Chemistry SM XI 2021-22

CHEMISTRY
STUDY
MATERIAL
XI
2021-22
1
Chapter - 1
Some Basic Concepts of Chemistry
Chemistry and its importance
Chemistry is the branch of science that studies the composition properties and interaction of matter.
Chemistry plays an important role in meeting human needs for food, health care products and other
materials aimed at improving the quality of life.
Nature of matter
Matter can exist in three physical states, Solid, Liquid and Gas.
Classification :
Matter
Mixture Pure Substances
Homogeneous Heterogeneous Elements Compounds
Measurement of Matter
Two different systems of measurement i.e. English system and the Metric system were being used in
different parts of the world. The need of a common standard system was being felt by the scientific
community. Following is such a system :-
The International System of Units (SI)

The SI system has seven base units listed in following table :-
Base Physical Symbol for Name of Symbol for

Quantity Quantity SI Unit SI Unit
Length l metre m
Mass m kilogram kg
Time t second s
Electric Current I ampere A
Thermodynamic - T kelvin K
Temperature
Amount of substance n mole mol
Luminous Intensity I candela cd
Temperature - Different scales used to measure temperature are related to each other as follows :-
Fahrenheit and Celsius:-
9
 F  (C )  32
5
Kelvin and Celsius:-
K  C  273.15
XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

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Scientific Notation - In chemistry atoms and molecules have extremely low masses and present in
large numbers. To express extremely small and large numbers scientific notation is used:- 232.508
can be written as 2.32508×102 or 0.00016 can be written as 1.6 × 10-4.
Significant Figures - Precision refers to the closeness of various measurement for the same quality.
However accuracy is the agreement of a particular value to the true value of the result. e.g. if the true
value for a result is 2g and students observations are tabulated as
Measurement
Student A 1.95 1.93 Precise, inaccurate
Student B 1.94 2.05 not Precise, inaccurate
Student C 2.01 1.99 Precise, accurate
Significant figures are meaningful digits which are known with certainty.
Rules for determining the number of significant figure.
1) All non zero digits are significant. For example in 285 cm, there are three significant figures, in
0.25 m, there are two significant figures.
2) Zero preceding to first non zero digit are not significant. 0.03 has one significant figure, 0.88 has
2 significant figures.
3) Zeros between two non zero digits are significant, 2.005 has four significant figures.
4) Zeros at the end or right of a number are significant provided they are on the right side of the
decimal point. e.g. 0.200 has 3 significant figures. But if otherwise the zeros are not significant
e.g. 100 has only one significant figure.
5) Exact numbers have an infinite number of significant figures e.g. 2 balls or 20 eggs there are
infinite significant figures because 2 = 2.0000.......(Countable objects)
(In first rule numbers are quantities)
6) When numbers are written in scientific notation the number of digits between 1 and 10 gives the
number of significant figures. e.g. 4.01 × 102 has 3 significant figures.
Mathematical operations:-
1. While adding or subtracting, the result cannot have more digits to the right of the decimal point
than either of the original numbers. e.g. 12.11+18.0+1.012 = 31.122, have result is reported as
31.1.
2. The result of a multiplication or division should be reported to the same number of significant
figures as is possessed by the least precise term used in the calculation e.g. 2.5 × 1.25 = 3.125,
the result is reported as 3.1
Rules to Round Off :- If right most digit is to be removed

1) last digit is more than 5 the preceding number is increased by one.
2) last digit is less than 5, the preceding number is not changed.
3) last digit is 5 and preceding digit is even, then no change and if preceding digit is odd, then
increase by one.

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Dimensional Analysis
It is used to convert units from one system to other. Also known as unit factor or factor label method.
e.g.
It is known that 1 inch = 2.54 cm
1inch 2.54 cm
or 2.54 cm  1  1inch
Laws of Chemical Combinations

1. Law of conservation of Mass - Matter can neither be created nor destroyed.
2. Law of definite proportions - A given compound always contains exactly the same proportion
of elements by weight.
3. Law of Multiple Proportions - If two elements can combine to form more than one compound,
the masses of one element that combine with a fixed mass of the other, element, are in the ratio
of small whole numbers.
4. Gay Lussac’s Law of gaseous volumes - When gases combine or are produced in a chemical
reaction they do so in a simple ratio by volume provided all gases and at same temperature and
pressure.
5. Avogadro Law - Equal volumes of gases at the same temperature and pressure should contain
equal number of molecules.
Atomic and Molecular Masses
1 amu = 1 u (unified masss) = 1.66 × 10-24g
= Mass exactly equal to one twelfth the mass of one carbon - 12 atom.
Average Atomic Mass
If different isotopes of element have different relative abundance the atomic mass can be calculated
as:-
Isotope Abundance Atomic Mass
12
C 98.892 % 12
13
C 1.108 % 13.0033
14
C 2×10-10 14.00317
Average atomic Mass = (0.98892) (12)u + (0.01108) (13.00335)u + (2×10-12) (14.00317)u.

= 12.011 u.
Molecular Mass and Formula Mass

Molecular Mass is the sum of atomic masses of the elements present in a molecule.
Formula Mass is the sum of atomic masses of the elements present in simplest formula of ionic com-
pound.
Mole Concept
One mole is the amount of a substance that contains as many particles or entities as there are atoms in
exactly 12g of the 12 C isotope. 1 mol = 6.022 × 1023 entities. (Avogadro’s Number)

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The mass of one mole of a substacne in grams is called its molar mass.
Percentage Composition
Mass % of an element = mass of that element in compound × 100
Molar mass of compound.
Empirical Formula. It represents the simplest whole number ratio of various atoms present in a
compound whereas the molecular formula shows the exact number of different types of atoms present
in a molecule of a compound.
Stoichiometry
When a chemical equation is written in the balanced form, it gives quantitative relationships between
the various reactants and products in terms of moles, masses, molecules and volumes.This is called
stoichiometry. The coefficients of the balanced chemical equation are called stoichiometric coeffi-
cients
The general method of calculations for the problems consists of the following steps:
(i) Write down the balanced chemical equation.
(ii) Write the relative number of moles or the relative masses of the reactants and products below their
formulae.
(iii) In case of gaseous substances, write down 22.4 L of STP below the formula in place of 1 mole.
(iv) Apply unitary method to make the required calculations.
Limiting Reagent - The reactant which gets completely consumed in a reaction is called limiting agent or
limiting reactant.
The reactant which is not consumed completely in the reaction is called excess reagent.
Example:
3.0g of H2 reacts with 29.0g of O2 to form H2O.
(i) Which is the limiting reactant?
(ii) Calculate the maximum amount of H2O that can be formed? (iii) Calculate the amount of
water left unreacted.
Solution:
2 H 2 ( g )  O2 ( g )  2 H 2O( g )
4g 32 g 36 g
4g of H2 require O2 = 32g
32
3g of H2 require O2 =  3  24 g
4
Thus O2 (29g) is present in excess. Thus H2 is the limiting reactant.

5
36
Amount of H2O formed =  3  27 g
4
O2 left unreacted = 29 - 24 = 5.0g
Reactions in Solutions:- Concentration of solution can be expressed in numerous ways:-
Mass of solute
1. Mass percent = Mass of solution 100
No. of mole of B
2. Mole fraction (B) = No. of moles of B  No. of moles of A
No. of moles of solute

3. Molarity = volume of solution in litres
No. of moles of solute

4. Molality = Mass of solvent in kg .
Massof A
5. Parts per millionparts( ppmA )  1000000
Massof solution
Mass of solute( g )
6. Strength 
Volume of solution( L)
Molarity equation:
If a solution having molarity M1 and volume V1 is diluted to volume V2 so that the new molarity is M2,
then as the total number of moles in the solution remain the same, we have
M 1  V1  M 2  V2
During titration at equivalent point following formula holds.
n1× M1× V1 = n2× M2× V2 where n stands for no of electrons transferred for the given reactant

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Chapter - 2
Structure of Atom
Sub Atomic Particles :-
Dalton’s atomic theroy was not able to explain the results of many experiments like generation of
electricity upon rubbing glass or ebonite with silk or fur generate electricity.
Electron
Cathode ray tube experiment led to following conclusions:
1) The Cathode rays start from Cathode and move towards the anode.
2) These are invisible their behaviour can be observed with the help of certain kind of materials
(fluorescent or phosphorescent) which glow when hit by them.
3) In the absence of electrical or magnetic field these rays travel in a straight lines.
4) In the presence of electrical or magnetic field the behaviour of Cathode rays are similar to that
expected from negatively charged particle suggesting that the cathode rays consist of negatively
charged particles called electrons.
5) The characteristics of Cathode rays (electrons) do not depend upon the material of electrodes
and the nature of the gas present in the cathode ray tube.
e 11 1
Charge to Mass Ratio of Electron, m 1.75882010 C kg
e
(This was measured by British Physicist - J.J. Thomson)
Charge on the electron was determined by R.A. Millikan through oil drop experiment.
e = 1.6022 × 10-19C
 me = 9.1094 × 10-31kg
Protons and Neutrons

The modified Cathode ray tube led to the discovery of particles carrying positive charge called canal
rays. The characteristics of these positively charged particles are listed below:-
1. The charge to mass ratio of the particles is found to depend on the gas from which these
originate. These are simply the positively charged gaseous ions.
2. The behaviour of these particles in the magnetic or electrical field is opposite to that observe for
electron or Cathode rays.
The smallest positive ion was from hydrogen called Proton - Goldstein.
Neutrons were discovered by Chadwick by bombarding a thick sheet of beryllium by  par-
ticles.

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Important Terms
1) Atomic Number (Z) = no. of protons in nucleus of atom.
= no. of electrons in a neutral atom.
2) Mass Number (A) = no. of protons + no. of neutrons.
3) Isobars - Atoms of two different elements having same atomic mass numbers (different atomic
numbers).
4) Isotopes - Atoms of same element having different atomic mass numbers (same atomic num-
bers).
Developments leading to the Bohr’s Model of Atom:-

1. Dual character of electromagnetic radiation.
2. Experimental results regarding atomic spectra which can be explained only be assuming quan-
tized electronic energy levels in atoms.
Dual nature of electromagnetic radiations

a) Wave nature, feature:-
i) delocalised energy
ii) characterised by wavelength, frequency and speed. For electromagnetic radiation speed
is represented by c and expression is c  λ ν
c has value 2.997925 × 108 ms-1
iii) In electromagnetic radiation the oscillating electronic and magnetic fields produced by
oscillating charged particles are perpendicular to each other and both are perpendicular to
the direction of propagation of the wave.
b) Particle nature of electromagnetic radiation. Some observations regarding electromagnetic

radiation can only be accounted for when it is considered as particle. e.g.
1) Black body radiation
2) Photo electric effect
3) Variation of heat capacity of solids as a function of temperature.
4) line spectra of atoms.

8
Planck suggested that atoms and molecules could emit (or absorb) energy only in discrete
quantities and not in a continuous manner.
E  h (h is Planck' s Constant  6.626  10 34 Js )

Photo electric effect:- The ejection of electrons when metal surface is exposed to a beam of
light having particular threshold ferquency.
h ν  h ν   1 2 m ev 2
h   is also called work function and 1

2 me v 2
is kinetic energy..
Atomic Spectrum - Continous spectrum (eg-rainbow )

- Line spectrun - emission spectrum
- absorption spectrum
White light consists of waves with all the wavelengths in visible region, a ray of white light is spread out
into a series of coloured bands called spectrum. Such spectrum is called continuous spectrum.
Line Spectrum:- The emission spectra of atoms in the gas phase, do not show a continuous spread
of wavelength from red to violet, rather they emit light only at specific wave lengths with dark spaces
between them. Such spectra are called line spectra or atomic spectra.
Line Spectrum of hydrogen :- for hydrogen spectrum the wave number  can be given by
 1 1 
 109677  2
 2  cm 1
 n1 n2 
Where n is the principal quantum number.

Emission Spectra:- The spectrum of radiation emitted by a substance that has absorbed energy is
called an emission spectrum. To produce emission spectrum, energy is supplied to a sample by heat-
ing it or irradiating it and the wavelength of the radiation emitted.
Absorption Spectra:- It is like the photographic negative of an emission spectrum. A continuum of
radiation is passed through a sample which absorbs radiation of certain wavelengths. The missing
wavelength which corresponds to the radiation absorbed by the matter, leave dark spaces in the
bright continuous spectrum.
Bohr’s Model for Hydrogen atom

1. Electrons in an atom, revolve around nucleus in circular paths called stationary states.
2. Energy transaction takes place only when electron jumps from one stationary state to another.
3. The frequency of radiation absorbed or emitted when transition occurs is given by:-
(E1 energy of lower state)
- Bohr’s frequency rule.
4. Angular momentum of an electron in a given stationary state is :-
E E2  E1
h   
me  r  n. n  1, 2, 3...... h h
2

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Radius of stationary state can be given by rn  n 2 a , a  52.9 pm.
 1 
Energy of stationary, state can be given by En   RH  2  RH is called Rydberg contant.
n 
RH = 2.18×10-18 J.
Formulae can be modified to hydrogen like systems also.
Z 2
E n   2.18 1018  2  J
n 
52.9 n 2
rn  pm .
Z
(Z is atomic number)
Limitations of Bohr’s Model
1. It fails to account for finer lines (doublet) of hydrogen atom spectrum.
2. Bohr’s theroy was unable to explain Stark and Zeeman effects.
3. It could not explain the ability of atoms to form molecules by chemical bonds.
Cause of Failure
1. Did not consider wave nature of electrons.
2. Ignored. Heisenberg’s and deBroglie’s findings.
Development of Quantum Mechanical Model:-
Two important developments which contributed in formulation of quantum mechanical model were:
1) Dual behaviour of matter.
2) Heisenberg’s uncertainty principle.
1) Dual behaviour of matter:- deBroglie in 1922 put forth the idea of matter waves and experi-
mentally proved that also
h
λ  is wavelength of matter wave
mv
h = Planck’s constant, m is mass of moving particle, v is the velocity of moving particle.
(Note - matter behaves as wave, not that it becomes source/emitter of waves).
2) Heisenberg’s Uncertainity Principle:- It is important to determine simultaneously the exact
position and exact momentum of an electron.
h
x  Px 
4
x is uncertainty in position, Px is uncertainty in momentum in x direction.

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Significance of Uncertainty Principle :-

1. It rules out existence of definite paths or trajectories of electrons and other similar particles.
2. The effect of Heisenberg Uncertainty Principle is significant only for motion of mircoscopic
objects and is negligible for that of macroscopic objects.
It, therefore means the precise paths must be replaced by probable regions in case of electrons.
This is what is taken care in quantum mechanical model.
Quantum Mechanical Model of Atom
It was developed independently in 1926 by Werner Heisenberg and Erwin Schrodinger.
This model is based on Schrodinger wave equation.
H   E H is Hamiltonian
Operator  is wave function of electron wave E is energy..
Quantum Numbers:-
Complex mathematical calculations to solve Schrodinger wave equation lead to possible energy
levels which electrons can occupy. These energy levels are associated with three quantum numbers :-
a) principal (n), can have values 1, 2, 3 ........ signifies size of orbitals.
b) azimuthal (l), can have values 0 to (n-1) signifies, shapes of subshells in orbitals.
c) magnetic (me), can have vlaues -l to 0 to +l, signifies orientation of orbitals in space.
These quantum numbers are not enough to explain finer lines thus another quantum number spin m was
proposed and supported values it can attain are +½ and -½.
Shapes of Orbitals
, the orbital wave function has no physical meaning but it represents amplitude of wave but
 2 has physical significance. Latter represent probability density of electrons.
Nodes :- The region where probability density function reduces to zero is called node. The total
number of nodes is (n-1) out of which. l are angular nodes and (n-l-1) are radial nodes.
Energies of orbitals - Orbitals with same energies are called degenerate.
Lower is the value of (n+l) for an orbital, the lower is its energy. If two orbitals have the same
value of (n+l) the orbital with lower value of n will have lower energy.
Boundary surface diagrams for various orbitals
z z
x x x
y y y
2Px 2Py 2Pz
1s 1s

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Filling of Orbitals in Atom (Electronic Configuration) Following rules are followed while writing elec-
tronic configurations of elements.
a) Auf bau’s Principle :- In the ground state of the atoms, the orbitals are filled in order of the
increasing energies.
b) Pauli Exclusion Principle :- No two electrons in an atom can have the same set of four quantum
numbers.
c) Hund’s Rule of Maximum Multiplicity :- Pairing of electrons in the orbitals belonging to same
subshell does not take place until each orbital belonging to that subshell has got one electron
each i.e. it is singly occupied.
Stability of completely filled and half filled Subshells. They have extra stability due to -
1) Symmetrical distribution of electrons
2) Exchange energy
Examples
Electronic Configuration of Sodium (11) 1s 2 2s 2 2 p 6 3s 1
Vanadium (23) 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 3 4s 2
Chromium (24) 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5 4s 1
Boundary Surface Diagram for d orbitals

12
Chapter - 3
Classification of Elements & Periodicity In Properties
Historical Development of Periodic Table
1. Lothar Meyer arrangement

He plotted a graph between the atomic volumes and atomic weights of the elements and observed
that the elements with similar properties occupied similar positions on the curve.
eg.:
The most strongly electropositive alkali metals (Li, Na, K, Rb and Cs) occupy the peaks on the
curve.
2 MENDELEEV’S PERIODIC LAW
The physical and chemical properties of elements are a periodic function of their atomic weights i.e.
when the elements are arranged in order of their increasing atomic weights, elements with similar
properties were repeated after certain regular intervals.
Characteristics of Mendeleev’s Periodic Table

1) Eight vertical columns called groups
2) Six horizontal rows called periods
Significance of Mendeleev’s Periodic Table
1) Systematic Study of the elements
2) Prediction of properties of undiscovered elements.
3) Correction of doubtful atomic weights
Defects of Mendeleev’s Periodic Table
1) Anomalous position of hydrogen
2) Anomalous pairs of elements
3) Position of Isotopes
4) Some dissimilar elements are grouped together while some similar elements are placed in differ-
ent groups.
5) Position of elements of group VIII.
3. Modern Periodic Law(Henry Moseley)
Modern Periodic Law states that physical and chemical properties of the elements are periodic
function of their atomic numbers i.e. if the elements are arranged in order of their increasing atomic
numbers, the elements with similar properties are repeated after certain regular intervals.

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Present form or Long Form of the Periodic Table - Bohr’s Table

Features
1) 18 vertical columns called groups or families.
2) 7 horizontal rows called periods.
3) 14 elements of 5th period called the lanthanoids and 14 elements of the seventh period called
the actinoids are placed in separate panels at the bottom.
IUPAC Nomenclature of Elements with Atomic Number > 100
The new element first gets a temporary name, with symbol country of three letters. Later permanent
name and symbol are given by a vote of IUPAC representative from each country. The permanent
name might reflect the country (or state of the country) in which the element was discovered or pay
tribute to a notable scientists.
The IUPAC has made a recommendation that until a new element’s discovery is proved, and its name
is officially recognized, a systematic nomenclature is derived directly from the atomic number of the
element using the numerical roots for 0 and numbers 1-9. The roots are put together in order of digits
which make up the atomic number and ‘ium’ is added at the end.
Notation for IUPAC Nomenclature of Elements
Digit Name Abbreviation

0 nil n
1 un u
2 bi b
3 tri t
4 quad q
5 pent p
6 hex h
7 sept s
8 oct o
9 enn e
Electronic Configuration
We follow Auf Bau’s Principle.
Block Division of Periodic Table
I s-block elements - Groups 1 and 2
with general outer electronic configuration ns1-2
Group 1 - Alkali metals
Group 2 - Alkaline earth metals
II p-block elements - Groups 13 to 18
with general outer electronic configuration ns2 np1-6
Group 16 - Chalcogens
Group 17 - Halogens

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Group 18 - Noble gases

s-block and p-block elements are together called Representative elements.
III d-Block elements- Groups 3 to 12
Transition elements
General outer electronic configuration: (n-1)d1-10ns0-2
IV f - block elements
includes lanthanoids and Actinoids.general configuration (n-2) f1-14 (n-1) d0-1 ns2
Inner transition elements.
Periodic Trend in properties of elements
Atomic Radius
It refers to both Covalent and Metallic radius.
Covalent Radius: It is one half the distance between the nuclei of two covalently bonded atoms of the
same element in a molecule.
Metallic Radius: It is defined as one half the internuclear distance between the two adjacent metal ions
in the metallic radius.
Van der Waals Radius: It is defined as one half the distance between the nuclei of two identical non
bonded isolated atoms or two adjacent identical atoms belonging to two neighbouring molecules of an
element in the solid state.
Van der Waals radius > metallic radius > covalent radius.
Variation of Atomic Radii in the Periodic Table

Variation along a period
In general, the atomic radius decreases across a period.
(i) The alkali metals which are at the extreme left of the periodic table have the largest size in a
period .
(ii) The halogens present at the extreme right of the periodic table have the smallest size. However in
the second period, atomic size of Nitrogen is the smallest. It increases for oxygen and then
decreases for fluorine.
(iii) The size of the atoms of noble gases are larger than those of preceding elements. Inert gases are
expresssed in terms of van derWaals radius which is greater than covalent radius.
Explanation
Within the period the outer electrons are in the same valence shell and effective nuclear charge increases
as the atomic number increases resulting in the increased attraction of electrons to the nucleus.
Variation within a group
The atomic radii of elements increase with increase in atomic number as we move from top to bottom in a
group.

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Explanation
As we move down the group, a new energy shell is added at each succeeding element.With the increase in
atomic number, nuclear charge also increases. As a result, the force of attraction of the nucleus for the
electrons should increase and hence the atomic radii should decrease. But the effect of increased nuclear
charge is considerably reduced due to shielding effect on the valence electrons by the electrons present in
the inner shells. Thus the increase in atomic radii down the group is primarily due to the addition of new
energy shell.
Ionic Radii
Ionic radius may be defined as the effective distance from the centre of the nucleus of the ion upto which it
exerts its influence on its electronic cloud.
The size of the cation (formed by the loss of electron) is smaller than the corresponding atom due to (i)
decrease in the number of shells (ii) increase in the effective nuclear charge resulting in greater force of
attraction by the nucleus on the electrons.
The ionic radii of cations increase as we move down the group due to an increase in the number of shells.
The radius of the anion is always larger than its parent atom mainly because of decrease in the effective
nuclear charge i.e lesser for of attraction by the nucleus on the electrons.
The ionic radii of anions increase as we move down the group due to an increase in the number of shells.
Isoelectronic ions or species

Ions of different elements which have the same number of electrons but different magnitude of nuclear
charge.
Ionic radii of isoelectronic ions decrease with increase in the magnitude of nuclear charge.For example,
ionic radii of following isoelectronic species increase in the order:
Al3+ < Mg2+ < Na+ < F- < O2- < N3-

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IONIZATION ENTHALPY
The minimum amount of energy required to remove the most loosely bound electron from an
isolated gaseous atom so as to convert it into a gaseous cation is called its ionization enthalpy.
It is measured in units of electron volts (eV) or kilo calories per mole (kcal mol-1) or kilo Joules
per mole (kJ mol-1).
The ionization enthalpies required to remove first, second, third etc.electrons from an isolated
gaseous atom are called successive ionization enthalpies.
M ( g )   i H1  M  ( g )  e  ( g )
M  ( g )   i H 2  M 2 ( g )  e  ( g )
M 2 ( g )   i H 3  M 3 ( g )  e  ( g )
It may be noted that
 i H 3   i H 2   i H1
Explanation:
When one electron has been removed from the neutral gaseous atom, the positively charged ion
formed has one electron less than the number of protons in the nucleus. As a result, electrostatic
attraction between the nucleus and the remaining electrons in the cation increases i.e. effective
nuclear charge increases. Therefore energy required to remove another electron from positively
charge ion is more.
Factors affecting Ionization enthalpy:

1. Nuclear charge: The ionization enthalpy increases with increase in nuclear charge.
2. Atomic size: Ionization enthalpy decreases as the atomic size increases.
3. Screening effect of inner electrons: As the shielding or screening effect of the inner elec
trons increases, the ionization enthalpy decreases.
4. Penetration effect of electrons: Ionization enthalpy increases as the penetration effect of
the electrons increases. s-electrons of any shell are closer to the nucleus than p electrons of
the same shell. Thus, within the same shell, the penetration effect decreases in the order:
s>p>d>f
5. Electronic configuration:
If an atom contains exactly half filled or completely filled orbitals, then such an arrangement
has extra stability. Therefore, the removal of an electron from such an atom requires more
energy than expected.
Variation of Ionization Enthalpy in the Periodic Table:
Variation along a period:

As we move from left to right in a period, the ionization enthalpy increases with increasing atomic
numbers.
As we move across a period the nuclear charge increases and the atomic radius decreases though
the principal quantum number of the valence shell remains the same. The valence electrons are
more and more tightly held by the nucleus. Consequently, more and more energy is required to
remove the electron and hence ionization enthalpies keep on increasing.
Some elements show irregularities in the general trend.
These are due to (i) type of electron to be removed (ii) the extra stability of the exactly half filled

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and completely filled electronic configuration.
Let us consider the first ionization enthalpies of the elements of the second period:
Li to Be: As we move from Li to Be, the ionization enthalpy increases due to increased nuclear
charge and smaller atomic radius of Be as compared to that of Li.
Be to B: Although the nuclear charge of B is more than that of Be, yet the ionization enthalpy of B
is lower than that of Be. This is due to the following reasons:
(a) The electronic configuration of B (1s2 2s2 2p1) is less stable than that of Be (1s2 2s2)
(b) The outermost electron in B is present in 2p-orbital while in Be it is present in 2s-orbital. s-
electrons are more closer to the nucleus, thus difficult to remove.
Be to B to C: The first ionization enthalpies of these elements increases in order due to progres-
sively increasing nuclear charge and decreasing atomic radius.
N to O: The first ionization enthalpy of oxygen is lower than that of N although the nuclear charge
of oxygen is greater than nitrogen.. This is because Nitrogen has exactly half filled configuration
which is more stable( 1s2 2s2 2px1 2py1 2pz1 ). Thus it is difficult to remove electrons from Nitrogen
as compared to oxygen.
O to F to Ne: The first ionization enthalpy increases from O to F because of increasing nuclear
charge. Neon, being a noble gas has the highest first ionization enthalpy amongst the elements of
seccond period because of its stable electronic configuration.(1s2 2s2 2p6)
Variation within a Group:
The ionization enthalpies of elements keep on decreasing regularly as we move down a group from
one element to other. This is because the combined effect of increase in atomic size and screening
effect more than compensates the effect of increased nuclear charge. Thus the valence electrons
become less and less firmly held by the nucleus and hence the ionization enthalpies gradually de-
crease as we move down the group.
Electron Gain Enthalpy (  eg H )
Electron gain enthalpy of an element may be defined as the energy released when a neutral isolated
gaseous atom accepts an extra electron to form gaseous negative ion.
X ( g )  e  X  ( g ) H   eg H
Greater the amount of energy released in the process, more negative is the electron gain enthalpy of
the element.
Electron gain enthalpy of an element is the measure of the firmness or strength with which an extra
electron is bound to it.
It is measured in eV per atom or kJ per mole.
After the addition of one electron the atom becomes negatively charged. The addition of second
electron to the negatively charged ion is opposed by electrostatic repulsion and hence energy has to
be supplied for the addition of second electron.Thus the second gain enthalpy of an element is

18
positive. For example, when an electron is added to oxygen atom to form O- ion, energy is released
but when another electron is added to O- ion to form O2- ion, energy is absorbed to overcome the
strong electrostatic repulsion between the negatively charged O- ion and the second electron being
added.
Variation of Electron Gain Enthalpies in the Periodic Table
Variation along a period:

Electron gain enthalpy becomes more negative from left to right in a period. This is because as we
move across a period the atomic size decreases and the nuclear charge increases. Both these
factors tend to increase the attraction by the nucleus for the incoming electron.Thus electron gain
enthalpy becomes more and more negative as we move from left to right in a period.
Variation within a group:
The electron gain enthalpy becomes less negative as we move from top to bottom in a group.Down
the group, both atomic size and nuclear charge increase. But the effect of increase in atomic size is
much more pronounced than the nuclear charge. Thus, with increase in atomic size, the attraction of
the nucleus for the incoming electron decreases and hence the electron gain enthalpy becomes less
negative.
Some important Trends in Electron Gain Enthalpies
1. (a) Halogens have the most negative electron gain enthalpies. Halogens have electronic con
figuration ns2 np5. Since they require only one electron to become stable, they have a
strong tendency to accept an electron and hence their electron gain enthalpies are more
negative.
(b) The electron gain enthalpy of F is unexpectedly less negative than that of Cl. This is due to
its small size, the electron electron repulsions in the relatively compact 2p-subshell are
comparitively large and hence the incoming electron is not accepted with ease.
(c) As we move from Cl to I, the electron gain enthalpies become less and less negative due
to corresponding increase in atomic size. As the distance of the nucleus from the subshell
which recieves the additional electron increases, the force with which it is attracted by the
nucleus decreases.
Note-Similarly election gain enthalpy of O is less negative then that of S.
2. The electron gain enthalpy of noble gases is positive. The atoms of these elements have com
pletely filled subshells. There is no room for an additional electron. As a result energy has to be
supplied to add an additional electron. The electron gain enthalpy of Helium is unexpectedly
lowest of all the noble gases.
Electronegativity
Electronegativity of an element is the tendency of its atom to attract the shared pair of elctrons
towards itself in a covalent bond. It is the property of an atom in the bonded state. It is not a
measurable property.
A number of numerical scales of electronegativity of elements viz.Pauling scale, Mulliken-Jaffe scale,
Allred-Rochow scale have been developed. The most widely used is the Pauling scale. Linus
Pauling assigned arbitrarily a value of 4.0 to Fluorine, the element considered to have the greatest
ability to attract electrons. The electronegativity value of any given element is not constant. It varies
depending on the element to which it is bound.
Electronegativity and hence the non metallic character of elements increases across a period. while
it decreases down the group.

19
Chapter - 3 Chemical Bonding & Molecular Structure

Lewis Symbols
The symbol of the element with the valence electrons.
eg. Lewis Symbol of Lithium Li .
COVALENT BOND
Bond formed by sharing of electrons.
a) single bond
formed by sharing of one pair of electrons
eg. H2
b) double bond
formed by sharing of two pairs of electrons
eg. O 2
c) Triple bond
formed by sharing of three pairs of electrons
eg. N 2
Formal Change
Formal Change on an atom in a Lewis structure :
total number 
of valence  total number  total number 
   1
  of non bonding  of bonding 
electrons in the    2 
  electrons  electrons 
 free atom 
IONIC BOND / ELECTROVALENT BOND

* Bond formed by transfer of electrons.
* Formation of ionic compounds would depend upon.
* The case of formation of the positive and negative ions from the respective neutral atoms.
* The arrangement of the positive and negative ions in the solid that is, the lattice of the crystalline
compound.
POLAR COVALENT BOND
When covalent bond is formed between two dissimilar atoms, then the shared pair of electrons is not
shared equally.
As a result of polarizaton, the molecule possesses the dipole moment.

20
eg. HF
Dipole moment (m) = charge (q) × distance of separation (r)
unit of Dipole moment = Debye (D)
Dipole moment of HF may be represented as :
H F
The Valence Shell Electron Pair Repulsion Theory (VSEPR)
This theory provides a simple procedure to predict the shapes of covalent molecules.
There are a few postulates of VSEPR theory.
According to the (VSEPR) theory - the repulsive interaction of electron pairs decrease in the order l.P
lp-lp > lp - bp > bp - bp
Valence Bond Theory
Valence Bond Theory is based on the knowledge of atomic orbitals electronic configuration, the
overlap of atomic orbitals and the principles of variation and super position.
Types of Overlapping and Nature of Covalent Bonds
(i) Sigma ( ) Bond

(a) s - s overlapping
(b) s - p overlapping
(c) p - p overlapping
(ii) pi (Bond
(a) p - p overlapping
Hybridizations
The inter mixing of the atomic orbitals of approximately equal energy to give modecular - orbital of
same energy is called hybridization.
Type of hybridzation
a) sp - hybridization eg. ethyne
b) sp2 hybridization eg. ethene
c) sp3 hybridization eg. ethane, water, ammonia
d) sp3d hybridization eg. PCl5
e) sp3 d2 hybridization eg. SF6

21

22

23

24
VALENCE BOND THEORY

This theory is based on the knowledge of atomic orbitals, electronic configurations of elements, the
overlap criteria of atomic orbitals the hybridisation of atomic orbitals an d the principles of variation of
superposition.
When the two atoms are at large distance from each other, there is no interaction between them. As these
two atoms approach each other, new attractive and repulsive forces begin to operate.
Attractive forces arise between:
i) nucleus of one atom and its own electron that is NA -eA and NB-eB
ii) nucleus of one atom and electron of the other atom
NA -eA and NB-eB, where A and B are two atoms having nuclei NA and NB and electrons present
in them are represented by eA and eB.
Experimentally it has been been found that magnitude of new attractive force is more than the new
repulsive forces. As a result, two atoms approach each other and potential
energy decrease.
Since the energy gets released when the bond is formed between two or more atoms to form a molecule
which is more stable than that of isolated hydrogen atoms. The energy so released is called as bond
enthalpy.

25
ORBITAL OVERLAP CONCEPT

-When a molecule is formed, there is a minimum energy state and the atomic orbitals undergo partial
merging or overlapping which results in the pairing of electrons.
-The extent of overlap decides the strength of a covalent bond.
-The overlapping of atomic orbitals may be positive, negative or zero depending upon the
properties of overlapping atomic orbitals. There are depicted below.
TYPES OF OVERLAPPING AND NATURE OF COVALENT BONDS

The covalent bonds may be sigma and pi bond depending on the extent of overlap.
Sigma bond is formed by the end to end overlap of bonding orbitals along the internuclear axis and the
overlapping is to a larger extent. Hence it is always more stable than pi bond. Also a pi bond
cannot be formed before the formation of sigma bond. It is always present in the molecules
containing multiple bond. There is sideways overlapping of the atomic orbitals in pi bond.
Sigma bond can be formed between
- s-s overlapping
-s-p overlappiing
-p-p overlapping
Pi bond can be formed between

-p-p sidways overlapping

26

27
Molecular orbitals obtained from 2px and 2py orbitals are not symmetrical around the bond
axis because of the presence of positive lobes above and negative lobes below the molecu-
lar plane. They are designated as  and  *

28
Stability of molecules: If Nb is the number of electrons occupying bonding orbitals and Na the
number occupying the antibonding molecular orbitals, then
(i) the molecule is stable if Nb is greater than Na
(ii) the molecule is unstable if Nb is less than Na
Bond Order: It is defined as one half the difference between the number of electrons present in
the bonding and the antibonding orbitals. A positive bond order means a stable molecule while a
negative or zero bond order means an unstable molecule.
Magnetic nature: If all the molecular orbitals in a molecule are doubly occupied, the substance
is diamagnetic(repelled by magnetic field). If one or more orbitals are singly occupied-
paramagnetic(attracted by magnetic field)
Energy Level Diagram for Nitrogen Molecule
Electronic Configuration of N2+
Energy 

29
Energy Level Diagram for Oxygen molecule
Electronic Configuration of O2- ion
Energy 
Hydrogen Bonding
Hydrogen bond can be defined as the attractive force which binds hydrogen atom of one molecule
with the electronegative atom (F, O or N) of another molecule.
(i) The molecule must contain a highly electronegative atom (F, O, N) linked to Hydrogen atom.
(ii) The size of the electronegative atom should be small.
The magnitude of Hydrogen bonding depends on the physical state of the compound. It is maximum
in solid state and minimum in gaseous state.
Types of H - Bonds
a) Inter molecular hydrogen bond: It is formed between two different molecules of the same or
different compounds.
eg. - H-bond in case of HF molecule, alcohol or water molecules
b) Intra molecular hydrogen bond: It is formed when hydrogen atom is in between the two highly
electronegative atoms present within the same molecule.
eg. - o - nitro phenol

30
CHAPTER -5
STATES OF MATTER
Intermolecular Forces:
Forces of attraction and repulsion between interacting (atoms and molecules)
- Van der Waals forces : attractive intermolecules forces.

a) Dispersion forces or London forces : Force of attraction between two temporary dipoles.
* always attractive
1
* interaction energy  [r = distance between two particles]
r6
b) Dipole - Dipole forces : act between the molecules possessing permanent dipole.
* stronger than the London forces but is weaker than ion - ion interaction because only
partial charges are involved.
1
* interaction energy between stationary polar molecules  .
r3
1
* interaction energy between rotating polar molecules  .
r6
c) Dipole - Induced Dipole forces :
* attractive forces operate between the polar molecules having permanent dipole and the
molecules lacking permanent dipole.
* polar molecules induce dipole in the electrically neutral molecule.

31
Hydrogen bond :
is found in molecules in which highly polar N - H, O-H, H-F bonds are present.
   
e.g. H  F ........ H  F
THERMAL ENERGY
- due to motion of its atoms or molecules.
- directly proportional to the temperature of the system.
- measure of average kinetic energy of the particles.
INTERMOLECULAR FORCES Vs THERMAL INTERACTIONS :
Gas  Liquid  Solid

Predominance of intermolecular interactions.
Gas  Liquid  Solid
Predominance of thermal energy
GASES :
General physical properties
GAS LAWS :
- Boyle’s Law (P-V relationship)
1
p (at constant T and n)
v
1
p  k1 K1 = Proportionality constant value depends on the amount of the gas, temperature
v
of the gas & units of p & v.

32
p1 v1 = p2 v2 = constant
T3
T2
T1
Pressure (p) (bar)
600K
Pressure (p)
400K
200K
T1>T2>T1
3
Volume (V) (dm )
Volume (1/v)
1
Graph of pressure p vs volume V of a Graph of pressure of gas p vs
v
gas at different temperatures
CHARLES LAW : (Temperature - volume relationship)

 273.15  t 
V t V o  
 273.15 
Kelvin scale T = 273.15 + t
T 
V t V o  t 
T o 
V2 V1

T2 T1
P1
P1 <P2<P3<P4
V P2
  Cons tan t  K 2
T P3
V  K2 T
Volume
P4
GAY LUSSAC’S LAW (Pressure - Temperature Relationship)

-273.15
-300 -200 -100 0 100
Temperature(°C)

33
p
 Cons tan t  k3
T
V1
V1<V2<V3<V4
V2
V3
Pressure (p)
V4
0 100 200 300 400

Temperature(K)
Pressure vs temperature (K) graph (isochores of a gas)
AVOGADRO LAW (Volume - Amount Relationship)
V n
V  k4 n
- equal volumes of all gases under the same conditions of temperature and pressure contain equal
number of molecules.
STANDARD TEMPERATURE AND PRESSURE
(STP)
T = 273.15 K (0°C)
P = 1 bar
Ideal Gas : a gas that follows Boyle’s Law, Charles Law and Avogadro Law.
- Hypothetical
IDEAL GAS EQUATION :
1
At Constant T and n ; V  Boyles Law
P
At Constant P and n ; V  T Charles Law
At Constant P and T ; V  n Avogadros Law
nT
Thus V 
P
nT
V R
P

34
PV  nRT
R = Universal Gas Constant

= 8.314 JK-1 mol-1
Combined Gas Law :
p1v1 p2 v2

T1 T2
Density and Molar mass of a gaseous substance :
n p m
 n
v RT M
d p
 (d = density)
M RT
dRT
M
P
Dalton’s Law of Partial Pressures
The total pressures exerted by the mixtures of non-reacting gases is equal to the sum of the partial
pressures of individual gases.
p total = p1 + p2 + p3 + ................... (at constant T, V)
p dry gas = p Total - Aqueous tension

[Aqueous tension - Pressure exerted by saturated water vapour]
Partial Pressure in terms of mole fraction :
RT
p1  n1 at Temperature T,Volume V (enclosed)
V
RT
p 2  n2 Gases (1) & (2)
V
p1, p2 pressure exerted
P total = p1  p2  p3
RT RT RT
n1 n2 n3
V V V
Divide p1 by P total
p1  n1  RTV
  
P total  n1  n2  RTV
n1
  1
n
p1  1 Ptotal

35

36
KINETIC MOLECULAR THEORY OF GASES :

- Consist of large number of identical particles
- no force of attraction between particles
- Particles in constant random motion
- Particles move in all directions
- Collisions of gas molecules perfectly elastic.
- different particles have diffierent speeds and different kinetic energies.
- average kinetic energy  absolute temperature.
DEVIATION FROM IDEAL BEHAVIOUR
Faulty assumptions :
a) There is no force of attraction between molecules of gas.
b) Volume of molecules of a gas is negligibly small.
at high pressure molecular interaction operate.
an 2
 p ideal  p real 
v2
observed correction
pressure term
a = constant
The volume occupied by molecules become significant . (V - nb)
nb = total volume occupied by molecules themselves.
b = constant
 an 2 
 p  2  v  nb  n RT
 V 
a = measure of magnitude of intermolecular attractive forces & is independent of T & P.
CO
CH4
H2
Real gas
He Ideal gas
Ideal gas
pv
Pressure
0
p
0
Volume

37
Deviation from ideal behaviour can be measured by compressibility factor (Z)
PV
Z
nRT
ideal gas Z = 1 at all temperature and pressures.
Z>1 - at high pressure
- difficult to compress
- Real gases behave ideally at low pressures and high temperatures.
Boyle temperature or Boyle points - The temperature at which a real gas obeys ideal gas law over an
appreciable range of pressure.
V real
Z Real gas
V ideal
Ideal gas
Pressure
0
Volume
LIQUI FACTION OF GASES :

Critical Temperature (Tc) : The highest temperature at which liquid is observed.
Critical Volume (Vc) : Volume of one mole of the gas at critical temperature.
Critical Pressure (Pc) : Pressure at critical temperature.
LIQUID STATE : General characteristics

Equilibrium Vapour Pressure: Vapour pressure at equilibrium (between liquid phase and vapour phase).
Normal Boiling Point : at 1 atm pressure boiling temperature.
Standard boiling point : at 1 bar pressure boiling temperature.
VAPOUR PRESSURE: Liquid in an evacuated container evaporates to fill the volume & these vapours
exerts pressure which is called Vapour Pressure of that liquid.

38
SURFACE TENSION ( )
- force acting per unit length perpendicular to the line drawn on the surface of liquid.
Units Nm-1 (SI)
- lowest energy state is when surface area is minimum (i.e. why mercury drops are sphereical in
shape).
Consequences of Surface Tension :
- Sharp glass edges are heated for making them smooth.
- Liquid tends to rise (or fall) in the capillary tube.
- Spherical shapes of drops.
Variation
- Greater are the intermolecular forces , higher is the surface tension of the liquid.
- Surface tension of the liquids decreases as the temperature is raised.
VISCOSITY : is a measure of resistance to flow which arises due to internal friction between layers
of fluid as they slip past one another while liquid flows.
du du
F ηA  velocity gradient
dz dz
A = Area of cross section
 = proportionality constant (coefficient of visosity)
Units - Nsm-2 (SI)
- Poise (CGS)
1 Poise = 1g cm-1 s-1 = 10-1 kg m-1 s-1
- Greater are the intermolecular forces , higher is the viscosity of the liquid.
- Viscosity decreases as temperature rises.The kinetic energy of the molecules of the liquid in
creases which can overcome the intermolecular forces. Hence liquid flows faster

39
Chapter - 6
Thermodynamics
Universe = System + Surroundings.
Types of System -
a) Open system : Exchange of energy and matter between system and surrounding e.g. presence
of reactants in an open breaker.
b) Closed system : No exchange of matter, but exchange of energy between system and
surroundings.
e.g. presence of reactants in a closed vessel made of conducting material.
c) Isolated system : No exchange of energy or matter between the system and the surroundings.
e.g. presence of reactants in a thermos flask.
State Variables : Variables like P, V, T - values depend only on the state of the system and not on how
it is reached.
Internal Energy : (U)
- Total energy of the system.
Internal energy changes when
* heat passes into or out of the system.
* Work is done on or by the system.
* Matter enters or leaves the system.)
Work (W)
adiabatic process : no transfer of heat between the system and surroundings.
U  U B  U A
 U  W ad
+ve sign Wad = +ve work done on the system

-ve sign Wad = -ve work done by the system
b) heat (q)
q measured in terms of temperature difference
U  q when no work done at constant volume.

q = +ve heat transfer from the surroundings to the system.
q = -ve heat transfer from system to surrounding.
First Law of thermodynamics :

40
The energy of an isolated system is constant.
U  q  w
Work (Mechanical work)
(P - V work)
at constant pressure
W = - p V 
If Pressure is not constant

Vf
Vf
W = -  p dv  w   2.308 nRT log
Vi
Vi
p V= nRT
Reversible Process : If a change is brought out in such a way that the process, at any moment,
could be reversed by an infinitesimal change.
Irreversible process : process other than reversible process.
Free expansion : expansion of a gas in vacuum (pex = 0)
- no work is done
W   p V
U  q  pV
at constant volume V  0
U  qv
Isothermal and free expansion of an ideal gas :
T = Constant W =0 Since pex = 0
Joule experiment q = 0  U  0
U  q  W
1) for isothermal irreversible change
q   w  pex (V f  Vi )
2) For isothermal reversible change
Vf
q   w  nRT ln
Vi
Vf
 2.303 n RT log
Vi
3) for adiabatic change q = 0
 U  W ad

41
Enthalpy (H)
U  q p  p V
at constant pressure
qp = heat absorbed by the system
 pV = expansion work done by the system.
U 2  U 1  q p  p (V 2 V 1 )
q p  (U 2  pU 2 )  (U 1  pV 1 )
H  U  pV
q p  H 2  H 1  H
H is a state function.
- it depends on U, p and V. all are state functions.
H  U  pV (at constant p)
H  q p Heat absorbed by system at constant pressure.
H   ve exothermic reactions
H   ve endothermic reactions
H & U are not significant for solids/Liq. because there no significant change in volume upon
heating.
for gases (A & B)
pV A  n A RT , pV B  nB RT
p(VB  VA )  (nB  n A ) RT
H  U  n g RT
ng  number of moles of gaseous reactants.

pV  ng RT
Extensive Properties : Value depends on the quantity or size of matter present in the system.
e.g. - mass, volume, internal energy etc.
Intensive Properties : properties which do not depend on the quantity or size of matter present.
e.g. - temperature, density, pressure etc.

42
Heat Capacity :
q  C T C  heat capacity
C 
molar heat capacity Cm   
n
- quantity of heat needed to raise the temperature of one mole by one degree celsius (or one
Kelvin)
Specific heat capacity : Quantity of heat required to raise the temperature of one unit mass of a
substance by one degree celsium (or one kelvin).
q  C  m  T
qv Cv T  U
q p C p T  H
for one mole of ideal gas
H  U   ( pv )
H  U  RT
Cp  Cv  R
Cp  Cv  R
MEASUREMENT OF U :
- measured in bomb calorimeter
- no work done as reaction carried out at constant volume ( V  0)
MEASUREMENT OF H :

43
ENTHALPY CHANGE :
rH - The enthalpy change of a chemical reaction.
rH   ai H - b H
i reactants
ai & bi - Stoichiometric coefficients of products and reactants respectively in a balanced chemical

equation.
- Standard enthalpy of reaction when all the substances are in their standard states.
Standard State - of a substance at a specified temperature in its pure form at 1 bar.
changes during phase transformations :
 fus H o
- standard enthalpy of fusion
- the enthalpy change that accompanies melting of one mole of a solid substance in
standard state.
 vap H o
- standard enthalpy of vaporization
- Amount of heat required to vaporize one mole of a liquid at constant temperature

and under standard pressure.
 sub H o
- standard enthalpy of sublimation is the change in enthalpy when one mole of a solid
substance sublime at a constant temperature and standard pressure.
f Ho - standard molar enthalpy of formation.
- The standard enthalpy change for the fomration of one mole of a compound from
its elements in their most stable state.
- f H o of an element in reference state is taken as zero.

44
Hess’s law of constant Heat Summation : If a reaction takes place in several steps then its stan-
dard reaction enthalpy is the sum of the standard enthalpies of the intermediate reaction into which the
overall reaction may be divided at the same temperature.
rH  rH1  rH 2  rH 3 ...............
cH o - Standard enthalpy of combustion

- enthalpy change per mole of a substance when it undergoes combustion and all the
reactants and products being in their standard states at the specified temperature.
aH o - Enthalpy of atomization

- Enthlapy change on breaking one mole of bonds completely to obtain atoms in the
gas phase.
 bond H o
- Bond Enthalpy
Bond dissociation enthalpy : Change in enthalpy when one mole of covalent bonds of a gaseous
covalent compound is broken to form products in the gas phase.
rH o   bond enthalpies reactants -  bond enthalpies products
 Sol H o
- Enthalpy of solution
- Enthalpy change when one mole of its dissolves in a specified amount of solvent.
Enthalpy of Solution at infinite dilution is the enthalpy change observed on dissolving the sol-
vent when the interaction between the ions are negligible.
Ionic compound (AB) dissolves as
sol H o   Lattice H o   hyd H o
sol H o = +ve dissociation process is endothermic
 solubility of most salts in water increases with rise of temperature.

* If Lattice enthalpy is high, the dissolution does not take place.
Lattice Enthalpy - the enthalpy change which occurs when one mole of an ionic compound
dissociates into its ions in gaseous state.
Born - Haber Cycle -

45
Spontaneous process - is an irreversible process and may only be reversed by some external agency.
Entropy (S)
- measure of degree of randomness or disorder in the system.
- decrease of regularity in structure there is increase in entropy.
- is a state function
- A system at higher temperature has greater randomness in it than one at lower temperature
qrev, sys
S 
T
S Total =  S system +  S Surr > 0
S = 0 System is in equilibrium Entropy is maximum
Stotal decides the spontaniety of the process
* neither decrease in enthalpy non increase in entropy alone can determine the direction of spon-
taneous change for the system (closed or open system)
Gibbs Energy (G)
G = H - TS
- is an extensive property
- a state function
Gsys = H sys – TS sys – S sys  T

46
at T = 0
Gibbs Energy (G)
G  H  TS
- is an extensive property
- a state function
 Gsys   H sys  TS sys  S sys T at T  0
 Gsys  H sys  TS sys
STotal  S sys  S surr
H surr H sys
S surr  
T T
H sys
STotal  S sys  ( )
T
T S total  TS sys  H sys
for spontaneous process S total  0
T S sys  H sys  0
  ( H sys  T S sys )  0
 G  0
G  H  T S  0
H sys  enthalpy change of a reaction
TS sys = is the energy which is not available to do useful work.
G = net energy available to do useful work & is a measure of free energy..

= gives a criteria for spontaneity. at constant pressure and temperature.
i) G = -ve (<0), the process is spontaneous.
ii) G = +ve (>0) the process is non spontaneous.
Note :
H   ve , S   ve
It can be spontaneous TS is large to outweigh H :
a) S   ve but small So T is large.

47
 reactions are often carried out at high temperature.

b) S   ve but large So T is small
Gibbs Energy Change and Equilibrium
Sign and magnitude of the free energy change of a chemical reaction.
a) Prediction of spontaneity of the chemical reaction.
b) Prediction of the useful work that could be extracted from it.
- at equilibrium the free energy of the system is minimum.
rG  0
0  RG  RT ln K
rG   RT ln K
rG   2.303 RT log K
rG  rH   T rS    RT ln K

For endothermic reactions -
rH   large and +ve
 K  1
the reaction is unlikely to form much product.
For exothermic reactions -
rH   Large and –ve
rG  = is Large and –ve
 K  1
The reaction can go to completion
Effect of Temperature on Spontaneity of Reactions
rH  rS  rG  Description*

- + - Reaction spontaneous at all temperature
- - - (at low T) Reaction spontaneous at low temperature
- - + (at high T) Reaction nonspontaneous at high temperature
+ + + (at low T) Reaction nonspontaneous at low temperature
+ + - (at high T) Reaction spontaneous at high temperature
+ - + (at all T) Reaction nonspontaneous at all temperature

48
* The term low temperature and high temperature are relative. For a particular reaction, high
temperature could even mean room temperature.
Limitations of Thermodynamics:
It tells about the direction and feasiblity of the change but not the speed of the same.
This problem is tackled in Chemical Kinetics.
Third law of thermodynamics
Entropy of perfectly crystalline substance is zero at absolute zero .

49
Chapter - 7
Equilibrium
EQUILIBRIA INVOLVING PHYSICAL CHANGES.
- The equilibrium achieved in physical processes like dissolution of salt, evaporation of water etc.
is called physical equilibrium.
Examples -
a) Solid - Liquid Equilibrium
- At m.pt the solid substance is in equilibrium with the liquid state of substance.
Ice Water (at 273 K)
or H2O(s) H2O (l). (Amt of ice & water become constt.)
Rate of melting = Rate of freezing.
b) Liquid - Vapour Equilibrium
- Evaporation of water in a closed vessel.
H2O (l) H2O(g) Rate of evaporation = Rate of condensation
Vapour Pressure - The pressure exerted by the vapours in equilibrium with the liquid at a
particular temperature is called vapour pressure of the liquid. -
The vapour pressure of a liquid is constant at a given temperature. It does not depend up on the
liquid or size of the vessel.
c) Dissolution of solids in liquids.
A solution in which no more solute can be dissolved is called a saturated solution.
The saturated solution corresponds to the state of equilibrium.
e.g. Sugar (in solution) Sugar (solid)
Dynamic nature of equilibrium can be demonstrated by adding radioactive sugar into
a saturated solution of non-radioactive sugar. The solution and the rest of the non
radioactive sugar both become radioactive.
Rate of dissolution = Rate of precipitation.
Solubility of solid in liquid depends upon temperature.
Pressure does not have any significant effect on the solubilities of solids in liquids.
d) Dissolution of gases in liquids.
Henry’s Law :
The mass of a gas dissolved in a given mass of a solvent, at a given temperature, is directly
proportional to the pressure of the mass above the solvent.
p  m or
p = KHx
e.g. soda water bottle
At a given pressure

50
CO2(gas) CO2 (in solution)

When soda water bottle is sealed the gas it at high pressure, appreciable amount of CO2 is
dissolved in water.
When bottle is opened the pressure of gas above the solution decreases the dissolve gas es-
capes to attain a new equilibrium state. The solubility of a gas in a liquid with increase in tem-
perature.
Equilibrium in Chemical Process
Reversible and Irreversible reactions
Irreversible reactions :
The rections in which the products do not react under any condition to give back reactants are
called irreversible reactions. e.g. 2Na + 2H2O  2NaOH + H2.
Reversible reactions :
The reactions in which products under suitable condition react to give back reactants are called
reversible reactions. e.g. H2+I2 2HI
Equilibrium State
The state of equilibrium is a state in which the measurable properties of the system do not
undergo any noticeable change under a particular set of conditions.
Attainment of Equilibrium State
Hydrogen and Iodine are taken in a closed vessel maintained at 717K,
Initially
H2(g) + I2(g)  2HI(g) (1)
As molecules of HI are formed
2HI(s)  H2(g) + I2(g) (2)
As reaction progresses,
(i) Concentration of H2(g), I2(g) decrease, therefore rate of 1st reaction slows down.
(ii) Conc. of HI (g) increases rate of 2nd reaction increase.
H2(g) + I2(g) 2HI(g)
When, rate of forward reaction = rate of backward reaction
Equilibrium is attained
Graphically:
Equilibrium
Reaction rate
HI HI
H,
conc 2 +
I2
Fo
rw
su ard 2HI Equilibrium
m
H2, I2 I2
m rd
I2
su wa
,+
ck
H 2
Ba
I
2H
Time Time

51
Characteristics of chemical Equilibrium

1. Chemical equilibrium is dynamic in nature.
2. The observable properties of the system such as pressure, colour, concentration etc. become
constant at equilibrium.
3. The equilibrium can be attained from either direction.
4. The equilibrium can be attained only if system is closed.
5. A catalyst does not alter the equilibrium point.
Law of Mass Action and Equilbrium Constant.

Law of Mass Action
For any general reaction ,
aA + bB  cC + dD
The rate of the reaction, r   Aa B b
r  k  A B 
a b
A, B Molar concentrations of A and B.

k = rate constant
Law of chemical Equilibrium
For a general reaction
aA + bB cC + dD
Rate of forward reaction = kf  Aa Bb  Rate of backward reaction = kb C c Dd
At equilibrium, Rate of forward reaction = Rate of backward reactio|

k f A B   k b C  D 
a b c d
Kc 
Kf

C c Dd
Kb Aa B b
K c = Equilibrium constant

52
Concentration quotient
Qc 
C c D d
Aa B b
Qc  K c
Qc  K c
Qc  K c
Equilibrium constant in gaseous system.
Kp 
 pc c  pD d
PA a  pB b
p A , pB , pc , pD  partial pressures
Relationship between Kp and Kc

for ideal gas, pv = nRT
n
p  RT
v
= CRT
p A  C A RT pc  Cc RT
pB  C B RT pD  C D RT
Kp 
Cc RT c CD RT d
C A RT ]a CB RT b

C c  C D 
c d
. ( RT ) c  d  ( a  b ) 
C A  C B 
a b
K p  K c ( RT ) n
Steps for writing Equilibrium constant expression for reaction

1. Write a balanced equation for the reaction.
2. Write the products of equilibrium concentration of the products in the numerator. Omit pure
solids, pure liquids and the solvents in dilute solution.
3. Write the product of equilibrium concentrations of the reactants in the denominator. Omit pure
solids, pure liquids and the solvents in dilute solution.

53
4. Raise each concentration term to the power equal to stoichiometric coefficient of the species
in the equation.
RELATIONS BETWEEN EQUILIBRIUM CONSTANT. FOR A GENERAL REACTION AND

ITS MULTIPLES.
Chemical Equation Equilibrium Constant

aA+bB cC+dD Kc ,
1
cC+dD aA+bB K ' 'c 
Kc
n
naA+nbB ncC+ndD K '' c  K c
HOMOGENEOUS EQUILIBRIA
- all the reactants and products are in the same phase.
e.g. CH 3COOC2 H 5 (aq)  H 2O(l ) CH 3COOH (aq)  C2 H 5OH (aq)
HETEROGENEOUS EQUILIBRIA
- Equilibrium in a system having more than one phase is called heterogeneous equilibrium.
e.g. CaCO3 (s ) CaO ( s )  CO 2 ( g )
APPLICATION OF EQUILIBRIUM CONSTANT

1. Predict the extent of a reaction on the basis of its magnitude.
2. Predict the direction of the reaction.
3. Calculate equilibrium concentrations.
1. Predict the extent of a Reaction
The numerical value of equilibrium constant for a reaction indicates the extent of the reaction.
K c  103 Products predominate over reactants, reactions proceeds nearly to completion.
K c  10 3 Reactants predominate over products, reactions rarely proceeds.
K c is in the range 10-3 to 103 - Appreciable concentrations of both reactants and products are
present.
2. Predicting the direction of the reaction.
Reaction Quotient is defined as the same as the equilibrium constant
Kc
For a general reaction

54
aA + bB cC+dD
Qc 
C c D d
Aa B b
If Qc > Kc the reaction proceeds in the backward direction.
Qc < Kc the reaction proceeds in the forward direction.
Qc = Kc the reaction mixture is at equilibrium.
Kc QC KC
Qc
0 RP Equilibrium R P
Relationship between K, Q and Gibbs energy.
G  G   RT ln Q
When, G  0 Q  Kc , the equation becomes
G  G   RT ln K  0
 G 
ln K 
RT
K e G  / RT
The reaction spontaneity can be interpreted

55
a) If G  0, - G/RT    ve, e  G / RT  1, Than K  1.

Spontaneous reaction, proceeds in forward direction
Products are predominant.
 G 
b) If G   0, is  ve, e  G / RT  1, K  1
RT
Non Spontaneous or a reaction which proceeds in forward direction to a very small extent.
Factors Affecting Equilibrium

Le Chatelier’s Principle
- A change in any of the factors that determine the equilibrium conditions of a system will cause
the system to change in such a manner so as to reduce or to counter act the effect of the change.
a) Effect of the concentration change.
When the concentration of the reactants increase the equilibrium shifts in forward direction to
minimize the effect.
When the concentration of the products is increased the equilibrium shifts in backward direc-
tion.
for e.g. Fe+3(aq) + SCN–(aq) [Fe(SCN)]+2 (aq)
Yellow colourless Deep red
Fe( SCN ) (aq)2

Kc 
F (aq)SCN (aq)
e
3 
Red colour appears when potassium thiocyanate solution is added to Iron (III) nitrate solution
due to formation of [Fe(SCN)+2]. Intensity of red colour becomes constant on attaining equilib-
rium.
(i) Addition of oxalic acid, reduces the conc. of Fe+3 as it forms a stable complex ion
[Fe(C2O4)3]3-. [Fe(SCN)]2+ dissociates to give Fe+3 ions. If conc. of [Fe(SCN)]+2 de-
creases. The intensity of red colour decreases.
(ii) Addition of HgCl2 decreases red colour because Hg+2 reacts with SCN- ions to form
stable complex ion [Hg(SCN)4]2-.
(iii) Addition of KCNS increases the intensity of the colour.
(b) Effect of Pressure Change -
The effect of pressure changes on solids and liquids can be ignored as volume of a solution/
liquid is independent of pressure.
When pressure is increased the equilibrium shifts in the direction in which number of moles of
the gas decreases (Pressure is proportional to moles of the gas).

56
e.g. C(s) + CO2 (g) 2CO (g)

On increasing pressure the reaction moves in reverse direction.
(c) Effect of Inert gas Addition
When volume is kept constant and an inert gas is added (which does not take part in the
reaction) the equilibrium remains undisturbed.
(d) Effect of Temperature change
i) The equilibrium shifts to left side of an exothermic reaction as the temperature
increases.
ii) The equilibrium shifts to right side of an endothermic reaction increases as the tempera-
ture increases.
(e) Effect of Catalyst.
Catalyst increases the rate of forward and reverse reactions equally and does not affect
equilibrium.
IONIC EQUILIBRIUM IN SOLUTION

Electrolytes - conduct electricity in aqueous solution.
Non electrolytes - do not conduct electricity in aqueous solution
Strong electrolytes - Ionise completely on dissolution in water
Weak electrolytes - Partially dissociated
VARIOUS CONCEPTS OF ACIDS AND BASES

1. Arrhenius concept
Acids - Substances that dissociate in water to given hydrogen ions.
Bases - Substances that produce hydroxyl ions in water.
HX(aq) H+ (aq) + X–(aq)
H+ very reactive, exist as H3O+ (hydrated form)
MOH(aq)  M+ (aq) + OH– (aq)
The hydroxyl ion also exists in hydrated form.
Limitation :- a) Applicable only to aqueous solution
b) Does not account for the basicity of substances like ammonia.
2. Bronsted lowry Concept.
Acid - Proton donor , HCl
Base - . Proton acceptor, NH3
e.g. Dissolution of NH3 in H2O.
Accepts H+

57
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

Base Acid Conjugate Conjugate base
acid
loses H+
Conjugate acid - base pair - The acid - base pair that differs only by one protons is called a conjugate
acid - base pair.
3. Lewis Acids and Bases.
Acid  Accepts e- pair
Base  Donates an e- pair.
Electron dificient species  AlCl3, Mg2+ act as Lewis acids
Electron rich species  H2O, NH3, OH– act as lewis bases.
THE IONISATION CONSTANT OF WATER AND ITS IONIC PRODUCT
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Acid Base
K
H O OH 
3
 
H 2O

K w  H 3O  OH  ,   H 2O  Pure liquid, concentration remains constant.
[ H  ] 1.0 107 M at 298K
H  OH 1.0 10

  7
M
K w  (1107 ) 2 11014
K w = Temperature dependent
THE pH SCALE
pH = - log [H+]
[H+] = conc in moles/litre
pH of pure water
Conc of [H+] = 10-7 M
pH = - log 10-7 = 7
Acidic solution, pH<7
Basic solution, pH>7
Neutral solution, pH=7
Kw = [H3O+][OH-] = 10-14
- log Kw = - log{[[H3O+][OH-]}

58
IONISATION CONSTANT OF WEAK ACIDS

HX Weak acid partially ionised in aqueous solution.
HX(aq) + H2O (l) H3O+(aq) + X-(aq)
Initial C 0 0
Conc
Eqm C-C C C
Conc  = extent of ionisation
C 2α 2 Cα 2
Ka   Ka = Dissociation or ionisation constant of
C (1  α ) 1  α
acid.
Ka 
H X   
Also
HX 
pKa = - log Ka
Ionisation of Weak Bases
MOH(aq) M+(aq) + OH-(aq)
[ M  ][OH  ].
Kb  Kb = Base ionisation constant
[ MOH ].
Cα2
Also K b  α = Degree of ionisation of base.
1 α
pKb = – log Kb
RELATION BETWEEN Ka AND Kb
In case of conjugate acid - base pair
Ka × Kb = Kw
pKa + pKb = pKw = 14
Common Ion Effect
Suppression of ionisation of a weak electrolyte by adding a strong electrolyte having an ion common
with the weak electrolyte is called common ion effect.
It is based on Le Chatelier’s principle
Ka 
H 

(aq) Ac  (aq) 
HAc
= - log [H3O+] - log [OH-]
pKw = pH + pOH = 14
Addition of Ac- ions  decreasing conc. of H+ ions (reaction moves in backward direction)

59
Addition of H+ ion form external source  Reaction moves in backward direction.

Hydrolysis of Salts and the pH of their solution
Hydrolysis of Salt - The cations/anions formed on ionisation of salts interact with water form corre-
sponding acids/bases depending upon the nature of salts.
1) Salts of strong acids and bases - Simply get hydrated do not get hydrolysed.
e.g. NaCl, KNO3 etc.
2) Salts of weak acid and strong base e.g. CH3COONa.
CH3COONa  Salt of CH3COOH (weak acid) and NaOH (Strong Base)
CH3COONa (aq)  CH3COO-(aq) + Na+(aq)
CH3COO- ion undergoes hydrolysis.
CH3COO-(aq) + H2O (l) CH3COOH(aq) + OH-(aq).

Weak acid (remains unionised).
pH of such solution is more than 7. (Basic).
3) Salts of strong acid and weak base. e.g. NH4Cl.
NH4Cl  Salt of HCl (strong acid) and NH4OH (weak base).
NH4Cl(aq) (aq) + Cl-(aq)

NH4+ undergoes hydrolysis
NH4+(aq) + H2O (l) NH4OH(aq) + H+(aq)
Weak base (remains unionised)
pH of such solutions is less than 7 (Acidic).
4) Salts of weak acid and weak base e.g. CH3COONH4.
CH3COONH4  Salt of weak acid (CH3COOH) and NH4OH (Weak base)
The ions formed undergo hydrolysis
CH3COO– + NH4+ + H2O CH3COOH + NH4OH
1
pH = 7 + (pKa - pKb).
2
Degree of hydrolysis  independent of concentration of solution pH  determined by pK
values.
BUFFER SOLUTIONS The solutions which resist change in pH on dilution or with the addition of small
amounts of acids or alkali are called Buffer Solutions. For example
weak acid + salt formed from strong base
pH = pKa + log ( salt / acid)

weak base + conjugate acid
pH = pKa + log (conjugate acid BH)/(base)
e.g. Mixture of acetic acid and sodium acetate.

60
SOLUBILITY
For a salt to dissolve in a particular solvent its solvation enthalpy must e greater than its lattice en-
thalpy.
SOLUBILITY PRODUCT -
Consider equilibrium between sparingly soluble ionic salt and its saturated aqueous solution.
e.g.
BaSO4(s) saturated
  Ba (aq) + SO4 (aq)
so ln . +2 -2
K
Ba SO 
2
4
2
BaSO4 
K BaSO4  K sp  Ba 2 SO4  2

K sp  Solubility product constant or solubility product.
For a solid salt of general formula M x p  X q  y with molar solubility s, in equilibrium with its
saturated solution.
Common Ion Effect on Solubility of Ionic Salts

If we increase the concentration of any one ions it combines with ion of its opposite change and some
salt is precipitated.
Salts precipitate when ionic product is greater than solubility product.Common ion effect is used for
complete precipitation of a particular ion as its sparingly soluble salt.
p
M x X y (s ) xM ( aq )  y X q  ( aq )

K sp  M p   X   xS   y s
x q y x y
Ionic product any point of time the product
I.P =[MP+]X [XQ-]Y ;condition for precipitation: IONIC PRODUCT > SOLUBILITY PRODUCT

61
Chapter - 8
REDOX REACTIONS
Classical Idea of Redox Reactions
Oxidation : Addition of Oxygen/ electronegative element to a substance or removal of Hydrogen/
electropositive element from a substance. Example :2Mg (s) + O2(g)  2 MgO (s)
(addition of oxygen)
2H2S (g) + O2(g)  2 S (s) + 2H2O(l) (Removal of Hydrogen)
Mg (s) + F2(g)  MgF2 (s) (addition of electronegative elements)
2K4[Fe(CN)6](aq) + H2O2(aq) 2K3[Fe(CN)6](aq) + 2KOH(aq) (removal of
electropositive element)
Reduction : Removal of oxygen/electronegative element from a substance or addition of hydrogen/
electropositive element to a substance.Example :2HgO(s) 
 2Hg(l) + O2 (g) (removal of oxygen)
2FeCl3(aq) + H2(g)  2 FeCl2(aq) + 2HCl(aq) (removal of electronegative element)
CH2 = CH2(g) + H2(g)  H3C - CH3(g) (addition of hydrogen)
2HgCl2(aq) + SnCl2(aq)  Hg2Cl2(s) + SnCl4(aq) (addition of electropositive element)
Redox Reactions : Those reactions in which oxidation and reduction occurs simultaneously.
loss of 2e-
eg. 2Na(s) + Cl2(g) 2Na+ Cl– (s)
gain of 2e–
In terms of electron transfer:
Oxidation : loss of electrons by any species
Reduction : gain of electrons by any species
Oxidising agent : Acceptor of electrons
Reducing agent : Donor of electron (s)
OXIDATION NUMBER
Oxidation number denotes the oxidation state of an element in a compound ascertained according to
a set of rules formulated on the basis that electrons in a covalent bond belong entirely to a more
electronegative element.
Rules to determine Oxidation number
1. In elements, in the free or uncombined state, each atom bears an oxidation number zero. eg.
each atom in H2, Cl2, O3, Mg has oxidation number zero.
2. For ions composed of one atom : oxidation number is equal to the charge on the ion.
Na+ +1
O2-  -2
In compounds : alkali metals have oxidation number + 1

62
alkaline earth metals have oxidation number + 2

Aluminium has oxidation number + 3
3. Oxidation no. of Oxygen in most compounds is -2.
except :
(a) peroxides (eg. H2O2, Na2O2) -1
(b) Superoxides (eg. KO2, RbO2)  - ½
(c) In OF2, Oxygen has oxidation number +2
(d) In O2F2, oxygen has oxidation number + 1
4. Oxidation numbers of Hydrogen is + 1, except in binary compounds.
eg. LiH, NaH  -1
5. Fluorine and other halogens have oxidation number -1.
exception : in oxoacids, interhalogen compounds and oxoanions : Cl, Br, I have positive
oxidation numbers.
6. The algebraic sum of oxidation number of all the atoms in a compound must be zero. In polyatomic
ion, algebraic sum of all the oxidation numbers of atoms of ion is equal to charge on the ion.
Oxidation number denotes the oxidation state of an element in a compound.
STOCK NOTATION
Oxidation number is expressed by putting a Roman numeral representing the oxidation number in
parenthesis after the symbol of the metal in the molecular formula.
eg. Stannous Chloride : Sn (II) Cl2
Stannic Chloride : Sn (IV) Cl4
Charge in Oxidation number implies change in oxidation state which helps to identify whether the
species is present in oxidised form or reduced form.
Hg2(I) Cl2 is the reduced form of Hg(II) Cl2.
CALCULATION OF OXIDATION NUMBER OF UNDERLINED ELEMENTS

a) Cr2O72-
2x - 2 × 7 = -2
 2  14
x 6
2
b) CH2Cl2
x + 2 × 1 + 2 × (-1) = 0
 x=2-2=0  x=0
c) Pb3O4
3x + 4 (-2) = 0
 3x - 8 = 0
8 2
 x  2
3 3

63
Oxidation : An increase in oxidation number of the element in the given substance.

Reduction : A decrease in oxidation number of the element in the given substance.
Oxidising agent (Oxidants) : A reagent which can increase the oxidation number of an element in a
given substance.
Reducing agent (reductant) : A reagent which lowers the oxidation number of an element in a given
substance.
Redox reactions : Reactions which involves change in oxidation number of the interacting species.
TYPES OF REDOX REACTIONS

(a) Combination reaction
A+BC
either A and B or both A and B must be in the elemental form for such a reaction to be a redox
reaction.
eg. CH4(g) + 2O2(g) 

 CO2(g) + 2H2O(l)
C(s) + O2(g) CO2(g)
(b) Decomposition reactions :
Breakdown of a compound into two or more components at least one of which must be in the
elemental state.
eg. 2H2O(l) 
 2H2(g) + O2(g)
2NaH (s) 
 2Na(s) + H2(g)
All decomposition reaction are not redox reactions.
+2 +4 -2 +2 -2 +4 -2
eg. CaCO3(s) 
 CaO(s) + CO2(g)
 (not a redox reaction)
(3) Displacement Reactions
An ion (or an atom) in a compound is replaced by an ion (or an atom) of another element.
X + YZ  XZ + Y
(a) Metal dispalcement :
A metal in a compound can be displaced by another metal in uncombined state.
Application : Metallurgical processes (pure metals are obtained from their compounds in
Ores)
eg. CuSO4(aq) + Zn(s) Cu(s) + ZnSO4(aq)
TiCl4(l) + 2 Mg(s)  Ti(s) + 2MgCl2(s)
(b) Non metal displacement :
eg. 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

64
Fe(s) + 2HCl(aq)  FeCl2(aq) + H2(g)
Halogens : Power of these elements as oxidising agents decreases as we move down from
chlorine to iodine in group 17
F displaces the oxygen of water.
 reactions of halogens are not carried in aqueous solutions.
2H2O (l) + 2F2(g) 4HF(aq) + O2(g)
Layer Test : Br2 and I2 are coloured and dissolve in CCl4.
 can be identified from the colour of the solution
Cl2(g) + 2KBr (aq)  2KCl(aq) + Br2(l)
Cl2(g) + 2KI(aq)  2KCl(aq) + I2(s)
Halogen displacement reactions - direct industrial application 2X-  X2 + 2e- (for recovery of halo-
gens from halides). Chemical means are available to oxidis Cl-, Br-, I- but F- can be converted to F2
only electrolytically.
4. DISPROPORTIONATION REACTIONS
An element in one oxidation state is simultaneously oxidised and reduced. The element in the form of
reacting substance is in the intermediate oxidation state, and both higher and lower oxidation states of
the element are formed in the reaction.
-1 -2 0
2H2O2(aq)  2H2O(l) + O2(g) (oxygen experiences disproportionation)

Oxygen of Peroxide -1 state is converted to H2O (-2 oxidation state) and O2 (zero oxidation state)
Amongst halogens, F does not show a disproportionation tendency. (because it is most electronega-
tive element, cannot show positive oxidation state)
BALANCING OF REDOX REACTIONS

(a) Oxidation number method
Steps :-
(i) Write skeleton equation, indicate oxidation number of each element and thus identify atoms
undergoing change in oxidation number.
(ii) Determine the increase and decrease of oxidation number per atom. Multiply the increase
or decrease of ON with number of atoms undergoing change.
(iii) Equalise the increase in oxidation no. and decrease in oxidation number on the reactant
side by multiplying the respective formulae with suitable integers.
(iv) Balance the equation w.r.t atoms other than O and H atoms.
(v) Balance O by adding equal number of water molecules to the side falling short of O
atoms.

65
(vi) H atoms are balanced (ionic equations) depending upon the medium in which the reaction
is carried out.
Example :
Balance : Chloride ions reduce manganese dioxide to manganese (II) ions in acidic medium and
get itself oxidised to Chlorine gas.
+4 -2 -1 0 +1 -2
(i) Skeleton equation : MnO2 + Cl-  Mn2+ + Cl2 + H2 O
O.N decrease by 2 per Mn

(ii) MnO2 + Cl-  Mn2+ + Cl2 + H2O
ON increase by 1 per Cl
(iii) Equalise increase/decrease in ON by multiplying MnO2 by 1 and Cl- by 2.
MnO2 + 2Cl- Mn2+ + Cl2 + H2O
(iv) Balance other atoms except H and O. (already balanced)
(v) Balance O atoms by adding H2O molecules to the side falling short of O atoms.
MnO2 + 2Cl- Mn2+ + Cl2 + 2H2O
(vi) Balance H atoms by adding H+ ions to the side falling short of H atoms.
MnO2 + 2Cl-+4H+ Mn2+ + Cl2 + 2H2O
(b) Balancing by half reaction or ion electron method
STEPS:
(i) Indicate the oxidation number of each atom involved in the reaction and identify the ele-
ments which undergo a change in oxidation number.
(ii) Divide skeleton equation into oxidation half reaction and reduction half reaction.
(iii) Add electrons to whichever side is necessary in order to make up the difference in O.N.
(iv) Balance O atoms by addition of proper no. of H2O molecules to the side falling short of O
atoms.
(v) For ionic equation : balancing of H atoms in each half reaction.
For acidic medium : add proper number of H+ ions to the side falling short of H atoms.
For basic medium : add proper number of H2O molecules to the side falling short of H
atoms and equal no. of OH- ions to the other side.
(vi) Equalise the number of electron lost and gained by multiplying the half reactions with
suitable integer and add them to get the final equation.
+6 +1 -2
Example : Cr2O7 + Fe Cr + Fe + H2O (in acidic medium)
2- 2+ 3+ 3+
1) Writing oxidation and reduction half reaction

Cr2O72-  Cr3+ (Reduction half)

66
Fe2+  Fe3+ (Oxidation)

2) Addition of e’s to make up difference in ON
Cr2O72- + 6e-  2Cr3+ (2 Cr atoms gain 6e-)
Fe2+  Fe3+ + e-
3) Balance ‘O’ by adding equal number of H2O molecules to the side which is defficient in O
atoms.
Cr2O72- + 6e-  2Cr3+ + 7H2O
Fe2+  Fe3+ + e-
4) Balance H by adding H+ ions to side deficient in H atoms
Cr2O72- + 6e- + 14H+  2Cr3+ + 7H2O
Fe2+  Fe3+ + e-
5) Multiply oxidation half reaction by 6 to equalise the e’s lost and gained and add the two.
Cr2O72- + 6e- + 14H+  2Cr3+ + 7H2O
Fe2  Fe3  e  6
6Fe2  Cr2O72  14H   2Cr 3  6Fe3  7 H 2O
+3 -2 +1 +5 -2 +6 -2
2. Cr (OH)3 + IO3  I + CrO42-
- -
(basic medium)
(i) Writing oxidation and reduction half reactions.
Cr(OH)3  CrO42- (Oxidation half)
IO3–  I– (reduction half)
(ii) Addition of e- to make up difference in O.N.
Cr(OH)3  CrO42– + 3e–
IO3– + 6e–  I–
(iii) Balance O atoms by adding H2O molecules to the side dificient in O atoms.
Cr(OH)3 + H2O  CrO42- + 3e-
IO3– + 6e–  I– + 3 H2O
(iv) Balance H atoms since the medium is basic, therefore add proper number of H2O molecules to
the side following short of H atoms and equal number of OH- ions to the other side.
Cr(OH)3 + H2O + 5OH–  CrO42– + 3e– + 5H2O
IO3- + 6e- + 6H2O  I– + 3 H2O + 6 OH-
(v) Equalise the electrons lost and gained by multiplying the oxidation half reaction with 2.
Cr(OH)3 + H2O + 5OH-  CrO42– + 3e– + 5H2O ] × 2
IO3– + 6e– + 6H2O  I– + 3 H2O + 6 OH–

67
2Cr(OH)3 + 4 OH– + IO–3  2CrO42– + 5H2O + I–
Redox reactions as the basis for Titrations

In Redox systems, the titration method can be adopted to determine the strength of reductant/oxidant
using a redox sensitive indicator.
1) Potassium Permanganate Titrations
KMnO4 Oxidising agent (self indicator) purple
end point : colourless to pink
eg. MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
(acidic
medium)
2) Potassium dichromate titrations
Oxidising agent : K2Cr2O7 in acidic medium.
Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ +7H2O
3) Iodimetric Titrations
direct use of I2 as oxidising agent, used for the estimation of reducing agents like thiosulphate
sulphate, arsenites etc.
I2 + S2O32-  2 I- + S4O62-
4) Iodometric Titrations
involve indirect use of Iodine for estimation of oxidising agents like KMnO4, K2Cr2O7, CuSO4
etc.
Oxidising agent to be estimated is allowed to react with KI and I2 liberated is titrated against a
standard solution of sodium thiosulphate.
2CuSO4 + 4KI Cu2 I2 + 2K2SO4 + I2
Or (2Cu2+ + 2I-  2Cu+ + I2)
On addition of starch after liberation of I2, intense blue colour appears.
I2 + S2O32-  2I- + S4O62-
blue colour disappears as soon as I2 is consumed by thiosulphate ions.
Redox reactions and electrode processes
Direct redox reactions
Reactions in which oxidation and reduction take place in the same vessel and the chemical energy
appears as heat.
Indirect redox reactions
Reactions in which oxidation and reduction takes place in different vessels. Transference of electrons
takes place indirectly through the conducting wires.
Electrochemical cell - device in which chemical energy is converted to electrical energy.
eg. Daniell Cell

68
Arrangement consists of two beakers containing solutions of ZnSO4 and CuSO4 respectively. Zinc
rod is dipped in ZnSO4 and copper rod is dipped in CuSO4.
Reactions takes place in beakers and Zn/Zn2+ come in contact at interface. Similarly Cu comes in
contact with Cu2+ ions.
Redox couple : An arrangement involving contact between the oxidised and reduced form of the
substance at the interface.
The two metal rods act as electrodes and are connected by conducting wire through a galvanometer.
Two solutions are joined by inverted U-tube (Salt bridge)
[U-tube is filled with inert electrolyte like KCl, KNO3 or NH4Cl to which gelatin or agar agar has
been added.]
Oxidation takes place at anode . (Zinc)
(-) (negative)
Reduction takes place at cathode. (Copper)
(+) (Postive)
Salt bridge - allows the flow of current by completing the circuit.

- maintains electrical neurality.
The electrical potential difference set up between the metal and its solution is called half cell electrode
potential.
Half reactions are represented by reduction potentials.
(i) Reduction potential and oxidation potential of an electrode are numerically equal but have opposite
signs.
(ii) Reduction potential of an electrode when the concentration of ions in solutions is 1mol/L and
temperature is 298K is called standard reduction potential (E Θ ).
(iii) Standard hydrogen electrode (SHE) - electrode potential is arbitrarily taken to be zero.
(iv) A negative E Θ means that redox couple is stronger reducing agent than H+/H2 couple.
(v) A positive E Θ means that redox couple is a weaker reducing agent than H+/H2 couple.

69
Chapter - 9 Hydrogen
- Smallest and lightest element
- Hydrogen atom has one proton and one electron
Symbol : H
Atomic number (Z) : 1
Electronic configuration : Is1
Isotopes : (i) Protium 11 H

2
(ii) Deuterium H or D
3
(iii) Tritium H or T
2
Allotropes Orthohydrogen o-H
2
Parahydrogen p-H
[Also o-D2, p-D2
o-T2,p-T2 ]
1 2 3
Molecular forms : H , H (D ), H (T )
2 2 2 2 2
HD, HT etc.
Ionic forms : H–, H+, H 2 , H 3 ........................ H11
[Also corresponding ionic forms of D and T]

UNIQUE POSITION OF HYDROGEN IN THE PERIODIC TABLE
Hydrogen has resemblance to the halogens as well as Alkali metals.
Hydride ion Proton

(like halides) (like alkali metal ion)
uninegative ion unipositive ion
Hydrogen is different from halogen as well as alkali metals:

(i) H+ has small size (~1.5×10-3pm) compared to atomic and ionic sizes(50-220pm)
(ii) It cannot exist freely and is always associated with other atoms or molecules,
(iii) Ionization enthalpy is very high (1312kJ/mol) as compared to Alkali metals,
(iv) It forms numerous covalent compounds.
Hydrogen is therefore best placed separately in the periodic table of elements.
DIHYDROGEN (H2)

70
- 70% of the universe’s total mass consists of Hydrogen (most abundant element)
- Jupiter and Saturn consist mostly of Hydrogen
- Half the mass of the sun and some other stars is made of Hydrogen.
- It is third most abundant element on the surface of the globe.
- Constitutes 15.4% of the earth’s crust and the oceans
- In crustal rocks, it is 10th in the order of abundance.
ISOTOPES OF HYDROGEN
(a) Protium ( 11 H ) - Predominant form made up of a single proton and a single electron.
(b) Deuterium ( 12 H or D) - Nucleus made up of a proton and a neutron.
- Terrestrial Hydrogen contains 0.0156% of Deuterium in the form of HD.
(c) Tritium ( 13 H or T) - It’s concentration is 1 atom per 1018 atoms of Protium.
 Radioactive and emits low energy  - particles.

The three isotopes can be used in isotope studies, Radioactive tracer studies and nmr spectroscopy.
SMALL SCALE PREPARATION OF DIHYDROGEN
Zn + 2HCl  ZnCl2 + H2 (laboratory method)
Zinc Hydrochloric Zinc Hydrogen
Acid chloride
COMMERCIAL PRODUCTION OF DIHYDROGEN
(1) 2H2O(l) electrolys

  is
 2H2(g) + O2(g) [Pt electrodes used]
(2) By electrolyzing warm aqueous Barium hydroxide between Nickel electrodes
(3) CH4 + H2O 1270

 K
 CO + H2O
Methane Steam catalyst Dihydrogen
C(s) + H2O(g) 1270

 K
 CO(g) + H2(g)
(Coke) (steam) Water gas or synthesis gas or syngas
CO + H2O 673
K
 CO 2 +H2 Water gas shift reaction
Produced (steam) Fe2O3 or CaO
above)
(4) CH3OH 673

K
 CO + 2H2 produces small quantities of dihydrogen
(produced Basic metal
above) chromate catalyst
CO + H2O   CO2 + H2
673 K
(5) Produced as a byproduct of the brine electrolysis process for the manufacture of chlorine
and sodium hydroxide.
PROPERTIES OF DIHYDROGEN
Physical

71
- Colourless, Odourless and tasteless gas.

- Lighter than air
- Nearly insoluble in water
- Highly combustible
- Lightest of all elements
Chemical Properties
The relatively inert behaviour of Dihydrogen at room temperature is due to high enthalpy of H-H
bond (higher for a single bond)
(a) Decomposition of a H2 into its atom occurs above 2000 K (0.081%) which increases to
95.5% at 5000K.
(b) H2(g) + X2(g)  2HX (g)
Reaction with Fluorine takes place in dark
Reation with Iodine requires a catalyst
(c) 2H2(g) + O2 (g)  2HX (g) X= F, Cl, Br, I
(d) N2(g) + 3H2(g) 673

K  2NH3(g) H° = –92.6kJmol
, 200 atm
(Haber’s process)
(e) H2(g) + 2M(s)  2MH(s) M = Alkali metal
(Metal
hydride)
(f) Pd2+(aq) + H2(g)  Pd(s) + 2H+ (aq)
(metal ions)
(g) y H2(g) + MxOy(s)  xM(s) + y H2O(l)
(metal oxides
less reactive than
Iron)
(h) Hydrogenation of vegetable oils to solid edible fats.
(Margarine and Vanaspati)
(a) Hydroformylation of Olefins
RCH=CH2 + H2 + CO  RCH CH CHO
2 2
(b) Reduction of Aldehydes to Alcohols
RCH2CH2CHO + H2  RCH2CH2CH2OH
ORTHO AND PARA HYDROGEN
Nuclear spin isomers

72
Ortho - Hydrogen Para - Hydrogen

(Parallel nuclear spins) (Antiparallel nuclear spin)
Nuclear spin 1 Nuclear spin 0
- Conversion of one isomer to other is a slow process.
- Para Hydrogen with lower energy is favoured at low temperature. Above 0 K equilibrium
concentration of ortho isomer increases (3:1 limiting proportion of ortho : para isomer established.)
- Pure para Hydrogen can be obtained but it is not possible to obtain sample containing more
than 75 % of ortho-Hydrogen.
- Thermal conductivity of para - Hydrogen is 50 % greater than ortho - Hydrogen.
- Melting point of para - Hydrogen is 0.15 K below that of Hydrogen containing 75 % ortho
Hydrogen.
USES OF DIHYDROGEN
(1) Manufacture of Ammonia. (Haber’s process)
(2) Manufacture of Methanol:
CO(g) + 2H2(g) 

Co CH3OH(l)
(3) Preparation of Hydrogen Chloride :
H2(g) + Cl2(g) 2HCl(g)
(4) Manufacture of metal Hydrides.
(5) Reduction of metal oxides to metals in metallurgical processes.
(6) Used in Atomic Hydrogen and Oxy hydrogen torches for cutting and welding.
(7) Rocket fuel in space research, in bubble chambers as liquid hydrogen for the study of high
energy particles in a fuel cell.
HYDRIDES
Binary compounds of Hydrogen and other elements are called hydrides.
(1) Saline Hydrides / Ionic hydrides (salt like hydrides)
- Compounds of Hydrogen with most of the s-block elements.
- LiH, NaH, KH, RbH, CsH - hydrides of Alkali metals has rock salt structures.
- Non-volatile, non conducting, crystalline solids.
- Thermal stability decreases from LiH to CsH. (CaH2 > SrH2 > BaH2.)
- React violently with water:
- NaH(s) + H2O(1)  H2(g) + NaOH(aq)
- Fire produced cannot be extinguished by CO2 as it is reduced by hot metal hydride. Only
sand (solid) is useful.
- Hydrides of heavier members of each group have ionic bonds but there is covalent character
in the lighter metal hydrides ( LiH, MgH2, BeH2).
- Alkali metal hydrides are used as reagents for preparing other hydride compounds
(2) Metallic hydrides / Interstitial hydrides.

73
- Formed by d - block metals of groups 3,4,5 and f - block elements .(eg ScH2
LaH2,TiH2,ZrH2).
- In group 6 , Chromium alone forms hydride.
- Groups 7,8,9 - Hydride gap (do not form hydrides)
- Conductors and are non stoichiometric with variable composition (eg, ZrHx with x-1.30-
1.75).
- Used as Hydrogen storage media (source of energy for vehicles)
(3) Molecular / Covalent Hydrides
- formed by p - block elements (eg. CH4, NH3, H2O, HF)
- Volatile molecular compounds.
- Systematic names are usually formed from the name of the element and the suffix -ane.
Eg. PH3  Phosphane (Common name - Phosphine)
H2O  Oxidane (Common name - Water)
NH  Azane (Common name - Ammonia)
3
Types of Molecular hydrides :

(a) Electron deficient molecular hydrides:
Central atom does not have complete octet. Eg. Diborane (B2H ), BeH2, MgH2.
6
(b) Electron precise compounds (hydride)
- Central atom has complete octet.
- Formed by elements of group 14 (eg. CH4, SiH4)
- Tetrahedral structure.
- Bond distance increases on going down the group.
(c) Electron rich hydrides
- have lone pair of electrons (eg. NH3 - one lone pair
H2O - two lone pairs)
- Presence of lone pairs and electronegative atoms like N, O, F results in hydrogen bonding.
- High boiling points,
- High permittivity and aggregation.
WATER
- Most common, abundant and easily obtainable chemical compound.
- Easily transformed from liquid to solid and to gaseous states.
- Important solvent.
Physical properties.
- Colourless and volatile liquid.
- Abnormally high freezing point, boiling point, heat of vaporisation and heat of fusion (as

74
compared to hydrides of other elements of the same group.) (Due to hydrogen bonding)
- High specific heat; thermal conductivity and surface tension - plays vital role in biosphere.
- High heat of vaporization and high heat capacity:
- helps in moderation of the climate and body temperature of living organisms.
- excellent solvent (helps in plant and animal metabolism)
- behaves as non polar solvents under high temperature and pressure.
- Alcohols, carbohydrates have high solubility in water due to hydrogen bonding.
ICE
- Crystalline form of water.
- Nine structurally different forms of ice known.
- Ice crystallizes in normal hexagonal form (I) In at atmospheric pressure but at low tem-
perature it condenses to cubic form. It has lesser density then liquid phase -crucial signifi-
cance for preservation of aquatic life.
Association of Water
Salts crystallize from aqueous solutions as hydrated salts.
Types of association : Coordinated water

Hydrogen bonded water
Lattice water
Zeolitic water
Clatherate water.
STRUCTURE OF WATER
25
Bent structure
95.7PM HOH bond angle: 104.5° 1
104.5° OH bond length : 95.7 pm,
δ Highly polar: due to high electronegativity of oxygen.
H δ
H
Liquid State
Water consists of aggregates of varying number of water molecules held together by hydrogen
bonds.
Inter molecular hydrogen bonding
Extensive three dimensional network in which each oxygen atom is bonded to .but hydrogen atoms

75
two by hydrogen bonds and two by normal covalent bonds in a near tetrahedral configuration
(different from other polar molecules - HF, NH )
3
Ice - has three dimensional highly ordered hydrogen bonded structure which has open spaces.
Therefore, has lower density than water.
- Ice layer provides thermal insulation for the water below it and ensures survival of aquatic life.
CHEMICAL PROPERTIES OF WATER

- behaves as Amphoteric substance.
–
H2O (1) + NH3 (aq)  OH (aq) + NH4+ (aq)
(acid) (base)
–
H2S(aq) + H2O(1)  H3O+(aq) + HS (aq)
(acid) (base)
(acts as a base towards acids stronger than itself)
- Auto - protolysis of water
H2O (1) + H2O(l) H3O+(aq) + OH–(aq)1

Acid1 base2 acid2 base 1
- Acts as both oxidizing and reducing agents:

2H2O(1) + 2e– 2OH- (aq) + H2 (g) E° = -0.41V for [OH–] = 10–7 M
O2 (g) + 4 H+ (aq) + 4e–  2H2O E° = +0.82V for [H+] = 10–7 M
- Hydrolytic action : P4O10 (s) + 6H2O (I)  4H3PO4 (aq)

Ca3N2(s) + 6H2O (I)  3Ca(OH)2 (aq) + 2NH3 (g)
Hydrate Formation:
(a) Water molecules are coordinated to a metal ion eg. [Ni(OH2)6] (NO3)2
(b) Water molecule is hydrogen bonded to oxygen containing anions. Eg. CuSO4.5H2O)
(c) Water occupies interstitial sites in crystal lattice. Eg. BaCl2.2H2O.
HARD AND SOFT WATER
HARD WATER : contains soluble Calcium and Magnesium salts like bicarbonates, chlorides and
sulphates. - does not form lather with soap.
2CI7H35COONa + Ca2 / Mg2+ (Cl7H3sCOO)2Ca/Mg, + 2Na+
soap (from hard water) (scum)
- harmful for steam boilers.
Develop boiler scale which is largely calcium sulphate, calcium carbonate and Magnesium oxy-
chloride. (reduces efficiency of boiler, damages it)
SOFT WATER - free from calcium, Magnesium bicarbonate, chloride, sulphate. Gives lather with
soap.
TEMPORARY HARDNESS
- due to the presence of bicarbonates of Calcium and Magnesium.

76
Removal of temporary hardness

(a) Boiling
M(HCO3)2 MCO3 + H2O + CO  [M = Ca or Mg]
2
Insoluble
(can be removed)
(b) Clark’s process :

Addition of calculated quantities of lime causes precipitation
2Ca(HCO3)2 + Ca(OH) 2CaCO  2H2O

2 3
Mg (HCO3)2 + 2Ca (OH) 2CaCO3 + Mg(OH)2 + 2H2O

2
PERMANENT HARDNESS
- due to the presence of soluble Calcium / Magnesium sulphates / chlorides.

77

78
Chapter - 10
s - Block Elements
Physical Properties of the Alkali Metals
* ppm (part per million) , ** percentage by weight + Lithosphere : The Earth’s outer layer : its
crust and part of the upper mantle
Atomic Properties
1. Electronic Configuration : [NG] ns
n = 2 to7
2. Atomic / Ionic Radii
(i) Largest Size
(ii) Increases down the group (No. of shells increases and screening effect)
(iii) Ionic radii in gaseous state
Li+ < Na+< Rb+ < Cs+
but in aq state Li+ >Na+ > K+< Rb+ > Cs+
(smaller ions are hydrated the most)

79
3. Ionisation Energy and Electropositive Character

(i) Lowest I.E.
(ii) Decreases down the group
(iii) Low I.E. makes them electropositive & metallic in nature
(iv) 1st I.E. is low but IInd I.E. is very high (e-out from complete oclet)
(octet complete) PHYSICALPROPERTTES
1. Density, b.p and m.p
(i) Low
(ii) Li, Na, K are lighter than water
(iii) density increases down the group
(iv) Exception: K is lighter than sodium result of abnormal increase in size
(v) rap. & b.p. low, they increases with decreases in atomic number
2. Reducing properties & E° values
(i) Tendency to lose electron/low reduction potential/good reducing agents
(ii) Lithium being the most the sodium the least
(iii) Born-Haber Cycle
3. Oxidation state
(i) +1
(ii) Electropositive
(iii) Electrovalent compounds
(iv) Ionic character increases down the group
4. Flame colouration
(i) Li Na K Rb Cs
Crimson Golden Pale Violet Blue
Yellow Violet
Reason: low ionisation enthalpy
5. Photoelectric effect
Emission of electron from the metal surface when electromagenetic radiations strike
them
Low I.E.
CHEMICAL PROPERTIES : ALKALI METAL

80
1. High Reactivity
(i) Low I.E.
(ii) Low heat of atomisation
(iii) I.E. decreases down the group  reactivity increase from Li to Cs.
(iv) Strongest reducing agent is Lithium ( of its high I.E. it should be the weakest but Li+ is
hydrated the most & this hydration energy helps to release electrons).
2. Reaction with acidic hydrogens
2M + 2H2O  2 MOH + H2 (reactivity  from Li to Cs)
2M + 2C2H5OH  2C2H5OM + H2
+ – – +
2M + HC  CH  M C  C M + H2
3. Oxides & hydroxides
(i) M2O/MOH
(ii) 4Li + O2  Li2O (Alkali metals tarnish in air due to the formation of their oxides)
(iii) Perioxides 2Na + O2 575

  K
 Na2O2
(iv) Superoxides K+O2  KO2 (only for K, Rb, Cs)
(v) Reactivity decreases down the group
(vi) Reason: Li+ strong positive charge/restricts the spread of negative charge towards other oxygen
atom.
(vii) Lithium reacts directly with nitrogen in air to form nitrides, Li3N
4. Hydrides
(i) 2M + H2  2M H (ionic hydrides)
(ii) Reactivity decreases down the group (lattice energy decreases with increase in size of atom)
(iii) High m.p.
5. Halides
(i) 2M + X2  2M+ X– (ionic)
(ii) F2>Cl2>Br2> I2
(iii) Reactivity of alkali metals towards a particular halogen increases down the group.
6. Solubility in liquid ammonia.
(i) All alkali metals dissolve in liquid ammonia giving highly conducting deep blue solutions
M + (x + y ) NH3  M+(NH3)x + e–(NH3)y
(ii) When light falls on these ammoniated electrons they get excited to higher levels by absorbing
energy.
(iii) Solution is para magnetic.
(iv) Solution is conducting due to ammoniated cations & ammoniated electrons,
(v) On standing it decomposes to metal amides & hydrogen.

81
Anomalous behaviour of Lithium

(1) Small size and high polarising power of Li+
(2) Non-availability of d orbitals.
(3) 6 Li + N2  2 Li3N. (but other alkali metals donot)
(4) LiOH is a weak base while other alkali metals from strong bases.
2.LiOH 
 Li2O + 4NO2+O2
(5) 4 LiNO3  2 Li2O + 4NO2 + O2
2NaNO32NaNO2+O2
Diagonal relationship of Li & Mg
(1) Both LiOH &Mg(OH)2 are weak bases
(2) 6Li + N2  2Li3N & 3Mg + N2  Mg3 N2
(3) 2LiOH  Li2O + H2O & Mg(OH)2  MgO + H O
2
(4) LiCO3  Li2O + CO2 & MgCO3  MgO + CO2
(5) LiCl2 & MgCl2 are deliquesent
Alkaline Earth Metals

Atomic and Physical Properties of the Alkaline Earth Metals
*ppm (part per million) ** percentage by weight
ATOMIC PROPERTIES
1. Electronic Configuration : [NG]ns2
n = 2 to 7

82
2. Atomic and ionic sizes - Atomic and ionic radii of the alkaline earth metals are
smaller than alkali metals due to increased nuclear
charge.
3. Ionisation enthalpies - 1st ionisation enthalpies of alkaline earth metals are
higher than those of group 1 metals.
IInd ionisation enthalpies of alkaline earth metals are
smaller than alkali metals.
4. Physical appearance - Silvery white, lustrous, soft but harder than the alkali
metals.
5. Melting and boiling points - Higher than corresponding alkali metals due to
smaller atomic sizes.
Trend is not systematic
6. Electrical & thermal conductivities - Properties are characteristic of typical metals.
7. Flame Colour - Ca, Sr, Ba impart colours to the flame. In flame electrons
are excited to higher energy levels and when they drop
back to original state energy is emitted in form of visible
light.
Ca-Brick red
Sr - Crimson red
Ba - Apple green
Flame test is used in qualitative detection of these
elements.
Be, Mg - no flame test because electrons are tightly
bound to nucleus due to small size to get excited by
flame.
CHEMICAL PROPERTIES
(a) Towards air and water (i) Alkaline earth metals are reactive metals but less reac-
tive than alkali metals.
(ii) Be, Mg - Kinetically inert to O2 and water because of
formation of surface film of oxide.
(iii) Be - No reaction with water or steam even at red hot
and does not react with below 873 K.
(iv) Be - burns brilliantly in air on ignition to form BeO
and Be3N2
(v) Mg - burns with dazzling brilliance in air to give MgO
and Mg3N2
(vii) Ca,Sr,Ba-readily attacked by air to form the oxide &
nitride.
React with water with increasing vigour in cold.

83
(b) Towards the halogens - Alkaline earth metals react with halogen at elevated tem-
perature to form metal halides(MX2).
(c) Action of acids - Alkaline earth metals liberate H2 with acids.
(d) With ammonia - Alkaline earth metals dissolve in liquid NH3 to form
blue black solutions. From these ammoniates
[M(NH3)6]+2 can be recovered.
(e) Reducing power and E° values - E° (M+2/M) values for group 2 metals are nearly con-
stant.
These metals are electropositive & strong reducing
agents.
Be - less negative value because of large hydration
energy due to small size of Be-2 and large value of
enthalpy of atomisation.
Magnesium cation is easily reduced than the heavier
members of the group - because of smaller size which
leads to large negative value for its hydration energy.
ANOMALOUS BEHAVIOUR OF BERYLLIUM.
(i) Exceptionally small atomic and ionic size.
(ii) High ionisation enthalpy, small size forms covalent compounds which get hydrolysed easily.
(iii) Be does not exhibit coordination number more than four.  No d-orbitals.
(iv) The oxide and hydroxide of Be are amphoteric in nature.
DIAGONAL RELATIONSHIP BETWEEN BERYLLIUM AND ALUMINIUM

(i) Charge/radius ratio of Be+2 is nearly same as that of Al+3 ion Radius.
(ii) Like Al, Be is not readily attacked by acid.
- due to presence of an oxide film on the surface of the metal.
(iii) Beryllium hydroxide dissolves in excess of alkali to give Beryllate ion [Be(OH)4]2-.
Aluminium hydroxide gives aluminate ion [Al(OH)4]-
(iv) Chlorides of Be and Al have Cl- bridged chloride structure in vapour phase.
Both are strong Lewis acids and soluble in organic solvents used as Friedal Craft Catalysts.
(v) Be, Al ions have strong tendency form complexes Be F42-, Al F63-.
COMPOUNDS OF ALKALI AND ALKALINE EARTH METALS

1. Na2CO3. 10 H2O Sodium Carbonate Washing Soda
- prepared by Solvay Process
2. NaCl Sodium Chloride Common salt

84
Impurities present - CaCl2, MgCl2 deliquescent in nature.

3. NaOH Sodium Hydroxide Caustic Soda
- Prepared by electrolysis of NaCl: in Castner Kellner Cell.

Brine solution is electrolysed using mercury cathode and Carbon anode.
Na metal discharged at cathode combines with Hg to form sodium amalgam.
Cl2 gas is evolved at cathode.
Reaction at Cathode
Na   e  
Hg
Na  Ama lg am
Reaction at anode
1
Cl   Cl 2  e 
2
Na - amalgam treated with water to give NaOH solution and H2 gas.
2Na - amalgam + 2H2O 2NaOH + 2Hg + H2
4. NaHCO3 Sodium Hydrogen Carbonate Baking Soda
- Prepared by Solvay Process
5. CaO Calcium Oxide Quick lime
6. Ca(OH)2 Calcium hydroxide Slaked lime
7. CaCO3 Calcium carbonate Lime stone
1
8. CaSO4. HO Calcium sulphate hemihydrate Plaster of Paris
2 2
9. Cement
Raw materials to prepare Cement are - limestone and clay.
BIOLOGICAL IMPORTANCE OF Ca and Mg.

Ca - in neuromuscular function, blood coagulation
Mg - Cofactor in all enzymes that utilise ATP chlorophyll.

85
Chapter - 11
p- Block Elements
CHAPTER -11 SOME pBlock Elements
Group 13 : The Boron Family

86
PHYSICAL PROPERTIES
Oxidation States : +3 and +1 s-orbital 2 electron p-orbital 1 electron
• Stability of+-1 oxidation state increases as: Al < Ga <In< Tl
+
• In aq solution Tl is more stable than Tl3+
INERT PAIR EFFECT
• Oxidation state is exhibited when s-electrons of the valence shell do not participate in bond
formation, i.e. ns2 electron pair in Ga, In, Tl tends to remain paired (a) this is due to poor
shielding of the ns2 electron of the valence shell by intervening d and f electrons (b) BE de-
creases from Al  Tl Energy required to unpair ns2 electrons is not compensated by the energy
released in formation of two additional bonds.
• Inert pair effect is more predominant down the group Nuclear charge increases much more than
the increase in distance of the outer electrons from the nucleus - s electrons are more penetrat-
ing so reluctant to form bonds.
Atomic and ionic Radii
• Are smaller for group 13 elements as compared to corresponding elements of group 2 because
magnitude of nuclear charge increases.
• On moving down the group both atomic and ionic radii are expected to increase due to addition
of new shells
Deviation : at radii of Al is slightly more than that of Ga-
• From Al to Ga electrons filled into d-subshell. These intervening electrons do not screen the
nuclear charge effectively (poor penetration power) the electrons in Ga experience more force
of attraction than in Al causing a decrease in its radius.
• The ionic radii follow regular trend.
Ionisation enthalpies:
• I.E. decreases on moving down a group : Increase in atomic size and screening effect much
more than increase in nuclear charge.
I.E. of Ga higher than Al
Smaller size of Ga as compared to Al.
I.E. of Tl higher than In due to presence of 14 f-electrons in the inner electronic configuration of Tl
IE2, and 3E3 of Group 13 elements higher than IE
After the p-electron is lost, nuclear charge increases, ionic size increase so removal of 2nd &3 rd
electrons is difficult
2nd & 3rd electron is to be lost from ns-orbital (more penetrating) so large amount of energy required.
Melting and Boiling points
Melting point decrease down the group upto Ga and then increase from In to Tl. Gallium has a low mp
and exists as a liquid at room temperature Boiling points decrease regularly on moving down the
group.
Electronegativity
Decrease from B to Al show slight increase for heavier congeners.

87
Chemical Properties
Boron forms covalent bonds due to small size and high LE. Aluminium forms both covalent & ionic
compounds.
-Al, Ga, In, Tl exist in aqueous solution in their tripositive states.
-
[M(OH)4]– [M(H2O) (OH)4] , [M(OH2)6]3+
2
M=Al,Ga,In,Tl
1. HYDRIDES
• MH type formed whose thermal stability decrease down the group.
• Al forms polymeric hydrides (AiH ) , AIH is a solid, Al-H-AI bridging units.
• Stability of hydrides decreases from Al to Tl due to decrease in strength of M-H bond as size of
atom increases.
• These hydrides are weak lewis acids and form adducts with strong lewis base [B:] MH3:B
[M-Al or Ga]
• Complex hydrides ofAl, Li [AIH4] lithium tetra hydrido aluminate tetrahydrideanion
[MH]–4LiH + AICI3 Bi
2o
 LiAIH4 + 3LiCl
• Li ALH4 - - White crystallne solid
- Soluble in diethyl ether
- Powerful reducing agent used in organic reactions
2. HALIDES
• AL, Ga, In, Tl react with halogens to form trihalides (MX3) anhydrous Al Cl3 strong lewis
acid
• Tl (IE) iodide not known” Fluorides are ionic, high m.p.
• Chlorides, Bromides, Iodides, covalent compounds, low m.p.
• Structure of A1Cl3 exists as dimer(Al2Cl6)in vapour state as well as in solvent.
Cl
Cl
Cl 22
20 1p
6p
m m
101°
Al 79° (Al) 118°
Cl Cl Cl
• halogen bridge
• Each Al atom completes its octet by accepting a lone pair from the chlorine atom of
another A1Cl3 molecule.

88
BAl atomic size increases, I.E. decreases, strength of M-O bond goes on decreasing so basic
character increases down the group.
• 2 Al (OH)3(s) + 3H2 SO4(aq) --> Al (SO4)3(aq) + 6H2O(1)
• A1(OH)3(s) +NaOH(aq) -->Na[Al(OH) ](aq)+ .
4
• Above eqn’s show amphoteric character of Al (OH)3
• Tl (OH)3 insoluble in water.
• Tl(OH) is soluble and is strong base like alkali metal hydroxides.
• Al, Ga, In, Tl ions exist as octahedral aqua ions [M(OH2)6]3+ in aqueous solution.
4. HALIDES, SULPHATES, NITRATES ETC.
• Salts like halides, sulphates, nitrates and perchlorates exist as hydrates.
• Alums: Aluminium sulphate forms double salts with sulphates of other metal
[MA1(SO4)212H2O]
M – Na+ or K+
Uses of Alum: - Softening of hard water
As a mordant in dying and printing of textiles
(mordant - helps to bind the dye to fabric)
• Ga X, In X and Tl X, X=C1, Br and I
GaX and InX disproportionate in water
3MX(s)  2M(s) + M3+(aq) + 3X–(aq)
5. REACTIVITY TOWARDS AIR

B - Unreative in crystalline form.
Al - Thin oxide layer is formed, protects it from further attack.
Amorphous Boron forms B2O3.
Aluminium on heating in air form Al2O3.

2 E ( s )  3O2 ( g ) 
 2 E2O3 ( s )

2 E ( s)  N 2 ( g ) 
 2 EN ( s )
with denitrogen at high Temp. nitrides are formed.
6. REACTIVITY TOWARDS HALOGENS.
Elements react with halogens to form triholides (except Tl I3).

89
2E(s) + 3X2(g)  2EX3(g) (X=F, Cl, Br, I)
IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON

BORON
Group : 13, Configuration : 1s2 2s2 2p1
Small size, high ionisation enthalpy and low electronegativity.
 B forms covalent molecular compounds.
This shows B resembles C, Si than other members of the group 13.
Boron forms electron deficient compounds which behave as Lewis Acids e.g. BF3.
BF3 reacts with Lewis bases like NH3 to complete octet around Boron.
F3B + : NH3  F3BNH3
Maximum Covalency of B is 4 (no d - orbitals)
IMPORTANT COMPOUNDS OF BORON

1. BORAX - WHITE CRYSTALLINE SOLID
(a) Formula - Na2[B4O5(OH)4]. 8H2O or Na2B4O7. 10H2O
contains tetranuclear units [B4O5(OH)4]2
(b) Borax dissolves in water to give alkaline solution
Na2B4O7 + 2H2O  2NaOH + H2B4O7
(c) Borax is used as water softener and cleansing agent.
(d) Effect of Heat
Na 2 B4O7 .10 H 2O 

10 H 2 O
 Na 2 B4O7  2 NaBO2  B2O3
Sodium Boric anhydride

metaborate
metaborates transition metals have characteristic colour.
Borax Bead test is used to identify them in lab.
With Co - a blue coloured Co(BO2)2 bead is formed.
2. BORIC ACID/ORTHOBORICACID
(a) Formula : H3BO3 / B(OH)3
(b) Preparation :  Acidify an aqueous solution of Borax.
Na2B4O7 + 2HC1 +5H2O + 2NaCl + 4B(OH)3.
(c) Structure of Boric Acid :
Layered structure with planar BO3 units joined by H - bonds
(d) Properties
(i) White crystalline substance
(ii) Weak Monobasic acid

90
(iii) Not a protonic acid but acts as a Lewis acid

–
B(OH)3 + 2HOH  B(OH) 4 +H3O+
(iv) Effect of heat
-H2O
373 K >373K
H3BO3 HBO2 B2O3
SIMPLEST HYDRIDE: BH3

Does not exist as monomer but as a dimer
Simplest boron Hydrides is B2H6 called Diborane.
DIBORANE B2H6
PREPARATION
(1) BF3 with LiAlH4
Diethyle
4BF3 + 3 LiAlH4 2B7H6 + 3 Li F + 3 AIF3.
Ether
(2) By oxidation of sodium borohydride with I2

2 NaBH4 + I2  B2H6 + 2 Na I + H2
(3) Industrial preparation
2BF3 + 6NaH 450

  K
 B2H6 + 6NaF
(4) Higher boranes are prepared by heating B2H6 at 373 – 523 K.
PROPERTIES OF DIBORANE
(1) Colourless, toxic gas.
(2) B.pt l80K.
(3) Catches fire on exposure to air.
(4) It bums in oxygen to give heat.
B2H6 + 3O  B2O3 + 3H2O H comb = - 1976kJ/mol.
Most of the boranes are inflammable in air.
(5) B2H6 is hydrolysed by water to give boric acid
B2H6(g) + 6H2O(1)  2B(OH)3 + 6H2(g)
Boric acid
(6) Diborane reacts with Lewis bases to give borane adducts.
B2H6 + 2NMe3  2BH3. N Me3 Me = Methyl
B2H6 + 2CO  2BH3. CO
(7) Reaction with NH3.

91
2B2H6+6NH3  B2H6.2NH3
 formulated as
3[BH2(NH3)2]+[BH4]–
 heat
2 B3N3H6 + 12 H2
Borazine
(called as inorganic benzene with alternate BH, NH groups)
STRUCTURE OF DIBORANE
4 - Terminal B - H bonds Two centre - Two electron bonds.

2 - Bridge B - H - B bonds Three centre - Two electron bonds.(banana bonds)

92
BONDING IN DIBORANE
HYDRIDOBORATES
B forms series of hydridoborates. Simplest is [BH]4– ion -Tetrahedral
e.g. Li BH4, NaBH4 strong reducing agent.
PREPARATION
MH + B2H6 2M+[BH]–
M = Na, Li
GROUP 14
Atomic Radii - The atomic radii of group 14 elements is smaller than corresponding group
13 elements because of increase in effective nuclear charge.
- Atomic radii of group 14 elements increase as we go down the group
due to addition of new energy shell.
- Increase in atomic radii from Si onwards is due to ineffective shielding of
valence electron by intervening d- and f-orbitals.
Ionisation Engery - The 1 st ionisation enthalpies of group 14 elements are higher than corre-
sponding group 13 elements due to greater charge and samller size
The first ionisation energies of elements of group 14 follow the order:
C>Si>Ge>Sn<Pb.
Decrease in value is due to-1) increase in atomic size 2) screeening
effect of inner electrons increase in value from Sn to Pb is due to-1)
poor shielding effect of d- and f- electrons. 2) Increased atomic size of
the elements.
Electropositive
Character - Group 14 elements are less electropositive than group 13 elements
because of smaller size and higher Ionisation energy.
Down the group electropositive & metallic charcater increases
C S Ge Sn Pb
Non-metal Semi-metal Metalloid Metal Metal
Electronegativity - Group 14 elements are more electronegative than group 13 due to smaller
size. Electronegativity decreases down the group because of increase in
size,
M.pts&B.pts - M.pts & B pts of group 14 is higher than group 13 elements.
On moving down the group mpts & b.pts decrease regularly due to in-
crease in size of atom which decreases the interatomic forces of attrac-
tion.
Densities - Regular increase from C to Pb.- due to increase in atomic mass.
Oxidation states a) Due to higher ionisation energy M4+ions of the group are not known.
Formation of M4- - Energetically not favourable.
93
- Large amount of energy required to add four

electrons
But carbon forms carbides e.g. Be2 C, Ca C2, SiC, Al4 C3 carbon
in carbides supposed to be present as C22' or C4" ions
b) Group 14 elements- tetra covalent compounds.
Except C, other elements can have higher
coordination number eg. [SiF]– [SiF6]2, [PbCl6]2
c) Trend down the group +4 to +2 oxidation state. As we move down
the group,
Stability of+4 oxidation state decreases. Stability of+2 oxidation
state
- This is due to inert pair effect.
d) Trend down the group from covalent to ionic character. As we move
down the group.
- Tendency to form covalent compound decreases
- Tendency to form ionic compound increases
Catenation - Defined as ability of like atoms to link with one another through covalent
bonds.
Order for Catenation
C>>Si>Ge>Sn.
- due to decrease in M-M bond energy.
Allotropy - Except Pb all elements show allotropy,
C- graphite, diamond
p  - p  multiple - Ability to form p  -p  multiple bonds decreases as we move from
bonds carbon to lead, bonds
Carbon can form multiple bonds with itself, nitrogen and oxygen.
>C=C<, -C  C, >C  N, >C=O,>C = S are known.
Similar compound of Si & higher elements are rare.
IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF CARBON

Carbon - Group 14.
Configuration - 1s2 2s2 2p2
OCCURRENCE
(1) Isotopes 12C 14
C
(2) Allotropes

94
Crystalline - Diamond, graphite, Fullerenes

Amorphous - Coke, Charcoal, Carbon black etc.
1. DIAMOND
* C-atom - sp3 hybridised, linked to 4 other C-atoms in tetrahedral fashion.
* 3d network of C-atoms
* Hardest substance known
2. GRAPHITE
* Each C-atom - sp2 hybridised, forms 3 sigme bond with neighbouring C-atoms. fourth
electron forms  bond.
* Layered structure, layers are held by Vanderwaal’s forces.
* Each layer - planar hexagonal rings of C-atoms.
* Electrons are delocalised. Conducts electricity along the sheet.
* Easily cleaves between layers, used as a dry lubricant.
FULLERENES - A crystalline allotrope of carbon.

hollow cages of C-atoms.
large spheroidal molecules of composition C2n e.g. C60, C70.
PREPARATION
(1) Evaporation of graphite using a LASER.
(2) Heating graphite in an electric arc in presence of an inert gas like He or Ar  Mix of C60 / C70
obtained.
separated by extraction with Toluene followed by chromatography. Solution of C-60 in Toluene
- Purple in color.
C-70 in Toluene - Orange red in color.
(3) Structure of C-60
(a) Name of structure ; Buckminster Fullerene
Trends in Chemical a) HALIDES –
reactivity (i) - All elements form tetraahalides of type MX4
- Ionic character & thermal stability of halides decrease with in-
crease in atomic no. of Halogens.
PbCl4 and PbBr4 - Unstable
PbI4 -non existent.
- Except C, tetrachlorides of other elements are easily hydrolysed
by water.
SiCl4 + 4H O  Si(OH)4 +4HC1
2
SnCl4 + 2H2 O  SnO + 4HC1
2

95
Ge, Sn, Pb form diahalides MX2 The stability of dihalides increases as.
CX2 « SiX2 « GeX2 « SnX2<PbX2
b. OXIDES – Reactivity towards Oxygen
Si, Ge, Sn and Pb form oxides of composition MO2.
i) SiO2-SILICA
3 D network solid of silicon and oxygenatoms connected by single covalent bonds.
Si is bonded to oxygen in a tetrahedral arrangement.
3 crystalline modifications of SiO2 are(1) quartz(2) cristobalite and(3) tridymite,
Quartz-Piezoelectric material (crystal oscillator & transducers).
Amorphous form of silica
(1) Silica gel; Made by acidification of sodium silicate. Used as drying agent in chromato-
graphic and catalyst support.
(2) Fumed Silica
ii) GeO2? SnO2, PbO2-Solids & exist in several modifications,
iii) Basic / acidic behaviour SiO2-Acidic
GeO2? SnO2-Amphoteric, PbO2-Distinctly basic
Among monoxides
CO is neutral, GeO - Acidic, SnO + PbO - Amphoteric
c. REACTIVITY TOWARDS WATER
Ci, Si, Ge – No affected by water
Sn – decomposes steam to give H2
Sn + 2H2O 
 SnO2 + H2
Pb - Not affected by water ( of protective oxide layer)
SILICONES
- Synthetic organosilicon compounds containing repeated R SiO units held by Si-OSi linkages.
General formula (R2SiO)n R = Me or Ph group.
Formula similar to R CO  Name silicone similar to ketone.
Preparation
- Prepared by hydrolysis of dialkylchlorsilane (R2 SiCI2) or Diaryl dichlorosilane (Ar2SiCl2)

96
PROPERTIES
1. Chemically inert
2. Water repelling nature
3. Heat resistant
4. Good insulating properties
R-Me Or Ph.
Starting monomers R2SiCl2 are prepared by direct reaction of RC1 with Si in presence of metallic Cu
as a catalyst
2RCl + Si Cu  R2SiCl2

powder
370K
USES
1. Greases, Sealants
2. Electrical insulator
3. Water proofing fibres
4. Being biocompatible used in surgical and cosmetic implants.
(IMPORTANT COMPOUNDS OF CARBON AND SILICON
(a) Oxides of Carbon
I. CO - Carbon Monoxide
PREPARATION

97
(1) Incomplete combustion of carbon or carbon containing fuels.

(2) By passing steam over hot coke - Water Gas (CO + H )
(3) By passing air over hot coke - Produce gas (CO + N2)
PROPERTIES
(1) Colourless, Odourless, Poisonous gas.
(2) Powerful reducing agent - used in metallurgy.
(3) Combines with Cl2 to form phosgene.
(4) Combines with transition metals to form metal carbonyls.e.g.Ni(CO)4
2-Carbon Dioxide
PREPARATION
(1) Combustion of C and carbon containing fuels in excess of oxygen.
(2) Lab Preparation -Action of acids on carbonates.
(3) Formed during fermentation.
PROPERTIES OF CARBON DIOXIDE
(1) Colourless gas, heavier than air, sparingly soluble in water, weakly acidic.
(2) CO2 + H2O H2CO3(aq) SILICATE MATERIALS contain following:
Chapter - 13
Hydrocarbons

98
Chapter -12
Organic Chemistry-Basic Principle and Purification Techniques
Structural representation of organic compounds

Complete, condensed and bond-line structural formulae
Complete structural formulae
H H H H
| |
H-C-C-H C=C
| |
H H H H
Ethane Ethene
Condensed structural formulae

CH3 CH3 H2C = CH2 HC  CH CH3OH
Bond line structural representation

lines representing carbon carbon bonds are drawn in a zig zag fashion.
3- Methyl octane (CH3 CH2 CH CH2 CH2 CH2 CH2 CH3)
|
CH3
2 4 6 8
1 3 5 7
Cyclopropane CH2

H2C CH2
CH2
H2 C CHCl Cl
Cyclohexane H2C CH2 

CH2
Three dimensional representation of organic molecules

99
bonds in dashed wedge

the plane (bond away from observer)
of paper C H
H solid wedge
H (bond towards observer)
Classification of Organic Compounds
Acyclic or Open Chain
Organic
compound
Cyclic or closed chain

or Ring compounds (II)
Homocyclic or Carbocyclic Heterocyclic

compounds compounds
Alicyclic Aromtic
compounds compounds
Benzenoid Non-Benzenoid
compounds compounds
1. Acyclic or open chain compounds

(aliphatic compounds)
- straight or branched chain compounds)
O
||
eg. CH3CH3 CH3 - C - H
2. Alicyclic or closed chain or ring compounds
Alicyclic (aliphatic cyclic) compounds contain carbon atoms joined in the form of a ring (homocyclic).
Sometimes atoms other than carbon are also present in the ring (heterocyclic).
Cyclopropane Cyclohexane Cyclohexene Tetrahydrofuran

Aromatic compounds

100
Benzene and related ring compounds (benzenoid)

Heterocyclic aromatic compounds : Aromatic compounds have hetero atoms in the ring.
Benzenoid aromatic compounds

Benzenoid aromatic compounds
NH2
Non-Benzenoid Compounds
(Tropolone)
Heterocyclic aromatic compounds
S N
Furan Thiophene Pyridine
Functional Group
Atom or group of atoms joined in a specific manner which is responsible for the characteristic chemi-
cal properties of the organic compounds.
eg. hydroxyl group (-OH), carboxyl group (-COOH)
Homologous Series
Group or a series of organic compounds each containing a characteristic functional group forms a
homologous series.
Member of series - homologues.
- have general molecular formula
- successive members differ by - CH2 unit
IUPAC nomenclature of Alkanes

101
Straight Chain hydrocarbons :

names end with suffix - ane
members differ by - CH2 groups
Branched chain hydrocarbon
Small chains of carbon atoms are attached at one or more carbon atoms of the parent chain small
carbon chains are called alkyl groups.
CH3 - CH - CH2 CH3 - CH - CH2 -CH3

| Secbutyl
CH3 isobutyl
CH3 - CH - CH3 CH3

| | |
CH3 H3C - C - H3C - C - CH2–
Isopropyl - | |
CH3 CH3
tert - Butyl - Neo pentyl -
Nomenclature of branched chain alkanes

Rules :
(1) Longest carbon chain in the molecule is identified.
(2) The numbering of carbon atoms in the parent chain is done in such a way that the branched
carbon atoms get the lowest possible numbers.
(3) The names of alkyl groups attached as a branch are then prefixed to the name of parent alkane
and position of substituents is indicated by the appropriate numbers. If different alkyl groups are
present, they are listed in alphabetical order.
(4) If two or more identical substituent groups are present then the numbers are separated by
commas. The names of identical substituents are not repeated instead prefixes such as di, tri,
tetra are used.
(5) If the two substituents are found in equivalent positions, the lower number is given to the one
coming first in the alphabetical listing.
(6) The carbon atom of the branch that attaches to the root alkane is numbered 1. The name of
such branched chain alkyl group is placed in parenthesis while naming the compound.
(7) If there are two chains of equal size, then that chain is to be selected which contains more
numbers of side chains.
(8) After selection of the chain, numbering is to be done from the end closer to the substituent.

102
Examples :
CH3 CH3 H3CH2C CH3

| | | |
CH3 - CH - CH2 - CH - CH3 CH3 - CH2 - CH - C - CH2- CH2 - CH3
1 2 3 4 5 1 2 3 4| 5 6 7
CH3
2, 4 - Dimethyl pentane 3 - Ethyl - 4, 4 - dimethyl heptane
CH3 CH3
CH - C - CH - CH - CH3
3 2
1 2 3 4 5
(2, 2, 4 - Trimethyl pentane)
CH2CH3
CH - CH - CH - CH - CH - CH - CH - CH - CH - CH
3 2 2 2 2 2 2 3
CH 2
H C - C - CH
3 3
CH CH 2 3
2 1
5 - (2 - Ethylbutyl) -3, 3- dimethyldecane
1 2 3 4 5 6 7 8 9
CH - CH - CH - CH - CH - CH - CH - CH - CH
1|
CH2
2
|
H3C - C - CH3
3
|
CH3
5 - (2, 2 - Dimethyl propyl) nonane
Cyclic Compounds : Saturated monocyclic compound is named by prefixing ‘cycles’ to the corre-
sponding straight chain alkane.
1
2
3
(cyclopentane) 1 - Methyl - 3 - propylcyclohexane

(Alphabetical order)

103
1
2
3
3 - E thyl - 1, 1 - dimethyl cyclohexane

(more branched carbon gets lower number)
Nomenclature of organic compounds having functional group(s)

- longest chain of carbon atoms containing the functinal group is numbered in such a way that the
functional group is attached at the carbon atom possessing lowest possible number in the chain.
- In polyfunctional compounds, one of the functional group is principal functional group, remaining
functional groups are subordinate functional group.
Order of decreasing priority

- COOH, - SO3H, - COOR ( R= alkyl group), - COCl, - CONH2 ,
- CN, - HC = O, C = O, - OH, - NH2, C C , –C  C–
eg. HOCH2 (CH2)3 CH2 COCH3

7 - hydroxy heptan - 2 - one
CH2(OH) CH2(OH)
Ethane -1, 2 - diol
CH2 = CH - CH = CH2
Buta -1, 3 - diene
1 2 3 4 5 6 7 8
CH3 - CH2 - CH - CH2 - CH2 - CH - CH2 - CH3
| |
OH CH3
6 - Methyl octan - 3 -ol
O
5 || 4 3 2 1
CH3 - C - CH2 - CH4 - CH2 - COOH
5- Oxohexanoic acid
O O
|| ||
CH3 - CH2 - C - CH2 - C - CH3
Hexane -2, 4 - dione
CH  C- CH = CH - CH = CH2
6 5 4 3 2 1

104
Hexa - 1, 3 - dien - 5 - y ne
OH
1
2
Cyclohex - 2-en - 1 - ol
NO2
3
2
3 - Nitrocyclohexene
Nomenclature of substituted benzene compounds
Common names (written in brackets) of substituted benzene compounds are universally used.
OMe NH2
Methyl benzene Methoxybenzene Aminobenzene

(Toluene) (Anisole) (Aniline)
NO2 Br
Nitrobenzene Bromobenzene
Br
Br Br 1
1 2
Br 2
3
Br 4
3 Br
1, 2 – Dibromobenzene 1,3 - Dibromobenzene 1,4 - Dibromobenzene
(o-dibromobenzene) (m-dibromobenzene) (p-dibromobenzene)
Substituents of base compound is assigned number 1 and then the direction of numbering is chosen such that
the next substituent gets the lowest number.

105
NO2
4
1 Cl 3
4 2
NO2 2 Cl
O2N 3 1
CH3
1- chloro 2 - 4 - dinitrobenzene (2 - Chloro - 1 - methyl - 4 - nitrobenzene)
OMe NH2
1
1 2 Cl CH3
2
3 3
4 4
CH3 C2 H5
2 - Chloro - 4 - methylanisole 4 - Ethyl - 2 methylaniline
OH
1
2
3
4 CH3
CH3
3, 4 - Dimethyl phenol
When a benzene ring is attached to an alkane with a functional group, it is considered as a substituent,
instead of a parent compound.
Br
Br
2, 3 - Dibromo-1-phenylpentane

106
ISOMERISM
The phenomenon of existence of two or more compounds possessing the same molecular for-
mula but different properties is known as isomerism.
STRUCTURAL ISOMERISM
The phenomenon of existence of two or more compounds having the same molecular formula but
different structures.
Different types of structural isomerism :

(i) Chain isomoerism
Compounds having similar molecular formula but different carbon skeletons are called chain
isomers.
eg. CH3 CH2 CH2 CH2 CH3 CH3 CH3
(Pentane) | |
CH3- CH CH2 CH3 CH3 - C - CH3
(2 - Methyl butane) |
CH3
(2, 2 - Dimethyl butane)
(ii) Position isomerism

When two or more compounds differ in the position of substituent atom or functional group on
the carbon skeleton they are called position isomers.
eg. CH3 CH2 CH2 OH OH
(Propan - 1 - ol) |
CH3 - CH - CH3
(Propan - 2 - ol)
(iii) Functional group Isomerism
Two or more compounds having the same molecular formula but different functional groups are
called functional isomers.
eg. O H
|| |
CH3 - C - CH3 CH3 - CH2 - C = O
(Propanone) (Propanal)
(iv) Metamerism
It arises due to different alkyl chains on either side of the functional group in the molecule.
eg. CH3 OC3 H7 C2 H5 O C2 H5
(Methoxy propane) (Ethoxy ethane)
STEREO ISOMERISM
Compounds having same constitution and sequence of covalent bonds but differ in relative position of
their atoms or groups in space.
This special type of isomerism is classified as (i) geometrical (ii) optical isomerism.
REACTION MECHANISM
A sequential account of each step describing details of electron movement, energetic during
bond cleavage and bond formation, and the rates of transportation of reactants into products

107
(kinetics) is referred to as reaction mechanism.
organic molecule Re  [Intermediate]  Products (S)

agent

(substrate) Byproduct
Substrate : that reactant which supplies carbon to the new bond.

other reactant is called reagent.
FISSION OF A COVALENT BOND
HETEROLYTIC CLEAVAGE
The bond breaks in such a fashion that the shared pair of electrons remains with one of the fragments.
H3C - Br  H3C+ + Br -
|
(a) Carbocation
A species having a carbon atom possessing sextet of electrons and a positive charge is called
carbocation.
+
eg. CH3
Primary carbocation : one carbon attached directly to positively charged carbon.
+
(CH3 CH2)
Secondary carbocation : two carbons attached directly to positively charged carbon.

+
(CH3)2 CH
Tertiary carbocation : three carbons attached directly to positively charged carbon.

+
(CH3)3 C
Carbocation Stability :
+ + + +
CH3 < CH3 CH2 < (CH3)2 CH < (CH3)3 C
Alkyl groups directly attached to positively charged ion stabalise the carbocations due to induc-
tive and hyperconjugation effects.
Carbocations : Trigonal planar shape . positively charged carbon sp2 hybridised.

(b) Carbanion
formed due to heterolytic cleavage, when carbon gets the shared pair of electrons (carbon
species carrying a negative charge on carbon atom)
CH3 – Z  H3C –: + Z+

108
Order of stability
CH 3  (CH 3 CH 2 )  (CH 3 ) 2 CH  (CH 3 ) 3 C
HOMOLYTIC CLEAVAGE
One of the electrons of the shares pair in a covalent bond goes with each of the bonded atoms.
R  R 
X Homolysis
 X
Alkyl free radical
Free Radicals
Neutral species (atoms or group) which contains an unpaired electron formed due to homolytic
cleavage.
Order of stability :
. . . .
CH3 < CH2 CH3 < CH(CH3)2 < C (CH3)3
Nucleophiles and electrophiles

Nucleophile : A reagent that brings an electron pair i.e. Nucleus seeking and reaction is nucleophilic
 :, R N :, R NH
eg. negatively charged ions with lone pair of e’s. as OH  , NC  , R3C : , H 2O 3 2
Electrophile : A reagent that takes away an electron pair is called electrophile i.e. electron seeking.
e.g. Carbocations (  CH 3 ), neutral molecules having functional groups like carbonyl
group (> C = O) or alkyl halides (R3 C - X),
+ +
species like BF3, Cl , CH3-C = O, NO2

+
During bonding interactions. the electrophiles receive electron pair from nucleophile.
Electron movement in Organic reactions

Movement of single electrons - single barbed ‘fish hooks’ (half headed curved arrow)
HO Br movement of pair of electron

+ CH3 CH3 OH + Br
Electron displacement effects in covalent bonds

1. Inductive effect
When a covalent bond is formed between atoms of different electronegativity, the electron
density is more towards the more electronegative atom of the bond. Such a shift of electron
density results in polar covalent bond. The polar bond induces polarity in the adjacent bonds,
such polarisation of  bond in question, by the polarisation of adjacent  bond is referred to
as the inductive effect.
  +
 +
 -
CH3  CH2 ----Cl

109
2 1
Inductive effect decreases rapidly as the number of intervening bonds increases and becomes
vanishingly small after three bonds.
Electron withdrawing groups : Halogens, nitro (-NO2), Cyano (-CN), Carboxy (-COOH), ester
( -COOR), aryloxy (-OAr)
Electron donating groups : alkyl groups like methyl and ethyl.
Resonance Structure
According to Resonance theory, the actual structure of some organic molecules cannot be represented
by single Lewis structure but it is a hybrid of more than one structures called resonance structure
(hypothetical)
+ O + O
CH3 N CH3 N
O O
The two N - O bonds of nitromethane are of the same length.

- Energy of actual structure of the molecule (resonance hybrid) is lower than that of any of the
canonical structure s.
- Difference of energy between the actual structure and the lowest energy resonance structure is
called the resonance stabilisation energy or resonance energy.
Rules for writing resonance structure :

Resonance structure have :
(i) the some positions of nuclei.
(ii) the same number of unpaired electrons.
(iii) Amongst resonance structure, the one with more number of covalent bonds, all the atoms with
octet of electrons, less separation of opposite charges and more dispersal of charge is more
stable than others.
Resonance effect
The polarity produced in the molecule by the interaction of two  bonds or between a  bond and
lone pair of electrons present on an adjacent atom.
(i) Positive Resonance effect ( + R effect or M effect)
The transfer of electrons is away from an atom or substituent group attached to the conjugated
system.
eg. Aniline

110
+ + +
NH2 NH2 NH2 NH2
Atoms or substituent groups which represent + R effect :

halogen, - OH, -OR, -OCOR, -NH2 , -NHR, -NR2, -NHCOR
(ii) Negative Resonance effect (-R effect)
The transfer of electrons is towards the atom or substituent group attached to the conjugated
system
- -
O O O O O O O O
N N N N
+
+
Atom of substituent groups which represent - R effect :
-COOH, - CHO, C = O, - CN, -NO2
Conjugated system : Presence of alternte sngle and double bonds in an open chain or
cyclic system.
eg. Buta -1, 3 - diene, aniline, nitrobenzene.
Electromeric effect : (Temporary effect)
Compound having multiple bonds show this effect in the presence of an attcking agent.
It is the complete transfer of a shared pair of  electrons to one of the atoms joined by a
multiple bond on the demand of an attacking reagent.
(iii) Positive Electromeric effect ( + E effect) :
The  electrons of the multiple bond are transferred to that atom to which the reagent gets
attached.
+
C C + H+ C C
(attacking H
agent)
(iv) Negative Electromeric effect (- E effect)

 electrons of the multiple bond are transferred to that atom to which the attacking reagent
does not get attached.

111
HYPERCONJUGATION (permanent effect) - No bond resonance (Stablising interaction)  ele

trons of C - H bond of the alkyl group enters into partial conjugation with the attached unsaturated
system or with the unshared p-orbital.
Hyperconjugation stabilises the carbocation because electron dencity from the adjacent  bond
helps in dispersing the positive charge.
+
H H H H H H H H
| | | | | | |
H-C-C +
H-C=C H +
C=C H-C=C
| | | | | | |
H H H H H H H H
+
greater the number of alkyl groups attached to a positively charged carbon atom, the greater is the
hyperjugation interaction and stabalisation of the cation.
(CH3)3C+ > (CH3)2 CH > CH3CH2 > CH3
Methods of purification of organic compounds

1. Sublimation
Sublimable substance : substance which on heating, changes from solid to vapour state without
passing through liquid state.
eg. NH4Cl, Camphor, naphthalene, iodine
Technique separates sublimable compounds from non sublimable impurities.
2. Crystallisation
Based on the difference in the solubilities of the compounds and the impurities in a suitable
solvent.
eg. separation of crystals of alum from its impurities.
3. (a) Distillation
Used to separate :
(i) Volatile liquids from non volatile impurities
(ii) Liquids having sufficient difference in their boiling points.
eg. Mixture of chloroform and Aniline.

112
(b) Fractional distillation

Used when the difference in boiling points of two liquids is not much. The vapours of such
liquids are formed within the same temperature range and are condensed separately.
eg. separation of different fractions of crude oil in petroleum industry.
(c) Distillation under reduced pressure
This method is used to purify liquids having very high boiling points and those, which
decompose at or below their boiling point.
eg. separation of glycerol from spent - lye in soap industry
(d) Steam distillation

It is applied to separate substacne whicha re steam volotile and are immisible with water.
The liquid boils when the sum of vapour pressure due to the organic liquid(p1) and that
due to water (p2) becomes equal to the atmosphere pressure p. ie. p = p1+ p2.
eg. separation of Aniline from aniline - water mixture.
4. Differential extraction
When an organic compound is present in an aqueous medium, it is separated by shaking it with
an organic solvent in which it is more soluble than is water. The two distinct layers of organic
solvent and the aqueous solution can be separated by separating funnel.

113
5. Chromatography
Technique uses to separate mixture into their compounds, purify compounds and also test the
purity of compounds.
Stationary phase : Solid or a liquid
Mobile phase : A pure solvent, a mixture of solvents or a gas.
(a) Adsorption Chromatography

Based on that fact that different copounds are adsorbed on an adsorbent to different
degree.
Adsorbents - Silica gel, alumina
(i) Column Chromatography
Involves separation of a mixture over a column of adsorbent (stationary phase) packed in a glass
tube.
(ii) Thin layer Chromatography
TLC involves separation of substances of a mixture over a thin layer of an adsolbent coates on a glass plate
(Chromaplate)
Retardation factor
Dis tan ce moved by the subs tan ce from base line

or Rf value = Dis tan ce moved by the solent from base line
Spots of colourless compounds whose fluorescence can be detected by putting the palte under UV
light.
Plate is put in jar containigng Iodine. Compounds which adsorb iodine show brown spot.
- Reagent is sprayed on the plate eg. amino acids are detected by spraying the plate with Ninhydrin
solution.
Partition Chromatography
Based on the continuous partitioning of components of a mixture between stationary and mobile
phases.

114
eg. Paper Chromatography : stationary phase  water trapped in filter paper

mobile phase  solvent
QUANTITATIVE ANALYSIS
1. Carbon and Hydrogen
 y
CxHy   x   O2  xCO2  ( y / 2) H 2O CO absorbed on potassium hydroxide
 4 2
H2O absorbed on anhydrous CaCl2

mass of organic compound =mg
mass of water = m1 g
mass of CO2 = m2 g
12  m2  100
% of C 
44  m
2  m1  100
% of hydrogen 
18  m
2. Nitrogen
(a) Dumas Method
Cx Hy Nz  (2 x  y / 2) CuO  xCO2  y / 2 H 2O  Z / 2 N 2  (2 x  2y ) Cu

Volume of nitrogen collected = V1 mL
room temp = T1 K

115
p1V1  273
Volume of Nitrogen at STP  760  T  VmL
1
Where p1 = Atmospheric pr - aq. tension.

22400 mL . N2 at STP weighs 28g
28  V
VmL N2 at STP weighs g
22400
28  V  100
% of Nitrogen =
22400  m
(ii) Kjeldahl’s method

Organic compound + H2SO4 (NH4)2 SO4
2  Na2SO4 + 2NH3 + 2H2O

NaOH
2NH3 + H2SO4  (NH4)2SO4
14 M 2(V  V1 / 2) 100
% of N  
1000 m

116
Estimation of Halogens
Carius Method
mass of org. compound =mg

mass of Ag X formed = m1 g
at mass of X  m1 g
mass of halogen = molecular mass of AgX
at mass of  X m1  100
% of halogen = molecular mass of AgXm
Sulphur
mass of org. compound = mg
mass of BaSO4 = m1g.
32  m1  100
% of S =
233  m
Phosphorus
mass of ammonium phospho molybdate = m1 g
31 m1  100
% of P = % molar mass of (NH4)3 PO4. 12 Mo O3 = 1877 g
1877  m
It phosphorus is estimated as Mg2P2O7 (by adding magnesia mixture)
62  m1  100
% of P = %
222  m
Oxygen
Compound 
 O2 + other gaseous products
2C + O2 1373
 K
 2CO
I2O5 + 5CO  I2 + 5CO2

117
mass of org. compound = mg

mass of CO2 = m1 g
32  m1 100
% of Oxygen = %
44  m

118
Chapter -13 Hydrocarbons

ALKANES
I. Preparation
1. Hydrogenation
H2
RCH  CHR R CH 2 CH 2 R
Ni or Pt or Pd
RC  CR  2 H 2 Ni
or  R CH 2 CH 2 R
Pt or Pd
2. Reduction of Alkyl Halides

Zn / HCl
RX  H 2 RH  HX
or Zn  Cu Couple  Alcohol
3. Wurtz Reaction
R  X  2 Na  R  X Ether
  R  R  2 NaX
4. Decarboxylation
R COO  Na  NaOH
 / CaO
 RH  Na 2CO3
5. Kolbe’s Electrolytic Method
R COO  
e
RCOO   R  CO2
R   R   R  R.
II. Properties
1. Substitution Reaction
- Halogenation
h
RH  X 2 (Cl 2 or Br2 only )  CH 3Cl  CH 2Cl 2  CHCl 3  CCl 4
- Free Radical Mechanism
2. Combustion
CH 4  2O2  CO2  H 2O H   890kJ mol1
Large amount of heat given out.
3. Oxidation
Cu
CH 4  O2 2CH 3OH
573K / 1100 atm
CH 4  O2 MO
2O3
 H CHO  H 2O
2 R  CH 3  3O2  2 RCOOH  2 H 2O
Ag 2O
(CH 3 ) 3 CH  O  KMnO
4  (CH 3 ) 3 C  OH
(Alkanes with tertiary H)
4. Isomerisation
CH 3 (CH 2 ) 4 CH 3     CH 3  CH  CH 2 CH 2CH 3  CH 3 CH 2 CH  CH 2 CH 3
Anhy AlCl 3 / HCl
n - Hexene | |
2 - Methyl Pentane 3 - Methyl Pentane
5. Aromatization
CH3  (CH2 )4  CH3 Cr
 
2O3 orV2O3 or MO2O3
C6H6
773K, 10-20 atm
Hexane - 4H2

119
6. Reaction with steem

CH 4  H 2O Ni 1273
 K
 CO  3H 2
Industrial preparation of Hydrogen
ALKENES
I. Preparation
1. Dehydration of alcohols.
CH 3CH 2 OH  H     CH 2  CH 2  H 2 O
2 SO 4 or H 3 PO 4 443 K
2. From alkyl halides - Dehydrohalogenation.

RCH2  CH2   alc
KOH
CH2  CH2
3. Dehalogenation
CH2Br
| Zn,Heat
  CH2 = CH2 + ZnBr2
ethanol
CH2Br
4. Reduction of alkynes.
C
R  C  C  R Pd   RHC  CHR.
, H 2 or Na / Liq 3
Pd-C, H2 supported over BaSO4, poisoned with S/Quinoline - Lindlar’s catalyst gives cis
isomer.
Na, NH3 given trans - isomer.
II. Properties
1. Addition Reaction
a) Halogens
CH2 = CH2+Br2 CCl 4  CH2 - Br
Brown |
CH2-Br
Colourless
Decolorisation of Br2.
b) Halogen Acids (HX) - Halogenation
CH3CH = CH. CH3+HCl CH3CH2-CH-CH3
|
Cl
HBr
Markownikov Rule - More substituted product is formed.
Anti Markownikov rule / Kharasch Effect - Less substituted product is formed.
HBr
CH3CHCH3
No Peroxides
Br
CH3 - CH = CH2
HBr
CH3CH2CH2Br
Peroxides
c) Addition of water (Hydration)
CH2 = CH2+H2O H  CH3CH2OH
d) Addition of sulphuric acid

CH2 + CH2 + HOSO2OH H3C – CH2 – OS2OH

120
Ethyl hydrogen sulphate

2. Oxidation Reactions
a) Combustion
C2H4 + 3O2 2CO2+2H2O, H= –1411.0 kJ/mol
b) With cold, dil aqeous solution of KMnO4
- Vicinal glycols are produced.
- KMnO4 solution is decolorised. (Test for unsaturation).
ALKYNES
I. METHODS OF PREPARATION
1. From Calcium carbide
Calcium Carbide is CaC2
CaCO3 
 CaO + CO2
CaO + 3C  CaC2+CO
CaC2 + H2O  Ca(OH)2 + C2H2
ethyne
2. From vicinal dihalides
H H H
alcohol C C
H2 C C H + KOH
-KBr H Br
Br Br -H2O
Na NH2-
+
CH CH + NaBr + NH3
II. Chemical Properties

1. Acidic nature of alkynes.
Hydrogen attached to sp hybridised carbon atoms are acidic due to maximum percentage of s-
character. The c-atoms in alkynes have maximum electronegativity.
Monosodium
ethynide is formed
2. Addition reactions :
i) Addition of dihydrogen
HC  CH  H 2 Pt/ Pd
/ Ni
 H 2C  CH 2 
H2
CH 3  CH 3
ii) Addition of halogens
CH3  C CH Br  Br  CH3 C Br  CHBr
Brown 1, 2 Dibromopropene

121
colour 
Br Br
| |
CH3 - C - CH
| |
Br Br
Colourless 1,1,2,2 Tetra bromopropane
iii) Addition of hydrogen halides

H  C  C  H  H  Br  CH 2  CH  Br H
Br
 CH 3  CH Br2
(gem - dihalides)
1,1 - Dibromoethane
iv) Addition of water
2 
HC  CH  H  OH Hg
   CH 2  C  H Isomerisation CH 3CHO
/ H 333 K
| ethanol
OH
enol form
3. Polymerisation
i) Linear polymerisation
n CH  CH  [CH  CH  CH  CH ] n
Polyethyne
- Conducts electricity under special conditions.
ii) Cyclinc polymerisation
CH
CH Red Hot
CH or
CH iron Tube,
873 K
CH
ARENES
PREPARATION OF BENZENE
1. Cyclic polymerisation of ethyne
CH
CH Red Hot
CH
CH iron Tube,
873 K
CH
2. Decarboxylation of aromatic acids:

122
COO Na
CaO
+NaOH +Na2CO3
3. Reduction of phenol
OH
+Zn +ZnO
Chemical Properties of Benzene

1. Arenes are characterised by electrophilic substitution reactions
Mechanism of electrophilic substitution reactions
Three steps are involved
a) generation of electrophile
b) formation of carbocation
c) Removal of protion from the carbocation intermediate
a) generation of electrophile E+
i) Chlorination
Cl - Cl + AlCl3  Cl+ + [AlCl4]–

Chloronium ion
ii) Friedal Crafts Alkylation
CH 3  Cl  AlCl3  CH 3  AlCl4 
 
iii) Friedal Crafts Acylation

+
CH 3  C  Cl  AlCl3  CH 3  C   AlCl4 

|| ||
O O
iv) Nitration
H
1+ 
HO3SO  H  H  O  NO2 H  O  NO2  HSOCH
4
CH3 3

123
H +
+ 1 H2O + NO
H O NO2 
protonated Nitronium ions
nitric acid
here H2SO4 is acting as acid HNO3 as base

b) Formation of Carbocation
H
+ E
+ E
+
H
sigma complex, Arenium ion
The arenium ion gets stabilised by resonance
H H H H
E H H H
+
+
+
H H
c) Removal of proton
-
H Al Cl4 E
E
+ HCl + AlCl3
+
H
ii) Nitration
H E
HSO4
E
+H2SO4
+
H
2. Addition reactions : a)Under vigorous conditions ie. at high temp. and high
pressure int he presence of Ni catalyst, hydrogenation of benzene gives cyclohexane.

124
Ni
+3H2
b) Addition of halogens
Cl
Cl
Cl
Cl2
U.V. light Cl
Cl
500K
Cl
Benzene hexachloride
(BHC)
3. Combustion :
Benzene burns with sooty flame producing CO2 + H2O.
2C6H6 + 1502 12 CO2 + 6 H2O + Heat
4. Oxidation with hot KMnO4 solution
CH3 COOH
KMnO4/H2O
+3H[O] +3H2O
375-385
Ring remains intact but the side chain is oxidised to - COOH group irrespective of the length of
the side chain.

125
Chapter - 14
Environmental Chemistry
1. Environmental Pollution : It is the effect of undesirable changes in our surroundings that have harmful
effects on plants, animal and human beings e.g. DDT, plastsic materials, heavy metals, chemical,
nuclear wastes etc.
2. Atmospheric Pollution ; It is generally combination of tropospheric and stratospheric pollution.
a) Troposphere : The lowest region of atmosphere in which human beings along with other organ-
isms live is called Troposphere.
b) Stratosphere : Above troposphere between 10 and 50 km aove sea level lies stratosphere.
3. Tropospheric Pollution
(i) Gaseous air pollutants : Oxides of Sulphur, nitrogen and Carbon H2S, hyrdocarbons, ozone,
(ii) Particulate pollutants : Dust, mist, fumes, smoke smog.
(i) Gaseous air pollutants : - Presence of particulate matter in polluted air catalysis the oxidation of
SO2 to SO3.
(a) 2SO2(g) + O2(g)  2SO3(g)
SO2(g) + O3(g)  SO3(g) +O2(g)
SO2(g) + H2O2(l)  H2SO4(aq)
(b) N2(g) + O2(g) 1483

 K
 2NO(g)
2NO(g) + O2(g)  2NO2(g)
NO(g) + O3(g)  NO2(g) + O2(g)
The irritant red haze in the traffic and congested places is due to oxides of nitrogen. NO2 is a
lung irritant.
(c) Hydrocarbons : - Incomplete combustion of fuel.
(d) (i) Oxides of Carbon - CO combines with Hb to form Carboxy haemoglobin which is
300 times more stable than oxygen - haemoglobin complex. Oxygen carrying capac-
ity of blood is reduced.
(ii) Carbon dioxide - Deforestation & burning of fossil fuel increases CO2 level and
disturb the balance in the atmosphere.
4. Global warming and Green House effect :- CO2 molecules also trap heat as they are transparent to
sunlight but not to the heat radiation. If the amount of CO2 crosses. .03% the natural green house
balance may get disturbed.
5. A cid rain :- Rain water has a pH f 5.6 due to presence of H + ions formed by reaction of rain water
with CO2.
H2O (l) + CO2 (g)  H2CO3(aq)
H2CO3(aq) (aq) + HCO-3(aq)
SO2 and NO2 after oxidation and reaction with water fomrs/contributes to acid rain.

126
2SO2(g) + O2(g) +2H2O(l)  2H2SO4(aq)

4NO2(g) + O2(g) +2H2O(l)  4HNO3(aq)
Ammonium salts are also formed and can cause an atmospheric haze. Aerosol particles of oxides or
ammonium salts in rain drops results in wet deposition.
6. Particulate Pollulants - Particulates in the atmosphere may be viable or non viable. Viable particulates
e.g. bacteria, fungi, moulds.
Non viable particulars is divided into
(a) Smoke particulates e.g. Cigarette smoke, smoke from burning of fossil fuel.
(b) Dust to fine solid produced during crushing, grinding and attribution of solid materials.
(c) Mists and produced by particles of spray liquids and by condensation of vapours in air.
(d) Fumes are generally obtained by condensation of vapours during sublimation, distillation.
7. Smog - It is desired from smoke and fog.
(a) Classical smog : It is a mixture of smoke, fog and SO2. It is a reducing mixture called reducing
smog.
(b) Photo chemical smog : It is formed from the action of sunlight on unsaturated hydrocarbons and
nitrogen oxides. It has high conc. of oxidising agents called oxidising smog.
NO2 ( g ) Hr
Sunlight
 NO ( g )  O( g ) (i)
O( g )  O2 ( g )  O3 ( g ) (ii)
NO2 ( g )  O3 ( g )  NO2 ( g )  O2 ( g ) (iii)
Ozone also reacts with unburnt hydrocarbons

3CH4 + 2O3  3CH2 = O + 3H2O
Formaldehyde
CH2 = CHCH = O CH3COONO2
Acrolein ||
O
Peroxy acetyl nitrate (PAN)
Effects of photochemical smog
O3, NO, CH2 = CHCH = O, CH3COONO2 cause serious health prolem.
||
O
O3 and PAN act as powerful eye irritants O3 and NO irritate the nose.
Control of Photochemical smog : Primary precursors should be controlled. Such as NO2 and hydro
carbons and secondary precursors. Such as Ozone, PAN get automatically controlled.
8. Stratospheric Pollution :- Upper stratosphere consists of O3 protect us from the harmful UV radia-
tions coming from the sun.

127
These radiations cause skin cancer in humans.
O2 ( g ) UV
 O( g )  O( g )
O( g )  O2 ( g )  O3 ( g )
Ozone is unstable and decomposes to molecular oxygen. Dynamic equilibrium exists between pro-
duction and decomposition of ozone molecules. CFCS cause depletion of Ozone. Once CFCs are
released in the atmosphere, they mix with the normal atmospheric gases & react the stratosphere.
CF2Cl2 ( g ) UV
 Cl ( g )  F2Cl ( g ) (i)
Cl ( g )  O3 ( g )  ClO ( g )  O2 ( g ) (ii)
ClO( g )  O( g )  Cl ( g )  O2 ( g ) (iii)
Chlorine radicals are continuously regenerated and cause the breakdown of Ozone.
9. Ozone hole :- Antartica repored depletion of Ozone layer known as Ozone hole over the South Pole.
In summer season, NO2, CH4 reacts with Chlorine, atoms and chlorine monoxide forming chlorine
sinks, preventing much ozone depletion and in winters special type of clouds called Polar Strato-
spheric clouds are formed over Antarctica.
ClO( g )  NO2 ( g )  ClO NO2 ( g )
Cl ( g )  CH 4 ( g )  CH 3 ( g )  HCl ( g )
ClONO2 ( g )  H 2O( g )  HOCl ( g )  HNO3 ( g )
ClONO2 ( g )  HCl ( g )  Cl 2 ( g )  HNO3 ( g )
When sunlight returns to Antarctica the sun’s warmth breaks up the clouds, HOCl and Cl2 are
photolysed.
. .
h
HOCl ( g )  OH ( g )  Cl ( g )
.
h
Cl2 ( g )  2Cl ( g )
10. Effects of Depletion of Ozone layer : - UV radiations filters into troposphere. UV raditions leads to
ageing of skin, cataract, sunburn.
11. Water pollution :
Causes of water pollution
(i) Pathogens : It includes bacteria that enter water from domestic sewage.
(ii) Organic wastes : Too much of organic matter is added to water, all available O2 is used up.
Aerobic bacteria degrade these organic wastes. The amount of O2 required by bacteria to
break down the organic matter present in a certain volume of a sample of water is called
Biochemical Oxygen Demand (BOD).
(iii) Chemical Pollutants :- Heavy metals Cd, Hg, Ni, constilute an important class of pollutants.
Organic chemicals are another group of substances that are found in polluted water. Various
industrial chemicals like polychlorinated biphenyls (PCBs) which are used to cleansing solvent

128
add to list of water pollutant. The addition of phosphates in water enhances algae growth. It
results in lack of oxygen, which is eutrophication.
12. International standards for drinking water
(i) Fluoride :- F- ions make the enamel on teeth much harder by converting hydroxyapatite, the
enamel into much harder fluorapalite.
(ii) Lead :- Excess pH can damage Kidney, liver etc.
(iii) Sulphate :- Excess sulphate causes laxative effect.
(iv) Nitrate :- The maximum limit of NO3–. is 50 ppm. Excess causes methemo globinemia (‘blue
baby’ syndrome)
13. Soil Pollution :- Insectides, pesticides and herbicides cause soil pollution.
(i) Pesticides :- They are basically synthetic toxic chemicals with ecological repercussions. Most of
the organic toxins are water insoluble and non biodegradable. They disturb the food chain.
(ii) Herbicide :- Herbicides such as NaClO3, (Sodium Chlorate), Sodium Arsinite (Na3AsO3) are
toxic to mammals.
(iii) Industrial waste :- Industrial solid water are sorted out is biodegradable and non-biodegradeable
wastes. Non biodegradable waste are generated by thermal power plants which produce flyash.
Hazardous wastes such as composite explosives or highly reactive substances are produced by
industrial dealing in metals, chemical.
14. Strategies to control environmental pollution:
(i) Waste management : Improper disposal of wastes is one of the major causes of environmental
degradation.
(ii) Collection and Disposal :- Domestic wastes are transferred to community bins which are later
collected & carried to disposable site. The plastic waste like polythene bag choke the serves &
cause in convenience.
15. Green Chemistry :- The extent of any reaction depends upon physical parameters like Temp, press &
catalyst, if there are fully converted into useful environmental friendly products.
Green Chemistry in day to day life
(i) (Cl2C = C Cl2) Tetra Chloro ethene was used as solvent for dry cleaning, it contaminates
ground it now replaced by liquified CO2. H2O2 is used as bleaching agents which gives better
results.
(ii) Bleaching of paper :- H2O2 has now substituted Cl2 gas.
(iii) Synthesis of Chemicals :- CH3CHO is commercially prepared by one step Oxidation of ethene
with 90% yield.
Catalyst
CH2 = CH2+O2 Pd ( II ) / Cu ( II ) in H O CH3CHO (90%)
2

129
CHEMISTRY PRACTICAL
BASIC LABORATORY TECHNIQUES
EXPERIMENT 1A
AIM: To cut glass tube/rod.
MATERIAL REQUIRED: Glass tube, glass rod, triangular file, Bunsen burner, sand paper, asbestos
sheet, wire gauze.
PROCEDURE:
1. Place glass tube/rod on the table.
2. Make a small mark on the tubing at desired length with the help of marker.
3. Make a deep scratch on the glass tube at desired length with the help of triangular file on mark. The file
should be at right angles to the glass tubing.
4. Hold the tube with both the hands such that one thumb is on either side of the scratch but on the opposite
sides of the scratch. Now slightly press the tube with the thumbs. The tube will break at the scratch.
5. The tube or rod cut above can be rounded off using flame.
PRECAUTIONS:
1. The scratch should be made in one stroke only. 2. The file should be moved backwards only. 3. Do
not press file on the tube to such an extent that the tube may smash.

130
EXPERIMENT 1B
AIM: To bend a glass tube at given angle.
MATERIAL REQUIRED: Glass tubing, burner, asbestos sheet
PROCEDURE:
1. "Draw twolines on the asbestds sheet at angle at which the tube is to be bent.
Hold the tube horizontally with both the hands and heat it on the-oxidizing flame, keep rolling the
tube while heating
2 When.thetube starts softening at:the, point of heating, keep one side of the tube held firmly in one hand
and let the tube bend under its own weight, the other hand simply guiding the direction of bending.
3 Keep the tube on the asbestos sheet and if it is not in one plane do it by gently pressing, and let it cool
down.
PRECAUTIONS:
1. Point of heating must be away from hands.
2. Keep rotating the tube for uniform heating.
3. Don't bend the tube forcibly.
4. Bent tube should be in same plane.

131
EXPERIMENT: 1C
AIM: To bore a hole in cork.
MATERIAL REQUIRED:
Ccrft, cork pressure, cork borer set, NaOH solution, water.
PROCEDURE:
1.Place a rubber cork on the table with its small end in the upward direction.
2.Hold the cork with the left hand and put a suitable borer dipped in NaOH solution in
3.Hold the borer vertically and drill the cork by rotation the borer and applying the pressure
gently
4.Bore the cork from both the sides.
PRECAUTIONS:
1.Select the cork of appropriate size.
2.The cork should be free from cracks and holes.
3.Select the borer cautiously.
The boring should be done vertically downwards

132
EXPERIMENT NO. 2
DETERMINATION OF pH VALUES
AIM: To determine the pH malues of various samples using universal indicator.
MATERIAL REQUIRED: -Beakers, test tubes, pH paper otuniversilAidicator, distilled water; mud Water,
hydrochloric acid,acetic acid, sodium hydroxide, sodiurnbicarb-priate, tea..orange juice.
THEORY:
The pH of a solution is defined as the negative logarithrn of:hr:Inter-Lion concentration
pH = -:log[H 30+]
Neutral solutions have pH value as 7, acidic solutions have-pH values less thin -7 and basic Solutions have
pH values greater than 7.
PROCEDURE:
1. Take different samples in various test tubes.
2. Use pH paper or universal indicator solution to determine the pHUes,
3. Note down the colour and record the observations.
OBSERVATIONS:
S.No SAMPLE COLOUR pH [H3O+] Nature

1 HYDROCHLORIC ACID
2 ACETIC ACID
3 SODIUM HYDROXIDE
4 SODIUM
BICARBONATE
5 DISTILLED WATER
6 MUD WATER
7 TEA
8 JUICE
Precautions
1. Handle apparatus and chemicals carefully.

2. Match the colours with values carefully.

133
EXPERIMENT NO. 3
PREPARATION OF COPPER SULPHATE CRYSTALS
AIM: To prepare the crystals of copper sulphate from a given impure sample.
MATERIAL REQUIRED: Beaker, glass rod, funnel, tripod stand, china dish, burner, wire gauze,
filter paper.
THEORY: Recrystallisation is the process in which impure compound is dissolved in a suitable

solvent and • impurities are filtered off. The solution is allowed to get saturated and left for slow
cooling
shape of the crystals is triclinic.
PROCEDURE:
1. Dissolve 2g of sample in minimum amount of distilled water.
2. Stir the solution continuously and add few drops of dilute sulphuric acid in the same.,
3 Filter the solution.
4. Heat the filtrate on burner till the saturation point is reached.
5. Cover the beaker and allow the solution to get slowly cooled down.
6. Reject the mother liquOr and dry the crystal between the folds of filter papers. .
7. Weigh.the dried crystals.
PRECAUTIONS:
1. Stir gently
2. carefully note the saturation point
3.Keep the solution overnight for better yield
RESULT
1. Colour of crystals:
2. Shape of crystals:

134

135
II. Concentrated H2SO4 Group

136

137
For I−
(Iodide)
Yellow precipitate, which is I− is confirmed.

(a) Silver nitrate test
insoluble in Ammonium hydroxide.
Water extract + AgNO3 solution
(b)Organic Layer Test

Violet colour in the organic layer.
Water extract + CCl4 or CS2 + I− is confirmed.
Conc.HNO3. Shake vigorously.
For NO3− (Nitrate)
Ring Test
Water extract+ freshly prepared

FeSO4 solution. Shake well and −
add cone. H2SO4 along the sides A dark brown ring is formed at NO3 is confirmed.
of the test tube. the junction of two the layers.
For CH3COO− (Acetate)
(a) Ester Test

Salt + conc. H2SO4 + ethanol and
Fruity smell CH3COO− is confirmed
Heat
(b) Ferric Chloride Test

Water extract ¦+ few drops of
neutral FeC13 solution. Divide into
Deep red colouration CH3COO− is confirmed
2 parts-
(i) To one part add dil. HCI
(ii) To second part add water and

boil. Red colouration disappears.
Reddish brown precipitate
For C2O42− (oxalate)

138
Experiment Observation Inference
For SO42− (Sulphate)
(a) Water extract + BaCl2 White precipitate is formed which SO42− is confirmed.
is insoluble in dil. HCl
(b)Water extract + Lead acetate White precipitate is obtained. SO42− is confirmed.
For PO43− (Phosphate)
A canary yellow precipitate PO43− is confirmed.

Water extract + conc. HNO3 is formed.
and heat. Cool the test tube
and then add Ammonium
molybdate, (NH4)2MoO4
BASIC RADICALS
They are divided into 7 main groups
Group number Cations Group reagent
Zero group NH4+ --------

Group 1 Pb2+ dil.HCl
Group II Cu2+, As3+ dil.HCl + H2S gas.
Group III Fe3+, Al3+ NH4Cl + NH4OH
2+ 2+ 2+
Group IV Co , Mn , Zn , NH4Cl + NH4OH + H2S
Ni2+
Group V Ba2+, Sr2+, Ca2+ NH4Cl + NH4OH +(NH4)2CO3
2+
Group VI Mg NH4H2PO4

139
Zero Group
For NH4+ (Ammonium)
(a)Salt + NaOH. Heat. A gas with smell of NH4+ is confirmed.

Ammonia
Dense white fumes are formed.

Bring a rod dipped in dil. HCl NH4+ is confirmed.
near the mouth of the test tube.
Reddish brown
precipitate is formed NH4+ is confirmed.
(b) Original solution + NaOH
+Nessler’s Reagent
(K2HgI4)
Group I Group reagent – Dilute HCl

For Pb2+ (Lead)

(a) Original solution + dil
HCl White precipitate is Pb2+ may be present.
obtained
(b) Dissolve the precipitate in hot

water. Divide into 3 parts:
(i) Part I-Allow it to cool. White crystals reappear.
Pb2+ is confirmed.
(ii)Part II + KI Yellow precipitate is
formed
Pb2+ is confirmed.
(iii) Part III + K2CrO4
Yellow precipitate is
formed Pb2+ is confirmed

140
For Cu2+ (Copper )

(a) Original solution or solution of
group I if test is negative + dil. HCl Black precipitate is formed Cu2+ may be present.
+ H2S gas.
(b) Dissolve the ppt. in 50%

HNO3.Divide it into 2 parts:
(i) Part l + NH4OH in excess

Blue coloured solution Cu2+ is confirmed.
. is obtained.
(ii) Part II+ K4[Fe(CN)6] Chocolate brown
precipitate is formed. Cu2+ is confirmed.
(Potassium ferrocyanide).
For Arsenic (As3+)
Original solution + dil. HCl Yellow precipitate. As3+ may be present.

+ H2S gas.
Dissolve the precipitate in

hot conc. HNO3..
(i) Part I + Ammonium Yellow precipitate is As3+ is confirmed

molybdate formed.
(ii) Part II+ NH4OH White precipitate is

As3+ is confirmed
formed
& magnesia mixture

141
Group III Group reagent- NH4OH in presence of NH4Cl
For Fe2+/ Fe3+
(a) Original solution or Reddish brown precipitate Fe3+ may be present.

filtrate of group II+ conc. is obtained
HNO3 + boil
+ solid NH4Cl in excess

+NH4OH
Fe3+ is confirmed.
Dissolve the precipitate in dil.
HC1 and divide into2 parts:
Prussian blue colour is obtained

Fe3+ is confirmed.
(i) Part I + K4 [ Fe(CN)6]
Blood red colouration

Fe3+ is confirmed.
(ii) Part II + KCNS
(Potassium thiocyanate) .
For Al3+ Gelatinous white precipitate Al3+ may be present.

is formed
Original solution + solid
NH4Cl in excess +NH4OH.
Blue lake test A blue floating mass in the

colourless solution is Al3+ is obtained.
Dissolve the precipitate in obtained.
dilute HCl. Add blue litmus
solution and then add
ammonium hydroxide
solution drop by drop.

142
Group IV: Group reagent – H2S gas in presence of excess NH4Cl and NH4OH
For Co2+ (Cobalt)
(a) O.S. or filtrate of group

III +solid NH4Cl in excess +
NH4OH + H2S gas. A black precipitate is formed. Co2+ or Ni2+ may be
present.
(b) Dissolve the precipitate

in aqua regia (3 parts of conc.
HC1 + 1 part of conc. HNO3).
Heat to dryness + add water.
A pink coloured solution is
obtained. Co2+ may be present.
(c)To the above solution

add Amyl alcohol +
NH4SCN (Ammonium
thiocyanate).
(The above test may be
performed with the original
solution) Blue colour in alcoholic layer.
Co2+ is confirmed.
For Ni2+ (Nickel)
(a) O.S. + solid NH4Cl in

excess + NH4OH+ H2S gas
A black precipitate is formed. Co2+ or Ni2+ may be
present.
(b) Dissolve the precipitate

in aqua regia (3 parts of
conc. HC1 + 1 part of conc.
HNO3). Heat to dryness +
add water.
A green coloured solution is
obtained. Ni2+ may be present.
(c) To the above solution add

NH4OH + Dimethyl
glyoxime.

143
For Zn2+ (zinc)

O.S. + solid NH4Cl in excess + White precipitate is formed.
NH4OH+ H2S gas.
Zn2+ may be present.
Dissolve the precipitate in
dil.HCl. Divide into 2
parts:
(i) Part I + NaOH drop

White precipitate is formed which
wise.
is soluble in excess of NaOH.
Zn2+ is confirmed.
Bluish white precipitate.
(ii)Part II + NH4OH +
K4[Fe(CN)6] Zn2+ is confirmed.
For Mn2+ (Manganese)

O.S. + solid NH4Cl in excess + Buff coloured precipitate is Mn2+ may be present
NH4OH+ H2S gas. formed.
Dissolve the ppt. in dil. White precipitate is formed
HCl + NaOH. which turns grey on standing. Mn2+ is confirmed.

144
Group V Group reagent – (NH4)2CO3 in presence of presence of excess NH4Cl and NH4OH

For Ba2+(Barium)
(a) O.S. + solid NH4Cl in excess + White precipitate is obtained. Ba2+, Sr2+, Ca2+may be present.
NH4OH+ (NH4)2CO3
Dissolve the precipitate in hot acetic acid

and divide the solution into3 parts:
Part I + Potassium chromate.
(b)Flame test
Salt + conc. HCl Make a paste and Yellow precipitate. Ba2+is confirmed.
take it on a platinum wire. Bring it
near the flame and observe.
Apple green flame Ba2+is confirmed.
For Sr2+(Strontium)
(a) O.S. + solid NH4Cl in excess + White precipitate is obtained. Ba2+, Sr2+, Ca2+may be present.
NH4OH+ (NH4)2CO3
Dissolve the precipitate in hot acetic acid

and divide the solution into3 parts:
Part I + Potassium chromate.
Part II + Ammonium sulphate

No precipitate is obtained. Ba2+is absent.
(b)Flame test
Salt + cone. HCl Make a paste and White precipitate is obtained. Sr2+is confirmed.
take it on a platinum wire. Bring it
near the flame and observe.
Crimson red flame Sr2+is confirmed.

145
Group VI: Group reagent – NH4H2PO4 in presence of presence of excess NH4Cl and NH4OH
For Mg2+ (Magnesium)
O.S. + solid NH4Cl in excess + Crystalline white precipitate Mg2+ is confirmed.

NH4OH+ (NH4)2H2PO4. Scratch is obtained.
the inner sides of the test tube with
a glass rod.

146
ANALYSIS OF A SALT
Aim: To analyse the given salt for acid and basic radicals.

147
b) Ring test
To 2-3 mL of the salt A dark brown ring NO3 - confirmed.
solution added freshly formed at the
prepared FeSO4 junction of the two
solution. Now added liquids. .
cone. sulphuric acid
along the sides of the
test tube carefully. .
BASIC RADICAL
( CATION )
Heated a pinch of the salt with Ammonia gas was NH4 + absent.
conc. NaOH solution. not evolved.
Preparation of original -
solution ( 0.S.)
Shook a pinch of the salt with Clear solution was Original solution
water. obtained. obtained
To a part of the O.S. added No ppt. formed. Group. I abSent

1 -2 mL of dil. Hydrochloric (Pb2+absent ) maybe
acid
Through a part of the above No ppt. formed. Group II .absent.

solution, passed H2S. (Pb2+ , As3+and
Cu2.+ absent) maybe
To the remaining solution, Group III absent.

No ppt. formed.
added a pinch of solid (Fe3 + and Al 3 +
-
ammonium chloride. Boiled absent) maybe
the solution, cooled it and
added excess of ammonium
hydroxide solution.
Through a part of this No ppt. formed. Group IVabsent.

solution, passed 1-125 gas. (Zn2+ Mn2+ , Ni2+
and Co2+ absent)
maybe
To the remaining ammonical White,ppt. formed.
solution added ammonium Group
Group V present
carbonate solution. (CA2+,
(Ca2+,Ba2+Ba2+, Sr
,Sr2+ present

148
8. Confirmatory test for

barium ion
Filtered the above white

ppt dissolved the ppt. in hot dil
acedtic acid
a. Potassium chromate test Yellow ppt Ba2+ Confirmed

To one part of the above obtained
solution,added a few
drops of potassium
chromate solution.
b. Flame Test Persistent grassy Ba2+ Confirmed

Performed flamed test with green flame on
the salt / ppt prolonged heating

149
Chemical Equations Involved in the Reactions of NO3 -Ions

150
VOLUMETRIC ANALYSIS (CLASS XI)

Aim: To determine the molarity and strength of the give Sodium hydroxide solution, M/20 Oxalic acid
solution is provided to you.
Theory: Titration based upon the reaction between an acid and a base is called Acid-base titration. It is
a neutralsation reaction.
Chemical Equation Involved:
(COOH)2(aq) + 2NaOH (aq)  (COONa)2(aq) + 2H2O(l)
Solution in the Burette: Sodium hydroxide
Solution in the Pipette: Oxalic acid
Indicator: Phenolphthalein
End Point: Colourless to Pink
Procedure
1. Filled burette upto zero mark with sodium hydroxide solution
2. Pipetted 10ml of standard oxalic acid and poured it in conical flask with phenolphthalein
solution
3. Titrated it against NaOH Solution to reach permanent light pink colour.
4. Noted burette readings
5. Repeated thrice to get concordant readings.
Observation table:
Molarity of the given Oxalic acid solution = M/20
Volume of the acid solution take for each titration = 10 mL
S.No. Initial Burette reading Final Burette reading Volume of NaOH used (mL)
Concordant Reading =
Calculations:
n1M1V1 = n2 M2V2
M1V1 = 2 M2V2 M1 = Molarity of Sodium hydroxide solution
V1 = Volume of Sodium hydroxide solution
M2 = Molarity of Oxalic acid solution
V1 = Volume of Oxalic acid solution
M1 = _____ M
Strength of NaOH solution = Molarity × Molar mass of NaOH
= ——— g/L
Result: Molarity of the given Sodium hydroxide solution was found to be——— M.
The strength of the given Sodium hydroxide solution is ——g/L

151
CHEMICAL EQUATIONS, QUALITATIVE ANALYSIS
1. CO32- + 2H+  CO2 + H2O

Ca(OH)2 + CO2  CaCO3 + H2O
CO32- + Mg2+  MgCO3
2. S2- + 2H+  H2S
S2- + Pb2+  PbS
S2- + Na2[Fe(CN)5NO]  Na2[Fe(CN)5NOS]
3. SO32- + 2H+  SO2 + H2O
2KMnO4 + 5SO2 + 2H2O  K2SO4 + MnSO4 + 2H2SO4
SO32- + Ba2+  BaSO3
K2Cr2O7 + H2SO4 + 3SO2  Cr2(SO4)3 + K2SO4 + H2O
4. NO2- + H2SO4  HSO4- + HNO2
3HNO2  HNO3 + 2NO + H2O
2NO + O2  NO2
NO + 2KI + O2  KNO2 + I2
I2 + STARCH  BLUE COMPLEX
5. Cl- + H+  HCl
HCl + NH3  NH4Cl
Cl- + AgNO3  AgCl + NO3-
AgCl + NH3  [Ag(NH3)2]Cl
CHROMYL CHLORIDE TEST
4Cl- + K2Cr2O7 + 3H2SO4  K2SO4 + 2CrO2Cl2 + 3H2O + 2SO42-
CrO2Cl2 + 2NaOH  Na2CrO4 + 2NaCl + 2H2O
Na2CrO4 + Pb(CH3COO)2  PbCrO4 + 2CH3COONa
6. Br- + H2SO4  HSO4- + HBr
HBr + H2SO4  Br2 + SO2 + 2H2O
Br- + AgNO3  AgBr + NO3-
Br2 + CCl4  Orange colour in CCl4 layer
7. NO3- + H2SO4  HSO4- + HNO3
4HNO3  4NO2 + O2 + 2H2O
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O
BROWN RING TEST
HNO3 + 6FeSO4 + 3H2SO4  3Fe2(SO4)3 + 4H2O + 2NO
FeSO4 + NO  FeSO4.NO

152
8 .CH3COO- + C2H5OH  CH3COOC2H5 + OH-

FeCl3 + 3CH3COO-  Fe(CH3COO)3 + 3Cl-
9. C2O42- + Ca2+  CaC2O4
2MnO4- + 5 C2O42- + 16H+  2Mn2+ + 10CO2 + 8H2O
10 SO42- + BaCl2  BaSO4 + 2Cl-

SO42- + Pb(CH3COO)2  PbSO4 + 2CH3COO-
11HPO42- + 12(NH4)2MoO4 + 23HNO3  (NH4)3(PMo12O40) + 2NO3- +
21NH4NO3 + 12H2O
CATION ANALYSIS
1. NH4+ + NaOH  NaCl + NH3 + H2O
NH3 + HCl  NH4Cl
K2HgI4 + 2NH3  NH2 + NH4I + 2KI
Hg
I H2O
NH2
Hg
Hg
2. Pb2+ + Cl-  PbCl2 soluble in hot water

Pb2+ + K2CrO4  PbCrO4 + 2K+
Pb2+ + 2KI  PbI2 + 2K+
3. Cu2+ + H2S  CuS + 2H+
Cu2+ + 2NaOH + HNO3  Cu(OH)2 + 2Na+ + NO3-
Cu(OH)2 + 2NH4OH + 2NH4NO3  [Cu(NH3)4](NO3)2 + 4H2O
2Cu2+ + K4[Fe(CN)6]  Cu2[Fe(CN)6] + 4K+
4. 2As3+ + 3H2S  As2S3 + 6H+
5. Fe3+ + NH4OH  Fe(OH)3
Fe3+ + K4Fe(CN)6  KFe[Fe(CN)6] + 3K+
6. Al3+ + 3NH4OH  Al(OH)3 + 3NH4+
Al(OH)3 + NaOH  NaAlO2 + 2H2O

153
LAKE TEST
Al(OH)3 + 3HCl  AlCl3 + 3H2O
AlCl3 + NH4OH  Al(OH)3 + NH4Cl
Adsorbs blue litmus
7. Zn2+ + S2-  ZnS
ZnS + 2HCl  ZnCl2 + H2S
ZnCl2 + 2NaOH  Zn(OH)2 + 2NaCl
Dissolve to give Na2ZnO4
2Zn2+ + [Fe(CN)6]4-  Zn2[Fe(CN)6]
8.Mn2+ + S2-  MnS
Mn2+ + 2OH-  Mn(OH)2
2Mn(OH)2 + 2O  2MnO(OH)2 OH O
9. Ni2+ + S2-  NiS |
Ni2+ + CH3-C = NOH.NH4OH CH3-C = N N = C –CH3
|  | Ni |
CH3-C = NOH CH3-C = N N = C – CH3
|
O OH
10.Co2+ + S2-  CoS
Co2+ + 4NH4CNS  (NH4)2[Co(CNS)4] + 2NH4+
11.Ba2+ + CO32-  BaCO3
Ba2+ + CrO42-  BaCrO4
12.Sr2+ + CO32-  SrCO3
Sr2+ + (NH4)2SO4  SrSO4 + 2CH3COONH4
13.Ca2+ + CO32-  CaCO3
Ca2+ + COONH4
|  CaC2O4 + NH4+
COONH4
14.Mg2+ + HPO42- + NH4+  MgNH4PO4 + H+

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CHEMISTRY

Mixture Pure Substances

Homogeneous Heterogeneous Elements Compounds

The International System of Units (SI)

Base Physical Symbol for Name of Symbol for

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Rules to Round Off :- If right most digit is to be removed

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Laws of Chemical Combinations

Average atomic Mass = (0.98892) (12)u + (0.01108) (13.00335)u + (2×10-12) (14.00317)u.

Molecular Mass and Formula Mass

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

No. of moles of solute

No. of moles of solute

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

(This was measured by British Physicist - J.J. Thomson)

Protons and Neutrons

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Developments leading to the Bohr’s Model of Atom:-

Dual nature of electromagnetic radiations

b) Particle nature of electromagnetic radiation. Some observations regarding electromagnetic

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

E  h (h is Planck' s Constant  6.626  10 34 Js )

h   is also called work function and 1

Atomic Spectrum - Continous spectrum (eg-rainbow )

Where n is the principal quantum number.

Bohr’s Model for Hydrogen atom

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Radius of stationary state can be given by rn  n 2 a , a  52.9 pm.

x is uncertainty in position, Px is uncertainty in momentum in x direction.

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Significance of Uncertainty Principle :-

2Px 2Py 2Pz

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Electronic Configuration of Sodium (11) 1s 2 2s 2 2 p 6 3s 1

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

1. Lothar Meyer arrangement

Characteristics of Mendeleev’s Periodic Table

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Present form or Long Form of the Periodic Table - Bohr’s Table

Digit Name Abbreviation

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Group 18 - Noble gases

Periodic Trend in properties of elements

Variation of Atomic Radii in the Periodic Table

Variation within a group

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Isoelectronic ions or species

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

Factors affecting Ionization enthalpy:

Variation of Ionization Enthalpy in the Periodic Table:

Variation along a period:

XI-Study Material-Chemistry-2021 DPS VASANTKUNJ

and completely filled electronic configuration.

Variation within a Group:

Electron Gain Enthalpy (  eg H )

It is measured in eV per atom or kJ per mole.