
methods of generating electricity by burning hydrogen, carbon fuels first convert fuels into
thermal energy and then into electrical energy. Although theoretically, fuel cells are expected to
have an efficiency of 100%, practically only 60–70% efficiency has been attained. Efficiency
of the conventional method is only about 40%.
2. Use of the fuel cells do not cause any pollution problem.
Corrosion
Any process of deterioration (destruction) and consequent loss of a solid metallic material through an
unwanted chemical or electrochemical attack by its environment starting at its surface is called
corrosion. Corrosion always occurs at anodic areas. More active metals are corroded more easily.
Corrosion is enhanced by the presence of (a) impurities, (b) air and moisture, (c) electrolytes and (d)
strains in metal like dents, scratches, welding parts, etc., Corrosion of iron is called rusting.
Electrode reactions in rusting of iron
Oxidation at anode : Fe Fe2+ + 2e– ; E0ox = 0.44 V
Reduction at cathode: CO2 + H2O H+ + HCO3–

 
2H ( aq )  2e 
 2H
1
2H  O 2 
 H 2O
2
1
2H+ + O + 2e– H2O ; E0red = 1.23 V
2 2
Net reaction of corrosion cell
1
Fe + 2H+ + O Fe2+ + H2O ; E0cell = 1.67 V
2 2
The Fe2+ ions so formed move through water and reach at the surface of iron where they are
oxidised to Fe3+ ions by atmospheric oxygen and constitute the rust which is hydrated ferric oxide.
1
Fe2+ + O + 2H2O Fe2O3 + 4H+
2 2
Fe2O3 + x H2O Fe2O3 . xH2O
Rust
Prevention of corrosion:
1. By coating with a suitable material (barrier protection).

2. By alloying with suitable metals e.g. Fe, Cr, V, Ni, W, etc.
3. By cathodic protection.
4. By using artificial anode (Sacrificial protection).
[ 144 ]
Electro Chemistry

Problem 1: Calculate reduction potential at 25°C for Fe3+/Fe2+ electrode, if the concentration of Fe2+
ion is 5 times that of Fe3+ ion?
E 0Fe3 /Fe3  0.77 Volts
(a) + 0.73 V (b) –0.73V

(c) +5.0 V (d) –5.0 V
Solution: (a) Fe3  e 

 Fe2 (n  1)
0.059 [Fe2 ] 0.59

E  E0  log 3  0.77  log 5  0.73 Volts
n [Fe ] 1
Problem 2: Ecell at 25°C for the reaction

Zn  Cu 2 (0.2M) 
 Zn 2 (0.5M)  Cu
0 0
and construct in Cell. Given, E Zn 2 / Zn  0.76 V, E Cu 2 /Cu  0.34V
(a) 10.88V (b) 1.088V

(c) 108.8V (d) 0
Solution: (b) Zn 
 Zn 2  2e Zn | Zn 2 || Cu 2 | Cu
Cu 2  2e 
 Cu (L) Anode (R) cathode
–––––––––––––––––––––––––
Zn  Cu 2 
 Zn 2  Cu(n  2) E 0  0.34  (0.76)  1.10V
0.059 [Zn 2 ]  5
E  1.10  log 2
 1.10  0.029log    1.088V
2 [Cu ] 2
0
Problem 3: The ECu2 /Cu = +0.34V. Calculate reduction potential at pH = 14 for the above couple.
Ksp Cu(OH)2 is 10–19 at 25°C?

(a) –0.2205V (b) +0.2205V
(c) 2.205V (d) 22.05V
Solution: (a) pH = 14  [H+] = 10–14 [Cu2+] [OH–]2 = 10

1019
–
[OH ] = 1 [Cu 2 ]   1019
[OH  ]2
Cu 2   2e Cu(n  2)
0.059 1
E  0.34  log 19 = +0.34 – 0.029 × 19 log 10
2 10
= +0.34 – 0.029 × 19 = 0.340 – 0.551
= – 0.211V
[ 145 ]
Electro Chemistry
Problem 4: If E10 is standard electrode potential for Fe |Fe3+, E 02 is for Fe2+ | Fe3+, E 03 is for Fe | Fe3+
electrodes respectively then relation between E10 , E 20 , E30 is

(a) 3E30  2E10  E 02 (b) 2E 30  2E10  2E 20
(c) E30  2E10  3E 02 (d) 3E 02  E 30  2E 20
Solution:  Fe2  2e, E10 

(a) Fe  Fe2 
 Fe3  e, E 02 Fe 
 Fe3  3e, E03
ΔG10  2FE10 ...(i)
ΔG02  1FE02 ...(ii)
ΔG30  3FE03 ...(iii)
(iii) - (i) + (ii)  ΔG 03  ΔG10  ΔG 02
3FE03  2FE10  1FE03
3E 03  2E10  E 02
3E30  2E10  E 20
[ 146 ]
Electro Chemistry
SOLVED EXAMPLES
Example 1 : Calculate the volume of a gas liberated at anode at N.T.P. from the electrolysis of CuSO4
solution by a current of 2 ampere passed for 10 minutes. When Pt electrodes are used.
Solution: As we know, Q = Ct
= 2 × 10 × 60
= 1200 Coulomb.
For electrolysis of CuSO4 solution the gas liberated is oxygen according to the following
electrochemical reaction :
2H2O(l) 4H+ (aq.) + 4e– + O2(g)
4 Faraday 1 mol
i.e., 4 × 96500 coulomb liberate = 22.4 litre O2 at N.T.P.
22.4  1200
1200 coulomb will liberate = 4  96500 litre at N.T.P. = 0.0696 litre
Example 2 : Chromium metal can be plated out from an acidic solution containing CrO3 according to
following equation.
CrO3(aq) + 6H+(aq) + 6e–  Cr(s) + 3H2O
Calculate:
(a) the mass of chromium plated out by 24,000 C.
(b) how long will it take to plate out 1.5 g of chromium by using 12.5 A current.
52  24000
Solution : (a) w = ZQ = 6  96500 g = 2.155 g
(b) Q = It
52  12.5  t
So 1.5 = 6  96500  60
or t = 22.27 min
Example 3: Electric current is passed through two cells A and B. Cell A contains an aqueous solution of
Ag2SO4 with platinum electrodes. Cell B contains aqueous solution of CuSO4 and copper
electrodes. The current is passed till 1.6 g of oxygen is liberated at the anode in cell A.
Calculate the quantities of copper and silver deposited at the cathodes of two cells. (At Wt.
of O = 16, Cu = 63.5, Ag = 108)
Solution : According to electochemical equation,
O2– O + 2e–
1 .6
1.6 g oxygen = = 0.2 g eq. of oxygen
8
Electrochemical equations for silver and copper are

Ag+ + e–  Ag
[ 147 ]
Electro Chemistry
Cu2+ + 2e–  Cu
108
Hence, equivalent weight of silver = = 108
1
63.5
and, equivalent weight of copper = = 31.75
2
For the same current; 0.2 g eq. of Ag and Cu each will be liberated at their respective
cathodes
Hence,
0.2 g eq. of Ag = 0.2 × 108
= 21.6 g
0.2 g eq. of Cu = 0.2 × 31.75
= 6.35 g
Example 4 : After electrolysis of a sodium chloride solution with inert electrodes for a certain period of
time, 600 ml of 1.0 N solution was left which was found to be sodium hydroxide. During the
same time 31.75 of copper was deposited in a copper voltameter in series with the electrolytic
cell. Calculate the percentage of the theoretical yield of sodium hydroxide obtained.
Solution : As we know, eq.wt. of NaOH = 40

1000 ml of N NaOH = 40 g NaOH
40
So 600 ml of N NaOH = × 600 g NaOH
1000
= 24 g NaOH
According to Faraday’s law of electrolysis,
Weight of Cu Eq. weight of Cu

Weight of NaOH = Eq. weight of NaOH
Suppose the weight of NaOH produced is x g.
31.75 31.75
= (since Eq. wt. of Cu = 31.75)
x 40
x = 40 g (which should theoretically be produced)
24
Hence, percentage of theoretical yield = × 100 = 60%
40
Example 5 : Consider the cell

Zn |Zn2+(aq)(1.0 M) || Cu2+(aq.) (1.0 M) | Cu
The standard reduction potentials are :
+0.35V for Cu2+(aq) + 2e–  Cu and –0.763 V for Zn2+(aq) + 2e–  Zn.
(a) Write down the cell reaction
(b) Calculate the e.m.f. of the cell
(c) Is the cell reaction spontaneous or not ?
[ 148 ]
Electro Chemistry
Solution : (a) Reaction at anode

Zn(s) Zn2+(aq) + 2e–
Reaction at cathode
Cu2+(aq) + 2e– Cu(s)
The cell reaction :
Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq)
(b) Ecell = EºR.H.S. – EºL.H.S.
= 0.35 – (–0.763)
= 1.113 Volt
(c) Since, e.m.f. of cell is positive the reaction is spontaneous.
Example 6: From the following standard electrode potentials at 25ºC

Cu2+ + 2e = Cu; Eº = 0.34 V
Cu2+ + e = Cu+; Eº = 0.15 V
Calculate equilibrium constant of the reaction Cu + Cu2+  2Cu+.
Solution: Cu = Cu2+ + 2e; Eº = + 0.34; Gº = –2(–0.34) F = 0.68 F

2Cu2+ + 2e–  2 Cu+; Eº = 0.15; Gº = –2(0.15) F = –0.30 F
On adding,
Cu + Cu2+ = 2Cu+; Gº = +0.38 F
–Gº = 2.303 RT log K
–0.38 F = 2.303 RT log K
2.303 RT
or –0.38 = log K
F
–0.38 = 0.0591 log K
0.38
or log K =– = –6.429
0.0591
 K = 3.72 × 10–7.
Example 7: For the reaction,

(1 atom) H2(g) + 2 AgCl(s) = 2Ag (s) + 2H+(aq) (0.1M) + 2Cl–(aq) (0.1 M)
Gº = –42927 joules at 25ºC.
Calculate the e.m.f. of the cell in which the given reaction takes place.
Solution : We know,
Gº= –nF Eº
Gº 42927
 Eº = – = 2  96500 = 0.2224 volt
nF
Now, for the above cell reaction
 2  2 2 2
0.0591 [H ] [Cl ] 0.0591 (0.1) (0.1)
Ecell = Eº – log = 0.2224 – log
2 [H 2 ] 2 (1)
= 0.3406 volt.
[ 149 ]
Electro Chemistry
Example 8: The resistance of a N/10 KCl solution is 245 ohms. Calculate the specific conductance and
the equivalent conductance of the solution if the electrodes in the cell are 4 cm apart and
each having an area of 7.0 sq. cm.
1 4
Solution : Cell constant = = cm–1
a 7
Specific conductance = Conductance × Cell constant
1 1
= ×
Resistance a
1 4
= × = 2.332 × 10–3 mho cm–1
245 7
Equivalent conductance = Sp. cond. × Volume (cc) (containing 1 eq. of the substance)
= 2.332 × 10–3 × 10,000 (for N/10 solution, V = 10,000 cc)
= 23.32 mho cm2.
Example 9: The specific conductance of a saturated solution of AgCl at 25ºC after subtracting the
specific conductance of conductivity of water is 2.28 × 10–6 mho cm–1. Find the solubility
product of AgCl at 25ºC. (AºAgCl = 138.3 mho cm2)
Solution: For equilibrium,

AgCl = Ag+ + Cl–
Ksp = [Ag+] [Cl–]
If the solubility of AgCl in water is, say, x mol / litre of x eq./1,
Ksp = x.x = x2.
1000
 Volume containing 1 eq. of AgCl =
x
AgCl = Specific conductance × V
1000
= 2.28 × 10–6 × .
x
Since, AgCl is sparingly soluble in water, AAgCl = AºAgCl = 138.3.
1000
 2.28 × 10–6 × = 138.3
x
or x = 1.644 × 10–5 eq./litre or mole/litre.
Ksp = x2 = (1.644 × 10–5)2
= 2.70 × 10–10 (mole/litre)2.
[ 150 ]
Chapter - 1
CHEMICAL KINETICS
Introduction
Chemical kinetics concerns with the measurements of rates of reactions proceeding under given conditions
of temperature, pressure and concentration. The study of this part of chemistry is highly useful in determining
the factors which influence the rates of reactions as well as the mechanisms of a number of chemical
reactions
1.1 Rate or Velocity of a Reaction

“The change in the concentration of reactant or product in unit time is called rate or velocity of a
chemical reaction.”
Thus,
Change in concentrat ion of reactant or product

Rate of chemical reaction = Time taken for the change
Let us consider a general chemical change
A B
Reactant Product
If [A] is the change in concentration of ‘A’ and [B] is the change in concentration of ‘B’ in t
time, then,
 [ A]  [ B ]
Rate of reaction = or
t t
The negative (–) sign shows that the molar concentration of reactant ‘A’ decreases with time while
the (+) sign indicates that the molar concentration of product ‘B’ increases with time.
For a general chemical transformation,
nA + mB  pC + qD
the rates of disappearance of reactants and rates of appearance of products are equalized by dividing
them with the coefficients in the balanced chemical equation. Thus,
1 [ A] 1 [ B ] 1 [C ] 1 [ D]
  =  = p  t =  q  t = Rate of chemical reaction
n t m t
For example, in the synthesis of ammonia
N2 + 3H2  2NH3
[ N 2 ] 1 [ H 2 ] 1 [ NH 3 ]
 =   =  = Rate of reaction
t 3 t 2 t
[1]
Chemical Kinetics
3
It can be concluded from these expression that the rate of disappearance of H2 is of the rate of
2
appearance of NH3.
Rates of Disappearance and Appearance
The rate of disappearance of H2
 d[H 2 ]  d[N 2 ]
also, =3
dt dt
 d[H 2 ] 3  d[NH 3 ] 
=  + 
dt 2  dt 
The rate of appearance of Ammonia
d[NH 3 ] 2   d[H 2 ] 
=   
dt 3  dt 
2
=  Rate of disappearance of hydrogen
3
  d[N 2 ] 
=2  
 dt 
= 2  Rate of disappearance of nitrogen
Average rate of reaction : By dividing the total change in concentration of reactant or product by
a time interval, we actually get the average rate of the reaction.
Instantaneous Rates : The instantaneous rate is obtained when a very small change in concentration
(dc) is divided by very small time interval (dt). It is assumed that in dt time, the rate of the reaction
dc
remains constant. Thus, instantaneous rate = .
dt
Graph for Instantaneous Rate and Average Rate

Concentration
Concentration
Slope = Instantanes rate of

Reactant reaction at time t
time time (t)
The theoretical rate of a reaction is given by law of mass action. Thus, for the general chemical
change
mA + nB  Products
dx
Theoretical Rate = = k[A]m  [B]n
dt
[2]
Chemical Kinetics
Rate Law or Rate Equation of a Reaction : The mathematical expression which gives a relation
between rate of the reaction and concentrations of reactants is known as rate law equation. The rate
law is established by the kinetic study of a reaction experimentally.
Let us consider a general reaction.
mA + nB  pC + qD
If it is observed experimentally that the rate of reaction varies directly as the concentration of
reactant ‘A’ raised to the power ‘a’ and reactant ‘B’ raised to the power ‘b’ then,
dx
 [A]a  [B]b
dt
dx
or = k[A]a  [B]b
dt
This expression is known as the observed rate law of the reaction.
1. The reaction is said to be of ‘a’ order with respect to reactant ‘A’ and of ‘b’ order with respect
to reactant ‘B’.
2. The overall order of the reaction is (a + b).
Rate constant, velocity constant or specific reaction rate (k):
The rate constant of a reaction is a measure of its rate of reaction. Fast reactions have higher value
of ‘k’ while for slow reactions ‘k’ is low. Suppose, in a general chemical change, ‘a’ is the initial
concentration of reactant A.
moles at time = 0 A 
B
a 0
mole at time = t a–x x
If ‘x’ moles of ‘A’ transform into product ‘B’ after time ‘t’, the moles of ‘A’ at time ‘t’ will be
(a – x). Since, the rate of reaction is proportional to the concentration of ‘A’, so the rate of the
reaction at time ‘t’ is –
dx
 (a – x)
dt
dx
or = k(a – x)
dt
dx
where, k is constant known as rate or velocity constant. When (a – x) = 1. = k.
dt
Definition of Rate Constant : At a given temperature, the rate constant is equal to the rate of
reaction when the concentration of reactant(s) is unity.
1. Rate constant, k is not affected by the concentration change of reactants, nor does it depend
upon the initial concentration of a reactant.
[3]
Chemical Kinetics
2. ‘k’ remains constant throughout the progress of the reaction.
3. Positive catalyst increases the value of ‘k’, the rate constant.
4. Rate constant, ‘k’ is always increased when temperature rises (for a certain temperature range).
5. The rate of reaction at any time = Rate constant  Concentrations of reactant(s) at that time.
6. Unit of ‘k’ depends upon the order of the reaction.

Illustration 1: The reaction OCl1  I  
OH
 OI  Cl takes place is following steps:
 K1
(i) OCl  H 2 O K2
HOCl  OH  (fast)
(ii) I   HOCl 
K3
 HOI  Cl (slow)
 K1
(iii) OH  HOI 
K2
 H 2 O  Cl (fast)
Write the rate expression in terms of rate of consumption of I–.
d [I  ]
Solution: By step (i) K 3 [I  ][HOCl] (a)
dt
K1 [HOCl][OH  ]
By step (ii)  (b)
K 2 [OCl ][H 2 O]
K1 [H 2O][OI  ]
By step (iii)   (c)
K 2 [OH  ][HOI]
By equations (b) and (a)
 d [I  ] K [OCI  [H 2O]
 K 3[I  ] 1
dt K 2 [OH  [HOI]
K1 [OCl ][I  ]
 K3 [Since [H2O] is constant]
k 2 [OH  ]
 d [I ] [OCl ][I  ]

  K
dt [OH  ]
Illustration 2 For a reaction 2A Product, it is found that the rate of reaction becomes 2.25
when the concentration of A is increased 1.5 times, calculate the order of reaction.
Solution: Rate, r = k [A]n .... (1)

When concentration is increased 1.5 times, the rate of reaction become 2.25.
 2.25 r = k [1.5A]n .... (2)
2.25r k [1.5 A]n

Divide (2) by (1) = k[ A]n
r
2.25 = (1.5)n
(1.5)2 = (1.5)n
n=2
[4]
Chemical Kinetics
Illustration 3: The following data are for the reaction A + B  products :

Conc. A Conc. B Initial rate
(M) (M) (mol L–1 s–1)
0.1 0.1 4.0  10–4
0.2 0.2 1.6  10–3
0.5 0.1 1.0  10–2
0.5 0.5 1.0  10–2
(a) What is the order with respect to A and B for the reaction?
(b) Calculate the rate constant.
(c) Determine the reaction rate when the concentration of A and B are 0.2 M and 0.35 M,
respectively.
Solution: R = K[A]m [B]n

4.0  10–4 = K (0.1)m (0.1)n ... (i)
1.6  10–3 = K (0.2)m (0.2)n ... (ii)
–2 m n
1.0  10 = K (0.5) (0.1) ... (iii)
1.0  10–2 = K (0.5)m (0.5)n ... (iv)
(a) Divide equation (iii) by (iv)
1.0  10 2 K (0.5) m (0.1) n

 2 = K (0.5) m (0.5) n
1.0  10
n
1
1 = 5
 
n=0
Thus the order of reaction with respect to B is zero.
Divide eq. (i) by (iii)
4.0 10  4 K (0.1) m (0.1) n

=
1.0 10 2 K (0.5) m (0.1) n
m
1
4  10–2 =  5 
 
(0.2)m = (0.2)2
m=2
Thus the order of reaction with respect to A is two
(b) Substituting the values of m and n in .....(ii)

–3 –1 –1 2
1.6  10 mol l s = 0.04 M K
1.6  103 mol l 1 s 1

K= 0.04 M 2 = 4.0  10–2 mol–1 s–1
(c) R = K[A]2[B]0
= 4  10–2 mol–1 l s–1  0.04 M2  1 = 1.6  10–3 mol l–1 s–1
[5]
Chemical Kinetics
Problem 1: The reaction: CO  Cl2 

 COCl2 has the following mechanism, order of reaction
will be:.
K1
(i) Cl2 K2
2Cl (fast)
K1
(ii) Cl  CO K2
COCl (fast)
K3
(iii) COCl  Cl2   COCl2  Cl (slow)
1
(a) 1 (b)
3
2 4
(c) (d)
3 3
d [COCl2 ]
Solution: By step (iii)  K 3[COCl][Cl2 ] ...(a)
dt
K1 [Cl]2
By step (i)  ...(b)
K 2 [Cl2 ]
K1 [COCl]
By step (iii) K   [CO][Cl] ...(c)
2
Thus from equations (b) and (c)

K1 K1
[COCl]   [CO]   [Cl2 ] ...(d)
K2 k2
From equations (a) and (d)
1/2
d [COCl 2 ] K  K 
 K 3 1  1  [CO][C2 ]1/ 2  [Cl 2 ]
dt K2  K 2 
d [COCl2 ]
 K  [CO][Cl2 ]1/3
dt
Problem 2: For the reaction
3BrO 
 BrO3  2Br 
in alkaline aqueous solution, the value of the second order (in BrO–) rate constant at 80°C in
the rate law –[BrO–]/t was found to be 0.056 mol–1 s–1. Rate constant when the rate law
Δ[BrO3 ]
is written for is:
Δt
0.056
(a) 0.056 L mol–1 s–1 (b) Lmol1s1
3
0.056  2 0.056
(c) Lmol1s 1 (d) Lmol1s1
3 2
[6]
Chemical Kinetics
Δ[BrO ] Δ[BrO3 ]
Solution:  3 is given up equation ....(1)
Δt Δt
Δ[BrO  ]
 k[BrO  ]2
Δt
Δ[BrO3 ]
 k[BrO  ]2
Δt
Put values in (1)
k[BrO ]2  3k[BrO ]2
k 0.056
k   L mol1s 1
3 3
Problem 3: When the constant is equal to rate of the reaction, order is:
(a) 1 (b) 2
(c) 3 (d) 0
 dt  n 0
Solution:    k[A]  k[A]  k
 dt 
Problem 4: Zn 2O3 
 4NO 2  O2
d[N 2 O3 ]
If   k1[N 2O3 ]
dt
d[NO2 ]
 k 2 [N 2O3 ]
dt
d[O 2 ]
 k 3 [N 2 O5 ]
dt
1 d[N3O5 ] 1 d[NO 2 ] d[O 2 ]
Solution:  
d dt 4 dt dt
Problem 5: For the reaction:
[Cu(NH 3 ) 4 ]2  H 2 O [Cu(NH 3 )3 H 2 O]2  NH 3

net rate is
 dv  4 1 3
 dt   2.0  10 s [[Cu(NH 3 )3 H 2 O] ]
 
ratio of rate constants of the forward and backward reactions is:
(a) 0.66 × 10–9 mol L–1 (b) 1.5 × 10–9 mol–1 L
(c) 2.0 × 10–4 s–1 (d) 3.0 × 105 L mol–1 s–1
Solution: (a) For a general reversible reaction


B C
A 

 dx 
 dt   k f [A]  k b [B][C]
 
[7]
Chemical Kinetics
Problem 6: For gaseous reactions, the rate if often expressed in terms of dP/dt instead of dC/dt or dn.dt
(where, C is concentration and n the number of mol). What is relation among these three
expressions?
dC 1  dn  1  dP  dC  dn   dP 
(a)      (b)   
dt V  dt  RT  dt  dt  dt   dt 
dC  dn  V  dP 
(c)      (d) None is correct
dt  dt  RT  dt 
n P
Solution: (a) C  
V RT
dc 1 dn 1 dP
 
dt V dt RT dt
Problem 7: For the reaction
 2NOBr, the following mechanism has been given

2NO  Br2 
heat
NO  Br2    NOBr2
slow
NOBr2  NO   2NOBr
Hence rate law is:
(a) k[NO]2 [Br2 ] (b) k[NO][Br2 ]
(c) k[NOBr2 ][NO] (d) k[NO][Br2 ]2
Solution: (a) NO  Br2 

 NOBr2
[NOBr2 ]
K
[NO][Br2 ]
For slow step
dx
 k 2 [NOBr2 ][NO]
dt
 k 2 [NO][NO][Br2 ]
 k[NO]2 [Br2 ]
Problem 8: Rate of formation of SO3, in the following reaction
2SO 2  O2 
 2SO3
is 100 kg min–1. Hence rate of disappearacne of SO2 will be:
(a) 100 kg min–1 (b) 80 kg min–1
(c) 64 kg min–1 (d) 32 kg min–1
Solution: (b) Convert quantity in mol and then into kg.
[8]
Chemical Kinetics
Problem 9: A2  2B 
 2AB
––––––––––––––––––––––––––––––––––
d[A 2 ]
[A 2 ]  [B]
dt
__________________________________
0.1 0.2 2 × 10–2 ms–1
0.2 0.2 2 × 10–2 ms–1
0.2 0.4 8 × 10–4 ms–1
Order of reaction w.r.t. A2 and B are respectively:
(a) 1, 2 (b) 2, 1
(c) 1, 1 (d) 2, 2
Solution: (a) When conc in made m times, rate becomes mn times in nth order reaction.
Rate law is
d[A 2 ]
  k 2 [A 2 ]a [B]b
dt
By doubling conc of A2 rate is doubled
 2n = 2  a = 1
By doubling conc. of B rate is four tiems
 2n = 4  b = 2
Problem 10: Rate constant k = 1.2 × 102 mol–1 L s–1 and Ea = 2.0 × 102 kJ mol–1. What T  :
(a) A = 2.0 × 102 kJ mol–1 (b) A = 1.2 × 103 mol–2 L s–1
(c) A = 1.2 × 103 mol L–1 s–1 (d) A = 2.4 × 103 kJ mol–1 s–1
Solution: k  Ae  Ea / RT
If T  , k  A
1.2 Molecularity and order of reaction

It may be defined as, “the total number of atoms, ions or molecules which collide with each other in
the rate determining step of a reaction.”
The slow step of the reaction is called rate determining step. Depending upon the number of molecules
taking part in the rate determining step, the reactions are divided into unimolecular, bimolecular or
trimolecular reactions according as the number of molecules is one, two or three.
Example
1. SO2Cl2(g)  SO2(g) + Cl2(g)

(Unimolecular reaction)
1
2. N2O5(g)  N2O4(g) + O (g)
2 2
(Unimolecular reaction)
3. H2(g) + I2(g)  2HI(g)
(Bimolecular reaction)
4. 2NO(g) + O2(g)  2NO2(g)
(Trimolecular reaction)
[9]
Chemical Kinetics
1. Molecularity of a reaction is always a whole number and can never be in fractions.
2. Molecularity of a reaction is never zero (but order can be zero, integral or fractional).
3. Reactions having molecularity more than three are rare. It is because the chances of simultaneous
collisions between three or more particles is rare.
Order of reaction
The number of reactant molecules whose concentration changes determines the rate of a reaction
and is called the order of the reaction.
OR
The order of a reaction is the sum of the powers or exponents to which the concentration terms are
raised in the rate law expression
aA + bB  pC + qD
If the rate law for this reaction comes out to be

dx
= k[A]m  [B]n, then,
dt
the overall order of the reaction is m + n.
1. Order of a reaction is experimentally determined quantity.
2. Order of a reaction can not be written from the balanced chemical equation.
3. Order of a reaction is equal to number of reactant molecules whose concentration changes in a

chemical reaction.
4. Order of a reaction may be zero, whole number, fractional or even negative.
5. Molecularity and order of a reaction may be the same or different.
Zero order Reactions: The reaction whose rate does not depend upon the concentration of reactants
is called a zero order reaction. Consider a zero order section :
AB
dx
= k[A]º = k, a constant
dt
dx
= k[A]º
dt
x Slope = K = rate constant
dx Change in concentrat ion for a zero order
or, k= = or reaction
dt Time interval
kdt = dx
on integration we get, t
kt = x
Where, x = concentration of Products/litre of solution
A graph of x (concentration of products) verses
time should give a straight line
unit of rate constant for a zero order reaction:
Mol / litre
=
second
 Unit of k is mole litre–1 sec–1.
[ 10 ]
Chemical Kinetics
Examples of Zero Order Reaction:
(i) Decomposition of hydrogen iodide(g), ammonia (g) on metal surfaces.
(ii) Combination of hydrogen and chlorine gases in the presence of sun light.
Characteristics of a Zero Order Reaction :
1. The concentration of reactant(s) does not vary with time in zero order reaction.
2. The rate of zero order reaction does not change with time.
3. Half life time for a zero order reaction is directly proportional to initial concentration of reactant.
4. Unit of rate constant and rate of reaction are the same (mol litre–1 sec–1) in zero order reactions.
First order reaction: When the rate of a reaction is determined by change in one concentration
term only, it is called a first order reaction. In such reactions, the rate is directly proportional to the
first power of the concentration of the reactant.
If a general reaction A B,
dx
follows first order kinetics, then its rate law is, = k[A] ... (i)
dt
where, k is the rate or velocity constant
dx
Unit of first order rate constant : From expression (i), k = dt  [ A]
Change in concentration Mol / litre

= Time interval  (concentration of reactant) =
time  Mol / litre
Thus, unit of k = time–1
Examples of First Order Reactions:
1
(i) H2O2(aq)  H2O(l) + O (g)
2 2
(ii) NH4NO2(aq)  N2(g) + 2H2O(R)
226
(iii) Radioactive decay : 88Ra  86Rn222 + 2He4
(iv) Decomposition of SO2Cl2 : SO2Cl2  SO2 + Cl2
First order Kinetic Equation: Let us consider a hypothetical first order reaction :
moles at time t = 0 A 
B
a 0
mole at time = t a–x x
Since, the reaction is of first order, its rate at any time is directly proportional to the concentration
of ‘A’
The rate of reaction at time ‘t’
dx
 (a – x)
dt
[ 11 ]
Chemical Kinetics
dx
or, = k(a – x) .... (ii)
dt
Rearranging the equation, we get
dx
(a  x) = k.dt ... (iii)
On integrating the above equation (ii)
dx
 (a  x)   kdt ,
we get
– ln (a – x) = kt + C .. (iv)
where, ‘C’ is the constant of integration. To evaluate ‘C’, we apply the conditions,
When t = 0, x = 0
 –ln a = k  0 + C
or, C = –ln a
Substituting, the value of ‘C’ in (iv)
–ln (a – x) = kt – ln a
or, kt = ln a – ln (a – x)
1 a
or, k= ln (a  x) ... (v)
t
On changing the base of logarithm from loge to log10
2.303 a
k= log (a  x) ... (vi)
t
This expression (vi) is known as first order kinetic equation. It gives a relation between the rate
constant (k), initial concentration of reactant (a), concentration of reactant after time ‘t’ and time ‘t’
for which the reaction has proceeded.
Half-life period (t1/2) :The time in which half of the initial amount of reactant is converted into
products or the time taken for the 50% completion of the reaction is known as half-life period.
From first order kinetic equation, (vi)
2.303 a
k= log (a  x)
t
when, t = t1/2 x = a/2
2.303 a
So, k= t log a
1/ 2 a
2
2.303 a 2.303
= t log a = t log 2,
1/ 2 1/ 2
2
0.693
or, t1/2 = ... (vii)
k
[ 12 ]
Chemical Kinetics
This expression for half-life period does not contain the initial concentration ‘a’ of the reactant. It
indicates that the half-life period of a first order reaction does not depend upon the initial concentration
of the reactant.
Characteristics of First Order Reactions:
1. All the first order reactions obey the equation
2.303 a
k= log (a  x)
t
2.303 [ A]0
or, k= log [ A] ... (viii)
t
where [A]0 = Initial concentration of reactant.
[A] = Concentration of reactant at time ‘t’
2. On rearranging equation (viii) we get
tk
log [A] = log [A]0 – ...(ix)
2.303
If a graph is plotted between time on x-axis and log A on y-axis
k
we get a graph as shown below whose Slope =
2.303
k log A
slope = –
2.303
t
a
3. The value of rate constant, ‘k’ does not change with the concentration units because (a  x) will
have the same value whatever be the units of concentration.
4. Time taken for the completion of any fraction of reaction is independent of initial concentration
of the reactant.
2
For example, time taken for completion of the reaction is t2/3 can be calculated from the Ist
3
order equation.
2.303 a
k= log (a  x)
t
2
when, t = t2/3, x = a
3
2.303 a
Thus, k= t log 2a
2/3 a
3
2.303
or, k= t log 3
2/3
2.303
or, t2/3 = log 3
k
2.303  0.4771 1.098
or, t2/3 = =
k k
This expression for t2/3 is also not containing ‘a’ the initial concentration of the reactant, hence
t2/3 is independent of the initial concentration of reactant
[ 13 ]
Chemical Kinetics
Pseudo-Unimolecular reactions : Those first order reactions whose molecularity is not one.
Examples:
(i) Hydrolysis of an ester :
CH3COOC2H5 + H2O H+ CH3COOH + C2H5OH
This reaction is bimolecular, but only concentration of the ester is changed because water is
present in excess. So, its concentration remains practically constant. The rate equation is
dx
= k[CH3COOC2H5]
dt
So, order of the reaction is one. Hence, this is a pseudo unimolecular reaction.
(ii) Inversion of sucrose (cane sugar)
C12H22 O11 + H2O  C6H12O6 + C6H12O6

Sucrose Glucose Fructose
Second order reactions: When the rate of a reaction is determined by variation of two concentration
terms, the reaction is said to be of second order. For a general reaction,
A + B  products, the rate law may be,

dx
= k [A]2 [B]0, or ... (x)
dt
dx
= k [A]0 [B]2, or ... (xi)
dt
dx
= k [A] [B] ... (xii)
dt
Thus, the rate of a second order reaction varies directly as the square of the concentration of
reactant.
Unit of the second order rate constant:
From equation (x) we get
dx Mol / litre –1 –1
k= 2 = 2 2 = lit. mol time .
dt  [A] Time interval Mol. /lit.
The unit of second order rate constant involves concentration as well as time.
Examples of Second Order Reactions :

373 K
1. Conversion of ozone into oxygen at 373 K : 2O3 3O2
2. Thermal decomposition of nitrous oxide : 2N2O — 2N2 + O2
3. Alkaline hydrolysis of an ester (saponification) : CH3 COOC2H5 + NaOH — CH3COONa +

C2H5OH
KCN alc.
4. Benzoin condensation, C6H5CHO + OHC.C6 H5 C6H5CH(OH)CO.C6H5
reflux
[ 14 ]
Chemical Kinetics
Second order rate equation: All the second order reactions obey the following kinetic equation,
1 x
k = t  a(a  x ) .... (xiii)
where k = second order rate constant

a = initial concentration of reactant (s)
x = concentration of reactant converted into products after time ‘t’
t = time elapsed
Characteristics of a Second Order Reaction :
1
(i) When a graph is plotted between ‘t’ and (a  x) a straight line
is obtained. On rearranging, equation (xiii).
Time
1 1 1
t = k (a  x)  ka . The slope of the line is .
k
l/(a-x)
From this ‘k’ an be evaluated.
(ii) The value of second order rate constant depends upon the unit in which concentration of the
x
reactant(s) is expressed, because the value of a(a  x) will be changed when the unit of
concentration is changed.
(iii) The half-life period (t1/2) of a second order reaction is inversely proportional to the initial
concentration of reactant.
From expression (xiii)

1 x
k = t  a(a  x ) ... (xiii)
when, t = t1/2, x = a/2
1 a/2
so, k = t  a(a  a / 2)
1/ 2
1
or, t1/2 = .. (xv)
ka
Thus, it is evident from equation (xv) that half life period for a second order reaction is inversely
proportional to the initial concentration of reactant.
Third order reactions: A chemical reaction is said to be of third order if its rate is determined by
the variation of three concentration terms. The rate of a third order reaction is proportional to the
third power of concentration of reactants. The rate law for the reaction 3A  products, is:
dx
= k[A]3.
dt
Unit of third order rate constant : From the above expression,
dx Mol / litre 2 –2 –1
k= 3 = 3 3 = litre mol time .
dt  [A] time  Mol / litre
[ 15 ]
Chemical Kinetics
Example of third order reactions:
1. Gaseous reactions:
2NO + O2  2NO2
2NO + Cl2  2NOCl
2. Reaction in solution:
SnCl2 + 2FeCl3  SnCl4 + 2FeCl2
Third order kinetic equation: The following is the kinetic equation obeyed by all the third order
reactions
1  1 1 
k = 2t  2
 2 ... (xvi)
 ( a  x ) a 
Characteristics of third order reactions:

1
(i) A graph plotted between time ‘t’ and 2 is straight line. The slope of this straight line is
( a  x)
1
equal to .
2k
(ii) The value of rate constant ‘k’ depends upon the unit in which the concentration of reactants are
expressed.
(iii) The half-life period of the third order reaction is inversely proportional to the initial concentration
1
of reactant raised to the power two i.e., t1/2,  2 ,
a
1
From expression (xvi), it can be derived that t1/2 = 2
2 k .a
General expression for t1/2 for any reaction
In general, the half-life period of any reaction of nth order is inversely proportional to the initial
concentration of the reactant ‘a’ raised to the power equal to (n – 1), i.e., one less than the order of
the reaction.
1
i.e., t1/2  n 1
(a)
The graphs obtained for different order reactions are
zero order Ist order IInd order
t1/2 t1/2 t 1/2
a a 1/a
Illustration 1: If in a reaction A  Products, the concentration of the reaction A is C0, C0, 2C0, 3C0 ....
after time values 0, t, 2t, 3t, .... where,  is a constant 0 <  < 1. Show that the reaction is of
first order . How is the rate constant k related to a and t ?
[ 16 ]
Chemical Kinetics
Solution: We know for first order reaction
2.303 a
k= log
t ax
Here, a = C0
(a – x) = C0, 2C0, 3C0 etc. at times t, 2t, 3t etc.
Now, substituting these values in the rate equation
2.303 C0 2.303
k1 = log C  = log–1 .... (1)
t 0 t
2.303 C0 2.303
k2 = log (C   ) = log –2
2t 0 2t
2.303 2.303
=  2log –1 = log –1 .... (2)
2t t
Similarly
2.303 C0 2.303
k3 = log (C   ) = log –3
3t 0 t
2.303 2.303
 3 log –1 = log –1 . ... (3)
3t t
Since the value of rate constant, k(k1, k2, k3) are constant. Hence, the reaction is of first
order.
The rate constant k is related to  and t as
2.303
k= log –1
t
Illustration 2: The decomposition of hydrogen peroxide in an aqueous solution is a first order reaction. It
can be studied by titrating quickly 10 ml. portions of reactions mixture at various times from
the t = 0 of reaction against a standard solution of KMnO4. Volume of KMnO4 solution used
in each case is proportional to the remaining concentration of H2O2.
From the following data calculate the rate constant of the reaction.
Time (seconds) 0 600 1200
KMnO4 solution used (ml) 22.8 13.8 8.2
Solution: Here, a = 22.8, a – x = Vol. of KMnO4 used at various times t.

At time 600 seconds :
2.303 22.8
K= log = 0.000837
600 13.8
At time 1200 seconds :
2.303 22.8
K= log =0.000852
1200 8. 2
0.000837  0.000852
Average value of K = = 0.000844 or 8.44  10–4 sec–1
2
[ 17 ]
Chemical Kinetics

Problem 1: Half life of the following first order reaction is
C2H4O(g) CH4(g) + CO2(g)
Given the initial pressure of C2H4O(g) is 84 mm and the total pressure at the end of 16 min
is 110 mm.
(a) 15 minutes (b) 30 minutes
(c) 45 minutes (d) 60 minutes
Solution: C2H4O(g) CH4(g) + CO2(g)
Initial conc. a 0 0
Conc. after 16 min. a – x x x
a  84 mm. Total no. of moles after 16 min = a – x + x + x = a + x
 a + x  110 mm
x  26
(a – x) 58
2.303 84 2.303
or 16 = log =  0.1608
t 58 k
2.303  0.1608
k= = 0.0231 min–1
16
0.693
 Half life period t1/2 = = 30 min.
0.0231min 1
Problem 2: The gas phase decomposition of dimethyl ether follows first order kinetics
CH3 – O – CH3(g) CH4(g) + H2(g) + CO(g)
The reaction is carried out in a constant volume container at 500ºC and has a half life of 14.5
minutes. Initially only dimethyl ether is present at a pressure of 0.40 atmosphere. What is the
total pressure of the system after 12 minutes ? Assume ideal gas behaviour.
(a) 0.50 atm (b) 0.74 atm
(c) 0.85 atm (d) 0.96 atm
Solution: (b) Given t1/2 = 14.5 min, initial pressure = 0.40 atm, t = 12 min
0.693
Now, K = = 4.78  10–2 min–1
14.5
2.303 0.4
4.78  10–2 = 12 min log
0. 4  x
which gives x = 0.175 atm.

Since volume and temp. are constant, final pressure :
CH3 – O – CH3(g) CH4(g) + CO(g) + H2(g)
0.4
0.4 – 0.175 0.175 0.175 0.175
Hence total pressure = 0.4 – 0.175 + 3  0.175 = 0.749 atm
[ 18 ]
Chemical Kinetics
Problem 3: The decomposition of A and B obeys 1 order with half-life 54.0 and 18.0 minutes respectively.
If [A]t = [B]0 then after how much time the ratio of concentration of A and B will be 4 : 1.
K
Solution: (c) [A]t  [A]0  e 1t
K t
[B]t  [B] 0  e 2
[A]t (  K1  K 2 )t
 [B]  e
t
[A]t
4  e(K 2 K1 )t 4if
[B]t
or (K 2  K1 )  t  ln 4
ln 4 1386
t   54 minutes
 K 2  K1 0.693  0.693
18 54
Problem 4: The following data are for the reaction A  B 

 Products:
Conc. of A (M) Conc. of B (M) initial rate (mol L–1s–1)
0.1 0.1 4.0 × 10–4
0.2 0.2 1.6 × 10–3
0.5 0.1 1.0 × 10–2
0.5 0.5 1.0 × 10–2
Rate constant of reaction will be:
(a) 2 × 10–2 L mol–1 sec–1 (b) 2 × 10–2 sec–1
(c) 4 × 10–2 sec–1 (d) 4 × 10–2 L mol–1sec–1
Solution: (d) R = k[A]m [B]n
By putting the value in the above equation we get, k = 4 × 10–2 L mol–1sec–1
Problem 5: The chemical reaction between K2C2O4 and HgCl2 is
2HgCl2  K 2 C2O 4 
 2KCl  2CO2  Hg 2 O2
The weights of Hg2Cl2 precipitated from different solutions in given time are as:
Time HgCl2 (mol litre–1) K2C2O4 (mol litre–1) Hg2Cl2 formed (mol litre–1)
60 0.0418 0.404 0.0032
65 0.0836 0.404 0.0068
120 0.0836 0.202 0.0031
Overall order of reaction will be
(a) 3 (b) 2
(c) 1 (d) 0
Solution: (a) Rate = K[HgCl2]n [K2C2O6]n

0.0032
 = K[0.0418]n [0.0505]n ...(1)
60
[ 19 ]
Chemical Kinetics
0.0068
 K[0.0836]n [0.404]n ...(2)
65
0.0031
 K[0.0836]n [0.202]n ...(3)
120
Solving equations (1), (2) and (3), we get
m=1
n=2
 O.R. = m + n = 1 +2 = 3
Problem 6: For a reaction at 800°C, 2NO  2H 2 

 N3  2H 2O the following data were obtained
1
[NO] × 10–4 [H2] × 10–1  d [NO]dt 102
2
mol/litre mol/litremol litre–1min–1
(i) 1.5 4.0 4.4
(ii) 1.5 2.0 2.2
(iii) 0.5 2.0 0.24
Rate constant of reaction will be
(a) 4.88 × 10–8 sec–1 (b) 4.88 × 10–8 mol L–1 sec–1
(c) 4.88 × 10–8 mol–2 L2 min–1 (d) 1.24 × 10–4 sec–1
Solution: Let the expression be,
r = K[NO]n [H2]n ...(1)
–4 4
Case I: [NO] × 10 = 1.5  [NO] = 1.5 × 10
–3
[H2] × 10 = 4.0  [H2] = 4.0 × 103
1 d [NO] 1 d [NO]
  4.4    4.4  104
2 dt 2 dt
By equation (1), 4.4 × 104 = K[1.5 × 104]n [4.0 × 105]n ...(2)
Similarly the case II and III, we can rite
Case II: 2.2 × 104 = K[1.5 × 104] [2.0 × 103]n ...(3)
4 4 n 3 n
Case III: 0.24 × 10 = K[0.5 × 10 ] [2.0 × 10 ] ...(4)
By equations (2) and (3), 2 × (2)n  n=1
n
By equations (3) and (4), 916 = (3)  n=2
 O.R w.r.t. NO is 2 and w.r.t. H2 = 1
For rate constant use equations (2) with n = 2 and n + 1
4.4 × 104 = K[1.5 × 104]3 (4.0 × 103]1
 K = 4.88 × 10–8 mol–2L2 min–1
Problem 7: The inversion of cane sugar proceeds with halflife of 500 minute at pH 5 for any concentration
of sugar. However if pH = 6, the halflife changes to 50 minute. The rate law expression for
the sugar inversion can be written as
2 6 1 0
(a) r = K[sugar] [H] (b) r = K[sugar] [H]
0 +6 0 +1
(c) r = K[sugar] [H ] (d) r = K[sugar] [H ]
[ 20 ]
Chemical Kinetics
Solution: (b) Since t1/2 does not depends upon the sugar concentration means it is first order respect
to sugar concentration. t1/2  [sugar]1.
t1/2 × an-1 = k
 t1/ 2 1 [H  ]11 n

 t1/ 2 2 [H  ]12 n
1 n
500  105 
 
50  106 
10 = (10)1-n
Hence, n = 0
Problem 8: Two substances A and B are present such that [A ] = 4[B ] and halflife of A is 5 minute
0 0
and that of B is 15 minute. If they start decaying at the same time following first order
kinetics how much time later will the concentration of both of them would be same.
n1
1
Solution: (a) Amount of A left in n1 have s =   [A 0 ]
2
n2
1
Amount of B left n2 halve s =   [B0 ]
2
At the end, according to the question
[A 0 ] [B0 ]
 n
2n 1 22
4 1
 n1
 n , [A 0 ]  4[B0 ]
2 22
n1
2
 n  4  2n1 n2  (2)2  n1  n2  2
22
 n2  (n1  2) …(1)
Also t = n 1 ´ t 1 / 2(A ) t  n2  t1/ 2( B )

(Let concentration both become equal after time t)
n 1 ´ t 1/ 2(A ) n1 ´ 5 n
\ = 1Þ = 1Þ 1 = 3 …(2)
n 2 ´ t 1/ 2( B ) n 2 ´ 15 n2
For equation (1) and (2)

n1 = 3, n2 = 1
t = 3  5 = 15 minute
Problem 9: For the first order reaction A  2B + C , the initial pressure is P = 90 mm Hg, the
(g) (g) (g) A
pressure after 10 minutes is found to be 180 mm Hg. The rate constant of the reaction is
–3 –1 –3 –1
(a) 1.15  10 sec (b) 2.3  10 sec
–3 –1 –3 –1
(c) 3.45  10 sec (d) 6  10 sec
Solution: (a) A  2B + C
P 0 0
P–x 2x x
[ 21 ]
Chemical Kinetics
At equilibrium
180 = P – x + 2x + x
180 = 90 + 2x
2x = 90, x = 45
2.303 P
K log
t Px
2.303 90
= log
10 90  45
2.303 0.6932
= log 2  = 0.6932
10 10
0.06932
= = 1.1555  10–3 sec–1
60
Problem 10: Following is the graph between (a – x)2 and to,e t for second
order reaction  = tan–1 (0.5)
OA = 2 L mol–1 hence
(a) 100 kg min–1
(b) 80 kg min–1
(c) 64 kg min–1
(d) 32 kg min–1
Solution: (b) Convert quantity in mol and then into kg.
1.3 Collision Theory And Activation Energy

According to collision theory of reaction rates, the reactant molecules must collide with each other
before forming products. Such collisions among reactant molecules which form products, are called
effective collisions. All the collisions are not effective collisions. The number of effective collisions is
much smaller than the total number of collisions taking place among reactant molecules. Only those
collisions result into products in which reactant molecules have energy equal to or excess of a
minimum energy known as Threshold Energy.
The reactant molecules which possess energy equal or greater than the threshold energy are called
activated molecules. The number of activated molecules is much smaller than the total number of
reactant molecules. Since, most of the reactant molecules possess less energy than the threshold
energy, therefore reacting molecules require certain energy known as activation energy to reach
upto the threshold energy. Thus, the energy of activation may be defined as the energy in excess to
the average energy of the reactant molecules which a molecule must be supplied before colliding
with one another, so that their collision may result into products.
 Activation energy (Eact) = Threshold energy – Average energy of reactant molecules,
Thus activation energy is required by the reactant molecules to reach threshold energy so that an
activated complex may be formed. An activated complex is unstable arrangement of reacting molecules
[ 22 ]
Chemical Kinetics
with high energy. This complex decomposes into products. Thus, there exists an energy barrier
between reactants and products. If the reactant molecules possess sufficient energy to cross this
energy barrier, their collision will lead to the formation of products. So, reactions having high activation
energy proceed slowly and those where activation energy is less, the rate of reaction is very high.
Collisions
A + BC A B C AB + C
Reactant molecules, Activated Complex Products
(Average energy High energy (Low energy
EReactions) (EThreshhold) EProducts)
Eact = Activation energy for forward reaction.

= Threshold energy (Energy of activated complex) – EReactants (Average energy of reactants)
Eact = Activation energy for the backward reaction.

= Eact f + H (where, Eact f is activation energy of forward reaction).
= Activation energy for the forward reaction + heat of reaction.
Heat of reaction = EProducts – EReactant

Energy profile for an exothermic reaction Energy profile for an endothermic reaction
Activated Complex Activated Complex

E(Threshold) A....B....C. Threshold Energy
A....B....C.
E act E act E act E act
Energy
Energy

H AB+C

A+BC H A+BC
AB+C
Progress of the reaction Progress of the reaction
Illustration 1: A given sample of milk turns sour of room temperature (27°C) in 64 hour. In a refrigerator
at 3°C, milk can be stored three times in long before it sours. Estimate (a) the activation
energy for souring of milk, (b) how long it table milk to sour at 40°C.
K 293
Solution: Given, K  3, F2  293K and T1  276K
236
K 2 E a [T2  T1 ]
(a) 2.303log10 K  R T T (R = 2 cal_
1 1 2
E [293  276]
 2.303log10 3  a
2 203  276
 Ea = 10453.95 cal = 10.454 kcal
K 3 E a [T3  T2 ]
(b) Also, 2.303log10 K  R T T
2 3 2
The time E a  10.454 kcal; T3  313K and T2  293K

K 3 10.454 103 [313  293]
 2.303log10 
k2 2 313  293
K3
 K  3.12
2
[ 23 ]
Chemical Kinetics
K3 t 2 1
Now, K  t  K  time
2 3
Also if milk is not soured up to 64 hr at 20°C, it will not sour up to 192 lie at 3°C, Similarly we
can have
K2 1
t3  t2   64   20.5 hr
K3 312
Illustration 2: The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers the
energy of activation by 75%. What will be effect on rate of reaction at 27°C after things
being equal?
Solution:  K  Ae E a /RT
Case I: K1  Ae100/RT
Case II: K 2  Ae25/RT
K1 e 100/RT
   e 75/RT
K 2 e 25/RT
K2 25/RT
or log e K  log e (H in kJ)
1
K 2 75 75  103
log e   (H in kJ)
K1 RT 8.314  293
K2
 2.35 1013
K1
Since r  K[ ]n n and[ ] are same for Case I and II.
r2 K 2
   2.35 ×1033
r1 K1
Illustration 3: What will be the initial rate of a reaction if its rate constant is 10–3 min–1 and the concentration
of reactant is 0.2 mol dm1? How much of reactant will be converted into products in 200
minute?
Solution: : Since K has unit min–1 and thus, given reaction is of 1 order
Now Rate = K [ ]t
Rate = 10–3 × [0.2]t = 2 × 10–4 mol dm–3 min–1
2.303 a
Also, K  log10
t (a  x)
3 2.303 100
 10  log10
20 (100  x )
 x = 18.12%
[ 24 ]
Chemical Kinetics
Illustration 4: Two reactions of same order have equal pre-exponential factors but their activation energies
differ by 24.9 kJ mol–1. Calculate the ratio between the rate constant of these reactions at
27ºC.
Solution: A, i.e., (pre-exponential factor) is same.

Ea1
log k1 = log A – .... (i)
2.303RT
Ea 2
log k2 = log A – .... (ii)
2.303RT
Subtract equation (i) from (ii)
E a1  E a 2
log k2 – log k1 =
2.303RT
k2 24.9  1000
or, log k =
1 2.303  8.314  300
= 4.334
k2
or, k1 = Antilog (4.334)
k2 4
 k1 = 2.162  10

Problem 1: If a reaction A + B  C is exothermic to the extent of 30 kJ/mol and the forward reaction
has an activation energy 70 kJ/mol, the activation energy for the reverse reaction is
(a) 30 kJ/mol (b) 40kJ/mol
(c) 70 kJ/mol (d) 100 kJ/mol
Sol.: (d)
70kJ
Energy 100kJ
Energy
30kJ
Progress of reaction
By seeing the curve, activation energy for backward reaction = 100 kJ
Problem 2: Given that the tempeature coefficient for the sponification of ethyl acetate by NaOH is 1.75.
Activation energy of reaction.is
(a) 5.25 kcal mol–1 (b) 5.25 kJ mol–1
(c) 10.27 kcal mol–1 (d) 10.27 kJ mol–1
K2
Solution: (c) Given, K  1.75
1
T1 = 25°C = 25 + 273 = 298 K

T2 = 35°C = 35 + 273 = 306 K
(Since, temperature coefficient is ratio of rate constants at 35°C and 25°C respectively.)
K Ea (T2  T1 )
 2.303log10 2 
K1 R T1T2
[ 25 ]
Chemical Kinetics
E a [308  298]
 2.303log10 1.75 
1.967 308  298
2.303  398  298 1.987
 Ea   log1.75 cal mol1
10
Ea = 10.27 kcal mol–1
Problem 3: At 380°, the half-life period for the first order decomposition of H2O2 is 360 minute. The
energyof activation of the reaction is 200 kJ mol–1. The time required for 75%, decomposition
at 450°C isL
(a) 10.30 min (b) 15.15 min
(c) 20.39 min (d) 25.45 min
–1
Solution: (c) K1 = 0.6937/360 min at 653 K mol
E a  300 103 J, K 2  ? at723K, R  8.3146J
 From 2.303 log10 (K2 / K1) = (Ea /R) (T2 – T1) (T1T2)
K2 = 0.068 min–1
2.303 100
Now, t  log10  20.39 minute
0.068 25
Problem 4:  C  D; ΔH  20 kJ mol1 ; the activation energy of the forward reaction is

For A  B 
85 kJ mol. Activation energy of the reverse reaction is
(a) – 85 kJ mol–1 (b) 65 kJ mol–1
–1
(c) – 65 kJ mol . (d) 105 kJ mol–1
Solution:: (b)
H of forward reaction = 20 kJ mol–1

Energy of activation for forward reaction
(Ea) = 83 kJ mol–1
 Energy of activation for backward reaction
= Ea = –H
= 85 – 20 = 65 kJ mol–1
Problem 5: In the Arrhenius equation for a certain reaction, the values of A and Ea (energy of activation)
are 4 × 1013 sec–1 and 98.6 kJ mol–1 respectively. If the reaction is of first order, at what
temperature will its half-life period be 10 minute?
(a) 300 K (b) 311.35 K
(c) 350 K (d) 362.1 K
Solution: Given,
K = ? A = 4 × 1013 sec–4
Ea = 98.6 × 103 J mol–1 t1/2 = 10 × 60 sec.
3
 K  Ae E a /RT  K  4 1013 e (98.610 )/8.314T
[ 26 ]
Chemical Kinetics
0.693 0.693 1
Now for 1 order reaction, K  t 
600
sec
1/2
0.693 3
  4 1013 e (98.610 )/8.314T
600
0.693 98.6  103
or log e  log3 4 1013 
600 8.314  T
0.693 13 98.6  103
or log 10  log 10 4  10 
600 8.314  2.303  T
 T = 311.35 K
Problem 6: A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in
presence of a catalyst at the same rate, the temperature required is 400 K. Activation
energy of the reaction, if the catalyst lowers the activation energy barrier by 20 kJ mol–1.
(a) 50 kJ mol–1 (b) 100 kJ mol–1
(c) 150 kJ mol–1 (d) 200 kJ mol–1
Solution: Leet Ea and E ar be the energy of activation in presence and absence of catalyst for
hydrogenation reaction, then
K  Ae E a /RT
In presence of catalyst: K1  Ae E a (R300)
r
In absence of catalyst: K1  Ae E a (R400)
Given, the two rates are same, i.e., r1  r2 ;  K1  K2

Therefore, e Ea (8500)  e Ear /(8400)
Ea E ar
or 
R  500 R  400
E a E a  20
or   E a  R ar  20
500 400
 Ea = 100 kJ mol–1
–1 –1
Problem 7: A catalyst lowers the activation energy of a reaction from 20 kJ mole to 10 kJ mole .
The temperature at which the uncatalysed reaction will have the same rate as that of the
catalysed at 27C is
(a) –123C (b) 327C
(c) –327C (d) + 23C

Ea E a 10 20
Solution: (b) T  T  300  T
1 2 2
T2 = 600 K = 327 C
Problem 8: What is the activation energy for the decomposition of N2O5 as?
1
N2O5 2NO2 + O2
2
If the values of the rate constants are 3.45  10–5 and 6.9  10–3 at 27°C and 67°C
respectively.
(a) 102  102 kJ (b) 488.5 kJ
(c) 112 kJ (d) 112.5 kJ
[ 27 ]
Chemical Kinetics
K2 Ea  T2  T1 
Solution: (d) log   
K 1 2.303R  T1T2 
6.9  10 3 Ea  40 
log 
3.45  10 5
2.303  8.31  300  400 

Ea = 112.5 kJ
Problem 9: The rate constant, the activation energy and the Arrhenius parameter of a chemical reaction
–4 –1 –1 14 –1
at 25°C are 3.0  10 s , 104.4 kJ mol and 6.0  10 s respectively the value of the
rate constant as T   is
18 –1 14 –1
(a) 2.0  10 s (b) 6.0  10 s
30 –1
(c)  (d) 3.6  10 s
Ea
Solution: (b) K  Ae  RT
When T  
K = A = 6  1014
Factors Affecting Rate of Chemical Reaction
The reaction rate is influenced by the following factors :
(i) Concentration of reactants

(ii) Temperature
(iii) Nature of reactants and products
(iv) Presence of a catalyst
(v) Surface area of solid reactant and
(vi) Exposure of radiations
(i) Effect of concentration : The rate of a reaction is directly proportional to the product of active
masses raised to the power equal to their coefficients in a balanced chemical equation, (Law of
mass action). Hence, the rate of reaction decreases as the reaction proceeds towards the products
because the concentration of reactant(s) decreases.
(ii) Effect of temperature : The rate of a reaction always increases on increasing temperature
whether the reaction is endothermic or exothermic, because the number of activated molecules
increase. In general, the rate of a reaction gets doubled with ten degree increase in temperature.
Arrhenius Equation : In order to give a quantitative relation between the rate constant and
temperature of a reaction, Arrhenius proposed the following equation which is known as Arrhenius
equation after his name.
k = Ae–Ea/RT .... (1)
Where, A = Arrhenius factor, pre-exponential factor, collision factor, frequency factor.

Ea = Energy of activation for the reaction
R = Molar gas constant
T = Temperature of the reaction in absolute scale.
[ 28 ]
Chemical Kinetics
On taking logarithm of both sides (1)
Ea
logek = logeA –
RT
On multiplying by 2.303 to convert the base of log from loge to log10
Ea
2.303 log k = 2.303 log A 
RT
On dividing the whole equation by 2.303, we get
Ea
log k = log A – 2.303 RT .... (2)
Expression (2) is the equation of a straight line, when log k is plotted
Ea
against 1/T, we get a straight line whose slope is equal to  2.303 R
If k1 and k2 are the rate constant at temperature T1 and T2 respectively,

then the Arrhenius equation takes the form,
k 
2 Ea  T T 
2 1
log  k  = 2.303 R  T T  ....(3)
 1  1 2 
In deriving (3), it has been assumed that ‘A’ and Ea are independent of temperature.
In the Arrhenius equation k = A e –Ea/RT, When the absolute
temperature of the reaction becomes infinity, the rate constant Slope = – Ea/2.303 R
of the reaction becomes equal to A, the pre-exponential factor.
log k
k = Ae–Ea/R  = Aeº
or k=A
I/T
When energy of activation Ea of a reaction is zero, the reaction rate becomes independent of
temperature.
with given kinetic energy
T1
Number of Particles
T2
e f
b c
KE a d
If one looks at the graph above then one would observe that as temperature increases from T1 to T2
the energy distribution changes:
(1) The number of molecules possessing average kinetic energy decreases?
(2) The number of molecules possessing higher kinetic energy increases as observed under the
area of shaded portion abcd and aefd.
(3) When T2 = T1 + 10 then the area shaded under the graph aefd is twice the area shaded under the
graph abcd.
[ 29 ]
Chemical Kinetics
(iii) Nature of reactants and products : Chemical reactions which involve complex molecules as
reactants and in which complex molecules are formed as products, proceed at a slower rate.
The reason is that, greater number of bond rearrangements are involved in complex reactants
and products which makes the reaction slow. Reactions involving lesser number of bond
rearrangements are fast reactions. For example, oxidation of Fe++ by MnO4– ion in acidic
medium takes place faster than the oxidation of oxalate ion (C2O4– –) under the same condition.
5Fe++ + MnO4– + 8H+  Mn++ + 5Fe+++ + 4H2O (Fast)
2 MnO4– + 16H+ + 5C2O4–  2Mn++ + 8H2O + 10CO2(Slow)
(iv) Presence of a catalyst: Generally, a positive catalyst enhances the rate of a reaction by changing
the path of reaction which requires less activation energy. But negative catalyst retards a chemical
reaction. Thus, a catalyst alerts the rate of reaction.
(v) Surface area of solid reactant: This factor is important for heterogeneous reactions involving
a solid as one of the reactants. The rate of such a reaction increases with increasing surface
area of solid reactant, i.e., Rate of reaction  Surface area of solid reactant
For example : Wood shavings burn more rapidly than a log of wood of same mass. Coal dust
burns at a faster rate than large piece of coal.
(vi) Exposure to radiation: Rates of certain reaction increases by absorption of photons of a

particular radiation. Such reactions are called photochemical reactions. For example, Hydrogen
and chlorine gases do not combine with each other in dark. But when their mixture is exposed
to light, a loud explosion occurs and the chemical combination takes place. Formation of a image
on a photographic plate, photosynthesis, fading of colour in sunlight, etc. are other examples of
photochemical reactions.
Temperature Coefficient of Rate Constant : The ratio of rate constant of a reaction at two
temperatures differing by ten degrees is called temperature coefficient of rate constant.
k110 º k 35 º
Temperature coefficient of rate constant = kt = k 25 º
It has been observed experimentally that for a large number of reactions, the rate increases (rate
constant increases) two to three time for a ten degree rise in temperature. Thus,
k t 10 º
kt = 2 to 3
Determination of Order of Reaction
(1) Half-change method : This method is based on the fact that half-change time is inversely
proportional to the initial concentration of reactant raised to the power one less than the order of
reaction. i.e.,
1
t1/2  n 1
(a)
[ 30 ]
Chemical Kinetics
If t1 and t2 are the half-life periods of a chemical reaction with different initial concentrations a1 and
and ‘n’ is the order of the reaction, then by using the following relation, order can be determined.
1
t1/2 (1)  n 1
(a1 )
1
t1/2 (2)  n 1
(a 2 )
n 1
t2  a1 
 t1 =  a 2 
(a) For a zero-order reaction, n = 0

0 1
t2  a1  a2
t1 =  a2  = a
1
t1 t2
or a1 = a2 = constant.
(b) For a first order reaction, n = 1
11 0
t2  a1   a1 
t1 = a  = a  = 1
 2  2
or t1 = t2 = constant.
(c) For a second order reaction, n = 2
2 1
t2  a1  a1
t1 =  a2  = a
2
t1  a1 = t2  a2 = constant
(d) For third order reaction, n = 3
31 2
t2  a1  a1
t1 = a  = 2
 2 a2
t1  a12 = t2  a22 = constant.
(2) Differential method : When the order of a reaction with respect to a particular component is ‘n’
and r1 and r2 are the rates of the reaction at different concentrations c1 and c2 of that reactant,
then
n
r1  c1 
r2 = c  .
 2
Thus, order of reaction with respect to individual reactants is determined. The sum of the orders
with respect to individual reactants, gives the overall order of the reaction.
[ 31 ]
Chemical Kinetics
CHAPTER ASSIGNMENT
MULTIPLE CHOICE QUESTIONS (Single Correct Option)
1. If a reaction A + B  C + D has the following mechanism
Fast
A+B AB
Slow
AB + A A2B
Fast
A2B+B C+D
the rate law is
(a) Rate = k[A][B]2 (b) Rate = k[A]2[B]
(c) Rate = k = [A] [B] (d) Rate = k[A]2 [B]2
2. In a reaction A  B, the rate of reaction increases two times on increasing the concentration of the
reactant four times, the order of reaction
(a) 0 (b) 2 (c) 1/2 (d) 4
3. A substance undergoes first order decomposition. The decomposition following two parallel first
order reaction as :
k1
B
A
k2 C
k1 = 1.26  10–4 sec–1 and k2 = 3.8  10–5 sec–1.

The percentage distribution of B and C are :
(a) 80% B and 20% C (b) 76.83% B and 23.17% C
(c) 90% B an 10% C (d) 60% B and 40% C
4. In a certain reaction, 10% of the reactant decomposes in one hour, 20% in two hours, 30% in three
hours and so on. The dimensions of the rate constant is
(a) Hour–1 (b) Mol lit–1 sec–1 (c) Lit mol–1 sec–1 (d) Mol sec–1
5. The rate of reaction, 2NO + O2  2NO2, at 25ºC is 0.028 mol l–1 s–1. The experimental rate is
given by
r = k[NO]2[O2]
If the initial concentrations of the reactants are O2 = 0.040 mol l–1 and NO = 0.01 mol l–1, the rate
constant of the reaction is :
(a) 7.0  10–2 l–2 mol2 s–1 (b) 7.0  10–4 l2 mol–2 s–1
(c) 7.0  102 l2 mol–2 s–1 (d) 7.0  103 l2 mol–2 s–1
6. The following data are for the decomposition for ammonium nitrite in aqueous solution.
Vol. of N2 in cm3 6.25 9.0 11.42 13.65 35.02
Time (min) 10 15 20 25 
The order of reaction is :
(a) 3 (b) 2 (c) 1 (d) 0
[ 32 ]
Chemical Kinetics
7. The ratio of number of molecules reacting in a given time to number of quanta of light absorbed in the
same time is called
(a) Activation energy (b) Activated complex (c) Quantum yield (d) None of these
8. The first order reaction is 15% complete in 20 min. The time taken for it to be 60% complete is
(a) 112.7 sec. (b) 1.127 sec. (c) 1127 sec. (d) None of these
9. The rate constant is numerically same for the three reaction of I order, II order, III order, then the
order of rates of reactions will be (A) < 1
r1 = k[A]1, r2 = k[A]2, r3 = k[A]3
(a) r1 = r2 = r3 (b) r2 > r1 > r3 (c) r3 > r2 > r1 (d) None of these
10. The rate constant of a reaction is 0.69  10–1 min–1 and initial conentration is 0.2 mol/L. The t½ is
(a) 400 sec (b) 600 sec (c) 800 sec (d) None of these
11. Select the rate law expression that corresponds to the data for the reaction A + B  H products
Exp.[A] [A] [B] Initial rate
1. 0.012 0.035 0.1
2. 0.024 0.070 0.8
3. 0.024 0.035 0.1
4. 0.012 0.070 0.8
3
(a) Rate = K [B] (b) Rate = K [B]4
(c) Rate = K [A] [B]3 (d) Rate = K [A]2 [B]2
12. The activation energy for a reaction is 12.9 k cals mol–1. The increase in the rate constant when its
temperature is increased from 298 K to 308 K is
(a) 100% (b) 50% (c) 10% (d) None of these
13. For an exothermic chemical process occurring in two steps as :

(i) A+B  X (slow) (ii) X  AB (fast)
The progress of the reaction can be best described by :
X
X
(1) X
(a) (b) (c) (d) All of these
A+B A+B AB
A+B AB AB
k1
14. In the reversible reaction 2NO 2 k2
N2O4, the rate of disappearance of NO 2 is equal to
(a) k1 [NO2]2 (b) 2k1 [NO2]2 – 2k2[N2O4]

(c)2k1 [NO2]2 – k2 [N2O4] (d) None of these
15. For the first order reaction A(g)  2B(g) + C(g) the initial pressure PA =90 mm Hg, the pressure
after 10 minute is found to be 180 mm Hg. The rate constant of the reaction is
(a) 1.15  10–3 sec–1 (b) 2.3  10–3 sec–1 (c) 3.45  10–3 sec–1 (d) None of these
[ 33 ]
Chemical Kinetics
INTEGER TYPE QUESTIONS

16. The rate of gaseous reaction is halved when the volume of the vessel is doubled. Thus the order of
reaction is
17. A reaction P  Q is completed 25% in 25 min. 50% completed in 25 min. if [P] is halved, 25%
complete in 50 min if [P] is doubled, the order of reaction is
18. For the decomposition of N2O5 at 127°C, i.e., N2O5(s)  N2O4(g) + 1/2O2(g), if the initial pressure
is 114 mm and after 25 minutes of the reaction, total pressure of the gaseous mixture is 133 mm, the
average rate of reaction is 10–x mol L–1 s–1 where x is.
19. A gaseous reaction is of first order in reactant A and second order in reactant B. If the reaction
mixture is compressed to half the volume, the rate of reaction will be....... times.
20. The rate constant of a reaction zero order in A is 3 × 10–3 mol L–1s–1. The time taken in seconds for
the initial concentration of A to fall from 0.10 M to 0.076 M will be...... .
21. For a first order reaction, the number of half-lives required for the initial concentration of the reactant
to fall to 3.125% of its initial concentration is
22. For a first order reaction, the ratio of the time taken for 7/8th of the reaction to complete to that of
half of the reaction to complete is
23. After 24 hours, only 0.125 g of the initial quantity of 1 g of a radioactive isotope remains behind. The
half-life period of the radioactive isotope in hours is.
24. If the temperature of a reaction is increased from 20°C to 50°C, the rate of reaction will
become.........times.
25. The concentration of R in the reaction R  P was measured as a function of time and the
following data is obtained.
[R] (molar) 1.0 0.75 0.40 0.10
t (min) 0.0 0.05 0.12 0.18
The order of reaction is
MULTIPLE CHOICE QUSTIONS (Multiple correct answer)

26. In acidic medium the rate of reaction between [BrO3–] and Br– ions is given by the expression
d[BrO3 ]
 = k[BrO3–] [Br–][H+]2. It means
dt
(a) Rate constant of the reaction depends upon the concentration of H+ ions
(b) Rate of reaction is independent of the conc. of acid added
(c) The change in pH of the solution will affect the rate of reaction
(d) Doubling the conc. of H+ ions will increase the reaction rate by 4 times
27. Which of the following is/are correct for reactions of first order?
1 2.303
(a) k  ln(C0 / Ct ) (b) t  log [a/(a – x)]
t k
(c) [A]0 = [A] e–kt (d) t1/2 = (ln 2)/k
[ 34 ]
Chemical Kinetics
28. Arrhenius equation may be represented as

A Ea d ln k E
(a) ln  (b) 
k RT dT RT 2
Ea  Ea  k
(c) log A = log k + (d) log   
2.303RT  RT  A
29. In a hypothetical reaction X  Y, the activation energy for the forward and backward reaction
are 15 and 9 kJ mol–1 respectively. The potential energy of X is 10 kJ mol–1
(a) The threshold energy of the reaction is 25 kJ (b) The potential energy of Y is 16 kJ
(c) Heat of reaction is 6 kJ (d) The reaction is endothermic
30. Reactions of second order among the following:
(a) 2N2O5 4NO2 + O2 (b) 2HI H2 + I2
(c) 2NO + Br2 2NOBr (d) 2NO2 + F2 2NO2F
31. For the first order reaction 2 N2O5 4NO2(g) + O2(g)
(a) the concentration of the reactant decreases exponentially with time
(b) the half-life of the reaction decreases with increasing temperature
(c) the half-life of the reaction depends on the initial concentration of the reactant
(d) the reaction proceeds to 99.6% completion in eight half-life duration
32. Which of the following statement(s) about the Arrhenius equation is/are correct?
(a) The pre-exponential factor becomes equal to the rate constant of the reaction at extremely high
temperature
(b) When the activation energy of the reaction is zero, the rate becomes independent of temperature
(c) The term e  Ea / RT represents the fraction of the molecules having energy in excess of threshold
value
(d) On raising temperature, rate constant of the reaction of greater activation energy increases less
rapidly than that of the reaction of smaller activation energy.
33. Which of the following statements are correct?

(a) Time required for 75% completion is 1.5 times of half life for zero order reaction
(b) Time needed for a definite fraction of first order reaction does not vary with the initial concentration
(c) Time for 25% reaction is one-third of half-life in second order process
(d) Rate of zero order reaction gets doubled if the concentration of the reactant is increased to a two
fold value.
34. Hydrolysis of a sugar is catalysed by H+ ion. Half-life of the reaction is independent of initial
concentration of sugar at a particular pH. At a constant concentration of sugar rate increases 10
times when pH is decreased by one unit. Pick out the correct statements of the following:
(a) Rate [sugar] (b) Rate [H+]
(c) Rate law : rate = k[sugar] (d) Rate law : rate = k[sugar] [H+]
35. Choose the incorrect statements.

(a) The units of zero order rate constant (k) is that of concentration × time–1.
(b) In zero order reaction the concentration of product increases linearly with time.
(c) The photochemical reaction of H2 and Cl2 over water surface is of zero order.
(d) The thermal decomposition of HI on gold surface is of zero order.
[ 35 ]
Chemical Kinetics
MATRIX MATCH TYPE QUESTIONS
36. Look at the following diagram and match the entries in the Table below
Potential Energy
70
40
25
Reaction coordinate
Column-I Column-II
A. Activation energy of forward reaction (p) 70 kJ mol–1
B. Threshold energy (q) 30 kJ mol–1
C. Activation energy of backward reaction (r) 15 kJ mol–1
D. Enthalpy change of the reaction (s) 45 kJ mol–1
(a) A-(p); B-(q); C-(s); D-(r) (b) A-(q); B-(p); C-(r); D-(s)
(c) A-(r); B-(p); C-(s); D-(q) (d) A-(q); B-(p); C-(s); D-(r)
37. Column - I Column - II
(A) (p) 0
(B) (q) 1
(C) (r) 2
(D) (s) (3)
(a) (A) – (p); (B) – (r); (C) – (q); (C) – (s) (b) (A) – (r); (B) – (p); (C) – (q); (C) – (s)
(c) (A) – (s); (B) – (r); (C) – (q); (C) – (p) (d) (A) – (q); (B) – (r); (C) – (p); (C) – (s)
[ 36 ]
Chemical Kinetics
COMPREHENSION TYPE QUESTIONS

Comprehension - 1
For the non-stoichiometre reaction 2A + B  C + D, the following kinetic data were obtained in three
separated experiments, all at 298 K
Initial Concentration (A) Initial Concentration (B) Initial rate of formation of C (mol
L–1 S–)
0.1 M 0.1 M 1.2 × 10 –3
0.1 M 0.2 M 1.2 × 10 –3

0.2 M 0.1 M 2.4 × 10 –3
38. The rate law for the formation of C is
dc dc dc dc
(a)  k[A][B]2 (b)  k[A] (c)  k[A][B] (d)  k[A]2 [B]
dt dt dt dt
39. The value of rate constant is
(a) 1.2 × 10–3 (b) 2.4 × 10–3 (c) 1.2 × 10–2 (d) 3.6 × 10–2
40. Rate of reaction when the concentration A is 0.2 and concentration of B is 0.6
(a) 2.4 × 10–3 (b) 6 × 10–3 (c) 4.8 × 10–3 (d) 3.6 × 10–4
Comprehension-II
Suppose 50 bacteria are placed in a flask containing nutrients for the bacteria so that they can multiply. A
study at 35°C gave the following results
Time (minutes) 0 15 30 45 60
Number of bacteria 100 200 400 800 1600
If the order of reaction is 1. Then
41. The rate constant for the reaction is

(a) 0.0462 min–1 (b) 0.462 min–1 (c) 4.62 min–1 (d) 46.2 min–1
42. The rate of the reactions initially is

(a) 4.62 bacterias per minute (b) 23.1 bacterias per minute
(c) 23.1 bacterias per sec (d) 0.231 bacterias per sec
43. The t1/2 for the reaction is

(a) 1.5 sec (b) 1.5 min (c) 150 min (d) 15 min

[ 37 ]

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PHYSICAL CHEMISTRY

1.MOLE CONCEPT 1-15

Law of constant composition or definite proportions: “A chemical compound is always found

Method of determining atomic weight

(i) By application of the relation

At. wt. = Eq. wt. × Valency

At. wt. × Specific heat = 6.4 (approx.)

Eq. wt. × exact valency = exact Atomic Weight.

Molecular wt. = 2 × Vapour density.

Mol. wt. of the chloride = 2 × V.D.

Molecular weight of the Chloride MClx = At. wt. of M + x × 35.5

(c) Alums, M2SO4.M 2(SO4)3.24H2O in which M is monovalent and M is trivalent are

Knowing the valency, Atomic wt. = Eq. wt. × Valency

Methods of determining molecular weight

(ii) Vapour density method

Molecular weight = 2 × Vapour Density

Wt. of certain volume of the vapour

(iv) Colligative property method: Discussed in the unit of ‘Solutions’.

e.g.,(i) one mole of Na contains 6.023 × 1023 atoms of Na.

e.g. one mole of Na weighs 23 gm (Gram atomic wt. of Na = 23)

(ii) one mole of Mg weighs 24 gms (GAM of Mg = 24)

e.g. one mole of O2 weighs 32 gms (GMM of O2 = 32)

e.g. one mole of CO2 at STP occupies 22.4 litres of volume.

(ii) one mole of SO2 at STP occupies 22.4 litres of volume.

* The number of atoms in w gms of an element whose atomic mass is A is :

* The number of atoms is given by:

Mol. wt. of the acid

Mol. wt. of the base

(iii) Double decomposition method: For a reaction of the type

(e.q. AgNO3 + NaCl  AgCl  + NaNO3)

Weight of AB taken Eq. wt. of AB Eq. wt. of A  Eq. wt. of B

(iv) Electrolytic method (based on Faraday’s laws of electrolysis)

1 Faraday (96500 coulombs) deposit one gram equivalent of the substance.

Electrochemical equivalent of a substance is the weight of the substance deposited by one

Wt. of X deposited Eq. wt. of X

Eq. wt. of RCOOAg Wt. of silver salt

Eq. wt. of acid (RCOOH) = Eq. wt. of RCOOAg–108.

Weight of compound I Eq. wt. of metal  Eq. wt. of anion of compound I

Relationship between eq. wt. atomic wt. and valency of an element:

Molecular weight of the substance

Number of parts by weight of Fe 56  2

Number of parts by weight of S 32  3

Thus, the empirical formula is Na2S2O3.

SAMPLE PROBLEMS 1.1 (MCQ)

Solution: (d) 1g molecule is 1 mole

Mole of SO24 4 × 1 = 4 g ion

Solution: (c) Mass of NaCl = 10 × 0.96 = 9.6 g

Solution: (c) No. of atoms = no. of moles × atomicity

molar mass 120

1.2 Expressing concentration of solutions

moles of solute millimoles of solute

gm  eq. of solute meq. of solute

Strength of a solution is generally expressed as grams of solute in one litre of solution.

strength = Normality × Eq. wt. = Molarity × Mole wt.

(M2 & V2 are molarity and volume of diluted solution)

Consider a balanced chemical reaction of equation:

The above balanced reaction is analysed as:

m moles of A react with n moles of B to produce p moles of C and q moles of D.