,

Chemistry is basically an experimental science. In it

we study physical and chemical properties of

substance and measure it upto possibility. The

results of measurement can we reported in two steps

: (a) Arithmetic number, (b) Unit of measurement.

Every experimental measurement vary slightly from

one another and involves some error or uncertainty

depending upon the skill of person making the

measurements and measuring instrument. The

closeness of the set of values obtained from identical

measurement called precision and a related term,

refers to the closeness of a single measurement to its

true value called accuracy.

1.1 Significant figures.

In the measured value of a physical quantity, the

digits about the correctness of which we are surplus

the last digit which is doubtful, are called the

significant figures. Number of significant figures in

a physical quantity depends upon the least count of

the instrument used for its measurement.

(1) Common rules for counting significant figures

: Following are some of the common rules for

counting significant figures in a given expression:

Rule 1. All non zero digits are significant.

Example : x = 1234 has four significant figures. Again

x = 189 has only three significant figures.

Rule 2. All zeros occurring between two non zero

digits are significant.

Example : x = 1007 has four significant figures. Again

x = 1.0809 has five significant figures.

Rule 3. In a number less than one, all zeros to the

right of decimal point and to the left of a non zero

digit are not significant.

Example : x = 0.0084 has only two significant digits.

Again, x = 1.0084 has five significant figures. This is

on account of rule 2.

Rule 4. All zeros on the right of the last non zero

digit in the decimal part are significant.

Example : x = 0.00800 has three significant figures

8, 0, 0. The zeros before 8 are not significant again

1.00 has three significant figures.

Rule 5. All zeros on the right of the non zero

digit are not significant.

Example : x = 1000 has only one significant figure.

Again x = 378000 has three significant figures.

 Rule 6. All zeros on the right of the last non zero

digit become significant, when they come from a

measurement.

Example : Suppose distance between two

stations is measured to be 3050 m. It has four

significant figures. The same distance can be

expressed as 3.050 km or 3.050 × 10 5 cm . In all these

expressions, number of significant figures continues

to be four. Thus we conclude that change in the units

of measurement of a quantity does not change the

number of significant figures. By changing the

position of the decimal point, the number of

significant digits in the results does not change.

Larger the number of significant figures obtained in

a measurement, greater is the accuracy of the

measurement. The reverse is also true.

(2) Rounding off : While rounding off

measurements, we use the following rules by

convention:

Rule 1. If the digit to be dropped is less than 5,

then the preceding digit is left unchanged.

Example : x = 7.82 is rounded off to 7.8, again

x = 3.94 is rounded off to 3.9.

Rule 2. If the digit to be dropped is more than 5,

then the preceding digit is raised by one.

 Example : x = 6.87 is rounded off to 6.9, again x

= 12.78 is rounded off to 12.8.

Rule 3. If the digit to be dropped is 5 followed by

digits other than zero, then the preceding digit is raised

by one.

Example : x = 16.351 is rounded off to 16.4,

again x = 6.758 is rounded off to 6.8.

Rule 4. If digit to be dropped is 5 or 5 followed

by zeros, then preceding digit is left unchanged, if it is

even.

Example : x = 3.250 becomes 3.2 on rounding

off, again x = 12.650 becomes 12.6 on rounding off.

 Rule 5. If digit to be dropped is 5 or 5 followed

by zeros, then the preceding digit is raised by one, if it

is odd.

Example : x = 3.750 is rounded off to 3.8. again

x = 16.150 is rounded off to 16.2.

(3) Significant figure in calculation

(i) Addition and subtraction : In addition and

subtraction the following points should be

remembered :

(a) Every quantity should be changed into same

unit.
 (b) If a quantity is expressed in the power of 10,

then all the quantities should be changed into power

of 10.

(c) The result obtained after addition or

subtraction, the number of figure should be equal to

that of least, after decimal point.

(ii) Multiplication and division

(a) The number of significant figures will be

same if any number is multiplied by a constant.

(b) The product or division of two significant

figures, will contain the significant figures equal to

that of least.
1.2 Units for measurement.

The chosen standard of measurement of a

quantity which has essentially the same nature as

that of the quantity is called the unit of the quantity.

Following are the important types of system for unit,

(1) C.G.S. System : Length (centimetre), Mass

(gram), Time (second)

(2) M.K.S. System : Length (metre), Mass

(kilogram), Time (second)

(3) F.P.S. System : Length (foot), Mass

(pound), Time (second)

(4) S.I. System : The 11th general conference of

weights and measures (October 1960) adopted

International system of units, popularly known as the

SI units. The SI has seven basic units from which all

other units are derived called derived units. The

standard prefixes which helps to reduce the basic units

are now widely used.

Dimensional analysis : The seven basic quantities

lead to a number of derived quantities such as

pressure, volume, force, density, speed etc. The

units for such quantities can be obtained by defining

the derived quantity in terms of the base quantities

using the base units. For example, speed (velocity)

 is expressed in distance/time. So the unit is m/ s or

ms −1 . The unit of force (mass × acceleration) is kg ms −2

and the unit for acceleration is ms −2 .

Seven basic SI units

Length Mass Time Temperatur Electric Luminous Amount

e Current Intensity of

substance

metre Kilogram Second Kelvin (K) Ampere Candela Mole

(m) (kg) (s) (A) (Cd) (mol)

 Derived Units

Physical quantity Unit Symbol

Area square metre m2

Volume cubic metre m3

Velocity metre per second ms–1

Acceleration metre per second square ms–2

Density kilogram per cubic kg m–3

metre

Molar mass kilogram per mole kg mol–1

Molar volume cubic metre per mole m3 mol–1

Molar concentration mole per cubic metre mol m–3

 Force newton (N) kg m s–2

Pressure pascal (Pa) N m–2

Energy work joule (J) kg m2 s–2, Nm

Standard prefixes use to reduce the basic units

Multipl Prefix Symbol Submultip Prefix Symbol

e le

1024 yotta Y 10–1 deci d

1021 zetta Z 10–2 centi c

1018 exa E 10–3 milli m

1015 peta P 10–6 micro µ

1012 tera T 10–9 nano n

109 giga G 10–12 pico p

106 mega M 10–15 femto f

103 kilo k 10–18 atto a

102 hecto h 10–21 zeto z

101 deca da 10–24 yocto y

 Conversion factors

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

C STP

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

molecules

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

mol–1

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

3.79 L MeV

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

3600 kJ

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

s–2 watt

1 J = 1 Nm =1 kg 1 joule = 107 erg 1 debye (D) = 1 × 10 –18 1nm = 10–9 m

m2 s–2 esu cm
1.3 Matter and its classification.

Matter is the physical material of the universe

which occupies space and has mass e.g., water,

sugar, metals, plants etc.

1.4 Separation of mixtures or purification of an

impure substance.

Each component of a mixture retains its own

properties and thus a mixture can be separated into

its components by taking advantages of the

difference in their physical and chemical properties.

The different methods which are employed to

separate the constituents from a mixture to purify an

impure sample of a substance are,

(1) Sedimentation : It is also called gravity

separation. It is used for a mixture in which one

component is a liquid and the other is insoluble solid

heavier than the liquid. Example : Sand dispersed in

water.

(2) Filtration : It is used for a mixture

containing two components one of which is soluble

in a particular solvent and the other is not. Example :

(i) A mixture of salt and paper using water as

solvent (ii) A mixture of sand and sulphur using

carbon disulphide as solvent. (iii) A mixture of glass

powder and sugar, using water as a solvent in which

sugar dissolves but glass does not. (iv) A mixture of

sand and sulphur, using carbon disulphide as the

solvent in which sulphur dissolves but sand does

not.
 (3) Sublimation : It is used for a mixture

containing a solid component, which sublimes on

heating from non-volatile solids. Example : A

mixture of sand + naphthalene or powdered glass +

NH 4 Cl / camphor / iodine etc. can be separated by the

method of sublimation because substances like

naphthalene, NH 4 Cl , iodine, camphor etc. form

sublimates whereas sand, glass etc. do not.

(4) Evaporation : It is used for a mixture in

which one component is a non–volatile soluble salt

and other is a liquid. Example : Sodium chloride

dissolved in sea–water.
 (5) Crystallization : It is a most common

method for a mixture containing solid components

and based upon the differences in the solubilities of

the components of the mixture into a solvent. For

separation, a suitable solvent is first selected. It is of

two types :

(i) Simple crystallization : It is applicable when

there is a large difference in the solubilities of

different components of a mixture.

(ii) Fractional crystallization : It is applicable

when there is a small difference in the solubilities of

different components of a mixture in the same

solvent. Example : K 2 Cr 2 O7 and KCl . Here K 2 Cr 2 O7 is

less soluble in water and hence crystallizes first. A

series of repeated crystallization separates the two

components in pure form.

(6) Distillation : It is the most important method

for purifying the liquids. It involves the conversion

of a liquid to its vapours on heating (vaporisation)

and then cooling the vapours back into the liquid

(condensation). It can be used to separate, (i) A

solution of a solid in a liquid. e.g., aqueous copper

sulphate solution. (ii) A solution of two liquids

whose boiling points are different. Several methods

of distillation are employed.

 (i) Simple distillation : It is used only for such

liquids which boil without decomposition at

atmospheric pressure and contain non–volatile

impurities. Example : (a) Pure water from saline

water. (b) Benzene from toluene.

(ii) Fractional distillation : It is used for the

separation and purification of a mixture of two or

more miscible liquids having different boiling

points. The liquid having low boiling point

vaporises first, gets condensed and is collected in the

receiver. The temperature is then raised to the

boiling point of second so that the second liquid

vaporises and is collected in other receiver. If two

liquids present in a mixture have their boiling points

closer to each other, a fractionating column is used.

Example : (a) Crude petroleum is separated into

many useful products such as lubricating oil, diesel

oil, kerosene and petrol by fractional distillation. (b)

A mixture of acetone and methyl alcohol.

(iii) Vacuum distillation or distillation under

reduced pressure : It is used for such liquids which

decompose on heating to their boiling points. At

reduced pressure, the boiling point of liquid is also

reduced.
Example : Glycerol is distilled under pressure as it

decomposes on heating to its boiling point.

(iv) Steam distillation : It is used for liquids

which are partially miscible with water, volatile in

steam. e.g., aniline, oils etc. are purified by steam

distillation. The principle involved is of reduced

pressure distillation. If Pw and Pl are vapour

pressures of water and liquid at distillation

temperature, then Pw + Pl = P = 76 cm i.e., atmospheric

pressure. Thus, a liquid boils at relatively low

temperature than its boiling point in presence of

steam.
 Example : Some solids like naphthalene, o-

nitrophenol which are steam volatile can be purified.

Nitrobenzene, chlorobenzene, essential oils are also

extracted or separated by this process

(7) Solvent extraction : It is used for the

separation of a compound from its solution by

shaking with a suitable solvent. The extraction

follows Nernst distribution law. The solvent used

must be insoluble with other phase in which

compound is present as well as the compound

should be more soluble in solvent. The extraction

becomes more efficient if the given extracting liquid

is used for more number of extractions with smaller

amounts than using it once with all extracting liquid.

Example : (i) Aqueous solution of benzoic acid by

using benzene. (ii) Aqueous solution of Iodine by

using chloroform or carbon tetrachloride. (iii)

Flavour of tea from the tea leaves by boiling with

water.

(8) Magnetic separation : It is used for a

mixture in which one component is magnetic while

the other is non–magnetic. Example : iron ore from

the non–magnetic impurities.

(9) Chromatography : It is based on the

differences in the rates at which different

components of a mixture are absorbed on a suitable

solvent. It is used in separation, isolation,

purification and identification of a substance. It was

proposed by a Russian botanist Tswett.

(10) Atmolysis : It is used for separation of the

mixture of gases or vapours. It is based on the

difference in their rates of diffusion through a

porous substance. Example :

H 2 , SO 2 , CH 4 and O2 , U 235 & U 238 in the form of their hexa–

fluorides.
 (11) Electrophoresis : It is based upon the

differences in the electrical mobility of the different

components of the mixture.

(12) Ultracentrifugation : It is based upon the

difference in sedimentation velocity of the

components in a centrifugal field.

1.5 Laws of chemical combination.

Various chemical reactions take place according to

the certain laws, known as the Laws of chemical

combination. These are as follows,

(1) Law of conservation of mass : It was

proposed by Lavoisier and verified by Landolt.

According to this law, Matter is neither created nor

destroyed in the course of chemical reaction though

it may change from one form to other. The total

mass of materials after a chemical reaction is same

as the total mass before reaction.

Example : A reaction between AgNO 3 solution

and KI solution.

AgNO 3 (aq) + KI (aq) → AgI + NaNO 3 (aq) (yellow ppt.)

Mass of

AgNO 3 (aq) + Mass of KI (aq) = Mass of the ppt. of AgI + Mass of NaNO 3 (aq)
 According to the modified statement of the law,

The total sum of mass and energy of the system

remains constant.

(2) Law of constant or definite proportion : It

was proposed by Proust. According to this law, A

pure chemical compound always contains the same

elements combined together in the fixed ratio of

their weights whatever its methods of preparation

may be.

Example : CO 2 can be formed by either of the

following processes:

(i) By heating CaCO 3 : Ca CO 3 →

∆
Ca O + CO 2
 (ii) By heating NaHCO 3 :

2 NaHCO 3 →
∆
Na 2 CO 3 + H 2 O + CO 2

CO 2 is collected separately as a product of each

reaction and the analysis of CO 2 of each collection

reveals that it has the combination ratio of carbon

and oxygen as 12 : 32 by weight.

(3) Law of multiple proportion : It was

proposed by Dalton and verified by Berzelius.

According to this law, When two elements A and B

combine to form more than one chemical

compounds then different weights of A, which

combine with a fixed weight of B, are in proportion

of simple whole numbers.

Example : Nitrogen forms as many as

five stable oxides. The analysis of these

oxides ( N 2 O, NO, N 2 O 3 , N 2 O 4 and N 2 O5 ) reveals

that for 28 gm. nitrogen, the weight of

oxygen that combines is in the ratio 16 : 32 :

48 : 64 : 80 i.e., 1 : 2 : 3 : 4 : 5 in

N 2 O, NO, N 2 O 3 , N 2 O 4 and N 2 O5 respectively.

(4) Law of equivalent proportion or law of

reciprocal proportion : It was proposed by Ritcher.

According to this law, The weights of the two or

more elements which separately react with same

weight of a third element are also the weights of

these elements which react with each other or in

simple multiple of them.

Example : Formation of H 2 S, H 2 O and SO 2 can be

done as follows,

H (2 g)

H2S H2O

S O
(32 g) SO2 (16 g)

(i) Hydrogen combines with sulphur forming

hydrogen sulphide; 2gm. of hydrogen reacts with

32gm of sulphur. (ii) Hydrogen combines oxygen

forming water; 2 gm. of hydrogen reacts with 16

gm. of oxygen. (iii) Sulphur combines with oxygen

forming sulphur dioxide; 32 gm. of sulphur reacts

with 32 gm. of oxygen i.e., in the ratio 32 : 32. This

ratio is double of the ratio weights of these elements

which combine with 2 gm. of hydrogen. i.e., 32/16 :

32/32 = 2 : 1

Law of Reciprocal proportion can be used to

obtain equivalent weights of elements. As elements

always combine in terms of their equivalent weights.

(5) Gay-Lussac’s Law: It was proposed by

Gay–Lussac and is applicable only for gases.

According to this law, When gases combine, they do

so in volumes, which bear a simple ratio to each

other and also to the product formed provided all

gases are measured under similar conditions. The

Gay-Lussac’s law, was based on experimental

observation.

Example : (i) Reaction between hydrogen and

1
oxygen. H 2 ( g) +
2
O2 ( g) → H 2 O (v)

One volume of H2 reacts with half volume

of O2 to give one volume of H2 O .

(ii) Reaction between nitrogen and hydrogen.

N 2 ( g) + 3 H 2 ( g) → 2 NH 3 ( g)
 One volume of N2 reacts with three

volumes of H2 to give two volumes of NH 3 .

1.6 Important hypothesis.

(1) Atomic hypothesis : Keeping in view

various law of chemical combinations, a theoretical

proof for the validity of different laws was given by

John Dalton in the form of hypothesis called

Dalton's atomic hypothesis. Postulates of Dalton's

hypothesis is as followes,

(i) Each element is composed of extremely small

particles called atoms which can take part in

chemical combination.
 (ii) All atoms of a given element are identical

i.e., atoms of a particular element are all alike but

differ from atoms of other element.

(iii) Atoms of different elements possess

different properties (including different masses).

(iv) Atoms are indestructible i.e., atoms are

neither created nor destroyed in chemical reactions.

(v) Atoms of elements take part to form

molecules i.e., compounds are formed when atoms

of more than one element combine.

(vi) In a given compound, the relative number

and kinds of atoms are constant.

 (2) Modern atomic hypothesis : The main

modifications made in Dalton’s hypothesis as a

result of new discoveries about atoms are,

(i) Atom is no longer considered to be

indivisible.

(ii) Atoms of the same element may have

different atomic weights. e.g., isotopes of oxygen

O 16 , O 17 , and O 18 .

(iii) Atoms of different element may have same

atomic weights. e.g., isobars Ca 40 and Ar 40 .

 (iv) Atom is no longer indestructible. In many

nuclear reactions, a certain mass of the nucleus is

converted into energy in the form of α, β and γ rays.

(v) Atoms may not always combine in simple

whole number ratios. e.g., in sucrose (C12 H 22 O11 ) , the

elements carbon, hydrogen and oxygen are present

in the ratio of 12 : 22 : 11 and the ratio is not a

simple whole number ratio.

(3) Berzelius hypothesis : “Equal volumes of all

gases contain equal number of atoms under same

conditions of temperature and pressure”. When

applied to law of combining volumes, this

hypothesis predicts that atoms are divisible and

hence it is contrary to Dalton's hypothesis.

(4) Avogadro’s hypothesis : “Equal volumes of

all gases under similar conditions of temperature and

pressure contain equal number of molecules.”

Avogadro hypothesis has been found to explain as

follows :

(i) Provides a method to determine the atomic

weight of gaseous elements.

(ii) Provides a relationship between vapour

density (V.D.) and molecular masses of substances.

Volume of definite amount of a gas

Vapour density = Volume of same amount of hydrogen
 Mass of 'n ' molecule of a gas
or Vapour denstiy = Mass of 'n ' molecule of hydrog en

Mass of 1 molecule of a gas

Vapour density = Mass of 1 molecule of hydrogen

Molecular mass
or Vapour density =
2
or

Molecular mass = 2 × vapour density

(iii) It helps in the determination of mass of fixed

volume of a particular gas.

Mass of 1 molecule of gas

Vapour density = Mass of 1 molecule of H 2
=

Mass of 1 ml of gas Mass of 1 ml of gas

Mass of 1 ml of H 2
= 0.0000897

( 1 ml H 2 = 0.0000897 gm.) at NTP

∴ Mass of 1 ml gas = V.D. × 0.0000897 gm.

 (iv) It also helps in the determination of molar

volume at N.T.P.

 V.D. × 0.0000897 gm. gas has volume =

1 ml

∴ 2 × V.D.(i.e., molecular mass) gm. has

1 × 2 × V.D.
volume = V.D. × 0.0000897
ml = 22400 ml

∴ Molar mass of a gas or its 1 mole occupies

22.4 L volume at S.T.P.

Note :  22.4 litres of any gas at

S.T.P. weigh equal to the molecular

weight of the gas expressed in grams. This

 is called Gram-molecular volume

(G.M.V.) law.

(v) It helps in determination of molecular

formulae of gases and is very useful in gas analysis.

By knowing the molecular volumes of reactants and

products of reaction, molecular composition can be

determined easily.

1.7 Atomic, Molecular and Equivalent masses.

(1) Atomic Mass : It is the average relative mass

of atom of element as compared with an atom of

carbon –12 isotope taken as 12.

 Average mass of an atom
Atomic mass =
1/12 × Mass of an atom of C 12

Average atomic mass : If an elements exists in

two isotopes having atomic masses ‘a’ and ‘b’ in the

ratio m : n, then average atomic mass = (m × ma) ++ (nn × b) .

Since the atomic mass is a ratio, it has no units and is

expressed in amu, 1 amu = 1.66 × 10 −24 g . One atomic

1
mass unit (amu) is equal to 12
th of the mass of an

atom of carbon-12 isotope.

Gram atomic mass (GAM) : Atomic mass of an

element expressed in grams is called Gram atomic

mass or gram atom or mole atom.

 (i) Number of gram atoms or mole atoms

= Mass ofGAM
an element

(ii) Mass of an element in gm. = Number of gm.

atom × GAM

(iii) Number of atoms in 1 GAM = 6.02 × 10 23

∴ Number of atoms in a given substance =

Mass
No. of GAM × 6.02 × 10 23 = GAM
× 6.02 × 10 23

(iv) Number of atoms in 1 gm of element =

6.02 × 10 23
Atomic mass

(v) Mass of one atom of the element (in gm.) =

GAM
6.02 × 10 23
 Methods of determination of atomic mass

(i) Dulong and Pettit's method : According to

Dulong and Pettit's law

Atomic mass × Specific heat = 6.4 (approx.)

6.4
Atomic mass (approx. ) = Specific heat (in cals.)

This law is applicable to solid elements only

except Be, B, C and Si.

Atomic mass = Equivalent mass × Valency

Approximat e atomic mass

Valency =
Equivalent mass

(ii) Vapour density method : It is suitable for

elements whose chlorides are volatile.

 Valency of the element
Molecular mass of chloride 2 × Vapour density of chloride
= Equivalent =
mass of chloride Equivalent mass of metal + 35.5

Atomic mass = Equivalent mass of metal

× Valency

(iii) Specific heat method : It is suitable only

for gases. The two types of specific heats of gases

are CP (at constant pressure) and Cv (at constant

volume). Their ratio is known as γ whose value is

constant (1.66 for monoatomic, 1.40 for diatomic

and 1.33 for triatomic gases).

Molecular mass
Atomic mass of a gaseous element =
Atomaticit y
 (iv) Volatile chloride method : Different

steps are given below

Step I. The element (M) whose atomic mass is to

be determined is converted into its volatile chloride

whose vapour density is determined by Victor

Meyer method.

Thus, Molecular mass of the chloride = 2 × V.

D.

Step II. Equivalent mass of the element (M) of

valency X is determined as usual.

Atomic mass of the element = Equivalent

mass of the element × X = Z ×X

 Step III. The formula of the volatile chloride is

derived as below,

MX Cl 1

M Cl X

Step IV. Molecular mass of the chloride =

(Z × X ) + (35 .5 × X ) = X (Z + 35.5)

From (I) and (IV) X (Z + 35 .5) = 2 × Vapour density

2 × V.D.
or X =
Z + 35 .5

Thus, Atomic mass of the element =

Z ×X
 (v) Isomorphism method : It is based on law of

isomorphism which states that compounds having

identical crystal structure have similar constitution

and chemical formulae.

Example : K 2 SO 4 , K 2 CrO 4 and K 2 SeO 4 (valency of S,

Cr, Se = 6),

ZnSO 4 . 7 H 2 O, MgSO 4 .7 H 2 O, FeSO 4 . 7 H 2 O (valency of

Zn, Mg, Fe = 2).

Applications of isomorphism

• The valencies of two elements forming

isomorphism salts are essentially same. Thus if

valency of one of the elements is known that of

other will be the same.

• Masses of two elements, that combine with the

same mass of other elements in their respective

isomorphous compounds, are in the ratio of their

atomic masses i.e.,

Mass of element A that combines with a certain mass of other elements

Mass of element B that combines with the same mass of other elements

Atomic mass of A
=
Atomic mass of B

• By knowing the percentage of two elements of

their isomorphous compound and atomic mass of

one element, atomic mass of other element can be

calculated.

(2) Molecular mass : Molecular mass of a

molecule, of an element or a compound may be

defined as a number which indicates how many

times heavier is a molecule of that element or

1
compound as compared with 12
of the mass of an

atom of carbon–12. Molecular mass is a ratio and

hence has no units. It is expressed in a.m.u.

Mass of one molecule of the substance

Molecular mass =
1 / 12 × Mass of one atom of C - 12

Actual mass of one molecule = Molecular mass

× 1.66 × 10 −24 gm.

 Molecular mass of a substances is the additive

property and can be calculated by adding the atomic

masses present in one molecule.

Gram molecular mass (GMM) and Gram

molar volume : Molecular mass of an element or

compound when expressed in gm. is called its gram

molecular mass, gram molecule or mole molecule.

Number of gm molecules or mole molecules

= Mass ofGMM
substances

Mass of substances in gm = Number of gm.

molecules × GMM
 Volume occupied by one mole of any gas at STP

is called Gram molar volume. The value of gram

molar volume is 22.4 litres. Volume of 1 mole of

any gas at STP = 22.4 litres

Expression for mass and density

Mass of 11 .2L of any gas at STP = V.D. of that gas

in gm.

Mol. mass in gm.

Density of a gas at NTP = 22400 ml
 Important generalisations

Number of atoms in a substance = Number of

GMM × 6.02 × 1023 × Atomaticity

Number of electrons in given substance =

Number of GMM × 6.02 × 1023 × Number of electrons

Methods of determination of molecular mass :

following methods are used to determine molecular

mass

(i) Diffusion method (For gases) : The ratio of

rates of diffusion of two gases is inversely

proportional to the square root of their molecular

masses.
 r1 M2
=
r2 M1

(ii) Vapour density method (For gases only) :

Mass of a fixed volume of the vapour is compared

with the mass of the same volume of hydrogen

under same conditions. The ratio of these masses is

called Vapour density or Relative density.

Molecular mass = 2 × Vapour desity

Note :  Vapour density of a

substance increases due to molecular

association (e.g., CH 3 COOH , HF ) and decreases

due to dissociation (e.g., NH 4 Cl , PCl 5 , etc.)

 (iii) Victor Meyer method (For volatile liquids

or solids) : It is based on Dalton's law of partial

pressure and Avogadro's hypothesis (gram molar

volume).

22400 ml of vapours of a substance =

Molecular mass of that substance

(iv) Colligative property method (For non-

volatile solids) : Discussed in colligative properties

of solutions.

Average atomic mass and molecular mass

 A (Average atomic mass) = ∑∑ AX X ; i i
M (Average
total

∑ M i Xi
molecular mass) = ∑ X total

Where
A1 , A2 , A3 ,.... are atomic mass of species 1, 2, 3,.... etc. with % ratio as X 1 , X 2 , X 3 .........
etc. Similar terms are for molecular masses.

(3) Equivalent mass : The number of parts by

mass of a substance that combines with or displaces

1.008 parts by mass of hydrogen or 8.0 parts of

oxygen or 35.5 parts of chlorine is called its

equivalent mass (EM). On the other hand quantity of

a substance in grams numerically equal to its

equivalent mass is called its gram equivalent mass

(GEM) or gram equivalent.

Mass of the substance in grams

Number of GEM =
GEM of the substance

Expressions for equivalent mass (EM)

Atomic mass
(i) EM of an element =
Valency

Molecular mass
(ii) EM of an acid =
Basicity

(Basicity of acid is the number of replaceable

hydrogen atoms in one molecule of the acid).

Molecular mass
(iii) EM of a base =
Acidity
 (Acidity of a base is the number of replaceable–

OH groups in one molecule of the base).

Formula mass
(iv) EM of a salt = Total posi tive or negative charge

(v) EM of a reducing agent =

Formula mass
Number of electrons lost per molecule or Total change in oxidation number

Example : Eq. mass of oxalic acid (C 2 H 2 O 4 )

2−
C 2 O4 → 2 CO 2 + 2 e −

(O.N. of C = + 3) (O.N. of C = + 4)

∴ Number of electrons lost = 2

or Change in O.N. per C atom (from + 3 to +

4) = 1
 ∴ Total change in O.N. = 1 × 2 = 2

90
∴ Equivalent mass of C 2 H 2 O4 =
2
= 45

(vi) EM of an oxidising agent

Formula mass
=
Number of electrons gained per molecule or Total change in O.N.

Equivalent mass of common oxidising agent

changes with the medium of the reaction.

Example : (a) Equivalent mass of KMnO 4 in acidic

medium

− +
MnO 4 + 8 H + + 5 e − → Mn 2 + 4 H 2 O + 5 e −

Change in O.N. of Mn from + 7 to + 2 = +

5
 158
∴ Equivalent mass of KMnO 4 =
5
= 31 .60

(b) Equivalent mass of KMnO 4 in neutral

medium

−
MnO 4 + 4 H + + 3 e − → MnO 2 + 2 H 2 O or

KMn O 4 → Mn O 2

158
∴ Equivalent mass of KMnO 4 =
3
= 52 .67

(c) Equivalent mass of KMnO 4 in basic medium

−
MnO 4 + e − → MnO 42− or

KMnO 4 → K 2 MnO 4

158
Equivalent mass of KMnO 4 =
1
= 158

Formula mass of radical

(vii) EM of radicals =
Number of units of charge
 96
Example : Equivalent mass of SO 42− =
2
= 48

Methods of determination of equivalent mass

(i) Hydrogen displacement method : The mass

of metal which displaces 11200 ml of hydrogen at

NTP from an acid, alkali or alcohol is the equivalent

mass of the metal.

(a) Equivalent mass of metal

Mass of metal W
= × 1.008 = × 1.008 g
Mass of H 2 displaced M

(b) Equivalent mass of metal

Mass of metal W
=
Vol. (ml) of H 2 displaced at STP
× 11200 = V
× 11200
 This method is useful for metals which can

displace hydrogen from acids or can combine with

hydrogen (Mg, Zn, Na, Ca etc.)

(ii) Oxide formation method : The mass of the

element which combines with 8 grams of oxygen is

the equivalent mass of the element.

Mass of metal
(a) Equivalent mass of metal = Mass of oxygen
×8

(b) Equivalent mass of metal =

Mass of metal
× 5600
Vol. of O 2 at S.T.P. in ml

(iii) Chloride formation method : The mass of

an element which reacts with 35.5 gm. of chlorine is

the equivalent mass of that element.

 Mass of metal
(a) Equivalent mass of metal =
Mass of chlorine
× 35 .5

(b) Equivalent mass of metal

Mass of metal
= × 11200
Vol. of Cl 2 (in ml.) at STP

(iv) Neutralisation method : (For acids and

bases).

W
Equivalent mass of acid (or base) =
V× N
, Where W = Mass

of acid or base in gm., V = Vol. of base or acid in

litre required for neutralisation and N is Normality

of base or acid
 (v) Metal displacement method : It is based on

the fact that one gm. equivalent of a more

electropositive metal displaces one gm equivalent of

a less electropositive metal from its salt solution.

Mass of metal added Eq. mass of metal added W1 E

=
Mass of metal displaced Eq. mass of metal displaced
; W2
= 1
E2

(vi) Electrolytic method : The quantity of

substance that reacts at electrode when 1 faraday of

electricity is passed is equal to its gram equivalent

mass.

Gram equivalent mass = Electrochemical

equivalent × 96500
 The ratio of masses of two metals

deposited by the same quantity of electricity

will be in the ratio of their equivalent masses.

W1 E
= 1
W2 E2

(vii) Double decomposition method :

AB + CD → AD ↓ + CB

Mass of compound AB Eq. mass of A + Eq. mass of B

=
Mass of compound AD Eq. mass of A + Eq. mass of D

Mass of salt taken (W1 ) Eq. mass of salt (E1 )

or =
Mass of ppt. obtained (W2 ) Eq. mass of salt in ppt. (E2 )

(viii) Conversion method : When one

compound of a metal is converted to another

compound of the same metal, then

 Mass of compound I (W1 ) E + Eq. mass of radical I
=
Mass of compound II (W2 ) E + Eq. mass of radical II
(E =

Eq. mass of the metal)

(ix) Volatile chloride method

2× V.D. of Chloride 2 × V.D.

Valency of metal = =
Eq. mass of metal chloride E + 35.5

2 × V.D. of Chloride
∴ E =
Valency
− 35 .5

(x) Silver salt method (For organic acids)

Equivalent Mass of acid

× Mass of silver salt
= 108Mass of Ag metal
− 107

Molecular mass of acid = Equivalent

mass of acid × Basicity

 Examples based on Atomic, Molecular and
Equivalent masses

Example: 1 Oxygen contains 90% O 16 and 10%

O 18 . Its atomic mass is

[KCET 1998]

(a) 17.4

(b) 16.2

(c) 16.5

(d) 17

Solution: (b) Average atomic mass of oxygen

90 × 16 + 10 × 18
= = 16 .20
100
Example: 2 The total number of electrons present

in 1.6 gm. of methane is

[IIT 1976; Roorkee 1985; CPMT 1987, 92]

(a) 6.02 × 10 23

(b) 6.02 × 10 22

(c) 6.02 × 10 21

(d) 4.02 × 10 20

Solution: (a) Number of GMM of methane in

1.6 gm. of methane

Mass of methane 1.6

= Mol. mass of methane
= 16
= 0.1
 Number of electrons in 1 molecule of

methane (CH 4 ) = 6 + 4 = 10

Hence, Number of electrons in 1.6 gm.

of methane

= Number of GMM × 6.02 × 10 23

× No. of electrons

= 0.1 × 6.02 × 10 23 × 10 = 6.02 × 10 23

Example: 3 KClO 3 on heating decomposes to KCl

and O . The volume of O at STP liberated by 0.1 mole

2 2

KClO3 is

[BIT 1991]
 (a) 4.36 L

(b) 3.36 L

(c) 2.36 L

(d) none of these

Solution: (b) On heating KClO 3 dissociates as:

∆
2 KClO 3 → 2 KCl + 3 O 2

2 moles 3 × 22 .4 L at STP

 2 moles of KClO3 on heating produces = 67.

2 L of O2 at STP

 0.1 mole of KClO3 on heating produces

= 672.2 × 0.1 L = 3.36 L of O2 at STP

Example: 4 At S.T.P. the density of CCl 4 vapour in g/L will be nea

(a) 6.84

(b) 3.42

(c) 10.26

Solution: (a) 1 mole of CCl 4 vapour = 12 + 4 × 35 .5

= 154 gm = 22 .4 L at S.T.P.

∴ Density =
154
22 .4
gmL −1 = 6.875 gmL −1

Example:5 4.4 g of an unknown gas occupies

2.24 litres of volume at NTP. The gas may be [MP PMT

(a) Carbon dioxide

(b) Carbon monoxide

 (c) Oxygen

(d) Sulphur dioxide

Solution: (a) Mass of 2.24 litres gas = 4.4 gm.

 Mass of 22.4 litres gas = 44 gm.

Here, out of four given gases, the

molecular mass of only carbon dioxide is 44 gm.

Example: 6 One gm. of a metal carbonate gave

0.56 gm. of its oxide on heating. The equivalent

mass of the metal is

(a) 40

(b) 30

(c) 20
 (d) 10

Mass of metal carbonate E + Eq. mass of CO 3 2−

Solution: (c) = or
Mass of metal oxide E + Eq. mass of O 2 2−

1.0 E + 30
=
0.56 E+8

or (E + 8) × 1.0 = (E + 30) (0.56) (Where E is

the equivalent mass of the metal)

∴ E = 20

1.8 The mole concept.

The mole (abbreviated as mol) is the SI base unit

Grams of A Given
for a amount of a Divide by
molar mass

Moles of A
chemical species. It is Multiply
by N0
Molecules of Find
Calculations are reversed if operations are
reversed
always associated with a chemical formula and

refers to Avogadro’s number ( 6.022 × 10 ) of particles 23

represented by the formula. It is designated as N0 .

Thus, 12 molecules of HCl is a dozen, 144 molecules

of HCl is a gross and 6.022 × 10 23 molecules of HCl is a

mole.

1 mole of a substance = 6.022 × 10 23 species

The molar mass of a substance is the mass in

grams of 1 mole of that substance.

mass in grams
Mole of a substance =
molar mass
 Under STP conditions when temperature is 273K

and pressure is 1 atm, volume of one mole of an

ideal gas is 22.4L

Examples based on Mole

Example: 7 The number of gram molecules of

oxygen in 6.02 × 10 24 CO molecules is

[IIT 1990]

(a) 10 gm molecules

(b) 5 gm molecules

(c) 1 gm molecules
(d) 0.5 gm molecules

Solution: (b) 6.02 × 10 23 molecules = 1 mole of CO

∴ 6.02 × 10 24 CO molecules = 10 moles of CO

= 10 gms of Oxygen atom =5 gm molecules

of O2

Example: 8 1 c.c of N 2O at NTP contains :

[CBSE PMT 1988]

1.8
(a) 224
× 10 22 atoms

6.02
(b) 22400
× 10 23 molecules

1.32
(c) 224
× 10 23 electrons

(d) All the above

Solution: (d) 22400 c.c. = 6.02 × 10 23 molecules

6.02 × 10 23
1 c.c. of N 2O =
22400
molecules

3 × 6.02 × 10 23
=
22400
atoms (Since N 2O has three atoms)

6.02 × 10 23
=
22400
× 22 electron (Because number of

electrons in N 2O are 22)

Example: 9 The mass of carbon present in 0.5 mole of K 4 [ Fe

(a) 1.8 g

(b) 18 g

(c) 3.6 g

(d) 36 g
Solution: (d) 1 mole of K 4 [ Fe(CN ) 6 ] = 6 gm atoms of

carbon

0.5 mole of K 4 [ Fe(CN ) 6 ] = 3 gm atoms of carbon

= 3 × 12 = 36 g

Example: 10 The number of moles of

oxygen in one litre of air containing 21%

oxygen by volume under standard

conditions is

(a) 0.186 mole

(b) 0.21 mole

(c) 0.0093 mole

(d) 2.10 mole

Solution: (c)  100 ml of air at STP contains 21

ml of O2.

∴ 1000 ml of air at STP contains 210 ml of O2.

Vol. of O2 in litres under STP conditions

∴ No. of moles of O2 = 22 .4 litre

= 21022/ 1000
.4
=
21
2240
= 0.0093 mole

Example: 11 The number of moles of BaCO 3 which

contains 1.5 moles of oxygen atoms is

Solution: (a)  1 mole of BaCO 3 contains 3 moles of

oxygen atoms.
 1
∴
2
mole (0.5) of BaCO 3 contains 1.5 moles of

oxygen atoms.

1.9 Percentage composition & Molecular

formula.

(1) Percentage composition of a compound :

Percentage composition of the compound is the

relative mass of each of the constituent element in

100 parts of it. If the molecular mass of a compound

is M and B is the mass of an element in the

molecule, then
 Mass of element X
Percentage of element = × 100 = × 100
Molecular mass M

(2) Empirical formula : The chemical formula that

gives the simplest whole number ratio between the

atoms of various elements present in one molecule

of the compound is known as empirical formula

(simplest formula).

For example, the empirical formula of glucose is

CH 2 O which shows that C, H and O are present in the

ratio 1 : 2 : 1 in a molecule of glucose.

Empirical formula mass of a compound is equal to

the sum of atomic masses of all atoms present in the

empirical formula of the compound.

Calculation of the empirical formula : The

empirical formula of a chemical compound can be

deduced by knowledge of the, (i) Percentage

composition of different elements. (ii) Atomic

masses of the elements.

The following steps are involved in the

calculation of the empirical formula,

Step I. Calculate the relative number of atoms or

atomic ratio.

Percentage of an element
Atomic ratio =
Atomic mass of the same element

Step II. Calculate the simplest atomic ratio.

Step III. Calculate the simple whole number ratio.

Step IV. Write the empirical formula.

(3) Molecular formula : The chemical formula that

gives the actual number of atoms of various

elements present in one molecule of the compound.

For example, the molecular formula of glucose is

C6 H 12 O6 .

Relation between empirical and molecular

formula : The molecular formula of a compound is

a simple whole number multiple of its empirical

formula.

Molecular formula = n × Empirical formula ;

Where n is any integer such as 1, 2, 3….etc.

 The value of ‘n’ can be obtained from the

Molecular mass
following relation: n=
Empirical formula mass
.

The molecular mass of a volatile compound can be

determined by Victor Meyer’s method or by

employing the relation, Molecular mass = 2 × Vapour density .

Calculation of the molecular formula : The

molecular formula of a compound can be deduced

from its :

(i) Empirical formula,

(ii) Molecular mass

The determination of molecular formula involvesthe

following steps:
Setp I. Calculation of empirical formula from the

percentage composition.

Setp II. Calculation of empirical formula mass.

Setp III. Calculation of the value of ‘n’.

Setp IV. Calculation of molecular formula by

multiplying the empirical formula of the compound

by ‘n’.
 Examples based on Percentage composition &

Example:12 The oxide of a metal contains 40% by

mass of oxygen. The percentage of chlorine in the

chloride of the metal is

(a) 84.7

(b) 74.7

(c) 64.7

8
Solution: (b) % of oxygen = m+ 8
× 100 = 40

or, 40 (m + 8) = 800 or, m + 8 = 20 or, m = 12

35 .5 35 .5
∴ % of chlorine = m + 35 .5
× 100 = 12 + 35 .5
× 100 = 74.7
(Where m is the atomic mass of metal)

Example: 13 The empirical formula of an organic

compound containing carbon and hydrogen is CH 2 .

The mass of one litre of this organic gas is exactly

equal to that of one litre of N2 . Therefore, the

molecular formula of the organic gas is

[EAMCET 1985]

(a) C2 H 4

(b) C3 H 6

(c) C 6 H 12

(d) C4 H 8
Solution: (a) Molar mass of 1L of gas = mass of

1L N2

∴ Molecular masses will be equal i.e., molecular

mass of the gas = 28, hence formula is C2 H 4

Example: 14 A sample of pure compound is found

to have Na = 0.0887 mole, O = 0.132 mole, C =

2.65 × 10 22 atoms.

(a) Na2 CO3

(c) Na0.0887 00.132 C2.65 × 10 22

Solution: (a)  6.02 × 10 23 atoms of C = 1 mole of C

 1 × 2.65 × 10 22 2.65
∴ 2.65 × 10 22 atoms of C = 6.02 × 10 23
mole = 6.02 × 10
= 0.044

mole

Relative number Simplest ratio of

Element
of moles moles

0.0887
Na 0.0887 =2
0.044

0.132
O 0.132 =3
0.044

0.044
C 0.044 =1
0.044
Example: 15 An organic compound containing C,

H and N gave the following on analysis: C = 40%,

H = 13.3% and

=46.67%.Itsempiricalformulawouldbe

[CBSEPMT1999,2002]

(a) CHN

(b) C H
2 2N

(c) CH 4 N

(d) C2 H 7 N

Solution: (c) Calculation of empirical formula

Elem Sym Percen At. Relative Simpl Simples

ent bol tage of mass number of est t whole

elemen of atoms atomi number

Percentage
t eleme = At. mass
c ratio atomic

nts ratio

Carb
40 3.33
C 40 12 = 3.33 =1 1
12 3.33
on

Hydr
13 .3 13 .3
H 13.3 1 = 13 .3 =4 4
1 3.33
ogen

Nitro
46 .67 3.33
N 46.67 14 = 3.33 =1 1
14 3.3
gen
Thus, the empirical formula is CH 4 N .

Example: 16 An organic substance containing C, H

and O gave the following percentage composition :

C = 40.687%, H = 5.085% and O = 54.228%. The

vapour density of the compound is 59. The

molecular formula of the compound is

(a) C4 H 6O4

(b) C4 H 6O2

(c) C4 H 4 O2

Solution: (a)
Elem Sym Percen Ato Relative Simple Simples

ent bol tage mic number of st t whole

of mass atoms atomic number

elemen of = Percentage
At. mass
ratio atomic

t elem ratio

ent

Carb
40 .687 3.390
C 40.687 12 = 3.390 =1 2
12 3.389
on

Hydr
5.085 5.085
H 5.085 1 = 5.085 = 1.5 3
1 3.389
ogen
Oxyg
54 .228 3.389
O 54.228 16 = 3.389 =1 2
16 3.389
en

∴ Empirical formula is C2 H 3O2

∴ Empirical formula mass of C2 H 3O2 = 59

Also, Molecular mass = 2 × Vapour density = 2 × 59 = 118

∴ n= Molecular mass 118

= =2
Empirical formula mass 59

Now, Molecular formula = n × (Empirical formula )

= 2 × (C H O ) = C H O
2 3 2 4 6 4

∴ Molecular formula is C4 H 6O4 .

1.10 Chemical equations and its balancing.

(1) Chemical equations : Chemical reactions are

represented in a concise way by chemical equations.

A chemical equation represents an actual chemical

change taking place in terms of the symbols and the

formulae of the reactants and products. e.g.,

Methane burns in oxygen to produce carbon dioxide

and water. The chemical reaction can be represented

as: CH 4 + 2O 2 → CO 2 + 2H 2 O
Reactants Products

Essentials of a chemical equation

(i) It must represent an actual chemical reaction.

(ii) It must be balanced i.e., the total number of

atoms of various substances involved on both sides

of the equation must be equal.

(iii) It should be molecular. The elementary gases

like hydrogen, oxygen etc. must be written in the

molecular form as H2, O2 etc.

Information conveyed by a chemical equation :

A Chemical equation conveys both qualitative and

quantitative information.

(i) Qualitative information : Qualitatively a

chemical equation conveys the names of the

reactants and products taking part in the reaction.

(ii) Quantitative information : Quantitatively a

chemical equation conveys the following

information :

(a) It conveys the actual number of reactants and

product species (atoms or molecules) taking part in

the reaction.

(b) It tells the relative masses of the reactants and

products participating in the reaction.

(c) It conveys the relative number of reactant and

product moles.

(d) It also conveys the volumes of the gaseous

reactants and products if present.

Example : Reaction between CaCO3 and aqueous

HCl.

CaCO 3 + 2HCl → CaCl 2 + H 2 O + CO 2

100 gm. 73 gm. 111 gm. 18 gm. 44 gm.
1 mole 2 mole 1 mole 1 mole 1 mole
22 .4 litres
at STP

Note :  All chemical equations are written under

STP conditions provided no other conditions are

mentioned.

Limitations of a chemical equation and their

removal : Although a chemical equation conveys

a number of informations, it suffers from certain

limitations or drawbacks. The major limitations

and the steps taken for their removal are given

below:
(i) Physical states of the reactants and products :

The chemical equation fails to convey the physical

states of the reactants and products. These are

specified by the use of letters ‘s’(for solids), ‘l’(for

liquids), ‘g’(for gases) and ‘aq’(for aqueous

solutions).

Example : CaCO 3 ( s) + 2HCl (aq) → CaCl 2 ( s) + H 2 O(l ) + CO 2 ( g)

(ii) Conditions of temperature, pressure and catalyst

: These conditions are normally not mentioned in the

equation. These can be expressed on the arrow head

which separates the reactants from the products.

Example : N 2( g) + 3 H 2( g)  → 2 NH 3( g)
Fe,723 K
600 atm
(iii) Speed of reaction : The speed of a particular

reaction whether slow or fast can be mentioned by

writing the word slow or fast on the arrow head.

Example : NO 2 ( g) + F2 ( g) 
→
slow
NO 2 F( g) + F( g)

NO 2 ( g) + F( g) 
→
fast
NO 2 F( g)

(iv) Heat change accompanying the reaction : The

heat evolved or absorbed in a chemical reaction can

be written on the product sides. The S.I. unit of heat

is kJ.

Example : CH 4 ( g) + 2O 2( g) → CO 2 ( g) + 2 H 2 O(l ) + 393 .5 KJ

(Heat is evolved)

H 2 ( g) + I 2 ( g) → 2 HI ( g) − 53 .9 KJ
(Heat is absorbed)
(v) Reversible nature of a reaction : Certain

chemical reactions proceed both in the forward and

backward directions. The reversible nature of the

reaction can be indicated by two arrows pointing in

the opposite direction (⇌).

Forward
Example : H 2 ( g) + Cl 2 ( g) 2 HCl ( g)
Backward

(vi) Formation of precipitate and evolution of a gas

: Formation of a precipitate in the chemical reaction

can be indicated by writing the word ppt. or by an

arrow pointing downwards.

Ag NO 3 (aq) + NaCl (aq) → AgCl ↓ + NaNO 3 (aq)

(ppt)
 The evolution of a gas is expressed by an arrow

which points upwards.

Mg( s) + 2 HCl (aq) → Mg Cl 2 (aq) + H 2 ( g) ↑

(2) Balancing of chemical equations : A correct

chemical equation must be in accordance with the

law of conservation of mass i.e., the number of

atoms of each kind in the reactants must be equal to

the number of atoms of same kind in the products.

Balancing of a chemical equation means to equalise

the atoms of different elements or compounds which

are involved in it.

Let us consider a chemical reaction which occurs

due to passing of steam over red hot iron forming

iron oxide and hydrogen gas. It can be represented

as:

Skeleton equation : Fe ( s) + H 2 O (v) → Fe3 O4 ( s) + H 2 ( g)

Balanced equation : 3 Fe( s) + 4 H 2 O(v) → Fe3 O4 ( s) + 4 H 2 ( g)

The balancing of equations is done by the following

methods:

(i) Hit and Trial method,

(ii) Partial Equation method

(iii) Oxidation-Number method,

(iv) Ion-Electron method

The first two methods are discussed here, while the

remaining two methods will be taken up for

discussion in redox reactions.

(i) Hit and Trial method : This method involves

the following steps:

(a) Write the symbols and formulae of the reactants

and products in the form of skeleton equation.

(b) If an elementary gas like H2, O2 or N2 etc.

appears on either side of the equation, write the

same in the atomic form.

(c) Select the formula containing maximum number

of atoms and start the process of balancing.

(d) In case the above method is not convenient, then

start balancing the atoms which appear minimum

number of times.

(e) Balance the atoms of elementary gases in the

last.

(f) When the balancing is complete, convert the

equation into molecular form.

Let us balance the skeleton equation

Mg 3 N 2 + H 2 O → Mg (OH ) 2 + NH 3

The balancing is done in the following steps

Step I. Balance the Mg atoms

Mg 3 N 2 + H 2 O → 3 Mg (OH ) 2 + NH 3
Step II. Balance the N atoms

Mg 3 N 2 + H 2 O → 3 Mg(OH ) 2 + 2 NH 3

Step III. Balance the O atoms

Mg 3 N 2 + 6 H 2 O → 3 Mg (OH ) 2 + 2 NH 3

The hydrogen atoms are already balanced.

Hence, final balanced equation is

Mg 3 N 2 + 6 H 2 O → 3 Mg (OH ) 2 + 2 NH 3

(ii) Partial equation method : Chemical equations

which involve a large number of reactants and

products can not be balanced easily by the hit and

trial method. In partial equation method, the overall

reaction is assumed to take place into two or more

simpler reactions known as partial equations. The

balancing of the equation involves the following

steps:

(a) Split the chemical equation into two or more

simpler equations or partial equations.

(b) Balance each partial equation separately by hit

and trial method.

(c) Multiply the partial equations with suitable

coefficient if necessary so as to cancel out the final

substances which do not appear in the final equation.

(d) Finally, add up the partial equations to get the

final equation.
 Let us balance the skeleton equation

NaOH + Cl 2 → NaCl + NaClO 3 + H 2 O

This reaction is supposed to take place in the

following steps:

The probable partial equations for the above

reaction are:

Na OH + Cl 2 → Na Cl + Na ClO + H 2 O and

Na Cl O → Na Cl O 3 + NaCl

Balance the partial chemical equations separately

by hit and trial method as

2 Na OH + Cl 2 → NaCl + Na ClO + H 2 O and

3 Na ClO 3 → Na ClO 3 + 2 NaCl

Multiply the first partial equation by 3 in order to

cancel out NaClO which does not appear in the final

equation. Finally add the two partial equations to get

the final equation.

2 NaOH + Cl 2 → NaCl + NaClO + H 2 O ] × 3

3 NaClO → NaClO 3 + 2 NaCl
6 NaOH + 3 Cl 2 → NaClO 3 + 5 NaCl + 3 H 2 O

1.11 Chemical Stoichiometry.

Calculation based on chemical equations is known

as chemical stoichiometry. Stoichiometry can be

broadly classified into two groups: (1) Gravimetric

analysis (Stoichiometry-I), (2) Volumetric analysis

(Stoichiometry-II)
(1) Gravimetric analysis (Stoichiometry-I) : With

the help of chemical equation, we can calculate the

weights of various substances reacting and weight of

substances formed. For example,

MgCO 3 → MgO + CO 2 ↑

This equation implies :

(i) 1 mol of MgCO 3 gives 1 mol of MgO and 1 mol of

CO 2 .

(ii) 84 g of MgCO 3 (Mol. wt. of MgCO 3 ) gives 40 g of

MgO and 44 g of CO 2 .

Hence, chemical equation provide us information

regarding :
(i) Molar ratio of reactants and products.

(ii) Mass ratio between reactants and

products.

(iii) Volume ratio between gaseous reactant

and products.

The calculation based upon chemical

equation (Stoichiometry–I) are based upon three

types namely :

(a) Mass-mass relationship (b) Mass-volume

relationship (c) Volume-volume relationship

(2) Volumetric analysis (Stoichiometry-II) : It is

a method which involves quantitative determination

of the amount of any substance present in a solution

through volume measurements. For the analysis a

standard solution is required. (A solution which

contains a known weight of the solute present in

known volume of the solution is known as standard

solution.)

To determine the strength of unknown solution with

the help of known (standard) solution is known as

titration. Different types of titrations are possible

which are summerised as follows :

(i) Redox titrations : To determine the strength of

oxidising agents or reducing agents by titration with

the help of standard solution of reducing agents or

oxidising agents.

Examples:

K 2 Cr 2 O7 + 4 H 2 SO 4 → K 2 SO 4 + Cr 2 (SO 4 )3 + 4 H 2 O + 3[ O]
[ 2FeSO 4 + H 2 SO 4 + O → Fe2 (SO 4 )3 + H 2 O] × 3
6 FeSO 4 + K 2 Cr 2 O7 + 7 H 2 SO 4 → 3 Fe(SO 4 )3 + K 2 SO 4 + Cr 2 (SO 4 )3 7 H 2 O
2KMnO 4 + 3 H 2 SO 4 → K 2 SO 4 + 2MnSO 4 + 3 H 2 O + 5[ O]
[ 2FeSO 4 + H 2 SO 4 + O → Fe2 (SO 4 )3 + H 2 O] × 5
10 FeSO 4 + 2KMnO 4 + 8 H 2 SO 4 → 5 Fe2 (SO 4 )3 + K 2 SO 4 + 2MnSO 4 + 8 H 2 O

Similarly with H 2 C 2 O4

2KMnO 4 + 3 H 2 SO 4 + 5 H 2 C 2 O4 → K 2 SO 4 + 2MnSO 4 + 8 H 2 O + 10 CO 2 etc.

(ii) Acid-base titrations : To determine the strength

of acid or base with the help of standard solution of

base or acid.
Example: NaOH + HCl → NaCl + H 2 O and

NaOH + CH 3 COOH → CH 3 COONa + H 2 O etc.

(iii) Iodiometric titrations : To determine the

reducing agents with the help of standard iodine

solution is known as iodiometry.

For example: As O + 2I 2 + 2H 2 O → As2 O3 + 4 HI

2 3
Reducing agent

Na 2 S2 O3 + I 2 → Na 2 S4 O6 + 2 NaI

(iv) Iodometric titrations : To determine the

oxidising agent indirectly by titration of liberated I2

with the help of standard hypo solution is known as

iodometric titrations.
Examples: Oxidising agents such as

KMnO 4 , K 2 Cr 2 O7 , CuSO 4 , ferric salts, etc. are reduced

quantitatively when treated with large excess of KI

in acidic or neutral medium and liberate equivalent

amount of I . 2

2CuSO 4 + 4 KI → Cu 2 I 2 + 2K 2 SO 4 + I 2

Kr 2 Cr 2 O7 + 7 H 2 SO 4 + 6 KI → Cr 2 (SO 4 )3 + 4 K 2 SO 4 + 7 H 2 O + 3 I 2

This I2 is estimated with hypo

I 2 + 2 Na 2 S2 O3 → Na 2 S4 O6 + 2 NaI

(v) Precipitation titrations : To determine the anions

like CN − , AsO 33− , PO43− , X − etc, by precipitating with AgNO 3

provides examples of precipitation titrations.

 NaCl + AgNO 3 → AgCl ↓ + NaNO 3 ;

KSCN + AgNO 3 → AsSCN ↓ + KNO 3

End point and equivalence point : The point at

which titration is stopped is known as end point,

while the point at which the acid and base (or

oxidising and reducing agents) have been added in

equivalent quantities is known as equivalence point.

Since the purpose of the indicator is to stop the

titration close to the point at which the reacting

substances were added in equivalent quantities, it is

important that the equivalent point and the end point

be as close as possible.
Normal solution : A solution containing one gram

equivalent weight of the solute dissolved per litre is

called a normal solution; e.g. when 40 g of NaOH

are present in one litre of NaOH solution, the

solution is known as normal (N) solution of NaOH.

Similarly, a solution containing a fraction of gram

equivalent weight of the solute dissolved per litre is

known as subnormal solution. For example, a

solution of NaOH containing 20 g (1/2 of g eq. wt.)

of NaOH dissolved per litre is a sub-normal

solution. It is written as N/2 or 0.5 N solution.

Formula used in solving numerical problems on

volumetric analysis

(1) Strength of solution = Amount of

substance in g litre−1

(2) Strength of solution = Amount of substance in g

moles litre−1

(3) Strength of solution = Normality × Eq. wt. of

the solute

Moles of solute
(4) Molarity =
Volume in litre

Wt. in gm Volume in litres

(5) Number of moles =
Mol. wt.
= M × V(in l ) =
22 .4
at NTP

(only for gases)

(6) Number of millimoles
Wt. in gm × 1000
= = Molarity × Volume in ml .
mol. wt.

(7) Number of equivalents

Wt. in gm
= = x × No. of moles × Normality × Volume in litre
Eq. wt.

(8) Number of milliequivalents (meq.)

Wt. in gm × 1000
= = normality × Volume in ml .
Eq. wt.

(9)
−1

Normality = x × No. of millimoles = x × Molarity = StrengthEq.inwt.

gm litre

Mol. wt.
where x=
Eq. wt.
, x* = valency or change in oxi.

Number.

(10) Normality formula, N 1 V1 = N 2 V2

 Wt. of solvent
(11) % by weight =
Wt. of solution
× 100

Wt. of solvent
(12) % by volume =
Vol. of solution
× 100

Vol. of solvent
(13) % by strength = Vol. of solution
× 100

Wt. of solution
(14) Specific gravity = Vol. of solution
= Wt. of 1 ml . of solution

Wt. of ionic solute

(15) Formality =
Formula Wt. of solute × Vin l

(16) Mol. Wt. = V.D × 2 (For gases only)

1.12 Limiting reagent or reactant.

In many situations, an excess of one or more

substance is available for chemical reaction. Some

of these excess substances will therefore be left over

when the reaction is complete; the reaction stops

immediately as soon as one of the reactant is totally

consumed.

The substance that is totally consumed in a reaction

is called limiting reagent because it determines or

limits the amount of product. The other reactant

present in excess are called as excess reagents.

Let us consider a chemical reaction which is

initiated by passing a spark through a reaction vessel

containing 10 mole of H2 and 7 mole of O2.

2 H 2 (g) + O 2 (g) → 2 H 2 O (v)

 Moles before reaction 10 7

Moles after reaction 0 2

10

The reaction stops only after consumption of 5

moles of O2 as no further amount of H2 is left to

react with unreacted O2. Thus H2 is a limiting

reagent in this reaction

 Examples based on Stoichiometry and Limiting

Example: 17 When a solution containing 4.77 gm.

of NaCl is added to a solution of 5.77 gm. of

AgNO3, the weight of precipitated AgCl is

(a) 11.70 gm.

(b) 9.70 gm.

(c) 4.86 gm.

(d)2.86gm.on:

(c) AgNO 3 + NaCl → AgCl + NaNO 3

 5.77 4.77
Moles before mixing 108 + 14 + 48 58 .5
0

0 = 0.0339 = 0.0815 (Here AgNO 3 is limiting

reactant, thus)

Moles after mixing

00.0815 – 0.0339

0.03390.0339

= 0.0476

∴ Moles of AgCl formed = 0.0339

∴ Mass of AgCl formed = Mol. mass × No. of moles =

143 .5 × 0.0339 = 4.864 gm.

Example: 18The volume of oxygen at STP required

to completely burn 30 ml of acetylene at STP is

 [Orissa JEE 1997]

(a) 100 ml

(b) 75 ml

(c) 50 ml

(d) 25 ml

Solution: (b) The balanced chemical equation for

the reaction can be written as:

C 2 H 2 + 5 / 2 O 2 → 2 CO 2 + H 2 O

1 Vol . 5 / 2 Vol .

1 ml 5 / 2 ml

30 ml 30 × 5 / 2 = 75 ml
Hence, volume of the oxygen at STP required to

burn 30 ml of acetylene at STP = 75 ml.

Example: 19 What is the volume (in litres) of

oxygen at STP required for complete combustion

of 32 g of CH 4

[EAMCET 2001]

(a) 44.8

(b)89.6

(c)22.4

(d)179.2
Solution: (b) According to Avogadro's

hypothesis, volume occupied by one mole of any gas

at STP is 22.4 litres.

1 mole

2 moles

2 moles

4 moles

2 × 16 gm. = 32 gm.

4 × 22 .4 litres = 89.6 litres

Example: 20 A metal oxide has the formula Z 2 O3 .

It can be reduced by hydrogen to give free metal

 and water. 0.1596 g of the metal oxide requires 6

mg of hydrogen for complete reduction. The

atomic weight of the metal is

[CBSE PMT 1989

(a)27.9

(b)159.6

(c)79.8

(d)55.8

Solution: (d) Valency of metal in Z 2 O3 = 3

Z 2 O 3 + 3 H 2 → 2 Z + 3 H 2 O

0.1596 gm of Z 2 O3 react with H2 = 6mg = 0.006 gm

0.1596
1 gm of H2 react with Z 2 O3 =
0.006
= 26 .6 gm
Equivalent wt. of Z 2 O 3 = 26 .6 = equivalent wt. of Z+

equivalent wt. of O = E + 8 = 26 .6 or E = 18 .6

Atomic weight of Z = 18 .6 × 3 = 55 .8
John Dalton 1808, believed that matter is made up

of extremely minute indivisible particles, called

atom which can takes part in chemical reactions.

These can neither be created nor be destroyed.

However, modern researches have conclusively

proved that atom is no longer an indivisible particle.

Modern structure of atom is based on Rutherford’s

scattering experiment on atoms and on the concepts

of quantization of energy.

2.1 Composition of atom.

The works of J.J. Thomson and Ernst Rutherford

actually laid the foundation of the modern picture of

the atom. It is now believed that the atom consists of

several sub-atomic particles like electron, proton,

neutron, positron, neutrino, meson etc. Out of these

particles, the electron, proton and the neutron are

called fundamental subatomic particles and others

are non-fundamental particles.

Electron (–1eo)

(1) It was discovered by J.J. Thomson (1897) and is

negatively charged particle. Electron is a component

particle of cathode rays.

(2) Cathode rays were discovered by William

Crooke's & J.J. Thomson (1880) using a

cylindrical hard glass tube fitted with two metallic

electrodes. The tube has a side tube with a stop

cock. This tube was known as discharge tube. They

passed electricity (10,000V) through a discharge

tube at very low pressure ( 10 to

−2
10 −3 mm Hg) . Blue rays

were emerged from the cathode. These rays were

termed as Cathode rays.

(3) Properties of Cathode rays

(i) Cathode rays travel in straight line.

(ii) Cathode rays produce mechanical effect, as they

can rotate the wheel placed in their path.

(iii) Cathode rays consist of negatively charged

particles known as electron.

(iv) Cathode rays travel with high speed

approaching that of light (ranging between 10 −9 to

10 −11 cm/sec)

(v) Cathode rays can cause fluorescence.

(vi) Cathode rays heat the object on which they

fall due to transfer of kinetic energy to the object.

(vii) When cathode rays fall on solids such as

Cu, X − rays are produced.

(viii) Cathode rays possess ionizing power i.e., they

ionize the gas through which they pass.

(ix) The cathode rays produce scintillation the

photographic plates.

(x) They can penetrate through thin metallic sheets.

(xi) The nature of these rays does not depend upon

the nature of gas or the cathode material used in

discharge tube.

(xii) The e/m (charge to mass ratio) for cathode rays

was found to be the same as that for an e − (−1.76 × 10 8

coloumb per gm). Thus, the cathode rays are a

stream of electrons.
Note :  When the gas pressure in the discharge

tube is 1 atmosphere no electric current flows

through the tube. This is because the gases are poor

conductor of electricity.

 The television picture tube is a cathode ray tube

in which a picture is produced due to fluorescence

on the television screen coated with suitable

material. Similarly, fluorescent light tubes are also

cathode rays tubes coated inside with suitable

materials which produce visible light on being hit

with cathode rays.

(4) R.S. Mullikan measured the charge on an

electron by oil drop experiment. The charge on each

electron is − 1.602 × 10 −19 C.

(5) Name of electron was suggested by J.S. Stoney.

The specific charge (e/m) on electron was first

determined by J.J. Thomson.

(6) Rest mass of electron

is 9.1 × 10 −28
gm = 0.000549 amu = 1 / 1837 of the mass of

hydrogen atom.

(7) According to Einstein’s theory of relativity, mass

Rest mass of electron(m )

of electron in motion is, m′ =
[1 − (u / c) 2 ]

Where u = velocity of electron, c= velocity of light.

When u=c than mass of moving electron =∞.

(8) Molar mass of electron = Mass of electron ×

Avogadro number = 5.483 × 10 −4

.

(9) 1.1 × 10 electrons =1gram.

27

(10) 1 mole electron = 0.5483 mili gram.

(11) Energy of free electron is ≈ 0. The minus sign

on the electron in an orbit, represents attraction

between the positively charged nucleus and

negatively charged electron.

(12) Electron is universal component of matter and

takes part in chemical combinations.

(13) The physical and chemical properties of an

element depend upon the distribution of electrons in

outer shells.

(14) The radius of electron is 4.28 × 10 −12 cm.

(15) The density of the electron is = 2.17 × 10 −17 g / mL .

•
+
Examples based on Einstein’s theory of

Example : 1 The momentum of electron moving

with 1/3rd velocity of light is (in g cm sec–1)

(a) 9.69 × 10 −8

(b) 8.01 × 10 10
(c) 9.652 × 10 −18

(d)None

Solution: (c) Momentum of electron, ‘p’ = m′ × u

Where m′ is mass of electron in

m
motion = ; Also u = c/3
1 − (u / c)2

Momentum

9.108 × 10 −28 3 × 10 10 9.108 × 10 −28 × 3 × 10 10

= × = = 9.652 × 10 −18 g cm sec −1
2 3 0.94 × 3
 c 
1− 
 3×c

Example: 2 An electron has a total energy of 2

MeV. Calculate the effective mass of the electron in

kg and its speed. Assume rest mass of electron 0.511

MeV.

(a) 2.9 × 10 8

(b) 8.01 × 10 8

(c) 9.652 × 10 8

(d)None

2
Solution: (a) Mass of electron in motion =
931
amu (1

amu = 931 MeV)

2
=
931
× 1.66 × 10 − 27 kg = 3.56 × 10 −30 kg (1 amu = 1.66 × 10 −27
kg )

Let the speed of the electron be u.

 m
m′ = or
1 − (u / c)
2

0.511
× 1.66 × 10 − 27
− 30 931 0.911 × 10 − 30
3.56 × 10 = =
2 2
 u   u 
1−  1 −  
 3 × 10 8   3 × 10 8 

2
 u 
or 1−  = 0.06548 or u 2 = 9 × 10 16 × 0.93452 or
 3 × 10 8 

u = 2.9 × 10 8 m

Example: 3 A electron of rest mass 1.67 × 10 −27 kg is

moving with a velocity of 0.9c (c = velocity of

light). Find its mass and momentum.

(a) 10.34 × 10 −19

(b) 8.01 × 10 10

(c) 9.652 × 10 −18

(d)None

Solution: (a) Mass of a moving object can be

calculated using Einsten’s theory of relativity :

m
m′ = m= rest mass (given), u = velocity
1 − (u / c)
2

(given), c = velocity of light

1.67 × 10 −27
m′ = = 3.83 × 10 − 27 kg
2
 0.9c 
1− 
 c 

Momentum ' p' = m′ × u

p = 3.83 × 10 −27 × 0.9c = 10 .34 × 10 −19 kg ms −1

Proton (1H1, H+, P)

(1) Proton was discovered by Goldstein and is

positively charged particle. It is a component

particle of anode rays.

(2) Goldstein (1886) used perforated cathode in the

discharge tube and repeated Thomson's experiment

and observed the formation of anode rays. These

rays also termed as positive or canal rays.

Cathode rays
Anode rays
TC Vaccum pump

Perforated High voltage

cathode – +

Perforated tube experiment for production of anode

rays

(3) Properties of anode rays

(i) Anode rays travel in straight line.

(ii) Anode rays are material particles.

(iii) Anode rays are positively charged.

(iv) Anode rays may get deflected by external

magnetic field.

(v) Anode rays also affect the photographic plate.

(vi) The e/m ratio of these rays is smaller than that

of electrons.

(vii) Unlike cathode rays, their e/m value is

dependent upon the nature of the gas taken in the

tube. It is maximum when gas present in the tube is

hydrogen.
(viii) These rays produce flashes of light on ZnS

screen.

(4) Charge on proton = 1.602 × 10 −19 coulombs =

4.80 × 10 −10 e.s. u.

(5) Mass of proton = Mass of hydrogen atom=

1.00728 amu = 1.673 × 10 −24 gram = 1837 of the mass of electron.

(6) Molar mass of proton = mass of proton

× Avogadro number = 1.008 (approx).

(7) Proton is ionized hydrogen atom (H + ) i.e.,

hydrogen atom minus electron is proton.

(8) Proton is present in the nucleus of the atom and

it's number is equal to the number of electron.

(9) Mass of 1 mole of protons is ≈ 1.007 gram.

(10) Charge on 1 mole of protons is ≈ 96500

coulombs.

4 3
(11) The volume of a proton (volume = 3
πr ) is ≈

1.5 × 10 −38
cm 3 .

(12) Specific charge of a proton is 9.58 × 10 4

Coulomb/gram.

Neutron (on1, N)

(1) Neutron was discovered by James Chadwick

(1932) according to the following nuclear reaction,

4 Be 9 + 2 He 4 → 6 C 12 + o n1 or 5 B11 + 2 He 4 → 7 N 14 + o n1
(2) The reason for the late discovery of neutron was

its neutral nature.

(3) Neutron is slightly heavier (0.18%) than proton.

(4) Mass of neutron = 1.675 × 10 −24 gram =

1.675 × 10 −27 kg = 1.00899 amu ≈ mass of hydrogen atom.

(5) Specific charge of a neutron is zero.

(6) Density = 1.5 × 10 −14 gram / c.c.

(7) 1 mole of neutrons is ≈ 1.008 gram.

(8) Neutron is heaviest among all the fundamental

particles present in an atom.

(9) Neutron is an unstable particle. It decays as

follows :

0n
1
→ 1 H 1 + −1 e +
0
0ν 0

neutron proton electron anti nutrino

(10) Neutron is fundamental particle of all the

atomic nucleus, except hydrogen or protium.

Comparison of mass, charge and specific charge

of electron, proton and neutron

Name of Unit Electron(e Proton(p+ Neutron(n

–
constant ) ) )

amu 0.000546 1.00728 1.00899

Mass (m) kg 9.109 × 1.673 × 1.675 ×

 Relative 10–31 10–27 10–24

1/1837 1 1

Coulomb – 1.602 × +1.602 × Zero

Charge(e) (C) 10–19 10–19 Zero

esu – 4.8 × 10– +4.8 × 10– Zero

10 10
Relative

–1 +1

Specific charge C/g 1.76 × 108 9.58 × 104 Zero

(e/m)

• The atomic mass unit (amu) is 1/12 of the mass of

an individual atom of 6C
12
, i.e. 1.660 × 10 −27 kg .
 Other non fundamental particles

Particle Symb Natu Charg Mass Discovered by

ol re e esu (amu)

×10–10

Positron e + , 1e 0 , β + + + 0.000 Anderson (1932)

4.8029 5486

Neutrino ν 0 0 < Pauli (1933) and

0.000 Fermi (1934)

02

Anti-proton p− – – 1.007 Chamberlain Sugri

4.8029 87 (1956) and

Weighland (1955)
Positive mu µ+ + + 0.115 Yukawa (1935)

meson 4.8029 2

Negative µ− – – 0.115 Anderson (1937)

mu meson 4.8029 2

Positive pi π+ + + 0.151

meson 4.8029 4

Negative pi π− – – 0.151
Powell (1947)
meson 4.8029 4

Neutral pi π0 0 0 0.145

meson 4

2.2 Atomic number, Mass number and Atomic

species.
(1) Atomic number or Nuclear charge

(i) The number of protons present in the nucleus of

the atom is called atomic number (Z).

(ii) It was determined by Moseley as,

ν = a(Z − b) or aZ − ab

ν s−1

where, ν = X − rays frequency

Z= atomic number of the metal

a& b are constant.

(iii) Atomic number = Number of positive charge on

nucleus = Number of protons in nucleus = Number

of electrons in nutral atom.

(iv) Two different elements can never have identical

atomic number.

(2) Mass number

(i) The sum of proton and neutrons present in the

nucleus is called mass number.

Mass number (A) = Number of protons + Number of

neutrons or Atomic number (Z)

or Number of neutrons = A – Z .
(ii) Since mass of a proton or a neutron is not a

whole number (on atomic weight scale), weight is

not necessarily a whole number.

(iii) The atom of an element X having mass number

(A) and atomic number (Z) may be represented by a

symboll,

Element Mass number

A
Atomic number
X
Z
e.g. 9 F 19 , 8 O 16 , 7 N 14 etc.

Note :  A part of an atom up to penultimate shell

is a kernel or atomic core.

  Negative ion is formed by gaining electrons and

positive ion by the loss of electrons.

 Number of lost or gained electrons in positive or

negative ion =Number of protons ± charge on ion.

(3) Different Types of Atomic Species

Atomic Similarities Differences Examples

species

(i) Atomic No. (i) Mass No. (A) (i) 1 2 3

1 H, 1 H, 1 H

Isotopes (Z) (ii) No. of (ii) 16 17 18

8 O, 8 O, 8 O

(Soddy) (ii) No. of protons neutrons

(iii) 35 37
17 Cl , 17 Cl

(iii) No. of (iii) Physical

 electrons properties

(iv) Electronic

configuration

(v) Chemical

properties

(vi) Position in

the periodic table

(i) Mass No. (A) (i) Atomic No. (Z) (i) 40

18
40
Ar , 19 K , 40
20 Ca

(ii) No. of (ii) No. of protons, (ii)

Isobars
nucleons electrons and 130
52 Te, 130 130
54 Xe, 56 Ba

neutrons
 (iii)Electronic

configuration

(iv) Chemical

properties

(v) Position in the

perodic table.

No. of neutrons (i) Atomic No. (i) 30

14
31
Si , 15 32
P, 16 S

(ii) Mass No., (ii) 39

19 K , 40
20 Ca

Isotones protons and

(iii) 3
1 H , 42 He

electrons.
(iv) 13 14
6 C, 7 N

(iii) Electronic
 configuration

(iv) Physical and

chemical

properties

(v) Position in the

periodic table.

Isotopic No. (i) At No., mass (i) 92 U

235
, 90 Th 231

(N – Z) or (A – No., electrons,
(ii) 19 K 39 , 9 F 19

2Z) protons, neutrons.

Isodiaphers (iii) 29 Cu
65
, 24 Cr 55

(ii) Physical and

chemical

properties.
 (i) No. of At. No., mass No. (i)

electrons N 2 O, CO 2 , CNO − (22e − )

(ii) Electronic
(ii)
configuration
Isoelectroni CO, CN − , N 2 (14 e − )

c species (iii)

H − , He, Li + , Be 2+ (2e − )

(iv)
P 3 − , S2 − , Cl − , Ar , K + and Ca 2 + (18

(i) No. of atoms (i) N2 and CO

Isosters
(ii) No. of (ii) CO 2 and N 2O
 electrons (iii) HCl and F2

(iii) Same (iv) CaO and

physical and MgS

chemical
(v) C6 H 6 and
properties.
B3 N 3 H 6

Note :  In all the elements, tin has maximum

number of stable isotopes (ten).

 Average atomic weight/ The average

isotopic weight
 % of 1st isotope × relative mass of 1st isotope + % of 2nd isotope × relative mass of 2nd isotope
=
100

Examples based on Moseley equation

Example : 4 The characteristics X- ray

wavelength for the lines of the kα series in elements

X and Y are 9.87Å and 2.29Å respectively. If

Moseley’s equation ν = 4.9 × 10 7 (Z − 0.75) is followed, the

atomic numbers of X and Y ar

(a) 12, 24

(b) 10, 12

(c) 6, 12
(d) 8, 10

c
Solution : (a) ν =
λ

3 × 10 8
νx = −10
= 5.5132 × 10 8
9.87 × 10

3 × 10 8
νy = = 11 .4457 × 10 8
2.29 × 10 −10

using Moseley’s equation we get

∴ 5.5132 × 10 8 = 4.9 × 10 7 (Z x − 0.75) …..(i)

and 11 .4457 × 10 8 = 4.90 × 10 7 (Zy − 0.75) ….. (ii)

On solving equation (i) and (ii) Z x = 12, Z y = 24 .

Example : 5 If the straight line is at an angle 45°

with intercept, 1 on ν − axis, calculate frequency

ν when atomic number Z is 50.

(a) 2000 s −1

(b) 2010 s −1

(c) 2401 s −1

(d) None

a= tan θ

ν s−1 ab=intercept

Solution : (c) ν = tan 45 ° = 1 = a

ab=1

∴ ν = 50 − 1 = 49
 ν = 2401 s−1 .

Example : 6 What is atomic number Z when

ν = 2500 s−1 ?

(a)50

(b)40

(c)51

(d)53

Solution : (c) ν = 2500 = Z − 1, Z = 51 .

A
ZX Examples based on Atomic number, Mass number and Atomic
Example : 7 Atomic weight of Ne is 20.2. Ne is a

mixutre of Ne 20 and Ne 22 . Relative abundance of

heavier isotope is

(a)90

(b)20

(c)40

(d)10

Solution:(d) Average atomic weight/ The average

isotopic weight

% of 1st isotope × relative mass of 1st isotope + % of 2nd isotope × relative mass of 2nd isotope
=
100
a × 20 + (100 − a) × 22
∴ 20 .2 =
100
;
∴ a = 90 ; per cent of heavier isotope = 100 − 90 = 10

Example : 8 The relative abundance of two

isotopes of atomic weight 85 and 87 is 75% and

25% respectively. The average atomic weight of

element is

(a)75.5

(b)85.5

(c)87.5

(d)86.0

Solution:(b)Average atomic weight/ The average

isotopic weight
 % of 1st isotope × relative mass of 1st isotope + % of 2nd isotope × relative mass of 2nd isotope
=
100
85 × 75 + 87 × 25
= = 85 .5
100

Example : 9 Nitrogen atom has an atomic number

of 7 and oxygen has an atomic number of 8. The

total number of electrons in a nitrate ion is

(a) 30

(b) 35

(c) 32

(d) None

Solution : (c) Number of electrons in an element =

Its atomic number

 So number of electrons in N=7 and

number of electrons in O=8.

Formula of nitrate ion is NO 3−

So, in it number of electrons

= 1× number of electrons of nitrogen +3 ×

number of electrons of oxygen +1 (due to negative

charge)

= 1 × 7 + 3 × 8 + 1 = 32

Example :10 An atom of an element contains 11

electrons. Its nucleus has 13 neutrons. Find out the

atomic number and approximate atomic weight.

(a) 11, 25
(b) 12, 34

(c) 10, 25

(d) 11, 24

Solution : (d) Number of electrons =11

∴ Number of protons = Number of electron =11

Number of neutrons = 13

Atomic number of element = Number of proton =

Number of electrons =11

Further, Atomic weight = Number of protons +

Number of neutrons =11 + 13=24

Example : 11 How many protons, neutrons and

electrons are present in (a) 31

15 P (b) 40
18 Ar (c) 108
47 Ag ?

Solution :The atomic number subscript gives the

number of positive nuclear charges or protons. The

neutral atom contains an equal number of negative

electrons. The remainder of the mass is supplied by

neutrons.

Atom Protons Electrons Neutrons

31
15 P 15 15 31 – 15=16

40
18 Ar 18 18 40 – 18=22

108
47 Ag 47 47 108 – 47=61
Example :12 State the number of protons,

neutrons and electrons in C 12 and C 14 .

Solution :The atomic number of C 12 is 6. So in it

number of electrons = 6

Number of protons =6; Number of neutrons =12 –

6=6

The atomic number of C 14 is 6. So in it number

of electrons = 6

Number of protons = 6; Number of neutrons

=14 – 6=8

Example :13 Predict the number of electrons,

protons and neutrons in the two isotopes of

magnesium with atomic number 12 and atomic

weights 24 and 26.

Solution :Isotope of the atomic weight 24, i.e.

12 Mg 24 . We know that

Number of protons = Number of electrons =12

Further, Number of neutrons = Atomic

weight – Atomic number =24 – 12 =12

Similarly, In isotope of the atomic weight

26, i.e. 12 Mg 26

Number of protons = Number of electrons

=12

Number of neutrons = 26 – 12 = 14
2.3 Electromagnetic Radiations.

(1) Light and other forms of radiant energy

propagate without any medium in the space in the

form of waves are known as electromagnetic

radiations. These waves can be produced by a

charged body moving in a magnetic field or a

magnet in a electric field. e.g. α − rays, γ − rays,

cosmic rays, ordinary light rays etc.

(2) Characteristics : (i) All electromagnetic

radiations travel with the velocity of light. (ii) These

consist of electric and magnetic fields components

that oscillate in directions perpendicular to each

other and perpendicular to the direction in which the

wave is travelling.

(3) A wave is always characterized by the following

five characteristics:

(i) Wavelength : The distance between two nearest

crests or nearest troughs is called the wavelength. It

is denoted by λ (lambda) and is measured is terms of

centimeter(cm), angstrom(Å), micron( µ ) or

nanometre (nm).

Crest Wavelength

Vibrating
source
Energy

Trough
 1 Å = 10 −8 cm = 10 −10 m

1µ = 10 −4 cm = 10 −6 m

1nm = 10 −7 cm = 10 −9 m

1cm = 10 8 Å = 10 4 µ = 10 7 nm

(ii) Frequency : It is defined as the number of waves

which pass through a point in one second. It is

denoted by the symbol ν (nu) and is expressed in

terms of cycles (or waves) per second (cps) or hertz

(Hz).

λν = distance travelled in one second = velocity =c

c
ν=
λ
(iii) Velocity : It is defined as the distance covered

in one second by the wave. It is denoted by the letter

‘c’. All electromagnetic waves travel with the same

velocity, i.e., 3 × 10 10 cm / sec .

c = λν = 3 × 10 10 cm / sec

Thus, a wave of higher frequency has a shorter

wavelength while a wave of lower frequency has a

longer wavelength.

(iv) Wave number : This is the reciprocal of

wavelength, i.e., the number of wavelengths per

centimetre. It is denoted by the symbol ν (nu bar). It

is expressed in cm −1 or m −1 .
 1
ν =
λ

(v) Amplitude : It is defined as the height of the

crest or depth of the trough of a wave. It is denoted

by the letter ‘A’. It determines the intensity of the

radiation.

The arrangement of various types of electromagnetic

radiations in the order of their increasing or

decreasing wavelengths or frequencies is known as

electromagnetic spectrum.

Name Wavelength Frequency Source

(Å) (Hz)
Radio wave 3 × 10 14 − 3 × 10 7 1 × 10 5 − 1 × 10 9 Alternating

current of high

frequency

Microwave 3 × 10 7 − 6 × 10 6 1 × 10 9 − 5 × 10 11 Klystron tube

Infrared (IR) 6 × 10 6 − 7600 5 × 10 11 − 3.95 × 10 16 Incandescent

objects

Visible 7600 − 3800 3.95 × 10 16 − 7.9 × 10 14 Electric bulbs,

sun rays

Ultraviolet 3800 − 150 7.9 × 10 14 − 2 × 10 16 Sun rays, arc

(UV) lamps with

mercury vapours
X-Rays 150 − 0.1 2 × 10 16 − 3 × 10 19 Cathode rays

striking metal

plate

γ− Rays 0.1 − 0.01 3 × 10 19 − 3 × 10 20 Secondary effect

of radioactive

decay

Cosmic Rays 0.01- zero 3 × 10 20 − infinity Outer space

2.4 Atomic spectrum - Hydrogen spectrum.

Atomic spectrum
(1) Spectrum is the impression produced on a

photographic film when the radiation (s) of

particular wavelength (s) is (are) analysed through a

prism or diffraction grating. It is of two types,

emission and absorption.

(2) Emission spectrum : A substance gets excited on

heating at a very high temperature or by giving

energy and radiations are emitted. These radiations

when analysed with the help of spectroscope,

spectral lines are obtained. A substance may be

excited, by heating at a higher temperature, by

passing electric current at a very low pressure in a

discharge tube filled with gas and passing electric

current into metallic filament. Emission spectra

is of two types,

(i) Continuous spectrum : When sunlight is passed

through a prism, it gets dispersed into continuous

bands of different colours. If the light of an

incandescent object resolved through prism or

spectroscope, it also gives continuous spectrum of

colours.

(ii) Line spectrum : If the radiations obtained by the

excitation of a substance are analysed with help of a

spectroscope a series of thin bright lines of specific

colours are obtained. There is dark space in between

two consecutive lines. This type of spectrum is

called line spectrum or atomic spectrum..

(3) Absorption spectrum : When the white light of

an incandescent substance is passed through any

substance, this substance absorbs the radiations of

certain wavelength from the white light. On

analysing the transmitted light we obtain a spectrum

in which dark lines of specific wavelengths are

observed. These lines constitute the absorption

spectrum. The wavelength of the dark lines

correspond to the wavelength of light absorbed.

Hydrogen spectrum
(1) Hydrogen spectrum is an example of line

emission spectrum or atomic emission spectrum.

(2) When an electric discharge is passed through

hydrogen gas at low pressure, a bluish light is

emitted.

(3) This light shows discontinuous line spectrum of

several isolated sharp lines through prism.

(4) All these lines of H-spectrum have Lyman,

Balmer, Paschen, Barckett, Pfund and Humphrey

series. These spectral series were named by the

name of scientist discovered them.

(5) To evaluate wavelength of various H-lines Ritz

introduced the following expression,

1 ν 1 1
ν = = = R 2 − 2 
λ c  n1 n2 

Where R is universal constant known as Rydberg’s

constant its value is 109, 678 cm . −1

2.5 Thomson's model.

(1) Thomson regarded atom to be composed of

positively charged protons and negatively charged

electrons. The two types of particles are equal in

number thereby making atom electrically neutral.

Positively charged sphere

–
+ +

– –
+ – +
+ Electron
+ –
– +

Positive charge spreaded throughout the sphere

(2) He regarded the atom as a positively charged

sphere in which negative electrons are uniformly

distributed like the seeds in a water melon.

(3) This model failed to explain the line spectrum of

an element and the scattering experiment of

Rutherford.

2.6 Rutherford's nuclear model.

(1) Rutherford carried out experiment on the

bombardment of thin (10–4 mm) Au foil with high

speed positively charged α − particles emitted from

Ra and gave the following observations, based on

this experiment :

(i) Most of the α− particles passed without any

deflection.

(ii) Some of them were deflected away from their

path.

(iii) Only a few (one in about 10,000) were returned

back to their original direction of propagation.

1
(iv) The scattering of α − particles ∝ .
4θ 
sin  
 2

Scattering of α -particle

θ
b

r0 Nucleus

α-particle
(energy E eV)
(2) From the above observations he concluded that,

an atom consists of

(i) Nucleus which is small in size but carries the

entire mass i.e. contains all the neutrons and protons.

(ii) Extra nuclear part which contains electrons.

This model was similar to the solar system.

Planetry electron

–
Nucleus
+

10–15 m

10–10 m
Size of the nucleus = 1 Fermi = 10–15 m
Size of the atom 1 Å = 10–10 m

(3) Properties of the Nucleus

(i) Nucleus is a small, heavy, positively charged

portion of the atom and located at the centre of the

atom.

(ii) All the positive charge of atom (i.e. protons) are

present in nucleus.

(iii) Nucleus contains neutrons and protons, and hence

these particles collectively are also referred to as

nucleons.

(iv) The size of nucleus is measured in Fermi (1

Fermi = 10–13 cm).

(v) The radius of nucleus is of the order of

= ro (= 1.4 × 10 −13 cm) × A1 / 3
1.5 × 10 −13 cm. to 6.5 × 10 −13 cm. i.e.r
n
1.5 to 6.5 Fermi.
Generally the radius of the nucleus ( r ) is given by n

the following relation,

This exhibited that nucleus is 10 −5 times small in size

as compared to the total size of atom.

(vi) The Volume of the nucleus is about 10 −39 cm 3 and

that of atom is 10 −24 cm 3 , i.e., volume of the nucleus is

10 −15 times that of an atom.

(vii) The density of the nucleus is of the order of

10 15 g cm −3 or 10 8 tonnes cm −3 or 10 12 kg / cc . If nucleus is

spherical than,

mass of the nucleus mass number

Density = =
volume of the nucleus 4
6.023 × 10 23 × πr 3
3

(4) Drawbacks of Rutherford's model

(i) It does not obey the Maxwell theory of

electrodynamics, according to it “A small charged

particle moving around an oppositely charged centre

continuously loses its energy”. If an electron does

so, it should also continuously lose its energy and

should set up spiral motion ultimately failing into

the nucleus.

(ii) It could not explain the line spectra of H− atom

and discontinuous spectrum nature.

e–

Unstability of atom
 +
Examples based on Properties of the nucleus

Example:14 Assuming a spherical shape for

fluorine nucleus, calculate the radius and the nuclear

density of fluorine nucleus of mass number 19.

Solution : We know that,

r = (1.4 × 10 −13 ) A 1 / 3 = 1.4 × 10 −13 × 19 1 / 3 = 3.73 × 10 −13 cm (A for

F=19)

Volume of a fluorine atom = 43 πr 3

=
4
3
× 3.14 × (3.73 × 10 −13 )3

= 2.18 × 10 −37 cm 3

Mass of one mol of nucleus 19

Mass of single nucleus = = g
Avogadro' s number 6.023 × 10 23
 Mass of single nucleus 10 1
Thus Density of nucleus = Volume of single nucleus
= ×
6.023 × 10 23 2.18 × 10 − 37

= 7.616 = 10 13 g cm −1

Example: 15 Atomic radius is the order of

10 −8 cm, and nuclear radius is the order of

10 −13 cm. Calculate what fraction of atom is occupied by

nucleus.

Solution : Volume of nucleus = (4 / 3)pr 3

= (4 / 3)p × (10 −13 )3 cm 3

Volume of atom = (4 / 3)pr 3

= (4 / 3)p × (10 −8 ) 3 cm 3

Vnucleus 10 −39
∴
Vatom
=
10 − 24
= 10 −15 or Vnucleus = 10 −15 × Vatom

2.7 Planck's Quantum theory and Photoelectric

effect.
 Planck's Quantum theory

(1) Max Planck (1900) to explain the phenomena of

'Black body radiation' and 'Photoelectric effect' gave

quantum theory. This theory extended by Einstein

(1905).

(2) If the substance being heated is a black body

(which is a perfect absorber and perfect radiator of

energy) the radiation emitted is called black body

radiation.

(3) Main points

(i) The radiant energy which is emitted or

absorbed by the black body is not continuous but

discontinuous in the form of small discrete packets

of energy, each such packet of energy is called a

'quantum'. In case of light, the quantum of energy is

called a 'photon'.

(ii) The energy of each quantum is directly

proportional to the frequency (ν ) of the radiation,

i.e.

hc
E ∝ν or E = hν =
λ

where, h= Planck's constant = 6.62×10–27 erg.

sec. or 6.62 × 10 −34 Joules sec .

 (iii) The total amount of energy emitted or

absorbed by a body will be some whole number

quanta. Hence E = nh ν , where n is an integer.

(iv) The greater the frequency (i.e. shorter the

wavelength) the greater is the energy of the

radiation.

E1 ν 1 λ 2
thus, = =
E 2 ν 2 λ1

hc hc hc
(v) Also E = E1 + E2 , hence, λ
=
λ1
+
λ2
or

1 1 1
λ
=
λ1
+
λ2
.

Examples based on Planck's Quantum theory

hc
E=
λ
Example: 16 Suppose 10 −17 J of energy is needed by

the interior of human eye to see an object. How

many photons of green light (λ = 550 nm) are needed to

generate this minimum amount of energy

(a) 14

(b) 28

(c) 39

(d) 42

Solution : (b) Let the number of photons required

=n

hc 10 −17 × λ 10 −17 × 550 × 10 −9

n
λ
= 10 −17 ; n=
hc
=
6.626 × 10 − 34 × 3 × 10 8
= 27 .6 = 28 photons
Example: 17 Assuming that a 25 watt bulb emits

monochromatic yellow light of wave length 0.57 µ .

The rate of emission of quanta per sec. will be

(a) 5.89 × 10 13 sec −1

(b) 7.28 × 10 17 sec −1

(c) 5 × 10 10 sec −1

(d) 7.18 × 10 19 sec −1

Solution: (d) Let n quanta are evolved per sec.

 hc  6.626 × 10 −34 × 3 × 10 8
n  = 25 J sec −1 ; n = 25 ; n = 7.18 × 10 19 sec −1
λ 0.57 × 10 − 6

Photoelectric effect
(1) When radiations with certain minimum

frequency (ν 0 ) strike the surface of a metal, the

electrons are ejected from the surface of the metal.

This phenomenon is called photoelectric effect and

the electrons emitted are called photo-electrons. The

current constituted by photoelectrons is known as

photoelectric current.

(2) The electrons are ejected only if the radiation

striking the surface of the metal has at least a

minimum frequency (ν 0 ) called Threshold frequency.

The minimum potential at which the plate

photoelectric current becomes zero is called

stopping potential.
(3)The velocity or kinetic energy of the electron

ejected depend upon the frequency of the incident

radiation and is independent of its intensity.

(4) The number of photoelectrons ejected is

proportional to the intensity of incident radiation.

(5) Einstein’s photoelectric effect equation :

According to Einstein,

Maximum kinetic energy of the ejected electron

= absorbed energy – threshold energy

1 1 1 
2
mv max = hν − hν 0 = hc  − 
2  λ λ0 
 where, ν0 and λ0 are threshold frequency and

threshold wavelength.

Note :  Nearly all metals emit photoelectrons

when exposed to u.v. light. But alkali metals like

lithium, sodium, potassium, rubidium and caesium

emit photoelectrons even when exposed to visible

light.

U.V. light Metal Photo electrons

Metal other
Visible light
than alkali No photo electrons
metals

Visible light Alkali

metals Photo electrons

 Caesium (Cs) with lowest ionisation energy

among alkali metals is used in photoelectric cell.

2.8 Bohr’s atomic model.

(1) This model was based on the quantum theory of

radiation and the classical law of physics. It gave

new idea of atomic structure in order to explain the

stability of the atom and emission of sharp spectral

lines.

(2) Postulates of this theory are :

(i) The atom has a central massive core

nucleus where all the protons and neutrons are

present. The size of the nucleus is very small.

(ii) The electron in an atom revolve around

the nucleus in certain discrete orbits. Such orbits are

known as stable orbits or non – radiating or

stationary orbits.

(iii) The force of attraction between the

nucleus and the electron is equal to centrifugal force

of the moving electron.

Force of attraction towards nucleus = centrifugal

force

(iv) An electron can move only in those

permissive orbits in which the angular momentum

(mvr) of the electron is an integral multiple of

h
h / 2π . Thus, mvr = n
2π
 Where, m = mass of the electron, r = radius

of the electronic orbit, v = velocity of the electron in

its orbit.

(v) The angular momentum can be

h 2h 3h nh
, ,
2π 2π 2π
,......
2π
. This principal is known as

quantization of angular momentum. In the above

equation ‘n’ is any integer which has been called as

principal quantum number. It can have the values

n=1,2,3, ------- (from the nucleus). Various energy

levels are designed as K(n=1), L(n=2), M(n=3) ------

- etc. Since the electron present in these orbits is

associated with some energy, these orbits are called

energy levels.

(vi) The emission or absorption of radiation by

the atom takes place when an electron jumps from

one stationary orbit to another.

E1 E1

E1 – E2 = hν E1 – E2 = hν
E2 E2
Emission Absorption

(vii) The radiation is emitted or absorbed as a

single quantum (photon) whose energy hν is equal to

the difference in energy ∆E of the electron in the two

orbits involved. Thus, hν = ∆E

 Where ‘h’ =Planck’s constant, ν = frequency

of the radiant energy. Hence the spectrum of the

atom will have certain fixed frequency.

(viii) The lowest energy state (n=1) is called

the ground state. When an electron absorbs energy,

it gets excited and jumps to an outer orbit. It has to

fall back to a lower orbit with the release of energy.

(3) Advantages of Bohr’s theory

(i) Bohr’s theory satisfactorily explains the

spectra of species having one electron, viz. hydrogen

atom, He + , Li 2+ etc.
 (ii) Calculation of radius of Bohr’s orbit :

According to Bohr, radius of orbit in which electron

moves is

 h2  n2
r =  2 2 .
 4π me k  Z

where, n =Orbit number, m =Mass number

[9.1 × 10 −31
] e =Charge on the electron [1.6 × 10 ]
kg , −19
Z

=Atomic number of element, k = Coulombic

constant [9 × 10 9
Nm 2 c −2 ]

After putting the values of m,e,k,h, we get.

n2 n2
rn = × 0.529 Å or rn = × 0.529 nm
Z Z

(a) For a particular system [e.g., H, He+ or

Li+2]
 r ∝ n2 [Z = constant]

r1 n12
Thus we have =
r2 n22
i.e.,

r1 : r2 : r3 .......... . :: 1 : 4 : 9....... r1 < r2 < r3

(b) For particular orbit of different species

1
r∝
Z
[Z =constant] Considering A and

rA Z
B species, we have rB
= B
ZA

Thus, radius of the first orbit H,

He + , Li +2 and Be +3 follows the order: H > He + > Li +2 > Be +3

(iii) Calculation of velocity of electron

1/ 2
2πe 2 ZK  Ze 2 
Vn = , Vn =  
nh  mr 
 2.188 × 10 8
For H atom, Vn =
n
cm. sec −1

(a) For a particular system [H, He+ or Li+2]

1 V1 n2
V∝
n
[Z = constant] Thus, we have, =
V2 n1

The order of velocity is V1 > V2 > V3 ......... or

1 1
V1 : V2 : V3 .......... :: 1 : : ........
2 3

(b) For a particular orbit of different species

V∝Z [n =constant] Thus, we have

H < He + < Li +2

(c) For H or He+ or Li+2, we have

V1 : V2 = 2 : 1 ; V1 : V3 = 3 : 1 ; V1 : V4 = 4 : 1
 (iv) Calculation of energy of electron in

Bohr’s orbit

Total energy of electron = K.E. + P.E. of

kZe 2 kZe 2 kZe 2

electron =
2r
−
r
=−
2r

− 2π 2 mZ 2 e 4 k 2
Substituting of r, gives us E=
n2h2

Where, n=1, 2, 3………. ∞

Putting the value of m, e, k, h, π we get

Z2
E = 21 .8 × 10 −12 × erg per atom
n2

Z2
= −21 .8 × 10 −19 × 2
J per atom (1J = 10 7 erg)
n
 Z2 Z2
E = −13 .6 × eV per atom(1eV = 1.6 × 10 -19
J ) = −313 . 6 × kcal . / mole
n2 n2

(1 cal = 4.18J)

− 1312 2
or n2
Z kJmol −1

(a) For a particular system[H, He+ or Li+2]

1 E1 n22
E∝− [Z =constant] Thus, we have =
E2 n12
n2

The energy increase as the value of n

increases

(b) For a particular orbit of different species

E A Z A2
E ∝ −Z 2 [n =constant] Thus, we have EB
= 2
ZB
 For the system H, He+ , Li+2, Be+3 (n-

same) the energy order is H > He + > Li +2 > Be +3

The energy decreases as the value of

atomic number Z increases.

When an electron jumps from an outer

orbit (higher energy) n2 to an inner orbit (lower

energy) n , then the energy emitted in form of

1

radiation is given by

2π 2 k 2 me 4 Z 2  1 1   1 1 
∆E = En2 − En1 =  2 − 2  ⇒ ∆E = 13 .6 Z 2  2 − 2  eV / atom
h2  n1 n2   n1 n2 

1 ∆E
As we know that E = hν , c = νλ and ν =
λ
=
hc
,

2π 2 k 2 me 4 Z 2  1 1 
=  
ch 3  n2 − n2 
 1 2 
  1 1 
This can be represented as λ1 = ν = RZ 2  2 − 2  where,
 n1 n2 

2π 2 k 2 me 4
R=
ch3
R is known as Rydberg constant. Its value

to be used is 109678 cm −1 .

(4) Quantisation of energy of electron

(i) In ground state : No energy emission. In ground

state energy of atom is minimum and for 1st orbit of

H-atom, n=1.

∴ E1 = −13 .6eV .

(ii) In excited state : Energy levels greater than n1 are

excited state. i.e. for H- atom n2 , n3 , n4 are excited

state. For H- atom first excitation state is = n2

(iii) Excitation potential : Energy required to excite

electron from ground state to any excited state.

Ground state → Excited state

Ist excitation potential = E2 − E1 = −3.4 + 13 .6 = 10.2 eV.

IInd excitation potential = E 3 − E1 = −1.5 + 13 .6 = 12 .1 eV .

(iv) Ionisation energy : The minimum energy required

to relieve the electron from the binding of nucleus.

2
Zeff.
Eionisation = E∞ − En = +13 .6 eV .
n2

Eionisation
(v) Ionisation potential : Vionisation =
e

(vi) Separation energy : Energy required to excite an

electron from excited state to infinity.

S.E. = E∞ − Eexcited .

(vii) Binding energy : Energy released in bringing

the electron from infinite to any orbit is called its

binding energy (B.E.).

Note :  Principal Quantum Number 'n' = 13 .6

(B.E.)
.

(5) Spectral evidence for quantisation

(Explanation for hydrogen spectrum on the basisof

bohr atomic model)

(i) The light absorbed or emitted as a result of an

electron changing orbits produces characteristic

absorption or emission spectra which can be

recorded on the photographic plates as a series of

lines, the optical spectrum of hydrogen consists of

several series of lines called Lyman, Balmar,

Paschen, Brackett, Pfund and Humphrey. These

spectral series were named by the name of scientist

who discovered them.

(ii) To evaluate wavelength of various H-lines Ritz

introduced the following expression,

1 ν 1 1
ν = = = R 2 − 2 
λ c  n1 n2 

where, R is = 2π
2
me 4
= Rydberg's constant
ch 3

It's theoritical value = 109,737 cm–1 and It's

experimental value = 109 ,677 .581cm −1

This remarkable agreement between the theoretical

and experimental value was great achievment of the

Bohr model.

(iii) Although H- atom consists only one electron yet

it's spectra consist of many spectral lines as shown in

fig.

n=8
n=7
n=6 Humphrey
n=5 i
Pfund
series
n=4
Bracket
t
Energy level

series
n=3
Paschen
series

n=2
Balmer
series

n=1
Lyman
series
 (iv) Comparative study of important spectral

series of Hydrogen

n12n22 n12 λ max n2

S. Spectr Lies Transiti λmax =
(n22− n12 )R
λ min =
R λ min
= 2 2
n2 − n

No al in the on

. series regio n2 > n1

(1) Lymen Ultrav n1 = 1 n1 = 1 and n 2 = 2 n1 = 1 and n 2 = ∞

4
series iolet n 2 = 2,3,4.... ∞ λ max =
4
λ min =
1 3
3R R

region

(2) Balme Visibl n1 = 2 n1 = 2 and n 2 = 3 n1 = 2 and n2 = ∞

 r e n 2 = 3,4,5.... ∞ λ max =
36
5R
λ min =
4
R
9
5

series region

(3) Pasche Infra n1 = 3 n1 = 3 and n 2 = 4 n1 = 3 and n 2 = ∞

16
n red n 2 = 4,5,6.... ∞ λ max =
144
λ min =
9 7
7R R

series region

(4) Bracke Infra n1 = 4 n1 = 4 and n2 = 5 n1 = 4 and n 2 = ∞

25
tt red n 2 = 5,6,7.... ∞ λmax =
16 × 25
λ min =
16 9
9R R

series region

(5) Pfund Infra n1 = 5 n1 = 5 and n 2 = 6 n1 = 5 and n 2 = ∞

36
series red n 2 = 6,7,8.... ∞ λ max =
25 × 36
λ min =
25 11
11 R R

region

49
(6) Hump Far n1 = 6 n1 = 6 and n 2 = 7 n1 = 6 and n 2 = ∞
13
 36 × 49
hrey infrar n 2 = 7,8.... ∞ λ max =
13 R
λ min =
36
R

series ed

region

(v) If an electron from nth excited state comes to

various energy states, the maximum spectral lines

n(n − 1)
obtained will be = 2
. n= principal quantum

number.

as n=6 than total number of spectral lines =

6(6 − 1) 30
= = 15 .
2 2
(vi) Thus, at least for the hydrogen atom, the Bohr

theory accurately describes the origin of atomic

spectral lines.

(6) Failure of Bohr Model

(i) Bohr theory was very successful in predicting

and accounting the energies of line spectra of

hydrogen i.e. one electron system. It could not

explain the line spectra of atoms containing more

than one electron.

(ii) This theory could not explain the presence

of multiple spectral lines.

 (iii) This theory could not explain the splitting

of spectral lines in magnetic field (Zeeman effect)

and in electric field (Stark effect). The intensity of

these spectral lines was also not explained by the

Bohr atomic model.

(iv) This theory was unable to explain of dual

nature of matter as explained on the basis of De

broglies concept.

(v) This theory could not explain uncertainty

principle.

(vi) No conclusion was given for the concept

of quantisation of energy.
 Examples based on Bohr’s atomic model and Hydrogen

Example: 18 If the radius of 2nd Bohr orbit of

hydrogen atom is r2. The radius of third Bohr orbit

will be

(a) 49 r 2

(b) 4r2

9
(c) 4
r3

(d) 9r2

2 2
r2 22 9
Solution : (c) r = 4πn mZe
2
h
2
∴
r3
= 2 ∴ r3 = r2
3 4

Example: 19Number of waves made by a Bohr

electron in one complete revolution in 3rd orbit is

(a) 2

(b) 3

(c) 4

(d) 1

Solution : (b) Circumference of 3rd orbit = 2πr3

According to Bohr angular momentum of electron in

3rd orbit is

h h 2πr3
mvr3 = 3
2π
or mv
=
3

h
by De-Broglie equation, λ=
mv

2πr3
∴λ = ∴2πr3 = 3λ
3
i.e. circumference of 3rd orbit is three times the

wavelength of electron or number of waves made by

Bohr electron in one complete revolution in 3rd orbit

is three.

Example: 20 The degeneracy of the level of

R11
hydrogen atom that has energy −
16
is

(a) 16

(b) 4

(c) 2

(d) 1

RH RH RH
Solution : (a) E n =−
n2
∴ −
n 2
=−
16

i.e. for 4 th sub-shell

 n=4 1 2 3

1=0

m=0 +1 0 +2 –1 0 +1 +2 –3 –2 –1 0 +1 +2 +3
+1
one s three p five d seven f

i.e. 1+3+5+7=16, ∴ degeneracy is 16

Example: 21 The velocity of electron in the ground

state hydrogen atom is 2.18 × 10 8

ms −1 . Its velocity in the

second orbit would be

(a) 1.09 × 10 8 ms −1

(b) 4.38 × 10 8 ms −1

(c) 5.5 × 10 5 ms −1

(d) 8.76 × 10 8 ms −1
Solution : (a) We know that velocity of electron in

nth Bohr's orbit is given by

Z
v = 2.18 × 10 6 m/ s
n

for H, Z = 1

2.18 × 10 6
 v1 = m/ s
1

2.18 × 10 6
 v2 = m / s = 1.09 × 10 6 m / s
2

Example: 22 The ionization energy of the ground

state hydrogen atom is 2.18 × 10 −18 J. The energy of an

electron in its second orbit would be

(a) − 1.09 × 10 −18 J

(b) − 2.18 × 10 −18 J

(c) − 4.36 × 10 −18 J

(d) − 5.45 × 10 −19 J

Solution : (d) Energy of electron in first Bohr's orbit

of H-atom

− 2.18 × 10 −18
E=
n2
J ( ionization energy of H =

2.18 × 10 −18 J )

− 2.18 × 10 −18
E2 = J = −5.45 × 10 −19 J
22

Example: 23 The wave number of first line of

Balmer series of hydrogen atom is 15200 cm −1 . What

is the wave number of first line of Balmer series of

Li 3+ ion.
(a) 15200 cm −1

(b) 6080 cm −1

(c) 76000 cm −1

(d) 1,36800 cm −1

Solution : (d) For Li 3+ v = v for H × z2 =15200 ×9=

1,36800 cm −1

Example: 24 The Bohr orbit radius for the

hydrogen atom (n = 1) is approximately 0.530Å.

The radius for the first excited state (n = 2) orbit is

(in Å)

(a)0.13

(b)1.06
(c)4.77

(d) 2.12

Solution : (d)The Bohr radius for hydrogen atom (n

= 1) = 0.530Å

The radius of first excited state (n = 2) will be =

n2 (2)2
0.530 × = 0.530 × = 2.120 Å
Z 1

Example: 25How many chlorine atoms can you

ionize in the process Cl → Cl + + e− , by the energy

liberated from the following process :

Cl + e − → Cl − for 6 × 10 23 atoms
Given electron affinity of Cl = 3.61eV , and IP of

Cl = 17 .422 eV

(a) 1.24 × 10 atoms 23

(b) 9.82 × 10 20 atoms

(c) 2.02 × 10 atoms

15

(d) None of these

Solution : (a)Energy released in conversion of 6 × 10 23

atoms of Cl − ions = 6 × 10 23 × electron affinity

= 6× 10 23
× 3.61 = 2.166 × 10 24 eV.

Let x Cl atoms are converted to Cl + ion

Energy absorbed = x× ionization energy

x × 17 .422 = 2.166 × 10 24 ; x = 1.243 × 10 23 atoms

Example: 26The binding energy of an electron in

the ground state of the He atom is equal to 24eV.

The energy required to remove both the electrons

from the atom will be

(a) 59eV

(b) 81eV

(c)79eV

(d) None of these

Z2
Solution : (c) Ionization energy of He =
n2
× 13 .6

22
= × 13 .6 = 54 .4 eV
12

Energy required to remove both the electrons

= binding energy + ionization energy

= 24 .6 + 54 .4 = 79eV

Example: 27 The wave number of the shortest

wavelength transition in Balmer series of atomic

hydrogen will be

(a) 4215 Å

(b) 1437Å

(c) 3942Å

(d) 3647Å

 1 1   1 1 
Solution : (d) λ 1 = RZ 2  2 − 2  = 109678 × 1 2 ×  2 − 2 
∞ 
shortest  n1 n2  2

λ = 3.647 × 10 −5 cm = 3647 Å
Example: 28 If the speed of electron in the Bohr's

first orbit of hydrogen atom is x, the speed of the

electron in the third Bohr's orbit is

(a) x/9

(b) x/3

(c) 3x

(d) 9x

Solution : (b) According to Bohr's model for

hydrogen and hydrogen like atoms the velocity of an

electron in an atom is quantised and is given by

2πZe 2 1
v∝
nh
so v∝
n
in this cass n=3
Example: 29 Of the following transitions in

hydrogen atom, the one which gives an absorption

line of lowest frequency is

(a) n=1 to n=2

(b) n=3 to n=8

(c) n=2 to n=1

(d) n=8 to n=3

Solution : (b) Absorption line in the spectra arise

when energy is absorbed i.e., electron shifts from

lower to higher orbit, out of a & b, b will have the

lowest frequency as this falls in the Paschen series.

Example: 30 The frequency of the line in the

emission spectrum of hydrogen when the atoms of

the gas contain electrons in the third energy level are

(a) 1.268 × 10 14 Hz and 2.864 × 10 16 Hz

(b) 3.214 × 10 10 Hz and 1.124 × 10 12 Hz

(c) 1.806 × 10 12 Hz and 6.204 × 10 15 Hz

(d) 4.568 × 10 14 Hz and 2.924 × 10 15 Hz

Solution : (d) If an electron is in 3rd orbit, two

spectral lines are possible

(a)When it falls from 3rd orbit to 2nd orbit.

1 1
In equation ν = 3.289 × 10 15  2
− 2
 n1 n 2 
 1 1  5
ν 1 = 3.289 × 10 15  2 − 2  = 3.289 × 10 15 × = 4.568 × 14 14 Hz
 2 3  36

(b) When it falls from 3rd orbit to 1st orbit :

1 1  8
ν 2 = 3.289 × 10 15 ×  − 2  = 3.289 × 10 15 × = 2.924 × 10 15 Hz
1 3  9

Example: 31 If the first ionisation energy of

hydrogen is 2.179 × 10 −18 J per atom, the second

ionisation energy of helium per atom is

(a) 8.716 × 10 −18

J

(b) 5.5250 kJ

(c) 7.616 × 10 −18 J

(d) 8.016 × 10 −13 J

Solution : (a)For Bohrs systems : energy of the

Z2
electron ∝
n2

Ionisation energy is the difference of energies of an

electron (E∞ ), when taken to infinite distance and Er

when present in any Bohr orbit and Eα is taken as

zero so ionisation energy becomes equal to the

energy of electron in any Bohr orbit.

Z H2 2
Z He EH 1
EH ∝
n 2
; EHe ∝ 2
nHe
or EHe
=
2× 2
[as Z H = 1, Z He = 2, n H = 1, n He = 1]
H

or E He = E H × 4 = 2.179 × 10 −18 × 4 = 8.716 × 10 −18 Joule per atom.

Example: 32The ionization energy of hydrogen

atom is 13.6eV. What will be the ionization energy

of He +

(a) 13.6eV

(b) 54.4eV

(c) 122.4eV

(d) Zero

Solution : (b) I.E. of He + = 13 .6eV × Z 2

13 .6eV × 4 = 54 .4 eV

Example: 33 The ionization energy of He + is

19 .6 × 10 −18 J atom–1. Calculate the energy of the first

stationary state of Li +2
(a) 19 .6 × 10 −18 J atom -1

(b) 4.41 × 10 −18 J atom–1

(c) 19 .6 × 10 −19 J atom -1

(d) 4.41 × 10 −17 J atom −1

Solution : (d) I.E. of He + = E × 2 2 (Z for He = 2)

I.E. of Li 2+ = E × 3 3 (Z for Li=3)

I .E.( He + ) 4 9 9
∴ =
I .E.( Li 2+ ) 9
or I.E. (Li 2+ ) =
4
× I .E.( He + ) = × 19 .6 × 10 −18
4
= 4.41 × 10 −17

J atom–1

2.9 Bohr – Sommerfeld’s model.

(1) In 1915, Sommerfield introduced a new atomic

model to explain the fine spectrum of hydrogen

atom.

(2) He gave concept that electron revolve round the

nucleus in elliptical orbit. Circular orbits are formed

in special conditions only when major axis and

minor axis of orbit are equal.

nh
(3) For circular orbit, the angular momentum = 2π

where n= principal quantum number only one

component i.e. only angle changes.

(4) For elliptical orbit, angular momentum = vector

sum of 2 components. In elliptical orbit two

components are,
 h
(i) Radial component (along the radius) = nr
2π

Where, n = radial quantum number

r

h
(ii) Azimuthal component = n φ 2π

Where, n φ = azimuthal quantum number

So angular momentum of elliptical orbit

h h
=nr
2π
+ nφ
2π

r
φ2 r
r φ2 r rr φ11
φ1

φ = change φ = change
r = change r = constant

h
Angular momentum = (n r + nφ )
2π

(5) Shape of elliptical orbit depends on,

 Length of major axis n nr + nφ
= =
Length of minor axis nφ nφ

(6) n φ can take all integral values from l to ‘n’

values of n depend on the value of n φ . For n = 3,

r

n φ can have values 1,2,3 and n can have (n –1) to r

zero i.e. 2,1 and zero respectively.

Thus for n = 3, we have 3 paths

n nφ n r Nature of path

3 1 3 elliptical

2 1 elliptical

3 0 circular

K= 3
K= 2

K= 1

• Nuclear
The possible orbits for n = 3 are shown in figure.

Thus Sommerfield showed that Bohr’s each major

level was composed of several sub-levels. therefore

it provides the basis for existance of subshells in

Bohr's shells (orbits).

(7) Limitation of Bohr sommerfield model :

(i) This model could not account for, why electrons

does not absorb or emit energy when they are

moving in stationary orbits.

(ii) When electron jumps from inner orbit to

outer orbit or vice –versa, then electron run entire

distance but absorption or emission of energy is

discontinuous.

(iii) It could not explain the attainment of

nh
expression of 2π
for angular momentum. This model

could not explain Zeeman effect and Stark effect.

2.10 Dual nature of electron.

 (1) In 1924, the french physicist, Louis de

Broglie suggested that if light has both particle and

wave like nature, the similar duality must be true for

matter. Thus an electron, behaves both as a material

particle and as a wave.

(2) This presented a new wave mechanical

theory of matter. According to this theory, small

particles like electrons when in motion possess wave

properties.

(3) According to de-broglie, the wavelength

associated with a particle of mass m, moving with

velocity v is given by the relation

 h
λ=
mv
, where h = Planck’s constant.

(4) This can be derived as follows according to

h.c  c
Planck’s equation, E = hν =
λ
 ν = 
λ


energy of photon (on the basis of Einstein’s

mass energy relationship), E = mc 2

hc h
equating both λ
= mc 2 or λ =
mc
which is same

as de-Broglie relation. ( mc = p)

(5) This was experimentally verified by

Davisson and Germer by observing diffraction

effects with an electron beam. Let the electron is

accelerated with a potential of V than the Kinetic

energy is
 1
2
mv 2 = eV ; m 2 v 2 = 2eVm

h
mv = 2eVm = P ; λ=
2eVm

(6) If Bohr’s theory is associated with de-Broglie’s

equation then wave length of an electron can be

determined in bohr’s orbit and relate it with

circumference and multiply with a whole number

2πr
2πr = nλ or λ =
n

h h 2πr
From de-Broglie equation, λ=
mv
. Thus mv
=
n
or

nh
mvr =
2π

Note :  For a proton, electron and an α-

particle moving with the same velocity have de-

broglie wavelength in the following order : Electron

> Proton > α - particle.

(7) The de-Broglie equation is applicable to all

material objects but it has significance only in case

of microscopic particles. Since, we come across

macroscopic objects in our everyday life, de-broglie

relationship has no significance in everyday life.

Examples based on de-Broglie’s

Example: 34 An electron is moving with a

kinetic energy of 4.55 × 10 −25

J. What will be de-

Broglie wavelength for this electron

(a) 5.28 × 10 −7 m
(b) 7.28 × 10 −7 m

(c) 2 × 10 −10
m

(d) 3 × 10 −5 m

Solution : (b) KE = 12 mv 2
= 4.55 × 10 − 25 J

2 × 4.55 × 10 −25
v2 =
9.1 × 10 − 31
= 1× 10 6 ; v = 10 3 m / s

h 6.626 × 10 −34
De-Broglie wavelength λ= = −
mv 9.1 × 10 × 10
31 3
= 7.28 × 10 −7 m

Example: 35 The speed of the proton is one

hundredth of the speed of light in vacuum. What is

the de Broglie wavelength? Assume that one mole

of protons has a mass equal to one gram,

h = 6.626 × 10 −27 erg sec

(a) 3.31 × 10 −3 Å

(b) 1.33 × 10 −3 Å

(c) 3.13 × 10 −2
Å

(d) 1.31 × 10 −2 Å

1
Solution : (b) m=
6.023 × 10 23
g

h 6.626 × 10 −27
λ= =
mv 1 × 3 × 10 8 cm sec −1
× 6.023 × 10 23 = 1.33 × 10 −11 cm

2.11 Heisenberg’s uncertainty principle.

(1) One of the important consequences of the

dual nature of an electron is the uncertainty

principle, developed by Warner Heisenberg.

 (2) According to uncertainty principle “It is

impossible to specify at any given moment both the

position and momentum (velocity) of an electron”.

h
Mathematically it is represented as , ∆x . ∆p ≥
4π

Where ∆x = uncertainty is position of the particle,

∆p = uncertainty in the momentum of the particle

Now since ∆p = m ∆v

h h
So equation becomes, ∆x. m∆v ≥
4π
or ∆x × ∆v ≥
4πm

The sign ≥ means that the product of ∆x and ∆p (or

of ∆x and ∆v ) can be greater than, or equal to but

 h
never smaller than 4π
. If ∆x is made small,

∆p increases and vice versa.

(3) In terms of uncertainty in energy, ∆E and

uncertainty in time ∆t, this principle is written as,

h
∆E . ∆t ≥
4π

Note : Heisenberg’s uncertainty principle

cannot we apply to a stationary electron because its

velocity is 0 and position can be measured

accurately.

∆x . ∆p ≥
h
4π
Examples based on uncertainty

Example: 36 What is the maximum precision

with which the momentum of an electron can be

known if the uncertainty in the position of electron

is ± 0.001 Å ? Will there be any problem in describing

h
the momentum if it has a value of 2πa0
, where a0 is

Bohr’s radius of first orbit, i.e., 0.529Å?

h
Solution : ∆x . ∆p =
4π

 ∆x = 0.001 Å = 10 −13 m

6.625 × 10 −34
∴ ∆p = = 5.27 × 10 − 22
4 × 3.14 × 10 −13

Example: 37 Calculate the uncertainty in

velocity of an electron if the uncertainty in its

position is of the order of a 1Å.

Solution : According to Heisenberg’s

uncertainty principle

h
∆v . ∆x ≈
4πm

h 6.625 × 10 −34
∆v ≈ = = 5.8 × 10 5 m sec −1
4πm.∆x 4×
22
× 9.108 × 10 − 31 × 10 −10
7

Example: 38 A dust particle having mass

equal to 10 −11 g, diameter of 10 −4 cm and velocity

10 −4 cm sec −1 . The error in measurement of velocity is

0.1%. Calculate uncertainty in its positions.

Comment on the result .

0.1 × 10 −4
Solution : ∆v =
100
= 1 × 10 −7 cm sec −1

h
 ∆v . ∆x =
4πm
 6.625 × 10 −27
∴ ∆x = = 5.27 × 10 −10 cm
4 × 3.14 × 10 −11 × 1 × 10 −7

The uncertainty in position as compared to

particle size.

∆x 5.27 × 10 −10
= = −4
= 5.27 × 10 −6 cm
diameter 10

The factor being small and almost being

negligible for microscope particles.

2.12 Schrödinger wave equation.

(1) Schrodinger wave equation is given by Erwin

Schrödinger in 1926 and based on dual nature of

electron.
(2) In it electron is described as a three dimensional

wave in the electric field of a positively charged

nucleus.

(3) The probability of finding an electron at any

point around the nucleus can be determined by the

help of Schrodinger wave equation which is,

∂ 2 Ψ ∂ 2 Ψ ∂ 2 Ψ 8π 2m
+ 2 + 2 + ( E − V) Ψ = 0
∂x 2 ∂y ∂z h2

Where x, y and z are the 3 space co-ordinates,

m = mass of electron, h = Planck’s constant,

E = Total energy, V = potential energy of

electron, Ψ = amplitude of wave also called as wave

function.
 ∂ = stands for an infinitesimal change.

(4) The Schrodinger wave equation can also be

written as :

8π 2m
∇2Ψ + ( E − V) Ψ = 0
h2

Where ∇ = laplacian operator.

(5) Physical Significance of Ψ and Ψ2

(i) The wave function Ψ represents the

amplitude of the electron wave. The amplitude Ψ is

thus a function of space co-ordinates and time i.e.

Ψ = Ψ(x, y, z...... times)

 (ii) For a single particle, the square of the

wave function (Ψ 2 ) at any point is proportional to the

probability of finding the particle at that point.

(iii) If Ψ2 is maximum than probability of

finding e− is maximum around nucleus. And the

place where probability of finding e− is maximum is

called electron density, electron cloud or an atomic

orbital. It is different from the Bohr’s orbit.

(iv) The solution of this equation provides a

set of number called quantum numbers which

describe specific or definite energy state of the

electron in atom and information about the shapes

and orientations of the most probable distribution of

electrons around the nucleus.

2.13 Quantum numbers and Shapes of orbitals.

Quantum numbers

(1) Each orbital in an atom is specified by a set

of three quantum numbers (n, l, m) and each

electron is designated by a set of four quantum

numbers (n, l, m and s).

(2) Principle quantum number (n)

(i) It was proposed by Bohr’s and denoted by ‘n’.

 (ii) It determines the average distance between

electron and nucleus, means it is denoted the size of

atom.

n2
r= × 0.529 Å
Z

(iii) It determine the energy of the electron in

an orbit where electron is present.

Z2
E=− × 313 .3 Kcal per mole
n2

(iv) The maximum number of an electron in

an orbit represented by this quantum number as 2n 2 .

No energy shell in atoms of known elements possess

more than 32 electrons.

 (v) It gives the information of orbit K, L, M,

N------------.

(vi) The value of energy increases with the

increasing value of n.

(vii) It represents the major energy shell or

orbit to which the electron belongs.

(viii) Angular momentum can also be calculated

using principle quantum number

nh
mvr =
2π

(3) Azimuthal quantum number (l)

 (i) Azimuthal quantum number is also known

as angular quantum number. Proposed by

Sommerfield and denoted by ‘l’.

(ii) It determines the number of sub shells or

sublevels to which the electron belongs.

(iii) It tells about the shape of subshells.

(iv) It also expresses the energies of subshells

s< p < d < f (increasing energy).

(v) The value of l = (n − 1) always where ‘n’ is the

number of principle shell.

(vi) Value of l = 0 1 2 3………..

(n-1)
 Name of = s p d f

subshell

Shape of = Spheri Dumbb Double Complex

subshell cal ell dumbbell

(vii) It represent the orbital angular

h
momentum. Which is equal to 2π
l (l + 1)

(viii) The maximum number of electrons in

subshell = 2(2l + 1)

s − subshell → 2 electrons d − subshell → 10 electrons

p − subshell → 6 electrons f − subshell → 14 electrons.

 (ix) For a given value of ‘n’ the total value of

‘l’ is always equal to the value of ‘n’.

(x) The energy of any electron is depend on the

value of n & l because total energy = (n + l). The

electron enters in that sub orbit whose (n + l) value

or the value of energy is less.

(4) Magnetic quantum number (m)

(i) It was proposed by Zeeman and denoted by

‘m’.

(ii) It gives the number of permitted

orientation of subshells.
 (iii) The value of m varies from –l to +l

through zero.

(iv) It tells about the splitting of spectral lines

in the magnetic field i.e. this quantum number

proved the Zeeman effect.

(v) For a given value of ‘n’ the total value of

’m’ is equal to n2 .

(vi) For a given value of ‘l’ the total value of

‘m’ is equal to (2l + 1).

(vii) Degenerate orbitals : Orbitals having the

same energy are known as degenerate orbitals. e.g.

for p subshell p x py pz
 (viii) The number of degenerate orbitals of s

subshell =0.

(5) Spin quantum numbers (s)

(i) It was proposed by Goldshmidt & Ulen

Back and denoted by the symbol of ‘s’.

(ii) The value of ' s' is + 1/2 and - 1/2, which is

signifies the spin or rotation or direction of electron

on it’s axis during movement.

(iii) The spin may be clockwise or

anticlockwise.

(iv) It represents the value of spin angular

h
momentum is equal to 2π
s(s + 1).
 (v) Maximum spin of an atom = 1/ 2× number of

unpaired electron.

Magnetic field

N S

+1/2 –1/2

S N

(vi) This quantum number is not the result of

solution of schrodinger equation as solved for H-

atom.

Distribution of electrons among the quantum

levels

n l m s Designati Electron Total

 on of s present no. of

orbitals electro

ns

1 (K 0 0 +1/2, – 1s 2 2

shell) 1/2

+1 / 2, − 1 / 2 2
2 (L 0 + 1 / 2, − 1 / 2
2s 

+ 1 / 2, − 1 / 2 6
shell) + 1 / 2, − 1 / 2
8

1 2p
 +1 / 2,−1 / 2 2 
3 (M 0 0 + 1 / 2,−1 / 2
3s 

+ 1 / 2,−1 / 2 6 

shell) +1 


+1 / 2,−1 / 2 


1 0 3p 




–1 10 

+ 1 / 2,−1 / 2
+ 1 / 2,−1 / 2
+ 1 / 2,−1 / 2 18

+ 1 / 2,−1 / 2
+ 1 / 2,−1 / 2

+2
+1 / 2,−1 / 2
+ 1 / 2,−1 / 2
+1 + 1 / 2,−1 / 2 3d
+ 1 / 2,−1 / 2

2 0

–1
 + 1 / 2,−1 / 2 2 
–2
+ 1 / 2,−1 / 2 

+ 1 / 2,−1 / 2 6 
 
+ 1 / 2,−1 / 2 
0 0 + 1 / 2,−1 / 2
4s 




+1 


10 

1 0 + 1 / 2,−1 / 2 4p 

+ 1 / 2,−1 / 2 
+ 1 / 2,−1 / 2 
 
–1 + 1 / 2,−1 / 2 

+ 1 / 2,−1 / 2 

+ 1 / 2,−1 / 2 
14 
+ 1 / 2,−1 / 2

+2

+1

2 0 4d 32

–1
 –2

4(N +3

shell) +2

+1

3 +0 4f

–1

–2

–3
 Shape of orbitals

(1) Shape of ‘s’ orbital

(i) For ‘s’ orbital l=0 & m=0 so ‘s’ orbital have

only one unidirectional orientation i.e. the

probability of finding the electrons is same in all

directions.

Z
Y

Nucleus

(ii) The size and energy of ‘s’ orbital with increasing

‘n’ will be 1s < 2s < 3s < 4 s.

(iii) It does not possess any directional property. s

orbital has spherical shape.

(2) Shape of ‘p’ orbitals

(i) For ‘p’ orbital l=1, & m=+1,0,–1 means there are

three ‘p’ orbitals, which is symbolised as p x , py , pz .

(ii) Shape of ‘p’ orbital is dumb bell in which the

two lobes on opposite side separated by the nodal

plane.

(iii) p-orbital has directional properties.

Z Z
Y Z
Y Y
Nodal Nodal
Plane Plane
Nodal
X Plane X
Nodal X
Plane
Px orbital Py orbital Nodal Pz orbital
Plane
 (3) Shape of ‘d’ orbital

(i) For the ‘d’ orbital l =2 then the values of ‘m’

are –2,–1,0,+1,+2. It shows that the ‘d’ orbitals has

five orbitals as d xy , d yz , d zx , d x 2 − y 2 , d z2 .

(ii) Each ‘d’ orbital identical in shape, size and

energy.

(iii) The shape of d orbital is double dumb bell .

(iv) It has directional properties.

Z Z Z Y Y
Y Y Y
Z
X X X X X

dZX dXY dYZ dX2– dZ2

2
(4) Shape of ‘f’ orbital

(i) For the ‘f’ orbital l=3 then the values of ‘m’ are

–3, –2, –1,0,+1,+2,+3. It shows that the ‘f’ orbitals

have seven orientation as

fx ( x 2 − y 2 ), fy( x 2 − y 2 ), fz( x 2 − y 2 ), fxyz , fz3 , fyz 3 and fxz 2 .

(ii) The ‘f’ orbital is complicated in shape.

2.14 Electronic configuration principles.

The distribution of electrons in different orbitals of

atom is known as electronic configuration of the

atoms.

Filling up of orbitals in the ground state of atom is

governed by the following rules:

(1) Aufbau principle

(i) Auf bau is a German word, meaning ‘building

up’.

(ii) According to this principle, “In the ground state,

the atomic orbitals are filled in order of increasing

energies i.e. in the ground state the electrons first

occupy the lowest energy orbitals available”.

(iii) In fact the energy of an orbital is

determined by the quantum number n and l with the

help of (n+l) rule or Bohr Bury rule.

(iv) According to this rule

 (a) Lower the value of n + l, lower is the energy

of the orbital and such an orbital will be filled up

first.

(b) When two orbitals have same value of (n+l)

the orbital having lower value of “n” has lower

energy and such an orbital will be filled up first .

Thus, order of filling up of orbitals is as follows:

1s < 2s < 2 p < 3s < 3 p < 4 s < 4 p < 5 s < 4 d < 5 p < 6 s < 6 f < 5d

(2) Pauli’s exclusion principle

(i) According to this principle, “No two

electrons in an atom can have same set of all the

four quantum numbers n, l, m and s .

 (ii) In an atom any two electrons may have

three quantum numbers identical but fourth quantum

number must be different.

(iii) Since this principle excludes certain

possible combinations of quantum numbers for any

two electrons in an atom, it was given the name

exclusion principle. Its results are as follows :

(a) The maximum capacity of a main energy

shell is equal to 2n 2 electron.

(b) The maximum capacity of a subshell is

equal to 2(2l+1) electron.

 (c) Number of sub-shells in a main energy

shell is equal to the value of n.

(d) Number of orbitals in a main energy

shell is equal to n 2
.

(e) One orbital cannot have more than two

electrons.

(iv) According to this principle an orbital can

accomodate at the most two electrons with spins

opposite to each other. It means that an orbital can

have 0, 1, or 2 electron.

(v) If an orbital has two electrons they must be

of opposite spin.

Correct Incorrect
(3) Hund’s Rule of maximum multiplicity

(i) This rule provides the basis for filling up of

degenerate orbitals of the same sub-shell.

(ii) According to this rule “Electron filling

will not take place in orbitals of same energy until

all the available orbitals of a given subshell contain

one electron each with parallel spin”.

(iii) This implies that electron pairing begins

with fourth, sixth and eighth electron in p, d and f

orbitals of the same subshell respectively.

 (iv) The reason behind this rule is related to

repulsion between identical charged electron present

in the same orbital.

(v) They can minimise the repulsive force

between them serves by occupying different orbitals.

(vi) Moreover, according to this principle, the

electron entering the different orbitals of subshell

have parallel spins. This keep them farther apart and

lowers the energy through electron exchange or

resonance.
 (vii) The term maximum multiplicity means

that the total spin of unpaired e− is maximum in case

of correct filling of orbitals as per this rule.

Energy level diagram

The representation of relative energy levels of

various atomic orbital is made in the terms of energy

level diagrams.

One electron system : In this system 1s2 level

and all orbital of same principal quantum number

have same energy, which is independent of (l). In

this system l only determines the shape of the

orbital.
 Multiple electron system : The energy levels of

such system not only depend upon the nuclear

charge but also upon the another electron present in

them.

5
4s 4p 4d 4f 6p
5d
4 4f
6s
5p
3s 3p 3d 4d
5s

Energy
4p
3 3d
4s
2s 2p 3p

2 3s
2p
Energy

2s
1s
1s

Energy level diagram of one Energy level diagram of multiple

electron system electron system

Diagram of multi-electron atoms reveals the

following points :

(i) As the distance of the shell increases from the

nucleus, the energy level increases. For example

energy level of 2 > 1.

 (ii) The different sub shells have different

energy levels which possess definite energy. For a

definite shell, the subshell having higher value of l

possesses higher energy level. For example in 4th

shell.

Energy level order 4f > 4d > 4p

> 4s

l= 3 l=2 l=1 l= 0

(iii) The relative energy of sub shells of different

energy shell can be explained in the terms of the

(n+l) rule.

(a) The sub-shell with lower values of (n + l)

possess lower energy.

 For 3d n=3 l= 2 ∴

n+l=5

For 4s n=4 l=0

n+l=4

(b) If the value of (n + l) for two orbitals is

same, one with lower values of ‘n’ possess lower

energy level.

Extra stability of half filled and completely

filled orbitals

Half-filled and completely filled sub-shell have

extra stability due to the following reasons :

(i) Symmetry of orbitals

 (a) It is a well kown fact that symmetry leads to

stability.

(b) Thus, if the shift of an electron from one

orbital to another orbital differing slightly in energy

results in the symmetrical electronic configuration.

It becomes more stable.

(c) For example p3,d5 , f 7 configurations are more

stable than their near ones.

(ii) Exchange energy

(a) The electron in various subshells can

exchange their positions, since electron in the same

subshell have equal energies.

 (b) The energy is released during the exchange

process with in the same subshell.

(c) In case of half filled and completely filled

orbitals, the exchange energy is maximum and is

greater than the loss of orbital energy due to the

transfer of electron from a higher to a lower sublevel

e.g. from 4s to 3d orbitals in case of Cu and Cr .

(d) The greater the number of possible

exchanges between the electrons of parallel spins

present in the degenerate orbitals, the higher would

be the amount of energy released and more will be

the stability.
(e) Let us count the number of exchange that are

possible in d4 and d5 configuraton among electrons

with parallel spins.

d4 (1) (2) (3)

3 exchanges by 1st e– 2 exchanges by 2nd e– Only 1 exchange by 3rd e–

To number of possible exchanges = 3 + 2 + 1 =6

d5 (1) (2) (3)

4 exchanges by 1st e– 3 exchanges by 2nd e–
2 exchange by 3rd e–

(4)
1 exchange by 4th e–

To number of possible exchanges = 4 + 3 + 2 +1 =

10

2.15 Electronic configurations of Elements.

 (1) On the basis of the elecronic configuration

priciples the electronic configuration of various

elements are given in the following table :

Electronic Configuration (E.C.) of Elements Z=1

to 36

Atom

Eleme ic
1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
nt Num

ber

H 1 1

He 2 2
Li 3 2 1

Be 4 2 2

B 5 2 2 1

C 6 2 2 2

N 7 2 2 3

O 8 2 2 4

F 9 2 2 5

Ne 10 2 2 6

Na 11 2 2 6 1

Mg 12 2
Al 13 2 1

Si 14 10 2 2

P 15 electrons 2 3

S 16 2 4

Cl 17 2 5

Ar 18 2 2 6 2 6

K 19 2 2 6 2 6 1

Ca 20 2

Sc 21 1 2

Ti 22 2 2
V 23 3 2

Cr 24 5 1

Mn 25 5 2

Fe 26 6 2

Co 27 18 7 2

Ni 28 electrons 8 2

Cu 29 10 1

Zn 30 10 2

Ga 31 10 2 1

Ge 32 10 2 2
As 33 10 2 3

Se 34 10 2 4

Br 35 10 2 5

Kr 36 2 2 6 2 6 10 2 6

(2) The above method of writing the electronic

configurations is quite cumbersome. Hence, usually

the electronic configuration of the atom of any

element is simply represented by the notation.

NUMBER OF
ELECTRONS

x
PRESENT

nl
NUMBER OF SYMBOL OF
PRINCIPAL SUBSHELL
SHELL

e.g. 1s2 means 2 electrons are present in the s- subshell

of the 1st main shell.
(3) (i) Elements with atomic number 24(Cr),

42(Mo) and 74(W) have ns1 (n − 1) d 5 configuration and

not ns 2 (n − 1) d 4 due to extra stability of these atoms.

(ii)Elements with atomic number 29(Cu), 47(Ag)

and 79(Au) have ns1 (n − 1) d 10 configuration instead of

ns 2 (n − 1) d 9 due to extra stability of these atoms.

Cr (24) [Ar] 3d5 Cu (29) [Ar] 3d10

4s1 4s1

(4) In the formation of ion, electrons of the outer

most orbit are lost. Hence, whenever you are

required to write electronic configuration of the ion,

first write electronic configuration of its atom and

take electron from outermost orbit. If we write

electronic configuration of Fe 2+
(Z = 26, 24 e − ), it will not

be similar to Cr (with 24 e − ) but quite different.

Fe[Ar ] 4 s2 3d 6 
 outer most orbit is 4th shell hence,
Fe2+ [Ar ] 4 s 3d 6 

electrons from 4s have been removed to make Fe2+ .

(5) Ion/atom will be paramagnetic if there are

unpaired electrons. Magnetic moment (spin only) is

µ = n(n + 2) BM (Bohr Magneton). (1BM = 9.27 × 10 −24

J / T)

where n is the number of unpaired electrons.

 (6) Ion with unpaired electron in d or f orbital

will be coloured. Thus, Cu + with electronic

configuration [Ar ]3d is colourless and

10
Cu 2+ with

electronic configuration [Ar ]3d (one unpaired electron

9

in 3d) is coloured (blue).

(7) Position of the element in periodic table on

the basis of electronic configuration can be

determined as,

(i) If last electron enters into s-subshell, p-

subshell, penultimate d-subshell and anti

penultimate f-subshell then the element belongs to s,

p, d and f – block respectively.

 (ii) Principle quantum number (n) of

outermost shell gives the number of period of the

element.

(iii) If the last shell contains 1 or 2 electrons

(i.e. for s-block elements having the

configuration ns ), the group number is 1 in the first

1− 2

case and 2 in the second case.

(iv) If the last shell contains 3 or more than 3

electrons (i.e. for p-block elements having the

configuration ns 2 np 1−6 ), the group number is the total

number of electrons in the last shell plus 10.

 (v) If the electrons are present in the (n –1)d

orbital in addition to those in the ns orbital (i.e. for

d-block elements having the configuration (n –1)

d 1−10 ns1− 2 ), the group number is equal to the total

number of electrons present in the (n –1)d orbital

and ns orbital.
 We know solids are the substances which have

definite volume and definite shape. A solid is nearly

incompressible state of matter. This is because the

particles or units (atoms, molecules or ions) making

up the solid are in close contact and are in fixed

positions or sites. Now, let us study some

characteristic properties of solids.

5.1 Characteristic Properties of Solids.

Solids can be distinguished from liquids and

gases due to their characteristic properties. Some of

these are as follows:

• Solids have definite volume, irrespective of

the size of the container.

• Solids are rigid and have definite shape.

• Solids are almost incompressible.

• Many solids are crystalline in nature. These

crystals have definite pattern of angles and

planes.

• The density of solids is generally greater than

that of liquids and gases.

• Solids diffuse very slowly as compared to

liquids and gases.

 • Most solids melt on heating and become

liquids. The temperature at which the solid

melts and changes into liquid state under

normal atmospheric pressure is called its

normal melting point.

• Solids are not always crystalline in nature.

• Solids can be broadly classified into following

two types :

(i) Crystalline solids/True solids(ii)

Amorphous solids/Pseudo solids

(1) Difference between crystalline and

amorphous solids
 Property Crystalline solids Amorphous solids

Shape They have long range They have short range

order. order.

Melting They have definite They do not have definite

point melting point melting point

Heat of They have a definite heat They do not have definite

fusion of fusion heat of fusion

Compressibi They are rigid and These may not be

lity incompressible compressed to any

appreciable extent
Cutting with They are given cleavage They are given irregular

a sharp i.e. they break into two cleavage i.e. they break

edged tool pieces with plane into two pieces with

surfaces irregular surface

Isotropy and They are anisotropic They are isotropic

Anisotropy

Volume There is a sudden change There is no sudden

change in volume when it melts. change in volume on

melting.

Symmetry These possess symmetry These do not possess any

symmetry.
Interfacial These possess interfacial These do not possess

angles angles. interfacial angles.

Note :  Isomorphism and polymorphism :

Two subtances are said to be isomorphous if these

possess similar crystalline form and similar

chemical composition e.g., Na 2 SeO 4 and Na 2 SO 4 . NaNO 3

and KNO 3 are not isomorphous because they have

similar formula but different crystalline forms. The

existence of a substance in more than one crystalline

form is known as polymorphism e.g., sulphur shows

two polymorphic forms viz. rhomibic and

monoclinic sulphur.
  Glass is a supercooled liquid.

(2) Classification of solids : Depending upon the

nature of interparticle forces the solids are classified

into four types :

Typ Constit Bondi Exampl Phys M.P. B.P. Electri

es uents ng es ical cal

of Natu Condu

Soli re ctivity

Ioni Positive Coulo NaCl, Hard High High Conduc

c and mbic KCl, but (≃100 (≃2000 tor (in
negative CaO, brittl molten
0K) K)
ions MgO, e state

network LiF, and in

systema ZnS, aqueou

tically BaSO4 s

arrange and solutio

d K2SO4 n)

etc.

Cov Atoms Electr SiO2 Hard Very Very Insulat

alen connect on (Quartz), Hard high high or

t ed in sharin SiC, C except

 covalent g (diamon Hard (≃400 (≃500K graphit

bonds d), e
0K) )
C(graphi

te) etc.

Mol Polar or (i) I2,S8, P4, Soft Low Low (≃ Insulat

ecul non- Molec CO2, or
(≃300 450 to
ar polar ular CH4,
K to 800 K)
molecul intera CCl4 etc.
Soft 600K)
es ctions
Low Insulat
(inter
Starch, or
molec (≃400 Low
sucrose,
u-lar
 forces water, K) (≃373K
) dry ice
to
(ii) or
500K)
Hydro drikold

gen (solid

bondi CO2)

ng etc.

Met Cations Metall Sodium , Duct High High Conduc

allic in a sea ic Au, Cu, ile (≃800 (≃1500 tor

of magnesi mall
K to K to
 electron um, eable 1000 2000K)

s metals K)

and

alloys

Ato Atoms Londo Noble Soft Very Very Poor

mic n gases low low thermal

disper and

sion electric

force al

conduc

tors
 (i) Liquid Crystal : There are certain solids

which when heated undergo two sharp phase

transformations one after the other. Such solids first

fuse sharply yielding turbid liquids and then further

heating to a higher temperature these sharply change

into clear liquids. The first temperature at which

solids changes into turbid liquid is known as

transition point and the second temperature at

which turbid liquid changes into clear liquid is

known as melting point. Such substances showing

liquid crystal character are as follows :

p-chloesteryl benzoate, p− Azoxyamisole,

Diethylbenzidine etc.

145oC p- Chloestery l benzoate

(Solid)
178oC p − Chloestery l benzoate
(liquidcrystal )

p − Chloestery l benzoate
( Liquid )

A liquid crystal reflects only one colour, when

light falls on it. If the temperature is changed it

reflects different colour light. So, such liquid

crystals can be used to detect even small

temperature changes. The liquid crystals are of

two types : (i) Nematic liquid crystals, (needle

like), (ii) Smectic liquid crystals (soap like)

 (ii) Dispersion forces or London forces in

solids : When the distribution of electrons around

the nucleus is not symmetrical then there is

formation of instantaneous electric pole. Field

produced due to this distorts the electron distribution

in the neighbouring atom or molecule so that it

acquires a dipole moment itself. The two dipole will

attract and this makes the basis of London forces or

dispersion forces these forces are attractive in nature

and the interaction energy due to this is proportional

 1
to  6 . Thus, these forces are important as short
r 
distances (~− 500 pm) . This force also depends on the

polarisability of the molecules.

(3) Amorphous Solids (Supercooled liquid) :

Solids unlike crystalline solids, do not have an

ordered arrangement of their constituent atoms or

ions but have a disordered or random arrangement,

are called amorphous solids. Ordinary glass (metal

silicate), rubber and most of the plastics are the best

examples of amorphous solids. In fact, any material

can be made amorphous or glassy either by rapidly

cooling or freezing its vapours for example, SiO 2

crystallises or quartz in which SiO 44 − tetrahedra are

linked in a regular manner but on melting and then

rapid cooling, it gives glass in which SiO 44 −

tetrahedron are randomly joined to each other.

Properties of Amorphous solids

(i) Lack of long range order/Existence of short range

order : Amorphous solids do not have a long range

order of their constituent atoms or ions. However,

they do have a short range order like that in the

liquids.

(ii) No sharp melting point/Melting over a range.

(iii) Conversion into crystalline form on heating.

Uses of Amorphous solids

 (i) The most widely used amorphous solids are

in the inorganic glasses which find application

in construction, house ware, laboratory ware

etc.

(ii) Rubber is amorphous solid, which is used in

making tyres, shoe soles etc.

(iii) Amorphous silica has been found to be the

best material for converting sunlight into

electricity (in photovoltaic cells).

5.2 Crystallography.
“The branch of science that deals with the study of

structure, geometry and properties of crystals is

called crystallography”.

Constancy of interfacial angles

(1) Laws of crystallography : Crystallography

is based on three fundamental laws. Which are as

follows
 (i) Law of constancy of interfacial angles : This

law states that angle between adjacent

corresponding faces of the crystal of a particular

substance is always constant inspite of different

shapes and sizes. The size and shape of crystal

depend upon the conditions of crystallisation. This

law is also known as Steno's Law.

(ii) Law of rational indices : This law states that

the intercepts of any face of a crystal along the

crystallographic axes are either equal to unit

intercepts (i.e., intercepts made by unit cell) a, b, c

or some simple whole number multiples of them

e.g., na, n' b, n''c, where n, n' and n'' are simple

whole numbers. The whole numbers n, n' and n'' are

called Weiss indices. This law was given by Hally.

(iii) Law of constancy of symmetry : According

to this law, all crystals of a substance have the same

elements of symmetry.

(2) Designation of planes in crystals (Miller

indices) : Planes in crystals are described by a set of

integers (h, k and l) known as Miller indices. Miller

indices of a plane are the reciprocals of the

fractional intercepts of that plane on the various

 z

c
N

b
y
M

a
L

A parametral plane (intercepts, a, b, c

x along x, y and z axes)

crystallographic axes. For calculating Miller

indices, a reference plane, known as parametral

plane, is selected having intercepts a, b and c along

x, y and z-axes, respectively. Then, the intercepts of

the unknown plane are given with respect to a, b and

c of the parametral plane.

Thus, the Miller indices are :

 a
h=
intercept of the plane along x - axis

b
k=
intercept of the plane along y - axis

c
l=
intercept of the plane along z - axis

Consider a plane in which Weiss notation is

given by ∞a : 2b : c . The Miller indices of this plane

may be calculated as below.

(i) Reciprocals of the coefficients of Weiss

indices = ∞1 , 12 , 11

(ii) Multiplying by 2 in order to get whole

numbers = 0, 1, 2
 Thus the Miller indices of the plane are 0, 1, and

2 and the plane is designated as the (012) plane, i.e.

h=0 , k =1 , l=2 .

The distance between the parallel planes in

crystals are designated as d hkl . For different cubic

lattices these interplanar spacing are given by the

general formula,

a
d(hkl ) =
h + k2 + l2
2

Where a is the length of cube side while h, k and

l are the Miller indices of the plane.

 Note :  When a plane is parallel to an axis, its

intercept with that axis is taken as infinite

and the Miller will be zero.

 Negative signs in the Miller indices is

indicated by placing a bar on the intercept.

 All parallel planes have same Miller

indices.

 The Miller indices are enclosed within

parenthesis. i.e., brackets. Commas can be used for

clarity.

Examples based on
crystallography
Example 1: Calculate the Miller indices of crystal

planes which cut through the crystal axes

at (i) (2a, 3b, c), (ii) ( ∞, 2b, c )

(a) 3, 2, 6 and 0, 1, 2 (b) 4, 2, 6 and 0,

2, 1 (c) 6, 2, 3 and 0, 0, 1 (d) 7, 2, 3

and 1, 1, 1

Solution: (a)

(i) x y z (ii) x y z

2a 3b c Intercepts ∞ 2b c Intercepts

2a 3b c ∞ 2b c
a b c
Lattice parameters a b c
Lattice parame

1 1 1 1 1
2 3 1
Reciprocals ∞ 2
1
1
Reciprocals

3 2 6 Multiplying by LCM (6) 0 1 2 Multiplying by

Hence, the Miller indices are (3, 2, 6) Hence,

the Miller indices are (0, 1, 2).

Example 2. Caculate the distance between 111 planes in a crystal of

(a) 016.1 nm

(b) 01.61 nm

(c) 0.610 nm

(d) None of the above

a
Solution:(b) We have, d= ;
h + k 2 + 2
2
 0.556 0.556
d111 = = 0.321nm and d222 = = 0.161nm
1 +1 +1
2 2 2
2 + 22 + 22
2

The separation of the 111 planes is twice as

great as that of 222 planes.

5.3 Study of Crystals.

(1) Crystal : It is a homogeneous portion of a

crystalline substance, composed of a regular pattern

of structural units (ions, atoms or molecules) by

plane surfaces making definite angles with each

other giving a regular geometric form.

(2) Space lattice and Unit cell : A regular array of

points (showing atoms/ions) in three dimensions is

commonly called as a space lattice, or lattice.

(i) Each point in a space lattice represents an atom

or a group of atoms.

(ii) Each point in a space lattice has identical

surroundings throughout.

A three dimensional group of lattice points which

when repeated in space generates the crystal called

unit cell.
The unit cell is described by the lengths of its edges,

a, b, c (which are related to the spacing between

layers) and the angles between the edges, α , β , γ .

Space

c
β
α
γ b Unit
a
Unit cell
Space lattice & unit cell

(3) Symmetry in Crystal systems : Law of

constancy of symmetry : According to this law, all

crystals of a substance have the same elements of

symmetry. A crystal possess following three types

of symmetry :
(i) Plane of symmetry : It is an imaginary plane

which passes through the centre of a crystal can

divides it into two equal portions which are exactly

the mirror images of each other.

(a) (b) (c)

Plane of symmetry Rectangular plane of Diagonal plane

symmetry of symmetry

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

axis of rotation is an imaginary line, passing through

the crystal such that when the crystal is rotated about

this line, it presents the same appearance more than

once in one complete revolution i.e., in a rotation

through 360°. Suppose, the same appearance of

crystal is repeated, on rotating it through an angle of

360°/n, around an imaginary axis, is called an n-fold

axis where, n is known as the order of axis. By order

is meant the value of n in 2π / n so that rotation

through 2π / n, gives an equivalent configuration. For

example, If a cube is rotated about an axis passing

perpendicularly through the centre so that the similar

appearance occurs four times in one revolution, the

axis is called a four – fold or a tetrad axis, [Fig (iii)].

If similar appearance occurs twice in one complete

revolution i.e., after 180°, the axis is called two-fold

axis of symmetry or diad axis [Fig (i)]. If the

original appearance is repeated three times in one

revolution i.e. rotation after 120°, the axis of

symmetry is called three-fold axis of symmetry or

triad axis [Fig (ii)]. Similarly, if the original

appearance is repeated after an angle of 60° as in the

case of a hexagonal crystal, the axis is called six-

fold axis of symmetry or hexad axis [Fig (iv)].

Fig. (i) Axis of Fig. (ii) Axis of Fig. (iii) Axis of

two Fig. (iv) Axis of
three four six
fold symmetry fold symmetry. fold symmetry. fold symmetry
(iii) Centre of symmetry : It is an imaginary point in

the crystal that any line drawn through it intersects

the surface of the crystal at equal distance on either

side.

Centre of
symmetry of a
cubic crystal

Note :  Only simple cubic system have one

centre of symmetry. Other system do not

have centre of symmetry.

 (4) Element of symmetry : (i) The total number

of planes, axes and centre of symmetries possessed

by a crystal is termed as elements of symmetry.

(ii) A cubic crystal possesses total 23 elements of

symmetry.

(a) Plane of symmetry ( 3 + 6) = 9

(b) Axes of symmetry (3+4 + 6) = 13

(c) Centre of symmetry (1) = 1

Total symmetry = 23

(5) Formation of crystals : The crystals of the

substance are obtained by cooling the liquid (or the

melt) of the solution of that substance. The size of

the crystal depends upon the rate of cooling. If

cooling is carried out slowly, crystals of large size

are obtained because the particles (ions, atoms or

molecules) get sufficient time to arrange themselves

in proper positions.

Atoms of molecules  →

Dissolved
cluster  →
dissolved

dissolved embryo → nucleus

(unstable)
→ crystal

(If loosing units dissolves as embryo and if

gaining unit grow as a crystals).

(6) Crystal systems : Bravais (1848) showed

from geometrical considerations that there can be

only 14 different ways in which similar points can

be arranged. Thus, there can be only 14 different

space lattices. These 14 types of lattices are known

as Bravais Lattices. But on the other hand Bravais

showed that there are only seven types of crystal

systems. The seven crystal systems are :

(a) Cubic

(b) Tetragonal

(c) Orthorhombic

(d) Rhombohedral

(e) Hexagonal
 (f) Monoclinic

(g) Triclinic

Bravais lattices corresponding to different crystal

systems

Crystal Space lattice Examples

system
Cubic Simple : Body Face Pb, Hg, Ag,

a=b=c , Lattice centered centered : Au, Cu, ZnS ,

points at the : Points Points at diamond,

Here a, b
eight corners at the the eight KCl ,
and c are
of the unit eight corners NaCl , Cu 2O, CaF2
parameters
cells. corners and at the and alums.
(diamensio
and at six face etc.
ns of a unit
the body centres.
cell along
centred.
three axes)

size of

crystals

depend on

parameters.

α = β = γ = 90 o
Tetragonal Simple : Body centered SnO 2 , TiO2 , ZnO 2 , NiSO 4

a=b≠c , Points at the : Points at the ZrSiO4 . PbWO , white

4 Sn etc.

α = β = γ = 90 o
eight corners eight corners

of the unit and at the body

cell. centre

KNO 3 , K 2 SO 4
Orthorho Simple: End Body Face
,
mbic Points at centered centered : centere PbCO 3 , BaSO 4

,
(Rhombic) the eight : Also Points at the d: Points
rhombic
corners called eight corners at the
a≠b≠c ,
α = β = γ = 90 o of the side and at the eight sulphur,
MgSO 4 . 7 H 2O
unit cell. centered body centre coreners
etc.
or base and at

centered. the six

Points at face

the eight centres.

corners

and at

two face

centres

opposite

to each
 other.

Rhombohe Simple : Points at the eight corners of NaNO 3 , CaSO 4 , calcite,

dral the unit cell quartz, As, Sb , Bi

or etc.

Trigonal

a=b=c ,

α = β = γ ≠ 90 o
Hexagonal Simple : Points at or Points at the ZnO, PbS, CdS, HgS,

the twelve corners twelve corners of graphite, ice,

a=b≠c ,
of the unit cell out the hexagonal Mg, Zn, Cd etc.
α = β = 90 o

lined by thick line. prism and at the

γ = 120 o

centres of the two

hexagonal faces.
 Na2 SO 4 .10 H 2O,
Monoclinic Simple : Points at End centered : Na2 B4 O7 .10 H 2O,

CaSO 4 .2H 2O,

the eight corners Point at the eight
a≠b≠c ,
monoclinic
of the unit cell corners and at
α = γ = 90 o , β ≠ 90 o

sulphur etc.
two face centres

opposite to the

each other.
Triclinic Simple : Points at the eight corners of CaSO 4 .5 H 2O,

the unit cell. K 2Cr2O7 , H 3 BO3

a≠b≠c ,

α ≠ β ≠ γ ≠ 90 o etc.

Note :  Out of seven crystal systems

triclinic is the most unsymmetrical ( a ≠ b ≠ c,

α ≠ β ≠ γ ≠ 90) .s
 3.1 Types of bonding and Forces

5 in solids

Assignment (Basic and Advance

Level)

Answer Sheet of Assignment

The basic questions which we search are, what is the

Molecules are the smallest particles of matter which

are capable of independent existence and which

show the characteristic properties of the substance.

Molecules are stable combinations of a group of

atoms. Molecules are stable because they have lower

energy as compared to that of the constituent atoms.

Atoms of different elements excepting noble gases

donot have complete octet so they combine with

other atoms to form chemical bond. The force which

holds the atoms or ions together within the molecule

is called a chemical bond and the process of their

combination is called Chemical Bonding.

Chemical bonding depends on the valency of

atoms. Valency was termed as the number of

chemical bonds formed by an atom in a molecule or

number of electrons present in outermost shell i.e.,

valence electrons. Valence electrons actually

involved in bond formation are called bonding

electrons. The remaining valence electrons still

available for bond formation are referred to as non-

bonding electrons.
 •
• • • • • • + • •–
• • • • • • • • •
• • • p+ n • •
• •
• • • • • •
p+n p +n p+ n
• • • • • •• •
• • •
• • • • • • • • • •
• •
• •
Na (2, 8, 1) Cl (2, 8, 7) Bond formation takes place

3.1 Cause and Modes of chemical combination.

Chemical combination takes place due to

following reasons.

(1) Chemical bonding takes place to acquire a

state of minimum energy and maximum stability.

(2) By formation of chemical bond, atoms

convert into molecule to acquire stable configuration

of the nearest noble gas.

 Modes : Chemical bonding can occur in the

following manner.
Transfer of electrons from one
atom to another Ionic bond

Mutual sharing of electrons between

Covalent bond
the atoms

Mutual sharing of electrons Co-ordination bond

provided entirely by one of the

3.2 Electrovalent bond.

When a bond is formed by complete transfer of

electrons from one atom to another so as to complete

their outermost orbits by acquiring 8 electrons (i.e.,

octet) or 2 electrons (i.e., duplet) in case of

hydrogen, helium etc. and hence acquire the stable

nearest noble gas configuration, the bond formed is

called ionic bond, electrovalent bond or polar

bond. Compounds containing ionic bond are called

ionic, electrovalent or polar compounds.

+ −
• • •
  • • • •
Example : Na + • Cl •
• →  Na  • Cl •  or Na + Cl −
• •    • • 

Some other examples are: MgCl2, CaCl2, MgO,

Na2S, CaH2, AlF3, NaH, KH, K 2O , KI, RbCl, NaBr,

CaH2 etc.

(1) Conditions for formation of electrovalent

bond

(i) Number of valency electrons : The atom which

changes into cation (+ ive ion) should possess 1, 2 or

3 valency electrons. The other atom which changes

into anion (– ive ion) should possess 5, 6 or 7

electrons in the valency shell.

(ii) Electronegativity difference : A high difference

of electronegativity (about 2) of the two atoms is

necessary for the formation of an electrovalent bond.

Electrovalent bond is not possible between similar

atoms.

(iii) Small decrease in energy : There must be

overall decrease in energy i.e., energy must be

released. For this an atom should have low value of

Ionisation potential and the other atom should have

high value of electron affinity.

(iv) Lattice energy : Higher the lattice energy, greater

will be the ease of forming an ionic compound. The

amount of energy released when free ions combine

together to form one mole of a crystal is called lattice

energy (U).

Magnitude of lattice energy ∝ Charge of ion

size of ion

A + (g) + B − (g) → AB(s) + U

Determination of lattice energy (Born Haber

cycle)

When a chemical bond is formed between two

atoms (or ions), the potential energy of the system

constituting the two atoms or ions decreases. If there

is no fall in potential energy of the system, no

bonding is possible, the energy changes involved in

the formation of ionic compounds from their

constituent elements can be studied with the help of

a thermochemical cycle called Born Haber cycle.

Example : The formation of 1 mole of NaCl from

sodium and chlorine involves following steps :

Step I : Conversion of metallic sodium into

gaseous sodium atoms: Na(s)+ S → Na(g)

1 mole
, where S=

sublimation energy i.e., the energy required for the

conversion of one mole of metallic sodium into

gaseous sodium atoms.

 Step II : Dissociation of chlorine molecules into

chlorine atoms : Cl 2 (g) + D → 2Cl (g) , where D =

Dissociation energy of Cl 2 so the energy required for

the formation of one mole of gaseous chlorine atoms

= D/2 .

Step III: Conversion of gaseous sodium atoms

into sodium ions : Na(g)+ IE → Na + (g) + e − , where

1 mole

IE = Ionisation energy of sodium.

Na(s) 1
+ Cl 2 (g)
2
∆H f
+S
1/2D
Na(g)
Cl (g) NaCl
+e–
(Crystal)
–)
+IENa + (g e– – EACl − (g)
–U
+
(Born Haber
Cycle)
Step IV:

Conversion of

gaseous chlorine

atoms into

chloride ions :

Cl (g)+ e − → Cl − (g) + EA ,
1 mole

where EA =

Electron affinity of

chlorine.

Step V : Combination of gaseous sodium and

chloride ions to form solid sodium chloride crystal.

 Na + (g) + Cl − (g) → NaCl (s)+ U
1 mole
, where U= lattice energy of

NaCl

The overall change may be represented as :

1
Na(s) +
2
Cl 2 (g) → NaCl (s), ∆H f , where ∆H f is the heat of

formation for 1 mole of NaCl (s) .

According to Hess's law of constant heat

summation, heat of formation of one mole of NaCl

should be same whether it takes place directly in one

step or through a number of steps. Thus,

1
∆H f = S + D + IE + EA + U
2

(2) Types of ions

 The following types of ions are encountered :

(i) Ions with inert gas configuration : The atoms

of the representative elements of group I, II and III

by complete loss of their valency electrons and the

elements of group V, VI, and VII by gaining 3,2 and

1 electrons respectively form ions either with

ns 2 configuration or ns 2 p 6 configuration.

(a) Ions with 1s2 (He) configuration : H − , Li + , Be 2+ etc.

The formation of Li + and Be 2+ is difficult due to their

small size and high ionisation potential.

(b) Ions with ns 2 p 6 configuration : More than three

electrons are hardly lost or gained in the ion

formation

Cations : Na + , Ca 2+ , Al 3+ etc.

Anions : Cl − , O 2− , N 3− , etc.

(ii) Ions with pseudo inert gas configuration :

The Zn 2+ ; ion is formed when zinc atom loses its

outer 4s electrons. The outer shell configuration of

Zn 2+ ions is 3s2 3 p 6 3d 10 . The ns 2 np 6 nd 10 outer shell

configuration is often called pseudo noble gas

configuration which is considered as stable one.

Examples: Zn 2+ , Cd 2+ , Hg 2+ , Cu + Ag + , Au + , Ga 3+ etc
 (iii) Exceptional configurations : Many d- and

f block elements produce ions with configurations

different than the above two. Ions like Fe 3+ , Mn 2+ , etc.,

attain a stable configuration half filled d- orbitals

Fe 3+ 3s2 3 p 6 3d 5 ; Mn 2+ 3s2 3 p 6 3d 5

Examples of other configurations are many.

Ti 2+ (3s2 3 p 6 3d 2 ) ; V 2+ (3s2 3 p 6 3d 3 )

Cr 2+ (3s2 3 p 6 3d 4 ) ; Fe 2+ (3s2 3 p 6 3d 6 )

However, such ions are comparatively less

stable

(iv) Ions with ns 2 configuration : Heavier

members of groups III, IV and V lose p-electrons

only to form ions with ns 2 configuration.

Tl + , Sn 2+ , Pb 2+ , Bi 3+ are the examples of this type. These

are stable ions.

(v) Polyatomic ions : The ions which are

composed of more than one atom are called

polyatomic ions. These ions move as such in

chemical reactions. Some common polyatomic ions

are

NH 4+ (Ammonium); NO 3− (Nitrate)

PO43− (phosphate); SO 42− (Sulphate)

CO 32− (Carbonate) ; SO 32− (Sulphite),

etc.
 (vi) Polyhalide ions : Halogens or

interhalogens combine with halide ions to form

polyhalide ions. I 3− , ICl 4− , ICl 2− etc. Fluorine due to highest

electronegativity and absence of d-oribitals does not

form polyhalide ions.

The atoms within the polyatomic ions are

held to each other by covalent bonds.

The electro valencies of an ion (any type)

is equal to the number of charges present on it.

(3) Method of writing formula of an ionic

compound
 In order to write the formula of an ionic

compound which is made up of two ions (simple or

polyatomic) having electrovalencies x and

y respectively, the following points are followed :

(i) Write the symbols of the ions side by side in

such a way that positive ion is at the left and

negative ion at the right as AB.

(ii) Write their electrovalencies in figures on the

top of each symbol as A x By

(iii) Divide their valencies by H.C.F

x y
(iv) Now apply criss cross rule as A B
, i.e.,

formula Ay Bx
 Examples :

Name of Exchan Formul Name of Exchan Formul

compou ge of a compou ge of a

nd valencie nd valencie

s s

2 1 3 2
Calcium Ca Cl
CaCl 2 Alumini Al O
Al 2 O3

chloride um

oxide

1 3 2 3
Potassiu K PO4 K 3 PO4 Magnesi Mg N Mg3 N 2

m um

phosphat nitride
 e

2 2 1 2
Calcium CaO or CaO Ammoni NH 4 SO 4
( NH 4 ) 2 SO 4

1 1
oxide Ca O
um

sulphate

(4) Difference between atoms and ions

The following are the points of difference between

atoms and ions.

Atoms Ions

1. Atoms are perfectly neutral in Ions are charged particles, cations

nature, i.e., number of protons are positively charged, i.e., number

equal to number of electrons. Na of protons more than the number of

(protons 11, electrons 11), Cl electrons. Anions are negatively

(Protons – 17, electrons –17) charged, i.e., number of protons

less than the number of electrons.

Na+ (protons 11, electrons 10), Cl–

(protons 17, electrons 18)

2. Except noble gases, atoms have Ions have generally 8 electrons in

less than 8 electrons in the the outermost orbit, i.e., ns2np6

outermost orbit configuration.

Na 2,8,1; Ca 2,8,8,2 Na+ 2,8; Cl– 2,8,8

 Cl 2,8,7; S 2,8,6 Ca2+ 2,8,8

3. Chemical activity is due to loss The chemical activity is due to the

or gain or sharing of electrons as to charge on the ion. Oppositely

acquire noble gas configuration charged ions are held together by

electrostatic forces

(5) Characteristics of ionic compounds

(i) Physical state : Electrovalent compounds are

generally crystalline is nature. The constituent ions

are arranged in a regular way in their lattice. These

are hard due to strong forces of attraction between

oppositely charged ions which keep them in their

fixed positions.

(ii) Melting and boiling points : Ionic compounds

possess high melting and boiling points. This is

because ions are tightly held together by strong

electrostatic forces of attraction and hence a huge

amount of energy is required to break the crystal

lattice. For example order of melting and boiling

points in halides of sodium and oxides of IInd group

elements is as,

NaF > NaCl > NaBr > NaI , MgO > C

(iii) Hard and brittle : Electrovalent compounds are

har in nature. The hardness is due to strong forces of

attraction between oppositely charged ion which

keep them in their alloted positions. The brittleness

of the crystals is due to movement of a layer of a

crystal on the other layer by application of external

force when like ions come infront of each other. The

forces of repulsion come into play. The breaking of

crystal occurs on account of these forces or

repulsion.

(iv) Electrical conductivity : Electrovalent

solids donot conduct electricity. This is because the

ions remain intact occupying fixed positions in the

crystal lattice. When ionic compounds are melted or

dissolved in a polar solvent, the ions become free to

move. They are attracted towards the respective

electrode and act as current carriers. Thus,

electrovalent compounds in the molten state or in

solution conduct electricity.

(v) Solubility : Electrovalent compounds are

fairly soluble in polar solvents and insoluble in non-

polar solvents. The polar solvents have high values

of dielectric constants. Water is one of the best polar

solvents as it has a high value of dielectric

 constant. The dielectric constant of a solvent is

defined as its capacity to weaken the force of

attraction between the electrical charges immersed

in that solvent. In solvent like water, the electrostate

force of attraction between the ions decreases. As a

result there ions get separated and finally solvated.

The values of dielectric constants of some of the

compounds are given as :

Compound Water Methyl Ethyl Acetone Ether

AIc AIc.

Dielectric 81 35 27 21 4.1
constant

Capacity to dissolve electrovalent compounds decreases

Lattice energy and solvation energy also explains

the solubility of electrovalent compounds. These

compounds dissolve in such a solvent of which

the value of solvation energy is higher than the

lattice energy of the compound. The value of

solvation energy depends on the relative size of the

ions. Smaller the ion more of solvation, hence

higher the solvation energy.

Note :  Some ionic compounds e.g.,

BaSO 4 , PbSO 4 , AgCl , AgBr , AgI , Ag 2 CrO 4 etc. are sparingly

soluble in water because in all such cases higher

values of lattice energy predominates over solvation

energy.

(vi) Space isomerism :The electrovalent bonds are

non-rigid and non-directional. Thus these compound

do not show space isomerism e.g. geometrical or

optical isomerism.

(vii) Ionic reactions : Electrovalent compounds

furnish ions in solution. The chemical reaction of

these compounds are ionic reactions, which are fast.

Ionic bonds are more common in inorganic

compounds.
 + − + − + −
K + Cl − + Ag NO 3 → Ag Cl ↓ + K NO 3
(Precipitat e)

(viii) Isomorphism : Electrovalent compounds show

isomorphism. Compound having same electronic

structures are isomorphous to each other.

(ix) Cooling curve : Cooling curve of an ionic

compound is not smooth, it has two break points

corresponding to time of solidification.

A liquid

M.Pt-
Temp B C

Time

Solidification time
 (x) Electrovalency and Variable electrovalency :

The capacity of an element to form electro-valent or

ionic bond is called its electro-valency or the

number of electrons lost or gained by the atom to

form ionic compound is known as its electro-

valency. Certain metallic element lose different

number of electrons under different conditions,

thereby showing variable electrovalency. The

following are the reasons:

(a) Unstability of core : The residue

configuration left after the loss of valency electrons

is called kernel or core. In the case of the atoms of

transition elements, ions formed after the loss of

valency electrons do not possess a stable core as the

configuration of outermost shell is not ns 2 np 6 but

ns 2 np 6 d 1 to 10 . The outer shell lose one or more electrons

giving rise to metal ions of higher valencies.

Example : Fe2+ = 3s2 3 p 6 3d 6 ,4 s0 (not stable)

Fe3+ = 3s2 3 p 6 3d 5 ,4 s0 (stable)

(b) Inert pair effect : Some of heavier

representative elements of third, fourth and fifth

groups having configuration of outermost shell

ns 2 np 1 , ns 2 np 2 and ns 2 np 3 show valencies with a

difference of 2, i.e., (1 : 3) (2 : 4) (3 : 5)
respectively. In the case of lower valencies, only the

electrons present in p–subshell are lost and ns2

electrons remain intact. The reluctance of s-electron

pair to take part in bond formation is known as the

inert pair effect.

3.3 Covalent bond.

Covalent bond was first proposed by Lewis in

1916. The bond formed between the two atoms by

mutual sharing of electrons so as to complete their

octets or duplets (in case of elements having only

one shell) is called covalent bond or covalent

linkage. A covalent bond between two similar

atoms is non-polar covalent bond while it is polar

between two different atom having different

electronegativities. Covalent bond may be single,

double or a triple bond.

Example : Formation of chlorine molecule :

chlorine atom has seven electrons in the valency

shell. In the formation of chlorine molecule, each

chlorine atom contributes one electron and the pair

of electrons is shared between two atoms. both the

atoms acquire stable configuration of argon.

 Formation of HCl molecule : Both hydrogen and

chlorine contribute one electron each and then the

pair of electrons is equally shared. Hydrogen

acquires the configuration of helium and chlorine

acquires the configuration of argon.

Formation of water molecule : Oxygen atom has

6 valency electrons. It can achieve configuration of

neon by sharing two electrons, one with each

hydrogen atom.
 Formation of O2 molecule : Each oxygen atom

contributes two electrons and two pairs of electrons

are the shared equally. Both the atoms acquire

configuration of neon.

Formation of N2 molecule : Nitrogen atom has

five valency electrons. Both nitrogen atoms achieve

configuration of neon by sharing 3 pairs of

electrons, i.e., each atom contributes 3 electrons.

• * •
Some other examples are : H2S, NH3, HCN, PCl3,

PH3, C2 H 2 , H2, C2H4, SnCl 4 , FeCl 3 , BH 3 , graphite,

BeCl 2 etc.

(1) Conditions for formation of covalent

bonds

(i) Number of valency electrons : The combining

atoms should be short by 1, 2 or 3 electrons in the

valency shell in comparison to stable noble gas

configuration.

(ii) Electronegativity difference : Electronegativity

difference between the two atoms should be zero or

very small.
 (iii) Small decrease in energy : The approach of

the atoms towards one another should be

accompanied by decrease of energy.

(2) Characteristics of covalent compounds

(i) Physical state : These exist as gases or liquids

under the normal conditions of temperature and

pressure. This is because very weak forces of

attraction exist between discrete molecules. Some

covalent compounds exist as soft solids.

(ii) Melting and boiling points : Diamond,

Carborandum (SiC), Silica (SiO2), AlN etc. have

giant three dimensional network structures; therefore

have exceptionally high melting points otherwise

these compounds have relatively low melting and

boiling points. This is due to weak forces of

attraction between the molecules.

(iii) Electrical conductivity : In general covalent

substances are bad conductor of electricity. Polar

covalent compounds like HCl in solution conduct

electricity. Graphite can conduct electricity in solid

state since electrons can pass from one layer to the

other.

(iv) Solubility : These compounds are generally

insoluble in polar solvent like water but soluble in

non-polar solvents like benzene etc. some covalent

compounds like alcohol, dissolve in water due to

hydrogen bonding.

(v) Isomerism : The covalent bond is rigid and

directional. These compounds, thus show isomerism

(structural and space).

(vi) Molecular reactions : Covalent substances show

molecular reactions. The reaction rates are usually

low because it involves two steps (i) breaking of

covalent bonds of the reactants and (ii) establishing

of new bonds while the ionic reactions involved

only regrouping of ions.

(vii) Covalency and Variable covalency : The

number of electrons contributed by an atom of the

element for sharing with other atoms is called

covalency of the element. The variable covalency of

an element is equal to the total number of unpaired

electrons in s, p and d-orbitals of its valency shell.

Covalency = 8 – [Number of the group to which

element belongs]

Examples : Nitrogen 7N = 2s 2p
Covalency

of N = 3

The element such as P, S, Cl, Br, I have vacant d-

orbitals in their valency shell. These elements show

variable covalency by increasing the number of

unpaired electrons under excited conditions. The

electrons from paired orbitals get excited to vacant

d-orbitals of the same shell.

Promotion rule : Excitation of electrons in the same

shell

Covalency 3
3s 3p

Covalency-5
3s 3p 3d

Phosphorus : Excited state

PCl3 is more stable due to inert pair effect.

3s 3p Covalency-2 (as in SF2)

3d
Sulphur : Excited state

Covalency-4 (as in SF4)

3s 3p 3d

Covalency-6 (as in SF6)

3s 3p 3d

2nd excited state

So variable valency of S is 2, 4 and 6.

Iodine can have maximum 7 unpaired electrons

in its orbitals. It's variable valencies are 1, 3, 5 and

7.

Four elements, H, N, O and F do not possess d-

orbitals in their valency shell. Thus, such an

excitation is not possible and variable valency is not

shown by these elements. This is reason that NCl3

exists while NCl5 does not.

(3) The Lewis theory : The Lewis theory gave

the first explanation of a covalent bond in terms of

electrons that was generally accepted. The tendency

of atoms to achieve eight electrons in their

outermost shell is known as lewis octet rule.

Octet rule is the basis of electronic theory of

valency. It is suggested that valency electrons

themselves are responsible for chemical

combination. The valency electrons in atoms are

shown in terms of Lewis dot formulae. To write

Lewis formulae for an element, we write down its

symbol surrounded by a number of dots or crosses

equal to the number of valency electrons. Lewis dot

formulae are also used to represent atoms covalently

bonded in a molecule. Paired and unpaired valency

electrons are also indicated.

1 2 13 14 15 16 17
Group IA IIA IIIA IVA VA VIA VIIA
• • • •• ••
Lewis symbol X • •X• • X• •X• • X• • X• •X•
•• •• •• •
•

− +

CO is not an exception to octet rule :C ≡O: or :C=O:
..

(4) Failure of octet rule :

 There are several stable molecules known in

which the octet rule is violated i.e., atoms in these

molecules have number of electrons in the valency

shell either short of octet or more than octet.

In BF3 molecules, boron atom forms three single

covalent bonds with three fluorine atoms, i.e., it

attains six electrons in the outer shell.

••
• •
• F •
*
•• •• •∗ ••
* B * + 3 •• F • • F • • •
• • * B * F •
• •• ••

PCl5 molecule : Phosphorus atom have five

electrons in valency shell. It forms five single

covalent bonds with five chlorine atoms utilising all

the valency electrons and thereby attains 10

electrons in the outer shell.

•• •
•
• Cl •
•∗
••
•• •• ∗
*
P* •
• •
Cl • • Cl ••
*
*
*
+
5 Cl •
• •
••
∗ P ••
•
•∗ • ∗
•
• Cl•
•
•
• Cl •
•
•• ••

•• •
•
• Cl •
•∗
Cl Cl •• ∗ •••
P •
•• •
Cl •
P Cl ••
• Cl•• •
••
∗ ••
•∗ ∗
•∗
Cl Cl • •
• Cl
•
•
•
• Cl••
Cl •• ••

(i) Sugden’s concept of singlet linkage explains the

stability of such molecules. In PCl 5 , three chlorine

atoms are linked by normal covalent bonds and two

chlorine atoms are linked by singlet linkages, thus,

phosphorus achieves 8 electrons in the outermost

shell.
 Cl
Cl
Cl P
Cl
Cl

This structure indicates that the nature of two

chlorine atoms is different than the other three as

singlet linkage is weaker than normal covalent bond.

The above observation is confirmed by the fact that

on heating, PCl 5 dissociates into PCl 3 and Cl 2 .

PCl 5 ⇌ PCl 3 + Cl 2

Similarly, in SF6 four singlet linkages are

present while in IF7 , six singlet linkages are present.

 •
•• •
•
• •• F
• F •
•
• F •
• F F
∗ ∗
•• • •• S
•
• F •
S ∗ F
•
•
•• ••
F F
•∗ •∗
•
F • •
• F• F
• • •
•• ••

(ii) Sidgwick’s concept of maximum covalency

• This rule states that the covalency of an element

may exceed four and octet can be exceeded.

• The maximum covalency of an element actually

depends on the period of periodic table to which it

belongs.

• This rule explains the formation of PCl5 and SF6.

• This also explains why nitrogen does not form

NF5 or NCl 5 because nitrogen belongs to second

period and the maximum covalency of nitrogen is

three.

(iii) Odd electron bond : In 1916 Luder postulated

that there are number of stable molecules in which

double bonds are formed by sharing of an odd

number of electrons, i.e., one, three, five, etc.,

between the two bonded atoms. the bonds of this

type are called odd electron bonds.

The normal valence bond structure of oxygen

•• * *
molecule, •
• O=O *
* , fails to account for the
paramagnetic nature of oxygen. Thus, structure

involving three electrons bond has been suggested

by Pauling. The following structure : •

• O  → O••
• • •
• • •
.

Explains the paramagnetic nature and high

dissociation energy of oxygen molecule.

N
Some other examples are : •
•N O ••
•

Nitric oxide •O O ••
(NO) •• ••
Nitrogen dioxide ( NO 2 )

–
 
• O O••
• • • •• 
 
−
Superoxide ion (O 2 )

The number of singlet bonds = Total number of

bonds – Number of electrons required to complete

the octet.
Properties of Odd Electron bond

(i) The odd electron bonds are generally

established either between two like atoms or

between different atoms which have not more than

0.5 difference in their electronegativities.

(ii) Odd electron bonds are approximately half as

strong as a normal covalent bond.

(iii) Molecules containing odd electrons are

extremely reactive and have the tendency to

dimerise.

(iv) Bond length of one electron bond is greater

than that of a normal covalent bond. Whereas the

bond length of a three electron bond is intermediate

between those of a double and a triple bond.

(v) One electron bond is a resonance hybrid of

the two structures i.e., A • B ←→ A • B

Similarly, a three electron bond is a resonance

hybrid of the two structures i.e., A• •

• B ←→ A •• • B

(5) Construction of structures for molecules and

poly atomic ions : The following method is

applicable to species in which the octet rule is not

violated.
 (i) Determine the total number of valence

electrons in all the atoms present, including the net

charge on the species (n1).

(ii)

(iii)

(iv) Determine the number of non-bonding

electrons, n4, which equals n1 – n3. No. of lone pairs

equals n4/2.

(v) Knowing the central atom (you’ll need to know

some chemistry here, math will not help!), arrange

and distribute other atoms and n3/2 bonds. Then

complete octets using n4/2 lone pairs.

(vi) Determine the ‘formal charge’ on each atom.

(vii) Formal Charge = [valence electrons in atom) –

(no. of bonds) – (no. of unshared electrons)]

(viii) Other aspects like resonance etc. can now be

incorporated.

Illustrative examples :

(i) CO32− ; n1 = 4 + (6 × 3) + 2 = 24 [ 2 added for net charge]

n2 = (2 × 0) + (8 × 4) = 32 (no. H atom, 4 other

atoms (1’C’ and 3 ‘O’)

n3 = 32 – 24 = 8, hence 8/2 = 4 bonds

n4 = 24 – 8 = 16, hence 8 lone pairs.

 Since carbon is the central atom, 3 oxygen atoms

are to be arranged around it, thus,

O
|
O−C −O , but total bonds are equal to 4.

O
|
Hence, we get O−C = O . Now, arrange lone pairs to
..
.O :
. | ..
complete octet :O − C = O:
..

(ii) CO2 ; n1 = 4 + (6 × 2 ) = 16

n2 = (2 × 0) + (8 × 3) = 24

n3 = 24 – 16 = 8, hence 4 bonds

n4 = 16 – 8 = 8, hence 4 lone-pairs
 Since C is the central atom, the two oxygen

atoms are around to be arranged it thus the structure

would be; O – C – O, but total no. of bonds = 4

Thus, O = C = O. After arrangement of lone

.. ..
pairs to complete octets, we get, :O =C =O: and thus
.. ..
final structure is :O =C =O:

3.4 Co-ordinate covalent or Dative bond.

This is a special type of covalent bond where the

shared pair of electrons are contributed by one

species only but shared by both. The atom which

contributes the electrons is called the donor while

the other which only shares the electron pair is

known as acceptor. This bond is usually represented

by an arrow (→) pointing from donor to the acceptor

atom.

For example, in BF3 molecule, boron is short of

two electrons. So to complete its octet, it shares the

lone pair of nitrogen in ammonia forming a dative

bond as shown in figure

∗∗ ∗∗
∗
H
∗
∗F ∗
∗
H ∗ F ∗∗ H F
•∗ •∗ ∗∗ •∗ •∗ ∗∗ | |
H *• N + B*
*
•
∗ F ∗
∗ → H •
* N ∗
∗ B •
∗ F ∗
∗ → H − N→ B − F
•∗ •∗ ∗∗ •∗ ∗∗ | |
•∗
H ∗ ∗ ∗ ∗ H F
∗F ∗
H F
∗ ∗
∗∗ ∗ ∗

Formation of a co- ordinate

bond between NH 3 and BF3
 Examples : CO, N2O, H2O2, N2O3, N2O4, N2O5,

HNO3, NO 3− , SO2, SO3, H2SO4, SO 42− , SO 22− ,

H 3 PO4 , H 4 P2 O7 ,
H 3 PO3 , Al 2 Cl 6 (Anhydrous) , O3 , SO 2 Cl 2 , SOCl 2 , HIO3 , HClO 4 , HClO 3 , CH 3 NC, N 2 H 5+
,

CH 3 NO 2 , NH 4+ , [ Cu( NH 3 )4 ] 2+ etc.

(1) Characteristics of co-ordinate covalent

bond

(i) Melting and boiling points : Their melting

and boiling points are higher than purely covalent

compounds and lower than purely ionic compounds.

 (ii) Solubility : These are sparingly soluble in

polar solvent like water but readily soluble in non-

polar solvents.

(iii) Conductivity : Like covalent compounds,

these are also bad conductors of electricity. Their

solutions or fused masses do not allow the passage

to electricity.

(iv) Directional character of bond : The bond is

rigid and directional. Thus, coordinate compounds

show isomerism.
 Table: Electron dot formulae and Bond formulae

or Dash formulae of some compounds

No Molecular formula Electron dot Dash formula or

. formula Bond formula

Sodium
1. NaCl ••
Na+ •× Cl ••
–
Na + Cl −
••
chloride Cl

Magnesium
2. MgCl2 • • • •–
×Cl Mg++ •× Cl •• –
••
•
• •
• •
Cl − Mg + + Cl −
Cl
chloride

Calcium
•• ••– • • –
Cl Ca++ •× Cl ••
3. CaCl2 ×
• •
•
Cl N
•• Cl − Ca + + Cl −

chloride

4. Magnesium MgO • • ––
Mg++ ×× O ••
• •
Mg + + O − −
Cl
 oxide

Sodium
5. Na2S ••
Na+ •× S •× – – Na+
••
Na + S− − Na +
Cl Cl
sulphide

Calcium
–
6. CaH 2 H•× Ca++ ו H– H − Ca + + H −
Cl Cl
hydride

Aluminium •• ••
• •– 3+× • –
•F Al× F
• • F − Al 3+ F −
7. AlF3 • •
Cl
F
×
• •–
• •
• • •
F−
••
flouride

Hydrogen
8. HCl ••
Hו Cl •• H − Cl

chloride Cl • •
9. Water H 2O • •
H •× O •× H H −O−H
• •
Cl Cl

Hydrogen ••
H ו S ו H
10. H 2S Cl
• •
Cl H −S− H

sulphide

H
H |
ו
11. Ammonia NH 3 Cl••
H ו N
•×
H−N
|
Cl H H
Cl

Hydrogen
H ו C ×× •••N ••
×

12. HCN H −C ≡ N

cyanide

H
H |
13. Methane CH 4 •×
Clו H
H •× C
H − C− H
|
•×
Cl H Cl H
Cl

H H
H H | |
14. Ethane C2 H 6 •× •×
Clו H H − C− C− H
H×C
• Cl×× C | |
•× •×
Cl H H Cl H H
Cl Cl
 H H H
|
H
|
ו ו
CCl×××× C
Cl
15. Ethene C2 H 4 ו ו
C =C
| |
H H H H
Cl Cl

16. Ethyne C2 H 2 H•× C ×××××× C •× H H −C ≡ C−H

Cl Cl

17. Phosphene PH 3 ••
H − P− H
H •× P •× H |
•× H
Cl H Cl
Cl

Phosphorou
18. PCl 3 ×× •• × × Cl − P − Cl
×
× Cl •× P •×Cl ×× |
×× • × ××
s trichloride Cl×Cl ×Cl
× × Cl
××
Cl

Sodium
19. NaOH •• – Na + [O − H ]−
Na+ • O • H
* ×
hydroxide Cl ••
Cl
 Potassium
–
20. KCN K+ ×*C ××× •••N •
• K + [C ≡ N ]−
Cl
cyanide

Calcium  
2−

++  
21. CaCO 3 Ca++ *• O
••
• C • O•
• • × × ×× • • *
••
2–
Ca O − C − O
||
 
Cl • • ••  
carbonate • O•
O

Carbon
22. CO •
• C ••××××O ××

C=O
mono oxide N N

Nitrous
×× ••
×
23. N 2O × N ×× ×× N×× O •• N ≡ N→O
•
Cl Cl•
oxide

Hydrogen •• ••
H •× O •• O •× H or H •× O •
•O •
•
•• • •

Cl
• • • •
Cl Cl Cl
•× • •
H H −O−O−H or H−O→O
24. H 2 O2
Cl
|
•• ×× • • H
peroxide •
• O • × N× × × • O •
•×
××
N ו •

•O •
• •
••
 Dinitrogen O = N− N = O
25. N 2 O3 ↓
O
trioxide

Hydronium
• •
H − O → H+
26. H 3O+ H •× O •• H+ |
×
Cl H• Cl H
ion Cl

Nitrogen O= N− N =O
•• ••
• × N×
× N × •O
ו
27. N 2 O4 O •×
•• × × × × ••
↓ ↓
• O • •O •
• • • • O O
•• ••
dioxide

Nitrogen O = N− O − N = O
× × × × × ×
28. N 2 O5
×
× O ו
ו N O N
•
×
• • × × • •
•
×
•×
•×O ×
× ↓ ↓
O × × O O
×
× O ×
× × ×
pentaoxide × × × ×

H −O− N = O
29. Nitric acid HNO 3 H O N O
*
×
××
•
×
•×
•×
×× • • ××
×× ↓
O
O × ×
× ×
××
 −
O− N =O
30. Nitrate ion NO3− –*O× × × × ↓
×N • O ×
• •× ×
×
× × • • × O
× Cl ×
×O ×
× ×

31. Nitrous acid HNO 2 H •× O

××
××
•
••
×N• × O ×
•× ×
××
H −O− N = O
Cl

32. Nitrite ion NO 2− – * × ×• • • • × × × ×

O N O
× ×
−
O−N =O
× •×
××
Cl

33. Sulphur SO 2 ×
×
× × • •
O •S •×O
• •×
× ×
×
O←S=O
×
× ×
Cl
 dioxide

Sulphur O←S=O
× × × ×
34. SO 3 ×
× O •
•S • O
•×
× × • • ×
×
×
↓
O
× Cl ×
×O ×
trioxide × ×

Peroxysulph
O O
uric acid • • • • ↑ ↑
•
O •
•O •
• •

35. H 2 S2 O8 ••
•
× ×
•
•• •• × × •• H −O− S−O−O− S−O−H
H* • O• • ××S × • •O• • • O • ××S × • O • *H
• ×
Cl Cl •• OCl•• Cl Cl •• O
•• × ••
Cl•• Cl Cl ↓ ↓
(Marshal • • • •
O O

acid)

Hypochloro
36. HOCl H* × O
× ×
× • Cl ••
• •
H − O − Cl
× × • •
us acid Cl
 Chlorous
37. HClO 2
H* • O
•• × ×
• × Cl ×× O ••
• •
H − O − Cl → O
•• × × • •
acid Cl

Perchloric O •
•
• •
•
• O • •
• •
O O
• •
• • × × •• × × • •
38. O Cl O Cl − O − Cl O
Cl 2 O7 •
•
×
×
•• × ×
ו O × Cl × O
• × •
•
× × ••
Cl • ••
Cl •Cl
O •
• •
•
O • O O
anhydride •• •
•
•

O
Sulphuric ••
↑
O • •
H −O− S−O−H
39. H 2 SO 4
H O S O H
• •
•
•• ×× • •
•
•
•
*••× ×
×× • •
*
↓
acid O •
•
••
•
•
O

O
••
↑
−
40. Sulphate SO 42− O •
•
•
• O − S− O−
–• • • • × × • • • •– ↓
O S O
*••× × •* O
×× •
O •
•
••
•
•
 ion

Sulphurus •• ×× • • H − O − S− O − H
H •* O• •× S •× O •* H
41. H 2 SO 3 • ×× ••
•O •
• •
↓
O
••
acid

– • • • • × ×• • •• – −
O S O
* • • × ×× • *
O − S − O−
42. Sulphite ion SO 32− O •
×
•
•
• ↓
• O
• •

O
Phosphoric O
××
× ×
× ×
↑
H − O − P− O − H
× × ×• • •• × ××
43. H 3 PO4 HO P O H
* × × ×• × × × × *
|

O × × O
× ×
acid H
×*
H
|
 O O
↑ ↑
Pyrophosph ××
O
××
× × H − O − P− O − P− O − H
O
× ×
× × × × | |
× × • • × × •• × ×
44. H 4 P2 O7 P O P O H
*× •× •× •× •× *×
H O
× × × • × × × • × ××
O
|
O
|
×O × ×
O
× ×
×
oric acid H
*×
H
*×
×
H H

Persulphuri
× ×
O ×
×
×
× O
× × • • × × ××
c acid H O * •
S O O H
× ×× ×
×
•
× ×
×
• • ×× × ×
*×
↑
O ×
×
×
45. H 2 SO 5 ×× H −O− S−O−O−H
↓
(caro’s O

acid)

Thiosulphur •
•• •
S
S •
× × • •• × ×
↑
46. H 2 S2 O3 H O S O H
*
×
×
•
×× •• ××
×
• ×
* H − O − S− O − H
↓
× ×
ous acid O ×
××
× O
 H
Phosphorou ×× •× ××
*× •× ו *×
H
H O P O H
× × • • ××
|
47. H 3 PO3 O ×
×
××
×
×
H − O − P− O − H
↓
O
s acid

• • • • • •
Al 2 Cl 6 •
• Cl •• •• Cl •
• Cl ••
Al Al
Aluminium •
Cl •Cl Cl
• • Cl •
••

• •• • •• •
•• Cl Cl Cl
48. (Anhyd Cl
Al
Cl
Al
Cl
chloride
rous)
 ••
O O
49. Ozone O3 •
• O •
• O
••
•
•
••
O O

Sulphuryl Cl
*
**
*
Cl
|
× × * • * *× ×
50. SO 2 Cl 2 ×
× O S O
• •
• • ×
× O← S →O
× × * • ×× |
*Cl *
Cl
chloride *
**
*

Sulphonyl *
* • • × ××
* *•
O S Cl
•
•
× × O ← S − Cl
* * •× × ×
51. SOCl 2 Cl×
×
× ×
×
× |
Cl
chloride

H −O− I →O
52. Iodic acid HIO3 H O I O
*
×
× × •• × ×
× •
• •
× × •• × ×
×
× O
↓
×
O × ×
××
×
 × ×
O ×
×
×
×
× × • • × ×
H O Cl O
*
×
•
×
•
•
× × • • × ×
×
×

O ×
×
× ×
×
×

Perchloric O
••
↑
53. HClO 4 S • •
•
× × • •• ×× × ×
H − O − Cl → O
↓
H O S O O H
*× •
× •×
× *
× × O
acid O
×× • • × × × ×
×
×
×
×
××

Hyposulphu S
••
↑
54. H 2 S2 O4 S •
• •
× × × × • •• ×× ××
H − O − S− O − O − H
↓
H O O S O O H
*× × •
× × ×
• × *
× × O
rous acid × × ×× • • × × ××
O ×
×
×
×
××

Pyrosulphur S
↑
55. H 2 S2 O5
H*× O
×× • • ××
× Cl • O ×
• • ×
H − O − O − S− O − O − H
↓
× × • •× × × O
us acid ×
×O ×
××

H − O − Cl → O
56. Chloric acid HClO 3 ↓
O
3.5 Polarity of covalent bond.

A covalent bond in which electrons are shared

equally between bonded atoms, is called non polar

covalent bond while a covalent bond, in which

electrons are shared unequally and the bonded atoms

acquire a partial positive and negative charge, is

called a polar covalent bond. The atom having

higher electronegativity draws the bonded electron

pair more towards itself resulting in partial charge

separation. This is the reason that HCl molecule in

vapour state contains polar covalent bond

+δ
Polar covalent bond is indicated by notation : H

−δ
– Cl

(1) Bond polarity in terms of ionic character :

The polar covalent bond, has partial ionic character.

Which usually increases with increasing difference

in the electronegativity (EN) between bonded atom

H – F H – Cl H – Br H

– I

EN 2.1 4.0 2.1 3.0 2.1

2.8 2.1 2.5

Difference in EN 1.9 0.9

0.7 0.4

Ionic character decreases as the difference in

electronegativity decreases

(2) Percentage ionic character : Hennay and

Smith gave the following equation for calculating

the percentage of ionic character in A–B bond on the

basis of the values of electronegativity of the atoms

A and B.

Percentage of ionic character = [16 (χ A − χ B ) + 3.5 (χ A − χ B )2 ] .

Whereas (x A − x B ) is the electronegativity

difference. This equation gives approximate

calculation of percentage of ionic character, e.g.,

50% ionic character corresponds to (xA ∼ xB) equals

to 1.7.

3.6 Dipole moment.

“The product of magnitude of negative or

positive charge (q) and the distance (d) between the

centres of positive and negative charges is called

dipole moment”.

It is usually denoted by µ. Mathematically, it can

be expressed as follows :

µ = Electric charge × bond length

 As q is in the order of 10–10 esu and d is in the

order of 10–8 cm, µ is in the order of 10–18 esu cm.

Dipole moment is measured in “Debye” (D) unit.

1D = 10 −18 esu cm = 3.33 × 10 −30 coulomb metre.

Generally, as electronegativity difference

increases in diatomic molecules, the value of dipole

moment increases. Greater the value of dipole

moment of a molecule, greater the polarity of the

bond between the atoms.

Dipole moment is indicated by an arrow having a

symbol ( ) pointing towards the negative end.

Dipole moment has both magnitude and direction

and therefore it is a vector quantity.

Symmetrical polyatomic molecules are not

polar so they do not have any value of dipole

moment.

O C O

H
F

C
B H H
F F
H

µ = 0 due to symmetry

Some other examples are – CCl4,CS2 , PbCl 4 , SF 6 , SO 3 , C6 H 6 ,

naphthalene and all homonuclear molecules (H2, O2,

Cl2 etc)
 Note :

 Amongst isomeric dihalobenzenes, the

dipole moment decreases in the order : o > m > p.

must be sp3, sp2 hybridization respectively (e.g.

CH4, CCl4, SiF4 , SnCl4, BF3 , AlCl3 etc.)

sp 3 sp 2

Unsymmetrical polyatomic molecules always have

net value of dipole moment, thus such molecules are

polar in nature. H2O, CH3Cl, NH3, etc are polar

molecules as they have some positive values of

dipole moments.
 Cl

S N
O C
O O H H
H H H H
H
Water µ = 1.84D Sulphur H Ammonia
dioxide Methyl µ = 1.46D
1 60D chloride
1 86D

µ ≠ 0 due to unsymmetry

Some other examples are – CH3Cl, CH2Cl2,

CHCl3, SnCl2, ICl, C6H5CH3 , H2O2, O3, Freon etc.

Applications of dipole moment

(i) In determining the symmetry (or shape) of

the molecules : Dipole moment is an important

factor in determining the shape of molecules

containing three or more atoms. For instance, if any

molecule possesses two or more polar bonds, it will

not be symmetrical if it possesses some molecular

dipole moment as in case of water (µ = 1.84 D) and

ammonia (µ = 1.49 D). But if a molecule contains a

number of similar atoms linked to the central atom

and the overall dipole moment of the molecule is

found to be zero, this will imply that the molecule is

symmetrical, e.g., in case of BF3 , CH 4 , CCl 4 etc.,

(ii) In determining percentage ionic character

: Every ionic compound having some percentage of

covalent character according to Fajan’s rule. The

percentage of ionic character in a compound having

some covalent character can be calculated by the

following equation.
The percent ionic character
Observed dipole moment
= × 100
Calculated dipole moment assuming 100% ionic bond

(iii) In determining the polarity of bonds as

bond moment : As µ = q×d , obviously, greater is the

magnitude of dipole moment, higher will be the

polarity of the bond. The contribution of individual

bond in the dipole moment of a polyatomic

molecule is termed as bond moment. The measured

dipole moment of water molecule is 1.84 D. This

dipole moment is the vectorial sum of the individual

bond moments of two O-H bonds having bond angle

104.5o.
Note :  ∆ EN ∝ dipole moment, so HF > HCl > HBr >

HI ,

Where, ∆EN = Electronegativity

difference

 ∆ EN ∝ bond polarity, so HF > H2O > NH3 > H2S.

 If the electronegativity of surrounding atom

decreases, then dipole moment increases.

NCl 3 < NBr 3 < NI 3

(iv) To distinguish cis and trans forms : The trans

isomer usually possesses either zero dipole moment

or very low value in comparision to cis–form

H − C − Cl H − C − Cl
|| ||
H − C − Cl Cl − C − H

Cis – 1, 2 – dichloro ethene µ = 1.9 D Trans – 1, 2 –

dichloro ethene, µ=0

Example: Calculate the % of ionic character of a

bond having length = 0.92 Å and 1.91 D as its

observed dipole moment.

(a) 43.25

(b) 86.5
(c) 8.65

(d) 43.5

Solution: (a) Calculated µ considering 100% ionic

bond [When we consider a compound ionic, then

each ionic sphere should have one electron charge

on it of 4.80 × 10 −10 esu (in CGS unit) or 1.60 × 10 −19 C (in SI

unit)]

= 4.8 × 10–10 × 0.92 × 10–8 esu cm = 4.416 D

1.91
% Ionic character =
4.416
× 100 = 43 .25 .

Important Tips
 The dipole moment of CO molecule is greater than expected. T

due to the presence of a dative (co-ordinate) bond.

 Critical temperature of water is higher than that of O2 becaus

molecule has dipole moment.

 Liquid is not deflected by a non uniform electrostatic field in h

because of µ = 0

3.7 Change of ionic character to covalent

character and Fajan’s rule.

Although in an ionic compound like M+X– the

bond is considered to be 100% ionic, but it has some

covalent character. The partial covalent character of

an ionic bond has been explained on the basis of

polarization.

Polarization : When a cation of small size

approaches an anion, the electron cloud of the bigger

anion is attracted towards the cation and hence gets

distorted. This distortion effect is called polarization

of the anion. The power of the cation to polarize

nearby anion is called its polarizing power. The

tendency of an anion to get distorted or polarized by

the cation is called polarizability. Due to

polarization, some sort of sharing electrons occurs

between two ions and the bond shows some covalent

character.

Fajan’s rule : The magnitude of polarization or

increased covalent character depends upon a number

of factors. These factors were suggested by Fajan

and are known as Fajan’s rules.

Factors favouring the covalent character

(i) Small size of cation : Smaller size of cation

greater is its polarizing power i.e. greater will be the

covalent nature of the bond. On moving down a

group, the polarizing power of the cation goes on

decreasing. While it increases on moving left to

right in a period. Thus polarizing power of cation

follows the order Li + > Na + > K + > Rb + > Cs + . This explains

why LiCl is more covalent than KCl .

(ii) Large size of anion : Larger the size of

anion greater is its polarizing power i.e. greater will

be the covalent nature of the bond. The

polarizability of the anions by a given cation

decreases in moving left to right in a period. While it

increases on moving down a group. Thus

polarzibility of the anion follows the order

I − > Br − > Cl − > F − . This explains why iodides are most

covalent in nature.
 (iii) Large charge on either of the two ions :

As the charge on the ion increases, the electrostatic

attraction of the cation for the outer electrons of the

anion also increases with the result its ability for

forming the covalent bond increases. FeCl3 has a

greater covalent character than FeCl2. This is

because Fe3+ ion has greater charge and smaller size

than Fe2+ ion. As a result Fe3+ ion has greater

polarizing power. Covalent character of lithium

halides is in the order LiF < LiCl < LiBr < LiI.

(iv) Electronic configuration of the cation :

For the two ions of the same size and charge, one
 with a pseudo noble gas configuration (i.e. 18

electrons in the outermost shell) will be more

polarizing than a cation with noble gas configuration

(i.e., 8 electron in outer most shell). CuCl is more

covalent than NaCl, because Cu+ contains 18

electrons in outermost shell which brings greater

polarization of the anion.

Important tips

 ∆en (Electronegativity difference) ∝ Covalent

Ionic character
character

 Increase of polarization brings more of covalent character in

an ionic compound. The increased covalent character is indicated

by the decrease in melting point of the ionic compound

 Decreasing trends of melting points with increased covalent

character

M.Pt (oC) 988 801 755 651

M.Pt (oC) 960 872 772 712 405

 Lithium salts are soluble in organic solvents because of their

covalent character

 Sulphides are less soluble in water than oxides of the same

metal due to the covalent nature of sulphur.

3.8 Quantum theory (Modern theory) of covalent

bond and overlapping.

(1) A modern Approach for covalent bond

(Valence bond theory or VBT)

(i) Heitler and London concept.

(a) To form a covalent bond, two atoms must

come close to each other so that orbitals of one

overlaps with the other.

(b) Orbitals having unpaired electrons of anti

spin overlaps with each other.

 (c) After overlapping a new localized bond

orbital is formed which has maximum probability of

finding electrons.

(d) Covalent bond is formed due to electrostatic

attraction between radii and the accumulated

electrons cloud and by attraction between spins of

anti spin electrons.

(e) Greater is the overlapping, lesser will be the

bond length, more will be attraction and more will

be bond energy and the stability of bond will also be

high.

(ii) Pauling and slater extension

 (a) The extent of overlapping depends upon:

Nature of orbitals involved in overlapping, and

nature of overlapping.

(b) More closer the valence shells are to the

nucleus, more will be the overlapping and the bond

energy will also be high.

(c) Between two sub shells of same energy level,

the sub shell more directionally concentrated shows

more overlapping. Bond energy : 2s − 2s < 2s − 2 p <

2p − 2p

(d) s -orbitals are spherically symmetrical and

thus show only head on overlapping. On the other

hand, p -orbitals are directionally concentrated and

thus show either head on overlapping or lateral

overlapping.

(iii) Energy concept

(a) Atoms combine with each other to minimize

their energy.

(b) Let us take the example of hydrogen

molecule in which the bond between two hydrogen

atoms is quite strong.

(c) During the formation of hydrogen molecule,

when two hydrogen atoms approach each other, two

types of interaction
 ••
Attraction
+ Repulsion +
Attraction
••

become operative as shown in figure. The force of

attraction between the molecules of one atom and

electrons of the other atom. The force of repulsion

between the nuclei of reacting atoms and electrons

of the reacting atoms

(d) As the two hydrogen atoms approach each

other from the infinite distance, they start interacting

with each
 +ve

O
P.E. decreases as
E

–ve d0

other when the magnitude of attractive forces is

more than that of repulsive forces a bond is

developed between two atoms.

(e) The decrease in potential energy taking place

during formation of hydrogen molecule may be

shown graphically (→) )

(f) The inter nuclear distance at the point O have

minimum energy or maximum stability is called

bond length.
 (g) The amount of energy released (i.e., decrease

in potential energy) is known as enthalpy of

formation.

(h) From the curve it is apparent that greater the

decrease in potential energy, stronger will be the

bond formed and vice versa.

(i) It is to be noted that for dissociation of

hydrogen molecule into atoms, equivalent amount of

energy is to be supplied.

(j) Obviously in general, a stronger bond will

require greater amount of energy for the separation

of atoms. The energy required to cleave one mole of

bonds of the same kind is known as the bond energy

or bond dissociation energy. This is also called as

orbital overlap concept of covalent bond.

(2) Overlapping

(i) According to this concept a covalent bond is

formed by the partial overlapping of two half filled

atomic orbitals containing one electron each with

opposite spins then they merge to form a new orbital

known as molecular orbital.

(ii) These two electrons have greater probability

of their presence in the region of overlap and thus

get stabilised i.e., during overlapping energy is

released.

Examples of overlapping are given below :

Formation of hydrogen molecule : Two hydrogen

atoms having electrons with opposite spins come

close to each other, their s-orbitals overlap with each

other resulting in the union of two atoms to form a

molecule.

+ – + – + + +

H-atom H-atom H2-molecule

Formation of fluorine molecule : In the formation of

F2 molecule p-orbitals of each flourine atom having

electrons with opposite spins come close to each

other, overlapping take place resulting is the union

of two atoms.

2px 2px
2py 2py

2pz + 2pz

F- F- F2-
Formation of fluorine molecule

+
s-orbital s-orbital s-s overlap
s-s σ-
Types of overlapping and nature of covalent

bonds (σ - and π - bonds) : overlapping of different

type gives sigma (σ) and pi (π) bond. Various

modes of overlapping given below :

s – s overlapping : In this type two half filled s-

orbitals overlap along the internuclear axis to

form σ-bond.

s-p overlapping : It involves the overlapping of half

filled s-orbital of one atom with the half filled p-

orbital of other atom This overlapping again gives

σ-bond e.g., formation of H – F molecule involves

the overlapping of 1s orbital of H with the half filled

2pz – orbital of Fluorine.

s-orbital p-orbital s–p overlap

s – p overlapping σ-bond

p-p overlapping : p-p overlapping can take place in

the following two ways.

(i) When there is the coaxial overlapping between

p-orbitals of one atom with the p-orbitals of the

other then σ-bond formation take place e.g.,

formation of F2 molecule in which 2pz orbital of one

F atom overlap coaxially with the 2pz orbitals of

second atom. σ-bond formation take place as shown

below :

pz-orbital pz -orbital pz – pz overlap

σ-bond
p – p overlapping

(ii) When p–orbitals involved in overlapping are

parallel and perpendicular to the internuclear axis.

This types of overlapping results in formation of pi

bond. It is always accompanied by a σ bond and

consists of two charge clouds i.e., above and below

the plane of sigma bond. Since overlapping takes

 place on both sides of the internuclear axis, free

rotation of atoms around a pi bond is not possible.

+ +
π

+ Internuclear axis
→
π
– – π -bond
p-orbital p-orbital
p-p overlapping

Table : Difference in σ and π bonds

Sigma (σ) bond Pi (π) bond

It results from the end to end It result from the sidewise

overlapping of two s-orbitals or (lateral) overlapping of two p-

two p-orbitals or one s and one p- orbitals.

orbital.
Stronger Less strong

Bond energy 80 kcals Bond energy 65 kcals

More stable Less stable

Less reactive More reactive

Can exist independently Always exist along with a σ-

bond

The electron cloud is symmetrical The electron cloud is above

about the internuclear axis. and below the plane of

internuclear axis.
 Important Tips

 To count the σ and π bonds in molecule having single,

double and triple bond first we write its expanded structure.

C≡N
H
| |
σ σ H\
ex. H −H , O=O , N ≡ N , C = C −C ≡ N , N ≡ C− C−C ≡ N ,
σ π 2π H / |
(3π , 6σ )
C≡N
(8π , 8σ )

H
|
C
H −C C−H
| ||
H −C C−H
Head on overlapping Sidewise
C overlapping
|
H
(3π , 12σ )

All the single bonds are σ-bond. In a double bond, one will be
σ and the other π type while in a triple bond, one will be σ and

other two π.

 The enolic form of acetone has 9σ, 1π and two lone pairs
OH
|
CH 2 = C − CH 3 (enol form of acetone)

 It is the π bond that actually takes part in reaction,

H H H H
\ σ / | σ |
C=C
/ π \
+ H2 → H − C − C − H
| |
, but the shape of molecule is decided by
H H H H

σ-bond.

 The number of sp2-s sigma bonds in benzene are 6.

 When two atoms of the element having same spin of electron

approach for bonding, the orbital overlapping and bonding both

does not occur.

 Head on overlapping is more stronger than lateral, or sidewise

overlapping.

 p-p > s-p > s-s > p-p

3.9 Hybridization.

The concept of hybridization was introduced by

Pauling and Slater. It is defined as the intermixing

of dissimilar orbitals of the same atom but having

slightly different energies to form same number of

new orbitals of equal energies and identical shapes.

The new orbitals so formed are known as hybrid

orbitals.

Characteristics of hybridization

(1) Only orbitals of almost similar energies and

belonging to the same atom or ion undergoes

hybridization.

(2) Hybridization takes place only in orbitals,

electrons are not involved in it.

(3) The number of hybrid orbitals produced is equal

to the number of pure orbitals, mixed during

hybridization.
(4) In the excited state, the number of unpaired

electrons must correspond to the oxidation state of

the central atom in the molecule.

(5) Both half filled orbitals or fully filled orbitals of

equivalent energy can involve in hybridization.

(6) Hybrid orbitals form only sigma bonds.

(7) Orbitals involved in π bond formation do not

participate in hybridization.

(8) Hybridization never takes place in an isolated

atom but it occurs only at the time of bond

formation.
(9) The hybrid orbitals are distributed in space as

apart as possible resulting in a definite geometry of

molecule.

(10) Hybridized orbitals provide efficient

overlapping than overlapping by pure s, p and d-

orbitals.

(11) Hybridized orbitals possess lower energy.

Depending upon the type and number of orbitals

involved in intermixing, the hybridization can be of

various types namely sp, sp2, sp3, sp3d, dsp2, sp3d2,

sp3d3. The nature and number of orbitals involved in

 the above mentioned types of hybridization and their

acquired shapes are discussed in following table

No. Actua
Type No.
Geometry of of l
of of
molecules as bon shape
hy- Character lone Example
per VSPER ded of
brisat pair
theory ato molec
ion s
ms ules

s-
CO2 , HgCl 2 , BeF2 , Zn
180o

character=50 A
Linear
,
sp 2 0 Linear MgCl 2 , C 2 H 2 , HCN , B
%, C 2 H 2 , CS 2 , N 2 O, Hg

[ Ag{ NH 3 ) 2 ] +

p -character=
 50%

BF3 , AlCl 3 , SO 3− − , C 2

s-character=
120o NO3− , CO32− , HCHO
A
33.33%, Trigo C6 H 6 , CH 3+
Trigonal Planar, 120o

sp 2 p- 3 0 nal graphite,

character=66 Planar C 2 Cl 4 ,

C2 H 2Cl 2 , [ HgI 3 ]− ,
.67%
109o28′
A
[ Cu(PMe 3 ) 3 ] −

Tetrahedral , 109.5o

V-

<120o 2 1 shape NO 2− , SO 2 , SnCl 2

(bent)

sp 3 s-character = 4 0 Tetrah CH 4 , SiH 4 , SO 42− , Sn

25%, edral ,

ClO4− , BF4− , NH 4+ , CCl

p-character =

75% SiF4 , H 2 − NH 2 ,
[ BeF 4 ] − , XeO 4 ,
[ AlCl 4 ]− , SnCl 4 , PH 4+

Diamond,

silica,
Ni (CO) 4 , Si (CH 3 ) 4 , S
SF2 , [ NiCl 4 ] 2 , [ MnO 4 ] −

Trigo
NH 3 , PCl 3 , PH 3 , AsH

nal
o
< 109.5 3 1
pyram ClO 3− , POCl 3

H 3 O + , XeO 3

idal
 V-
H 2O, H 2S, PbCl 2 , OF2
104.5o 2 2 shape ClO 2

(bent)

s-character =
90o

25%
Squar
p – character [ Cu( NH 3 ) 4 ] 2+ , [ Ni (CN
dsp 2
Square planar 4 0 e [ Pt( NH 3 )4 ] 2+
= 50%
planar
d – character

= 25%

s-character = Trigo PCl 5 , SbCl 5 , XeO 3 F2

90o
sp 3 d 5 0 AsF5 , PCl 4+ , PCl 6− , [ Cu(C
A
20%, 120o
nal [ Ni (CN ) 5 ] 3− ,
p-character = Trigonal bipyra [ Fe(CO) 5 ]

60%, bipyramidal midal

d-character =

20%

Irregu

lar
4 1 TeCl 4 , SF 4

tetrah

edral

T-

3 2 shape ClF3 , IF3

d
 2 3 Linear I 3− , XeF 2

s-character =

25%

SF 6 , PF6− , SnCl 6− , Mo
p – character Octah (BaCl 6 )− , (PF6 )− ,
sp 3 d 2 6 0 [ Fe(CN ) 6 ] 4 − , [ Fe(H 2 O

= 50% edral
Octohedraz
d – character

= 25%

Squar

e ICl 5 , BrF5 , IF5

5 1 XeOF4
pyram

idal
 Squar
90o

72o
4 2 e XeF 4 , ICl 4−
A

planar

s-character=

14.28%, Penta

p-character= Pentagonal gonal IF7 , [ ZrF7 ]3 − [UF7 ]3 −

3
sp d 3
7 0 [UO 2 F5 ] 3−
42.86%, bipyramidal bipyra

d-character= midal

42.86%

Distor
6 1 XeF 6

ted
 octahe

dral

Short trick to find out hybridization : The

structure of any molecule can be predicted on the

basis of hybridization which in turn can be known

1
by the following general formulation. H=
2
(V + M − C + A)

Where H = Number of orbitals involved in

hybridization viz. 2, 3, 4, 5, 6 and 7, hence nature of

hybridization will be sp, sp2, sp3, sp3d, sp3d2, sp3d3

respectively.

V = Number electrons in valence shell of the

central atom, M = Number of monovalent atom

C = Charge on cation,

A = Charge on anion

Few examples are given below to illustrate this:

Type : (A) When the central atom is surrounded by

monovalent atoms only, e.g. BeF2, BCl3, CCl4, NCl3,

PCl5, NH3, H2O, OF2, TeCl4, SCl2, IF7, ClF3, SF4,

SF6, XeF2, XeF4, etc. Let us take the case of PCl5.

H =
1
2
(5 + 5 − 0 + 0) = 5 . Thus, the type of hybridization is

sp3d.

Type : (B) When the central atom is surrounded by

divalent atoms only; e.g. CO2, CS2, SO2, SO3, XeO3

 1
etc. Let us take the case of SO3. H=
2
(6 + 0 − 0 + 0) = 3 .

Thus, the type of hybridization in SO3 is sp2.

Type : (C) When the central atom is surrounded

by monovalent as well as divalent atoms, e.g. COCl2,

POCl3, XeO2F2 etc. Let us take the case of POCl3.

1
H =
2
(5 + 3 − 0 + 0) = 4 . Thus, the nature of hybridization in

POCl3 is sp3.

Type : (D) When the species is a cation, e.g.

NH4+, CH3+, H3O+ etc. Let us take the case of CH3+.

H =
1
2
(4 + 3 − 1 + 0) = 3 . Thus, the hybridization in CH3+ is

sp2.
 Type : (E) When the species is an anion, e.g.

SO42–, CO32–, PO43–, NO2–, NO3–, etc. Let us take the

case of SO42–. H = 12 (6 + 0 − 0 + 2) = 4 . Thus, hybridization in

SO 42 − is sp3 .

Type : (F) When the species is a complex ion of

the type ICl4–, I3–, ClF2–, etc. Let us take the case of

ClF2–. 1
H = (7 + 2 − 0 + 1) = 5
2
. Thus, in ClF2–, Cl is sp3d

hybridized.

Type : (G) When the species is a complex ion of

the type [PtF6]2 –, [Co(NH3)6]2+, [Ni(NH3)4Cl2] etc.

In such cases nature of hybridization is given by

counting the co-ordination number.Important Tips

 The sequence of relative energy and size of s – p type

hybrid orbitals is sp < sp2 < sp3.

 The relative value of the overlapping power of sp, sp2

and sp3 hybrid orbitals are 1.93, 1.99 and 2.00 respectively.

 An increase in s-character of hybrid orbitals, increases the

bond angle. Increasing order of s-characters and bond angle is

sp3 < sp2 < sp.

 Normally hybrid orbitals (sp, sp2, sp3, dsp2, dsp3 etc.) form

σ-bonds but in benzyne lateral overlap of sp2-orbitals forms a

π-bond.

 Some iso-structural pairs are [ NF3 , H 3O+ ], [ NO3− , BF3 ], [ SO 42− , BF4− ] . There
structures are similar due to same hybridization.

 In BF3 all atoms are co-planar.

In PCl5 the state of hybridization of P atom is sp3d. In its

trigonal bipyramidal shape all the P-Cl bonds are not equal.

 The π bond formed between S and O atoms in SO2

molecule is due to overlap between their p-orbitals ( Pπ − Pπ

bonding) or between p orbital of O-atom with d-orbital of S-

atom (called pπ – dπ bonding)

pπ- dπ pπ- pπ
bonding bonding
3p
d
2p
2p
••

S
S

d
S-atom undergoes sp2 hybridization leaving one half-filled

3pz orbital and one d-orbital unhybridized. Out of two half

filled orbitals of O-atom, one is involved in formation of σ-

bond with S-atom and the other in forming π-bond.

3.10 Resonance.

The phenomenon of resonance was put forward

by Heisenberg to explain the properties of certain

molecules.

In case of certain molecules, a single Lewis

structure cannot explain all the properties of the

molecule. The molecule is then supposed to have

many structures, each of which can explain most of

the properties of the molecule but none can explain

all the properties of the molecule. The actual

structure is in between of all these contributing

structures and is called resonance hybrid and the

different individual structures are called resonating

structures or canonical forms. This phenomenon is

called resonance.

To illustrate this, consider a molecule of ozone O3 .

Its structure can be written as

O O O

O O O O O O
(a) (b) (c)
It may be noted that the resonating structures have

no real existence. Such structures are only

theoretical. In fact, the actual molecule has no

pictorial representation. The resonating structures

are only a convenient way of picturing molecule to

account for its properties.

As a resonance hybrid of above two structures (a)

and (b). For simplicity, ozone may be represented by

structure (c), which shows the resonance hybrid

having equal bonds between single and double.

Resonance is shown by benzene, toluene, O3,

allenes (>C = C = C<), CO, CO2, CO 3− , SO3, NO,

NO2 while it is not shown by H2O2, H2O, NH3, CH4,

SiO2.

(1) Conditions for writing resonance structures

The resonance contributing structures :

(i) Should have same atomic positions.

(ii) Should have same number of bond pairs and

lone pairs.

(iii) Should have nearly same energy.

(iv) Should be so written such that negative charge

is present on an electronegative atom and positive

charge is present on an electropositive atom.

(v) The like charges should not reside on adjacent

atoms. But unlike charges should not greatly

separated.

(2) Characteristics of resonance

(i) The contributing structures (canonical forms) do

not have any real existence. They are only

imaginary. Only the resonance hybrid has the real

existence.

E1

E2

E3

Resonance energy
Energy

E0

Resonating structures
Concept of resonance energy. Energies E1, E2 and
E3 for three structures and E0 is the
experimentally determined bond energy
 (ii) As a result of resonance, the bond lengths

of single and double bond in a molecule become

equal e.g. O–O bond lengths in ozone or C–O bond

lengths in CO32– ion.

(iii) The resonance hybrid has lower energy

and hence greater stability than any of the

contributing structures.

(iv) Greater is the resonance energy, greater is

the stability of the molecule.

(v) Greater is the number of canonical forms

especially with nearly same energy, greater is the

stability of the molecule.

 (3) Resonance energy

It is the difference between the energy of

resonance hybrid and that of the most stable of the

resonating structures (having least energy). Thus,

Resonance energy = Energy of resonance hybrid

– Energy of the most stable of resonating structure.

(4) Bond order calculation

In the case of molecules or ions having

resonance, the bond order changes and is calculated

as follows:

Total no. of bonds between two atoms in all the structures

Bond order =
Total no. of resonating structures
 e.g., (i)

double bond + single bond 2 + 1

Bond order = = = 1.5
2 2

(ii) In carbonate ion

O− O O−
| || |
C ←→ C ←→ C
// \ / \ / \\
−
O O− O O− −
O O

2+1+1
Bond order = = 1.33
3

Important Tips

 Resonance structure (canonical form) must be planar.

 O 
 
 In case of formic acid H − C , the two C−O bond lengths
 O − H 

  O O − 

are different but in formate ion H − C

←→ H − C 

the two C−O
 O− O 

bond lengths are equal due to resonance.

 In resonance hybrid, the bond lengths are different from those

in the contributing structure.

 Resonance arises due to delocalisation of π electrons.

Resonating structures have different electronic arrangements.

 The resonating structures do not have real existence.

 Resonance energy = [Experimental heat of formation]–

[Calculated heat of formation of most stable canonical form].

 Three contributing structure of CO 2 molecule are –

 + − − +
O = C = O ↔ O ≡ C − O ↔ O− C ≡ O

•• ←
 Resonance structure of carbon monoxide is •
•C =O
••
↔ •
•C = O••

 Resonance energy of benzene is 152 .0 kJ / mol .

3.11 Bond characteristics.

(1) Bond length

“The average distance between the centre of the

nuclei of the two bonded atoms is called bond

length”.

It is expressed in terms of Angstrom (1 Å = 10–10 m)

or picometer (1pm = 10–12 m). It is determined

experimentally by X-ray diffraction methods or

spectroscopic methods. In an ionic compound, the

bond length is the sum of their ionic radii (d = r++ r–)

and in a covalent compound, it is the sum of their

covalent radii (e.g., for HCl, d = rH + rCl).

Factors affecting bond length

(i) Size of the atoms : The bond length increases

with increase in the size of the atoms. For example,

bond length of H−X are in the order , HI > HBr > HCl > HF

1
(ii) Electronegativity difference : Bond length ×
∆EN
.

(iii) Multiplicity of bond : The bond length

decreases with the multiplicity of the bond. Thus,

bond length of carbon–carbon bonds are in the order

, C≡C<C=C<C–C

(iv) Type of hybridisation : As an s-orbital is

smaller in size, greater the s-character shorter is the

hybrid orbital and hence shorter is the bond length.

For example, sp 3 C – H > sp 2 C – H > sp C – H

(v) Resonance : Bond length is also affected

by resonance as in benzene and CO 2 . In benzene

bond length is 1.39 Å which is in between C−C bond

length 1.54 Å and C = C bond length 1.34 Å

 ↔

In CO 2 the C-O bond length is 1.15 Å .

(In between C≡O and C=O )

+ +
O = C = O ↔ O −C ≡ O ↔ O ≡ C−O

(vi) Polarity of bond : Polar bond length is

usually smaller than the theoretical non-polar bond

length.

(2) Bond energy

“The amount of energy required to break one mole

of bonds of a particular type so as to separate them

into gaseous atoms is called bond dissociation

energy or simply bond energy”. Greater is the bond

energy, stronger is the bond.

Bond energy is usually expressed in kJ mol –1

.

Factors affecting bond energy

1
(i) Size of the atoms : Bond energy ∝
atomic size
Greater

the size of the atom, greater is the bond length and less

is the bond dissociation energy i.e. less is the bond

strength.

(ii) Multiplicity of bonds : For the bond between the

two similar atoms, greater is the multiplicity of the

bond, greater is the bond dissociation energy. This is

firstly because atoms come closer and secondly, the

number of bonds to be broken is more,

C−C < C = C < C ≡ C , C≡C<C≡N<N≡N

(iii) Number of lone pairs of electrons present :

Greater the number of lone pairs of electrons present

on the bonded atoms, greater is the repulsion

between the atoms and hence less is the bond

dissociation energy. For example for a few single

bonds, we have

Bond C–C N–N O–O F–F

Lone pair of 0 1 2 3
 electrons

Bond energy (kJ

348 163 146 139
–1
mol )

(iv) Percentage s–character : The bond energy

increases as the hybrid orbitals have greater amount

of s orbital contribution. Thus, bond energy

decreases in the following order, sp > sp 2 > sp 3

(v) Bond polarity : Greater the electronegativity

difference, greater is the bond polarity and hence

greater will be the bond strength i.e., bond energy,

H − F > H − Cl > H − Br > H − I ,

(vi) Among halogens Cl – Cl > F – F > Br – Br > I

– I, (Decreasing order of bond energy)

(vii) Resonance : Resonance increases bond energy.

(3) Bond angle

In case of molecules made up of three or more

atoms, the average angle between the bonded

orbitals (i.e., between the two covalent bonds) is

known as bond angle θ.

Factors affecting bond angle

(i) Repulsion between atoms or groups attached to

the central atom : The positive charge, developed

due to high electronegativity of oxygen, on the two

hydrogen atoms in water causes repulsion among

themselves which increases the bond angle, H–O–H

from 90º to 105º.

(ii) Hybridisation of bonding orbitals : In

hybridisation as the s character of the s hybrid bond

increases, the bond angle increases.

Bond type sp3 sp2 sp

Bond angle 109º28′ 120o 180o

(iii) Repulsion due to non-bonded electrons : Bond

1
angle ∝
No. of lone pair of electrons
. By increasing lone pair
of electron, bond angle decreases approximately by

2.5%.

CH4 NH3 H2O

Bond angle 109º 107o 105o

(iv) Electronegativity of the atoms : If the

electronegativity of the central atom decreases, bond

angle decreases.

H 2O > H 2S > H 2 Se > H 2 Te

o o o
Bond angle 104 .5 92 .2 91 .2 89 .5 o

remainsthesame,bondangleincreaseswiththedecrease
inelectronegativityofthesurroundingatom,e.g.

Example:Energyrequiredtodissociate4gramsofgaseo

ushydrogenintofreegaseousatomsis208kcalat25otheb

ondenergyofHHbond will be

(a) 104 Kcal

(b) 10 .4 Kcal

(c) 20 .8 Kcal

(d) 41 .6 Kcal

Answer: (a) 4 gram gaseous hydrogen has bond

energy 208 kcal So, 2 gram gaseous hydrogen has

208
bond energy =
2
kcal = 104 kcal.
 Important Tips

ore directional the bond, greater is the bond strength and vice

versa. For example : sp 3 − sp 3 > sp 2 − sp 2 > sp − sp > p − p > s − p > s − s

 The hybrid orbitals with more p-character are more

directional in character and hence of above order.

 The terms ‘bond energy’ and ‘bond dissociation’ energy are

same only for di-atomic molecules.

 The order of O–O bond length in O2, H2O2 and O3 is H2O2 >

O2 > O3
 Because of higher electron density and small size of F atom

repulsion between electron of it two F atoms, weakens the F-F

bond.

 The bond length increases as the bond order decreases.

 Carbon monoxide (CO) has the highest bond

energy(1070 kJmol ) of all the diatomic molecules. Bond energy

−1

of N 2(946 kJmol −1
) and that of H2(436 kJmol-1) are other diatomic

molecules with very high bond energies.

3.12 VSEPR (Valence shell electron pair

repulsion) theory.

The basic concept of the theory was suggested by

Sidgwick and Powell (1940). It provides useful idea

for predicting shapes and geometries of molecules.

The concept tells that, the arrangement of bonds

around the central atom depends upon the

repulsion’s operating between electron pairs(bonded

or non bonded) around the central atom. Gillespie

and Nyholm developed this concept as VSEPR

theory.

The main postulates of VSEPR theory are

(i) For polyatomic molecules containing 3 or

more atoms, one of the atoms is called the central

atom to which other atoms are linked.

 (ii) The geometry of a molecule depends upon

the total number of valence shell electron pairs

(bonded or not bonded) present around the central

atom and their repulsion due to relative sizes and

shapes.

(iii) If the central atom is surrounded by bond

pairs only. It gives the symmetrical shape to the

molecule.

(iv) If the central atom is surrounded by lone

pairs (lp) as well as bond pairs (bp) of e− then the

molecule has a distorted geometry.

 (v) The relative order of repulsion between

electron pairs is as follows : Lone pair-lone

pair>lone pair-bond pair>bond pair-bond pair

A lone pair is concentrated around the central

atom while a bond pair is pulled out between two

bonded atoms. As such repulsion becomes greater

when a lone pair is involved.

Steps to be followed to find the shape of

molecules :

(i) Identify the central atom and count the

number of valence electrons.

(ii) Add to this, number of other atoms.

 (iii) If it is an ion, add negative charges and

subtract positive charges. Call the total N.

(iv) Divide N by 2 and compare the result with

the following table and obtain the shape.

Total N/2 Shape of molecule or Example

ion

2 Linear HgCl 2 / BeCl 2

3 Triangular planar BF3

3 Angular SnCl 2 , NO 2

4 Tetrahedral CH 4 , BF4−

4 Trigonal Pyramidal NH 3 , PCl 3

4 Angular H 2O

5 Trigonal bipyramidal PCl 5 , PF5

5 Irregular tetrahedral SF 4 , IF4+

5 T-shaped CIF3 , BrF3

5 Linear XeF 2 , I 3−

6 Octahedral SF 6 , PF6

6 Square Pyramidal IF5

6 Square planar XeF 4 , ICI 4

 Geometry of Molecules/Ions having bond pair

as well as lone pair of electrons

Ty No. No.

pe of of
Hyb Expect Actua
of bond lone
ridi- Bond ed l
mo pairs pairs Examples
zatio angle geome geome
le- of of
n try try
cul elect electr

e ron ons

Trigon V-
SO2, SnCl2,
AX 3 2 1 sp 2 < 120o al shape,
NO2–
planar Bent,
 Angul

ar

V-
H2O, H2S,
o
< 109 Tetrah shape,
AX 4 2 2 sp 3 SCl2, OF2,
28′ edral Angul
NH2–, ClO2–
ar

NH3, NF3 ,

< 109o Tetrah Pyram PCl3, PH3,

AX 4 3 1 sp 3

28′ edral idal AsH3, ClO3–

, H3O+

Trigon Irregul SF4, SCl4,

AX 5 4 1 sp 3 d < 109o
al ar TeCl4
 28′ bipyra tetrahe

midal dron

Trigon

al T- ICl3, IF3,
o
AX 5 3 2 sp 3 d 90
bipyra shaped ClF3

midal

Trigon

al XeF2, I3–,
AX 5 2 3 sp 3 d 180o Linear
bipyra ICl2–

midal

Octahe Square ICl5, BrF5,

AX 6 5 1 sp 3 d 2 < 90o
dral pyram IF5
 idal

Octahe Square
AX 6 4 2 sp 3 d 2 – XeF4, ICl4–
dral planar

Pentag Distort

AX onal ed
6 1 sp 3 d 3 – XeF6
7 pyrami octahe

dal dral

3.13 Molecular orbital theory.

Molecular orbital theory was given by Hund and

Mulliken in 1932. When two or more constituent

atomic orbital merge together, they form a bigger

orbital called molecular orbital (MO). In atomic

orbital, the electron is influenced by only one

nucleus whereas in case of molecular orbital, the

electron is influenced by two or more constituent

nuclei. Thus, atomic orbital is monocentric and

molecular orbital is polycentric. Molecular orbitals

follow Pauli's exclusion principle, Hund’s rule,

Aufbau's principle strictly.

• • • • • • •

Atomic orbital According to VBT Molecular orbital According to MOT

(AO) (MO)

The main ideas of this theory are : (i) When two

atomic orbitals combine or overlap, they lose their

identity and form new orbitals. The new orbitals

thus formed are called molecular orbitals. (ii)

Molecular orbitals are the energy states of a

molecule in which the electrons of the molecule are

filled just as atomic orbitals are the energy states of

an atom in which the electrons of the atom are filled.

(iii) In terms of probability distribution, a molecular

orbital gives the electron probability distribution

around a group of nuclei just as an atomic orbital

gives the electron probability distribution around the

single nucleus. (iv) Only those atomic orbitals can

combine to form molecular orbitals which have

comparable energies and proper orientation. (v) The

number of molecular orbitals formed is equal to the

number of combining atomic orbitals. (vi) When

two atomic orbitals combine, they form two new

orbitals called bonding molecular orbital and

antibonding molecular orbital. (vii) The bonding

molecular orbital has lower energy and hence

greater stability than the corresponding antibonding

molecular orbital. (viii) The bonding molecular

orbitals are represented by σ ,π etc, whereas the

corresponding antibonding molecular orbitals are

represented by σ*, π* etc. (ix) The shapes of the

molecular orbitals formed depend upon the type of

combining atomic orbitals.

Formation of bonding and antibonding molecular

orbitals

(Linear combination of atomic orbitals – LCAO)

When two atomic orbitals overlap they can be in

phase (added) or out of phase (subtracted). If they

Antibonding
MO Subtractio
Repulsive
Energy

Atomic Atomic
orbital orbital

Addition
Bonding M.O.
Attractive
Formation of bonding and antibonding molecular
bit l

overlap in phase, constructive interaction occurs in

the region between two nuclei and a bonding orbital

is produced. The energy of the bonding orbitals is

always lower (more stable) then the energies of the

combining atomic orbitals. When they overlap out

of phase, destructive interference reduces the

probability of finding an electron in the region

between the nuclei and antibonding orbital is

produced. The energy of an antibonding orbital is

higher (less stable) than the energies of the

combining atomic orbitals. Thus, the number of

molecular orbitals formed from atomic orbitals is

equal to the number of atomic orbitals responsible

for their formation.

 According to LCAO method, the following

combination is not allowed. [consider the z-axis as

the molecular axis). np x + np y , np x + np z or np y + np z .

Table : Difference in Bonding molecular orbitals

and Antibonding molecular orbitals.

Bonding molecular orbitals Antibonding molecular orbitals

It is formed by linear It is formed by linear

combination of two atomic combination of two atomic

orbitals when their wave orbitals when their wave

functions are added. functions are subtracted.

i.e., Ψb = Ψ A + Ψ B i.e., Ψa = Ψ A − Ψ B
Its energy is less than the Its energy is more than the

combining atomic orbitals. combining atomic orbitals.

It increases the electron density It decreases the electron density

between the nuclei. It therefore between the nuclei. It therefore

stabilises the molecule. destabilises the molecule.

It has no nodal plane (plane It has nodal plane.

where electron density is zero).

It is symmetrical about It is symmetrical about

internuclear axis. internuclear axis and about a

line perpendicular to it.

σ and π – Molecular orbitals

 A sigma (σ) M.O. is one that has cylinderical

symmetry around the internuclear axis. It does not

show any change of sign or rotation through 180 o

about the axis. Sigma M.O. has no nodal plane (in

which electron density is zero) along the

internuclear axis. The bonding M.O. is designated

by σ and antibonding by σ *.

+ +
+ +
+ + +
• •
• • • • • •

σ(1s)
1s 1s Bonding M.O.

+ – + –
• • • • +• •–

σ*(1s)
1s 1s Antibonding M.O.

Formation of σ (1s) and σ * (1s) M.O. from 1s atomic

orbital

Sigma (σ) M.O. is also formed when two p-

atomic orbitals overlap in head on (along their axes)

position.

– • + + • – – • + – • +
2pz 2pz 2pz

– • + + • – + – • +
– •

– • + • – – • + – • +

σ(2pz) σ*(2pz)

Formation of σ (2 pz and σ * (2 p z ) molecular orbitals.

π-molecular orbital is formed by the sideways

overlapping of the p-atomic orbitals. It consists of

two electrons clouds, one lying above and the other

 + + + +
+

• • • • • •
–

– – – – Nodal Plane
2px 2px π (2px)
(or 2py) (or 2py) or π (2py)

+ – + – + –

• • • • • •

– +
– + – +
2px 2px Nodal Plane π* (2px)
(or 2py) (or 2py) or π* (2py)

lying below a plane passing through the nuclei. It

has nodal planes. Since the energy of a M.O. is

directly related to the nuclei of nodal planes. The π-

MO is more energetic than the σ-MO. This explains

why a π-bond is a weaker bond than a σ-bond.

Formation of π (2 p x ) or π (2 p y ) and π *
(2 px ) or π * (2 p y )

molecular orbitals.
 Relative energies of Molecular orbitals : Initial

energy of the atomic orbitals and the extent of their

overlap is the criteria which determines the energy

of the M.O.

(1) It is obvious that molecular orbitals formed

from lower energy atomic orbitals have lower

energy than the molecular orbitals formed from

higher energy atomic orbitals.

(2) As theσ overlap is much more effective than

π-overlap, σ p-molecular orbital is of lowest energy,

even though originally all the three p-orbitals are of

equal energy.
 (3) The relative energies of the M.O. are

obtained experimentally from spectroscopic data.

(4) The sequence in the order of increasing

energy for O , 2 F2 and Ne 2

σ 1s < σ * 1s < σ 2s < σ * 2s < σ 2 p z < π 2 p x = π 2 p y < π * 2 p x = π * 2 p y < σ * 2 p z

(5) It may be noted that π 2py an π 2p x bonding

molecular orbitals are degenerate (i.e. have same

energy). Similarly π * 2py and π * 2p x antibonding

molecular orbitals are also degenerate (have the

same energy).
 (6) The main difference between the two types of

sequences in energy level is that for molecules O2 , F2

and Ne 2 (Hypothetical) the σ 2pz M.O. is lower in

energy than π 2 p and x π 2py .

(7) It has been found experimentally that in some

of the diatomic molecules such as Li 2 , B2 , C2 and N2

σ 2pz M.O. is higher in energy than π 2py and π 2p x

M.O.’s. Therefore, the order of increasing energy of

these M.O.s changes to

σ 1s < σ * 1s < σ 2s < σ * 2s < π 2 p x = π 2 p y < σ 2 p z < π * 2 p x = π * 2 p y < σ * 2 p z

.

Cause of exceptional behaviour of MO’s in B2 ,

C2 and N2
 In atoms with Z upto 7, energy of 2s and 2p

atomic orbitals lie fairly close. As a result the

interaction between 2s and 2p orbitals is quite large.

Thus σ 2s and σ * 2s MO’s become more stable with

less energy at the cost of σ 2p x and σ * 2p x which gets

unstabilised (higher energy).

Stability of the molecules : Stabitity of the

molecules can be explain in following ways.

(1) Stability of molecules in terms of bonding

and antibonding electrons

 Since electrons in bonding orbitals (N b ) increase

the stability of the molecule, on the whole, depends

on their relative numbers. Thus

(i) If Nb > Na , the molecule is stable. (ii) If

Nb < Na , the molecule is unstable.

(iii) Even if Nb = Na , the molecule is unstable. This is

due to the fact the anti bonding effect is some what

stronger than the bonding effect.

(2) Stability of molecules in terms of bond order

(i) The relative stability of a molecule is further

evaluated by a parameter known as bond order.

(ii) It can be defined as number of covalent bonds

present between two atoms in a molecule.

(iii) It is given by one half of the differences

between the number of electrons in bonding

molecular orbitals and those in antibonding

molecular orbitals.

(iv) Bond order =

1
2
[No. of electrons in bonding

molecular orbitals – No. of electrons in antibonding

molecular orbitals].

(v) The bond order of 1, 2 and 3 corresponds to

single, double and triple bonds respectively. It may

be mentioned that according to M.O theory, even a

fractional bond order is possible, but cannot be

negative.

(vi) bond order ∝ Stability of molecule ∝

Dissociation energy ∝ 1
Bond length

(vii) If all the electrons in a molecule are paired then

the substance is a diamagnetic on the other hand if

there are unpaired electrons in the molecule, then the

substance is paramagnetic. More the number of

unpaired electron in the molecule greater is the

paramagnetism of the substance.

MO energy level diagrams of some molecules :

Energy level diagrams of some molecules are given

below.

H2 Molecule : H2 molecule is formed from 1s1 atomic

orbitals of two H- atoms. The atomic orbitals (1s1 )

will combine to form two molecular orbitals σ (1s) and

σ * (1s) . Two electrons are accommodated in σ (1s) and

σ * (1s) remains vacant. Thus bond order for

1
H2 =
2
(2 − 0) = 1 . It is stable and diamagnetic in nature.

σ*1s
Increasing energy

1s 1s
H H

σ1s
H2
 σ*(1s2)

Increasing energy
1s2 1s2
He He

σ(1s)2

He2 molecule : If two atoms of He (1s2 ) combine to

form He 2 , the probability of the formation of

molecular orbitals is as shown in the figure.

Filling of electrons is as follows

He 2 = σ (1s) 2 , σ * (1s) 2

Thus bond order = 12 (2 − 2) = 0

Hence there is no possibility for the existence of He 2

molecule.
 σ * (2 p z )

2p
2p
π*(2px) π*(2py)

σ (2pz)
Increasing
energy

π (2px)=π (2py)

σ* (2s)

2s 2s
N (AO) N (AO)

σ (2s)
N2 (MO)

N2 molecule : Total number of electrons in N2 are

14, of which 4 are in K shell and the 10 electrons are

arranged as, KK (σ 2s)2 (σ * 2s)2 (π 2 px )2 (π 2 py )2 (σ 2 pz )2

1
Bond order =
2
(10 − 4) = 3
M.O. energy level diagram for N2 molecule.

O2 molecule : Total number of electrons in O2 = 16

Electronic arrangement in M.O.’s ,

[ KK (σ 2s) 2 (σ * 2s) 2 (σ 2 p z ) 2 (π 2 p x ) 2 (π z 2 p y ) 2 (π * 2 p x )1 (π * 2 p y )1 ]

1
Bond order =
2
(8 − 4) = 2

σ * (2 p z )

π* 2px π* 2py

π 2px=π 2py
Increasing
energy

σ 2pz

σ* 2s

O (AO) O (AO)

σ 2s
O2 (MO)
 M.O. Energy level diagram for O2 molecule

Table : Bond order and magnetic nature of some

molecules & ions

Molecu Molecular Orbital Valence Magnetic .

Nb Na
le Configuration electrons Nature O

H2 (σ1s)2 2 2 0 Diamagnetic 1

H 2+ (σ1s)1 1 1 0 Paramagnetic .

5
 0

H 2− (σ1s)2 (σ* 1s)1 3 2 1 Paramagnetic .

2
Molecule does
He 2 (σ1s)  σ ∗ 1s
2
4 2 2 0
 
not exist

He +2 (σ1s)2 (σ* 1s)1 3 2 1 Paramagnetic .

He 2− KK ' (σ 2s)
1
1 1 0 Paramagnetic .

5
 KK ' (σ 2s) (σ* 2s) 4 2 2 Diamagnetic 0
2 2
Be2

B2 KK ' (σ 2s)2 (σ * 2s)2 (π 2 px )1 (π 2 py )1 6 4 2 Paramagnetic 1

C2 KK ' (σ 2s) (σ* 2s) (π 2 px ) π 2 py

2 2 2
( )2 8 6 2 Diamagnetic 2

KK '
(σ 2s)2 (σ* 2s)2 (π 2 px )2 (π 2 py )2 (σ 2 pz )2
N2 10 8 2 Diamagnetic 3

2
KK '
(σ 2s)2 (σ* 2s)2 (π 2 px )2 (π 2 py )2 (σ 2 pz )1
N 2+ 9 7 2 Paramagnetic .

2
KK '
(σ 2s)2 (σ* 2s)2 (π 2 px )2 (π 2 py )2 (σ 2 pz )2
N 2− 11 8 3 Paramagnetic .

5
 KK '
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2 (π
O2 12 8 4 Paramagnetic 2

2
KK′
O2+
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2 (π
11 8 3 Paramagnetic .

KK '
(σ 2s)2 (σ * 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2
O 22+ 10 8 2 Diamagnetic 3

1
KK′
O 2−
(σ2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2 (π
13 8 5 Paramagnetic .

O 22−
KK′ 14 8 6 Diamagnetic 1
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2 (π
 KK′
F2
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2 (π
14 8 6 Diamagnetic 1

KK '
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2 (π
Molecule does
Ne 2 (π* 2 pz )2 16 8 8 0
not exist

KK '
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2
CO 10 8 2 Diamagnetic 3

2
KK '
(σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px )2 (π 2 py )2
NO 11 8 3 Paramagnetic .

NO + KK ' 10 8 2 Diamagnetic 3
(σ 2s) (σ* 2s) (σ 2 pz ) (π 2 px ) (π 2 py )
2 2 2 2 2
3.14 Hydrogen bonding.

In 1920, Latimer and Rodebush introduced the

idea of “hydrogen bond” to explain the nature of

association of substances in liquid state like water,

hydrogen fluoride, ammonia, formic acid, etc.

(1) Conditions for the formation of hydrogen

bonding

(i) High electronegativity of atom bonded to

hydrogen : The molecule should contain an atom of

high electronegativity such as F, O or N bonded to

hydrogen atom. The common examples are H 2O , NH 3

and HF .

δ+ δ− δ+ δ− δ+ δ−
H — X− − − H — X− − − H — X

(ii) Small size of the electronegative atom : The size

of the electronegative atom should be quite small.

This is due to the fact that the smaller the size of

electronegative atom, the greater will be its

attraction for the bonded electron pair. This will

cause greater polarity in the bond between H and

electronegative atom, which results in stronger

hydrogen bond.

(2) Types of hydrogen bonding

(i) Intermolecular hydrogen bond : Intermolecular

hydrogen bond is formed between two different

molecules of the same or different substances. For

example:

(a) Hydrogen bond between the molecules of

hydrogen fluoride.

(b) Hydrogen bond in alcohol and water molecules

(ii) Intramolecular hydrogen bond (Chelation) :

Intramolecular hydrogen bond is formed between

the hydrogen atom and the highly electronegative

atom (F, O or N) present in the same molecule.

Intramolecular hydrogen bond results in the

 O H
|| |
O C C
H O O
H
O O H
N N O
|| || Salicyldehyde
(o-hydroxy benzaldehyde)
O O
Ortho nitrophenol Ortho nitrobenzoic acid

cyclisation of the molecules and prevents their

association. Consequently, the effect of

intramolecular hydrogen bond on the physical

properties is negligible. For example :

Intramolecular hydrogen bonds are present in

molecules such as o-nitrophenol, o-nitrobenzoic

acid, etc.

The extent of both intramolecular and

intermolecular hydrogen bonding depends on

temperature.
(3) Effects of hydrogen bonding

Hydrogen bond helps in explaining the abnormal

physical properties in several cases. Some of the

properties affected by H-bond are given below:

(i) Dissociation : In aqueous solution, hydrogen

fluoride dissociates and gives the difluoride ion (HF2− )

instead of fluoride ion (F − ) . This is due to H-bonding

in HF. This explains the existence of KHF . On the 2

other hand, the molecules of HCl , HBr , HI do not have

H-bonding (because Cl , Br , I are not so highly

electronegative). This explains the non-existence of

compounds like KHCl 2 , KHBr 2 or KHI 2 . H-bond formed

is usually longer than the covalent bond present in

the molecule (e.g. in H2O, O–H bond = 0.99 Å but

H-bond = 1.77 Å).

(ii) Association : The molecules of carboxylic acids

exist as dimers because of the hydrogen bonding.

The molecular masses of such compounds are found

to be double than those calculated from their simple

formulae. For example, molecular mass of acetic

acid is found to be 120.

(iii) High melting and boiling point : The

compounds having hydrogen bonding show

abnormally high melting and boiling points.

The high melting points and boiling points of the

compounds (H 2 O, HF and NH 3 ) containing hydrogen

bonds is due to the fact that some extra energy is

needed to break these bonds. A few examples are

given below:

(a) H 2O is a liquid whereas H 2 S, H 2 Se and H 2 Te are all

gases at ordinary temperature. The reason for this is

that in case of water, hydrogen bonding causes

association of the H 2O molecules with the result that

the boiling point of water is more than that of the

other compounds. On the other hand, there is no

such hydrogen bonding in H 2 S, H 2 Se and H2Te.

(b) NH 3 has higher boiling point than PH3. This is

again because there is hydrogen bonding in NH 3 but

not in PH3.

(c) Ethanol has higher boiling point than diethyl

ether because there is hydrogen bonding in the

former but there is no hydrogen bonding in the later.

Intramolecular hydrogen bonding is not possible in

case of m - and p -isomers because of the size of the

ring which would be formed. Thus, here the

intermolecular hydrogen bonding takes place which

causes some degree of association with the result the

m -and p -isomers melt and boil at higher

temperatures.

(iv) Solubility : The compound which can form

hydrogen bonds with the covalent molecules are

soluble in such solvents. For example, lower

alcohols are soluble in water because of the

hydrogen bonding which can take place between

water and alcohol molecules as shown below :

δ+ δ− δ+ δ− δ+ δ−
H − O .......... ...... H − O .......... ..... H − O

C2 H 5 H C2 H 5
 Similarly, ammonia ( NH 3 ) is soluble in water

because of hydrogen bonding as represented below:

δ+ δ+
H H
δ+ δ −−− δ+ δ −− δ+ δ −−− δ+ δ −−
H N ....... H — O ..... .... ...... H N ....... H — O
δ+ δ+ δ+
H H H H

The intermolecular hydrogen bonding increases

solubility of the compound in water while, the

intramolecular hydrogen bonding decreases. This is

due to the fact that the formation of internal

hydrogen bond prevents hydrogen bonding between

the compound and water which thus reduced

solubility of the compound in water.

 O
H

O
N
||
O
o- Nitrophenol
Due to chelation, – OH group is not available to form – OH group available to form hydrogen bond with
hydrogen bond with water hence it is sparingly soluble in water, hence it is completely soluble in water.
water.

(v) Volatility : As the compounds involving

hydrogen bonding between different molecules

(intermolecular hydrogen bonding) have higher

boiling points, so they are less volatile.

(vi) Viscosity and surface tension : The substances

which contain hydrogen bonding exist as associated

molecules. So their flow becomes comparatively

difficult. In other words, they have higher viscosity

and high surface tension.

(vii) Explanation of lower density of ice than water

and maximum density of water at 277K : In case of

solid ice, the hydrogen bonding gives rise to a cage

like structure of water molecules as shown in

following figure. As a matter of fact, each water

molecule is linked tetrahedrally to four other water

molecules. Due to this structure ice has lower

density than water at 273 K . That is why ice floats on

water. On heating, the hydrogen bonds start

collapsing, obviously the molecules are not so

closely packed as they are in the liquid state and

thus the molecules start coming together resulting in

the decrease of volume and hence increase of

density. This goes on upto 277K. After 277 K, the

increase in volume due to expansion of the liquid

water becomes much more than the decrease in

volume due to breaking of H-bonds. Thus, after

277 K , there is net increase of volume on heating

which means decrease in density. Hence density of

water is maximum 277 K .

H
0.90 Å
(99 pm) 1.77 Å
O
(177 pm)

H H H
Vacant
O O Spaces

H H H H

O O

H H H H
O O
H H H H

O O
H H
 Cage like structure of H2O in the ice

Important Tips

 Hydrogen bonding is strongest when the bonded structure is

stabilised by resonance.

 The bond length of hydrogen bond is the order of 250 to

275 pm.

 The bond that determines the secondary structure of protein

is hydrogen bond.

 Pairs of DNA are held together by hydrogen bonds.

 Chlorine has the same electronegativity as nitrogen but does

not form strong hydrogen bonds. This is because of the larger

size than that of nitrogen.

3.15 Types of bonding and forces in solids.

(1) Ionic bonding : Solid containing ionic bonds

consists of any array or a net work of positive and

negative ions arranged systematically in a

characteristic pattern. The binding forces are strong

electrostatic bonds between positive and negative

ions. e.g., Compounds of elements of group 1 and 2

with elements of group 16 and 17 e.g., NaCl, CaS

etc.
 (2) Covalent bonding : The solid containing

covalent bonding consists of an array of atoms that

share electrons with their neighbouring atoms. The

atoms are linked together by strong covalent bonds

extending into three dimensional structure. e.g.,

Diamond, Silicon carbide, Silicon dioxide etc.

(3) Molecular bonding : The solid containing

molecular bonding consists of symmetrical

aggregates of discrete molecules. However, these

molecules are further bound to other molecules by

relatively weak force such as dipole-dipole forces

(Vander Waal forces), dispersion forces or H-bonds

depending upon the nature of molecules. The

existence of weak attractive forces among the non

polar molecules was first proposed by S.D. Vander

waal. Vander waal's forces are non-directional, non

valence force of attraction. Vander Waal force

∝ molecular mass ∝ Boiling point ∝ Size of atom or

molecule. The forces present in the crystals of

naphthalene, Iodine and dry ices solid CH 4 , solid

hydrogen are Vander Waals forces. SiO 2 Possesses

giant covalent molecular structure due to

tetravalency and catenation nature of Si .

 (4) Metallic Bond

The constituent particles in metallic solids are

metal atoms which are held together by metallic

bond. Lorentz proposed a simple theory of metallic

bond. This theory is known as electron gas model or

electron sea model.

A metal atom consists of two parts, valence

electrons and the remaining part (the nucleus and the

inner shell electrons) called kernel. The kernels of

metal atoms occupy the lattice sites while the space

in-between is occupied by valence electrons. These

electrons are not localized but are mobile. The

attraction between the kernels and the mobile

electrons, which hold the kernel together, is known

as metallic bond. Low ionisation energy and

sufficient number of vacant orbital in the valency

shell are essential conditions for metallic bonding.

Metallic bond is electrostatic in nature. The strength

of the metallic bond depends on the number of

valency electron and the charge on the nucleus. As

the number of valency electron and the charge

increase, the metallic bond becomes strong. Due to

this fact alkali metals are soft and have low melting

and boiling points while transition metals and hard

and have high melting and boiling points. Strong

metallic bonding is also favoured by smaller size of

kernel. Ge, Cu, Zn has metallic bonding while brass

etc does not have metallic bonding.

Metals have properties like metallic lustre,

thermal and electrical conductivity due to

delocalized mobile electrons. Thermal conductivity

of metal decreases with increase in temperature

because the kernels start vibrating.

Since the metallic bond is non-directional;

metals can be twisted, drawn into wires or beaten

into sheets. This is because the kernels can slip over

each other when a deforming force is applied.

 The relative strength of various bonds is Ionic

>Covalent>Metallic>H-bond>vander waal forces.

 The state of matter in which the molecular forces

of attraction between the particles of matter are

minimum, is known as gaseous state. It is the

simplest state and shows great uniformity in

behaviour.

6.1 Characteristics of gases.

(1) Gases or their mixtures are homogeneous in

composition.

(2) Gases have very low density due to

negligible intermolecular forces.

 (3) Gases have infinite expansibility and high

compressibility.

(4) Gases exert pressure.

(5) Gases possess high diffusibility.

(6) Gases do not have definite shape and

volume like liquids.

(7) Gaseous molecules move very rapidly in all

directions in a random manner i.e., gases have highest

kinetic energy.

(8) Gaseous molecules are loosely packed

having large empty spaces between them.

 (9) Gaseous molecules collide with one another

and also with the walls of container with perfectly

elastic collisions.

(10) Gases can be liquified, if subjected to low

temperatures (below critical) or high pressures.

(11) Thermal energy of gases >> molecular

attraction.

(12) Gases undergo similar change with the

change of temperature and pressure. In other words,

gases obey certain laws known as gas laws.

6.2 Measurable properties of gases.

 (1) The characteristics of gases are described

fully in terms of four parameters or measurable

properties :

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

(ii) Its pressure, P

(iii) Its temperature, T

(iv) The amount of the gas (i.e., mass or

number of moles).

(2) Volume : (i) Since gases occupy the

entire space available to them, the measurement of

volume of a gas only requires a measurement of the

container confining the gas.

 (ii) Volume is expressed in litres (L),

millilitres (mL) or cubic centimetres (cm 3 ) or cubic

metres (m ) .
3

(iii) 1L = 1000 mL ; 1 mL = 10 −3 L

1 L = 1 dm 3 = 10 3 cm 3

1 m 3 = 10 3 dm 3 = 10 6 cm 3 = 10 6 mL = 10 3 L

(3) Mass : (i) The mass of a gas can be

determined by weighing the container in which the

gas is enclosed and again weighing the container

after removing the gas. The difference between the

two weights gives the mass of the gas.

 (ii) The mass of the gas is related to the

number of moles of the gas i.e.

moles of gas (n) = Mass in grams m

Molar mass
=
M

(iii) Mass is expressed in grams or kilograms,

1 Kg = 10 3 g

(4) Temperature : (i) Gases expand on

increasing the temperature. If temperature is

increased twice, the square of the velocity (v 2 ) also

increases two times.

(ii) Temperature is measured in centigrade

degree ( o C) or celsius degree with the help of

thermometers. Temperature is also measured in

Fahrenheit (Fo).

(iii) S.I. unit of temperature is kelvin (K) or

absolute degree.

K = o C + 273

o
C F o − 32
(iv) Relation between F and o
C is 5
=
9

(5) Pressure : (i) Pressure of the gas is the force

exerted by the gas per unit area of the walls of the

container in all directions. Thus, Pressure

F) Mass(m) × Accelerati on(a)

(P) = Force(
Area( A)
=
Area(a)

(ii) Pressure exerted by a gas is due to kinetic

1
energy (KE =
2
mv 2 ) of the molecules. Kinetic energy of
the gas molecules increases, as the temperature is

increased. Thus, Pressure of a gas ∝ Temperature

(T).

(iii) Pressure of a pure gas is measured by

manometer while that of a mixture of gases by

barometer.

(iv) Commonly two types of manometers are

used,

(a) Open end manometer; (b) Closed end

manometer
 (v) The S.I. unit of pressure, the pascal (Pa),

is defined as 1 newton per metre square. It is very

small unit.

1Pa = 1Nm −2 = 1 kg m −1 s−2

(vi) C.G.S. unit of pressure is dynes cm −2 .

(vii) M.K.S. unit of pressure is kgf / m 2 . The unit

kgf / cm 2 sometime called ata (atmosphere technical

absolute).

(viii) Higher unit of pressure is bar, KPa or

MPa.

1 bar = 10 5 Pa = 10 5 Nm −2 = 100 KNm −2 = 100 KPa

(ix) Several other units used for pressure are,

 Name Symbol Value

bar bar 1bar = 10 5 Pa

atmosphere atm 1 atm = 1.01325 × 10 5 Pa

101325
Torr Torr 1 Torr =
760
Pa = 133 .322 Pa

millimetre of mm Hg 1 mm Hg = 133 .322 Pa

mercury

(x) The pressure relative to the atmosphere is

called gauge pressure. The pressure relative to the

perfect vacuum is called absolute pressure.

Absolute pressure = Gauge pressure +

Atmosphere pressure.
 (xi) When the pressure in a system is less than

atmospheric pressure, the gauge pressure becomes

negative, but is frequently designated and called

vacuum. For example, 16 cm vacuum will be

76 − 16
76
× 1.013 = 0.80 bar .

(xii) If ‘h’ is the height of the fluid in a

column or the difference in the heights of the fluid

columns in the two limbs of the manometer d the

density of the fluid (Hg = 13 .6 × 10 3 Kg / m 3 = 13 .6 g / cm 3 ) and g

is the gravity, then pressure is given by, Pgas = Patm + h dg

Vacuum
ρgas
Gas Atmospheric
h pressure Height (h) of
mercury column
ρgas
Hg
ρgas=ρgashdg

An open arm Mercury Barometer

manometer
 (xiii) Two sets of conditions are widely used as

'standard' values for reporting data.

Condition T P Vm (Molar

volume)

S.T.P./N.T.P. 273.15 K 1 atm 22.414 L

S.A.T.P*. 298.15 K 1 bar 24.800 L

* Standard Ambient temperature and

pressure.

6.3 Boyle's law.

(1) In 1662, Robert Boyle discovered the first

of several relationships among gas variables (P, T,

V).
 (2) It states that, “For a fixed amount of a gas at

constant temperature, the gas volume is inversely

proportional to the gas pressure.”

1
Thus, P∝
V
at constant temperature and

mass

K
or P=
V
(where K is constant)

or PV = K

For two or more gases at constant temperature and

mass.

P1 V1 = P2 V2 = ....... = K
  dP  K
Boyle's law can also be given as,   =− 2
 dV  T v

(3) Graphical representation of Boyle's law :

Graph between P and V at constant temperature is

called isotherm and is an equilateral (or rectangular)

1
hyperbola. By plotting P versus V
, this hyperbola

can be converted to a straight line. Other types of

isotherms are also shown below,

T3
T1< T2< T3
T2 PV T3
T1< T2< T3
T1 T2
P P
T1 log P

T3
T2 T1< T2< T3
T1
O O O O
V or 1/d 1/V or d P log 1/V

Note :  The isotherms of CO 2 were first studied by

Andrews.
 (4) At constant mass and temperature density of

a gas is directly proportional to its pressure and

inversely proportional to its volume.

1  mass 
Thus, d∝P∝  V = d 
V  

d1 P V
or = 1 = 2 = ....... = K
d 2 P2 V1

(5) At altitudes, as P is low d of air is less. That

is why mountaineers carry oxygen cylinders.

(6) Air at the sea level is dense because it is

compressed by the mass of air above it. However the

density and pressure decreases with increase in

altitude. The atmospheric pressure at Mount Everest

is only 0.5 atm.

 Examples based on Boyle's law

Example : 1A sample of a given mass of a gas at a constant tempera

(a) 190 cm 3

(b) 93 cm 3

(c) 46 .5 cm 3

(d) 47 .5 cm 3

Solution: (b) P1 V1 = P2 V2

9.962 × 10 4 × 95 = 10 .13 × 10 4 × V2

V2 = 93 cm 3
Example : 2 A gas occupied a volume of 250 ml

at 700 mm Hg pressure and 25 o C . What additional

pressure is required to reduce the gas volume to its

4/5th value at the same temperature

(a) 225 mm Hg

(b) 175 mm Hg

(c) 150 mm Hg

(d) 265 mm Hg

Solution: (b) P1 V1 = P2 V2

4 
700 × 250 = P2 ×  × 250  ; P2 = 875 mm Hg
5 

Additional pressure required = 875 – 700

= 175 mm Hg
Example : 3 At constant temperature, if

pressure increases by 1%, the percentage decrease of

volume is

(a) 1%

(b) 100/101%

(c) 1/101%

(d) 1/100%

Solution: (b) P1 V1 = P2 V2

If P1 = 100 mm , P2 will be 101 mm

Hence 100 × V = 101 × V2 ,

100
V2 =
101
×V ,
 Decrease in volume = V − 100
101
V
=
1
101
of V i.e.

100
%
101

6.4 Charle's law.

(1) French chemist, Jacques Charles first

studied variation of volume with temperature, in

1787.

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

of a gas is directly proportional to the absolute

temperature (= o C + 273 ) at constant pressure”.

Thus, V∝T at constant pressure and mass

or V = KT = K (t( o C) + 273 .15) , (where k is constant),

 V
=K
T

For two or more gases at constant pressure and

mass

V1 V2
=
T1 T2
= ...... K ,

 dV 
Charle's law can also be given as,   =K .
 dT  P

(3) If t = 0o C , then V = V0

hence, V0 = K × 273 .15

∴ K=
V0
273 .15

V0  t 
V= [ t + 273 .15] = V0 1 + = V0 [1 + α v t]
273 .15  273 .15 
 where αv is the volume coefficient,

V − V0 1
αv = = = 3.661 × 10 − 3 o C −1
tV0 273 .15

Thus, for every 1o change in temperature, the

1  1 
volume of a gas changes by ≈ 
273 .15  273 
of the

volume at 0o C .

(4) Graphical representation of Charle's law :

Graph between V and T at constant pressure is

called isobar or isoplestics and is always a straight

line. A plot of V versus t( oC) at constant pressure is a

straight line cutting the temperature axis at − 273 .15 o C .

It is the lowest possible temperature.

 1/d or V

1/d or V

22.4 L mol–1 = V0

O t(oC)
–273.15oC 0oC
T(k)

(5) To lower the temperature of a substance, we

reduce the thermal energy. Absolute zero (0K) is the

temperature reached when all possible thermal

energy has been removed from a substance.

Obviously, a substance cannot be cooled any further

after all thermal energy has been removed.

(6) At constant mass and pressure density of a gas is

inversely proportional to it absolute temperature.

 1 1  mass  d1 T2 V2
Thus, d∝ ∝  V = d  or = = = ...... = K
T V   d 2 T1 V1

(7) Use of hot air balloons in sports and

meteorological observations is an application of

Charle's law.

Examples based on Charle's

Example : 4 When the temperature of 23 ml of dry

CO 2 gas is changed from 10 o to 30 o C at constant

pressure of 760 mm, the volume of gas becomes

closest to which one of the following

[CPMT 1992]

(a) 7.7 ml
(b) 25.5 ml

(c) 24.6 ml

(d) 69 ml

Solution: (c)

Example : 5The volume of a gas is 100 ml at 100 o C .

If pressure remains constant then at what

temperature it will be about 200 ml

[Roorkee 1993]

(a) 200 o C

(b) 473 o C

(c) 746 o C
(d) 50 o C

V1 V 100 200
Solution: (b) T1
= 2
T2
i.e. 373 K
=
T2

T2 = 746 k = 473 o C

Example : 6

(a) 135 ml

(b) 540 ml

(c) 350 ml

(d) 280 ml

V1 V 300 V2
Solution: (d) T1
= 2
T2
i.e. =
300 K 280 K

V2 = 280 ml
Example : 7A flask containing air (open to

atmosphere) is heated from 300 K to 500 K. the

percentage of air escaped to the atmosphere is nearly

[CBSE PMT 1991]

(a) 16.6

(b) 40

(c) 66

(d) 20

Solution: (c) VT
1
=
V2
T2
i.e. V1 V
= 2
300 500
; V2 =
5
3
V = 1.66 V
1

Volume escaped = 1.66 V − V = 0.66 V = 66 % of V

Example : 8
(a) 100.0366

(b) 99.9634

(c) 103.66

(d) 100.366

Solution: (a)

V0 1
Vt = V0 + × t = 100 + × 10 = 100 + 0.0366 = 100 .0366 ml
273 273

6.5 Gay-Lussac's law (Amonton's law).

(1) In 1802, French chemist Joseph Gay-Lussac

studied the variation of pressure with temperature

and extende the Charle’s law so, this law is also

called Charle’s-Gay Lussac’s law.

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

gas is directly proportional to the absolute

temperature (= o C + 273 ) at constant volume.”

Thus, P∝T at constant volume and mass

or P = KT = K (t( o C) + 273 .15) (where K is constant)

P
=K
T

For two or more gases at constant volume and

mass

P1 P2
= = ....... = K
T1 T2

(3) If t = 0o C , then P = P0

Hence, P0 = K × 273 .15

∴ K=
P0
273 .15

P0  t 
P= [ t + 273 .15] = P0 1 +  = P0 [1 + αt]
273 .15  273 . 15 

where α is the pressure coefficient,

P

P − P0 1
αP = = = 3.661 × 10 − 3 o C −1
tP0 273 .15

Thus, for every 1o change in temperature, the

1  1 
pressure of a gas changes by ≈ 
273 .15  273 
of the

pressure at 0o C .

(4) Graphical representation of Gay-Lussac's law

: A graph between P and T at constant V is called

isochore.
 P

O
T(k)

Note :  This law fails at low temperatures,

because the volume of the gas molecules become

significant.

Examples based on Gay Lussac’s law

Example : 9 A sealed tube which can withstand a

pressure of 3 atmosphere is filled with air at 27 o C

and 760 mm pressure. The temperature above which

the tube will burst will be

(a) 900 o C

(b) 627 o C

(c) 627 o C

(d) 1173 o
C

Solution: (b) The tube will burst when the final

pressure exceeds 3 atm. at constant volume,

P1 P2 760 3 × 760
=
T1 T2
i.e. 300 K
=
T2

T2 = 900 K = 627 o C

6.6 Avogadro's law.

(1) According to this law, “Equal volumes of any

two gases at the same temperature and pressure

contain the same number of molecules.”

Thus, V∝n (at constant T and P)

or V = Kn (where K is constant)

V1 V2
or =
n1 n2
= ....... = K

Example, 2H 2 (g)+ O2 (g) → 2H 2 O(g)

2 moles 1 mole 2 moles
2 volumes 1 volume 2 volumes
2 litres 1 litre 2 litres
1 litre 1 / 2 litre 1 litre
1n litre 1 / 2n litre 1n litre

(2) One mole of any gas contains the same number

of molecules (Avogadro's number = 6.02 × 10 23 ) and by

this law must occupy the same volume at a given

temperature and pressure. The volume of one mole

of a gas is called molar volume, Vm which is 22.4 L

mol −1
at S.T.P. or N.T.P.

(3) This law can also express as, “The molar gas

volume at a given temperature and pressure is a

specific constant independent of the nature of the

gas”.

Thus, Vm = specific constant = 22 .4 L mol −1

at S.T.P. or

N.T.P.

(4) This law is widely applicable to solve the

problems of reactive gaseous system.

Note :  Loschmidt number : It is the number of

molecules present in 1 c.c. of a gas or vapour at

S.T.P. Its value is 2.687 × 10 19 per c.c.

6.7 Ideal gas equation.

(1) The simple gas laws relating gas volume to

pressure, temperature and amount of gas,

respectively, are stated below :

1 1
Boyle's law : P∝
V
or V∝
P
(n and T

constant)

Charle's law : V∝T (n and P

constant)

Avogadro's law : V∝n (T and P

constant)

If all the above law's combines, then

nT
V∝
P
 nRT
or V=
P

or PV = nRT

This is called ideal gas equation. R is called

ideal gas constant. This equation is obeyed by

isothermal and adiabatic processes.

(2) Nature and values of R : From the ideal gas

PV Pressure × Volume
equation, R= =
nT mole × Temperatur e

Force
× Volume
Area Force × Length Work or energy
= = =
mole × Temperatur e mole × Temperatur e mole × Temperatur e
.

So, R is expressed in the unit of work or energy

mol −1
K −1 .

Different values of R are summarised below :

 −1
R = 0.0821 L atm mol K −1

−1
= 8.3143 × 10 7 erg mol K −1

= 8.3143 joule mol −1

K −1 (S.I. unit)

−1
= 8.3143 Nm mol K −1

−1
= 8.3143 KPa dm 3 mol K −1

−1
= 8.3143 MPa cm 3 mol K −1

= 8.3143 × 10 −3 kJ mol −1
K −1

= 5.189 × 10 19 eV mol −1
K −1

= 1.99 cal mol −1

K −1

= 1.987 × 10 −3 K cal mol −1

K −1
Note :  Although R can be expressed in different

units, but for pressure-volume calculations, R must

be taken in the same units of pressure and volume.

(3) Gas constant, R for a single molecule is called

Boltzmann constant (k)

R 8.314 × 10 7
k= = ergs mole −1 degree −1
N 6.023 × 10 23

= 1.38 × 10 −16 ergs mol −1

degree −1 or 1.38 × 10 −23 joule mol −1
degree −1

(4) Calculation of mass, molecular weight and

density of the gas by gas equation

m  mass of the gas (m) 

PV = nRT = RT  n = 
M  Molecular weight of the gas (M ) 

∴ M = mRT
PV
 PM  m
d=  d = 
RT  V

dT M
or P
=
R

Since M and R are constant for a particular gas,

dT
Thus, P
= constant

Thus, at two different temperature and pressure

d1 T1 d 2 T2
=
P1 P2

(5) Gas densities differ from those of solids and

liquids as,

(i) Gas densities are generally stated in g/L

instead of g / cm 3 .
 (ii) Gas densities are strongly dependent on

pressure and temperature as,

d∝P

1
d∝
T

Densities of liquids and solids, do depend

somewhat on temperature, but they are far less

dependent on pressure.

(iii) The density of a gas is directly proportional to

its molar mass. No simple relationship exists

between the density and molar mass for liquid and

solids.

molar mass
(iv) Density of a gas at STP =
22 .4
 d( N 2 ) at STP = 2228.4 = 1.25 g L −1

32
d(O2 ) at STP =
22 .4
= 1.43 g L−1

Examples based on Ideal gas equation

Example : 10 The pressure of 2 moles of an ideal

gas at 546 K having volume 44.8 L is

[CPMT 1995]

(a) 2 atm

(b) 3 atm

(c) 4 atm

(d) 1 atm

Solution: (a) PV = nRT , P × 44 .8 = 2 × 0.082 × 546 P = 2 atm

Example : 11 The number of moles of H in 0.224 litre of hydrogen
2

(a) 1

(b) 0.1

(c) 0.01

(d) 0.001

Solution: (c) PV = nRT , 1 × 0.224 = n × 0.082 × 273 n = 0.01mol

Example : 12 120 g of an ideal gas of molecular weight 40 mole −1 are

(a) 4.90 atm

(b) 4.92 atm

(c) 5.02 atm

(d) 4.96 atm

 120
Solution: (b) 120 g =
40
= 3 moles

nRT 3 × 0.0821 × 400

P= = = 4.92 atm.
V 20

Example : 13 The volume of 2.8 g of carbon

monoxide at 27 o C and 0.821 atm pressure is

(R = 0.0821 lit atm K −1 mol −1

)

(a) 0.3 litre

(b) 1.5 litre

(c) 3 litre

(d) 30 litre

2.8
Solution: (c) 2.8 g CO =
28
= mol = 0.1 mol

nRT 0.1 × 0.0821 × 300

PV = nRT or V=
P
=
0.821
= 3 litre
Example: 14 3.2 g of oxygen (At. wt. = 16) and 0.2 g of hydrogen (

(a) 1 atm

(b) 4 atm

(c) 3 atm

(d) 2 atm

Solution: (b) 3.2 g O 2 = 0.1 mol , 0.2 g H 2 = 0.1 mol ,

Total n = 0.2 mol ,

nRT 0.2 × 0.082 × 273

P= = = 4 atm
V 1.12

Example : 15 The density of methane at 2.0 atmosphere pressure an

(a) 0.13 g L −1

(b) 0.26 g L −1
(c) 1.30 g L −1

(d) 2.60 g L −1

PM 2 × 16
Solution: (c) d=
RT
=
0.082 × 300
= 1.30 g L−1

Example : 16 The volume of 0.0168 mol of O2

obtained by decomposition of KClO 3 and collected by

displacement of water is 428 ml at a pressure of 754

mm Hg at 25 o C . The pressure of water vapour at 25 o C

is

[UPSEAT 1996]

(a) 18 mm Hg

(b) 20 mm Hg

(c) 22 mm Hg
(d) 24 mm Hg

Solution: (d) Volume of 0.0168 mol of O2 at

STP = 0.0168 × 22400 cc = 376 .3 cc

V1 = 376 .3 cc , P1 = 760 mm , T1 = 273 K

V2 = 428 cc , P2 = ? , T2 = 298 K

P1 V1 PV
T1
= 2 2
T2
gives P2 = 730 mm (approx.)

∴ Pressure of water vapour = 754 − 730 = 24 mm

Hg

6.8 Dalton's law of partial pressures.

(1) According to this law, “When two or more gases,

which do not react chemically are kept in a closed

vessel, the total pressure exerted by the mixture is

equal to the sum of the partial pressures of

individual gases.”

Thus, Ptotal = P1 + P2 + P3 + .........

Where P1 , P2 , P3 ,...... are partial pressures of gas

number 1, 2, 3 .........

(2) Partial pressure is the pressure exerted by a gas

when it is present alone in the same container and at

the same temperature.

Partial pressure of a gas

Number of moles of the gas (n1 ) × PTotal
(P1 ) = = Mole fraction ( X 1 ) × PTotal
Total number of moles (n) in the mixture
(3) If a number of gases having volume V1 , V2 , V3 ...... at

pressure P1 , P2 , P3 ........ are mixed together in container

of volume V, then,

P1 V1 + P2 V2 + P3 V3 .....
PTotal =
V

RT RT
or = (n1 + n2 + n3 .....)
V
( PV = nRT ) or =n
V

( n = n1 + n2 + n3 .....)

(4) Applications : This law is used in the

calculation of following relationships,

(i) Mole fraction of a gas (X1 ) in a mixture of gas

Partial pr essure of a gas (P1 )

=
PTotal
 (ii) % of a gas in

mixture = Partial pr essure

P
of a gas (P )
× 1001

Total

(iii) Pressure of dry gas collected over water :

When a gas is collected over water, it becomes

moist due to water vapour which exerts its own

partial pressure at the same temperature of the gas.

This partial perssure of water vapours is called

aqueous tension. Thus,

Pdry gas = Pmoist gas or PTotal − Pwater vapo ur

or Pdry gas = Pmoist gas − Aqueous tension (Aqueous

tension is directly proportional to absolute temperature)

 (iv) Relative humidity (RH) at a given

temperature is given by :

Partial pr essure of water in air

RH =
Vapour pre ssure of water
.

(5) Limitations : This law is applicable only when

the component gases in the mixture do not react with

each other. For example, N2 and O2 , CO and CO 2 , N2

and Cl 2 , CO and N2 etc. But this law is not applicable

to gases which combine chemically. For example,

H2 and Cl 2 , CO and Cl 2 , NH 3 , HBr and HCl, NO and

O2 etc.

Note :  N2 (80%) has the highest partial pressure

in atmosphere.
(6) Another law, which is really equivalent to the

law of partial pressures and related to the partial

volumes of gases is known as Law of partial

volumes given by Amagat. According to this law,

“When two or more gases, which do not react

chemically are kept in a closed vessel, the total

volume exerted by the mixture is equal to the sum of

the partial volumes of individual gases.”

Thus, VTotal = V1 + V2 + V3 + ......

Where V1 , V2 , V3 ,...... are partial volumes of gas

number 1, 2, 3.....

Examples based on Dalton's law of partial

Example: 17 What will be the partial pressure of H2 in a flask contai

(a) 1/2 the total pressure

(b) 1/3 the total pressure

(c) 1/4 the total pressure

(d) 1/16 the total pressure

2 14
Solution: (a) n (H 2 ) =
2
= 1, n ( N 2 ) =
28
= 0.5 ,

16 1 1
n (O 2 ) = = 0.5, p(H 2 ) = p= p
32 1 + 0.5 + 0.5 2

Example : 18 Equal weights of methane and oxygen are mixed in an

(a) 1/3

(b) 1/2

(c) 2/3
(d) 1 / 3 × 273 / 298

w w
Solution: (a) n (CH 4 ) =
16
= 1, n(O 2 ) =
32

w / 32 1 1
p(O 2 ) = = =
w / 16 + w / 32 2 + 1 3

Example : 19 In a flask of volume V litres, 0.2 mol of oxygen, 0

atmosphere, the partial pressure exerted by nitrogen

is

[Kerala MEE 2001]

(a) 1 atm

(b) 0.1 atm

(c) 0.2 atm

(d) 0.4 atm

Solution: (d)
0.4
PN 2 = Mol. fraction of N 2 × Total pers sure =
0.2 + 0.4 + 0.1 + 0.3
× 1 atm = 0.4 atm .

Example : 20 Equal weights of ethane and hydrogen are mixed in an

(a) 1 : 2

(b) 1 : 1

(c) 1 : 16

(d) 15 : 16

w w
Solution: (d) n (C 2 H 6 ) =
30
, n (H 2 ) =
2

w/2 1 15
p(H 2 ) = = =
w / 2 + w / 30 1 16
1+
15

Example : 21 A gaseous mixture contains 56 g of N2 , 44 g of CO 2 an

(a) 180 mm
(b) 360 mm

(c) 540 mm

(d) 720 mm

Solution: (a)

16 / 16 1 1
p(CH 4 ) =
5 / 28 + 44 / 44 + 16 / 16
× 720 =
2+1+1
× 720 = × 720 = 180 mm
4
.

6.9 Graham's law of diffusion and effusion.

(1) Diffusion is the process of spontaneous

spreading and intermixing of gases to form

homogenous mixture irrespective of force of gravity.

While Effusion is the escape of gas molecules

through a tiny hole such as pinhole in a balloon.

• All gases spontaneously diffuse into one another

when they are brought into contact.

• Diffusion into a vacuum will take place much

more rapidly than diffusion into another place.

• Both the rate of diffusion of a gas and its rate of

effusion depend on its molar mass. Lighter gases

diffuses faster than heavier gases. The gas with

highest rate of diffusion is hydrogen.

(2) According to this law, “At constant pressure and

temperature, the rate of diffusion or effusion of a gas

is inversely proportional to the square root of its

vapour density.”
 1
Thus, rate of diffusion (r ) ∝ (T and P constant)
d

For two or more gases at constant pressure and

temperature,

r1 d2
=
r2 d1

Note :  Always remember that vapour density is

different from absolute density. The farmer is

independent of temperature and has no unit while

the latter depends upon temperature and expressed

in gm −1 .

(3) Graham's law can be modified in a number of

ways as,
 (i) Since, 2 × vapour density (V.D.) = Molecular

weight

r1 d2 d2 × 2 M2
then, r2
=
d1
=
d1 × 2
=
M1

where, M1 and M2 are the molecular weights of the

two gases.

Volume of a gas diffused

(ii) Since, rate of diffusion (r ) =
Time taken for diffusion

r1 V /t d2
then, = 1 1 =
r2 V2 / t 2 d1

(a) When equal volume of the two gases diffuse, i.e.

V1 = V2

r1 t 2 d2
then, =
r2 t 1
=
d1
 (b) When volumes of the two gases diffuse in

the same time , i.e. t1 = t 2

r1 V1 d2
then, =
r2 V2
=
d1

(iii) Since, r∝p (when p is not constant)

r1 P M2  1 
then, = 1 =  r ∝ 
r2 P2 M1  M

Note :  It should be noted that this law is true only

for gases diffusing under low pressure gradient.

 CO 2 > SO 2 > SO 3 > PCl 3 is order of rates of diffusion.

(4) Rate of diffusion and effusion can be determined

as,
 (i) Rate of diffusion is equal to distance travelled

by gas per unit time through a tube of uniform cross-

section.

(ii) Number of moles effusing per unit time is

also called rate of diffusion.

(iii) Decrease in pressure of a cylinder per unit

time is called rate of effusion of gas.

(iv) The volume of gas effused through a given

surface per unit time is also called rate of effusion.

(5) Applications : Graham's law has been used as

follows :
 (i) To determine vapour densities and molecular

weights of gases.

(ii) To prepare Ausell’s marsh gas indicator,

used in mines.

(iii) Atmolysis : The process of separation of

two gases on the basis of their different rates of

diffusion due to difference in their densities is called

atmolysis. It has been applied with success for the

separation of isotopes and other gaseous mixtures.

Example, this process was used for the large-scale

separation of gaseous 235

UF6 and 238
UF6 during the

second world war.

Examples based on Grahm's law of

Example : 22 The time taken for a certain volume

of a gas ‘X’ to diffuse through a small hole is 2

minutes. It takes 5.65 minutes for oxygen to diffuse

under the similar conditions. The molecular weight

of ‘X’ is

[NCERT 1990]

(a) 8

(b) 4

(c) 16

(d) 32

rX M O2
Solution: (b) rO2
=
MX
 v/2 32 5.65 32
= , = ,MX = 4
v / 5.65 MX 2 MX

Example : 23 The rate of diffusion of methane at a given temperatu

(a) 64.0

(b) 32.0

(c) 4.0

(d) 8.0

rCH 4 MX MX
Solution: (a) rX
=
M CH 4
⇒ 2=
16
⇒ M X = 64 .

Example : 24 Density ratio of O2 and H is 16 : 1. The ratio of their r

2

(a) 4 : 1

(b) 1 : 16

(c) 1 : 4
(d) 16 : 1

r1 v d2 1
Solution: (c) = 1 =
r2 v 2 d1
=
16
=1: 4 .

Example : 25 The rate of diffusion of a gas having molecular weigh

(a) 79.19 ml s −1

(b) 112.0 ml s −1

(c) 56 ml s −1

(d) 90.0 ml s −1

rX M N2 28 1 56 1
Solution: (a) rN2
=
MX
=
56
=
2
; rN2
= or
2

r N 2 = 56 2 = 79 .19 ms −1

Example : 26 50 ml of gas A diffuse through a membrane in the sam

(a) 100
(b) 250

(c) 200

(d) 80

r1 M2 50 / t M2
Solution: (a) r2
=
M1
⇒
40 / t
=
64

50 M2 M2 25 M 2
40
=
64
or 45 = 64
or 16
=
64
or M 2 = 100

6.10 Barometric distribution law.

(1) For gaseous systems, gravitational force is

negligible but this is not true for the gases of high

molecular masses such as polymer. In this case, the

pressure will be different in vertical positions in a

container. The variation of pressure with altitude is

given by the so-called Barometric formula.

P = P o e − Mgh / RT

where, Po and P are the pressure of the gas at the

ground level and at a height 'h' from the ground

respectively.

M is molecular mass of the gas, g is acceleration

due to gravity, R is gas constant and T is temperature

in kelvin.

(2) Since number of moles of gas 'n' and density of

the gas 'd' are directly proportional to pressure hence

the above equation may be expressed as,

d = d o e − Mgh / RT and n = n o e − Mgh / RT .

(3) The above equations may be expressed as,

P d n 1 Mgh
log o
= log o = log o = − ×
P d n 2.303 RT

6.11 Kinetic theory of gases.

(1) Kinetic theory was developed by Bernoulli,

Joule, Clausius, Maxwell and Boltzmann etc. and

represents dynamic particle or microscopic model

for different gases since it throws light on the

behaviour of the particles (atoms and molecules)

which constitute the gases and cannot be seen.

Properties of gases which we studied earlier are part

of macroscopic model.

(2) Postulates

(i) Every gas consists of a large number of small

particles called molecules moving with very high

velocities in all possible directions.

(ii) The volume of the individual molecule is

negligible as compared to the total volume of the

gas.

(iii) Gaseous molecules are perfectly elastic so

that there is no net loss of kinetic energy due to their

collisions.
 (iv) The effect of gravity on the motion of the

molecules is negligible.

(v) Gaseous molecules are considered as point

masses because they do not posses potential energy.

So the attractive and repulsive forces between the

gas molecules are negligible.

(vi) The pressure of a gas is due to the

continuous bombardment on the walls of the

containing vessel.

(vii) At constant temperature the average K.E. of

all gases is same.

 (viii) The average K.E. of the gas molecules is

directly proportional to the absolute temperature.

(3) Kinetic gas equation : On the basis of above

postulates, the following gas equation was derived,

1
PV = 2
mnu rms
3

where, P = pressure exerted by the gas, V =

volume of the gas, m = average mass of each

molecule,

n = number of molecules, u = root mean

square (RMS) velocity of the gas.

(4) Calculation of kinetic energy

We know that,
 K.E. of one molecule = 12 mu 2

1 3
K.E. of n molecules =
2
mnu 2 = PV
2

1
( PV = mnu 2 )
3

3
n = 1, Then K.E. of 1 mole gas =
2
RT

( PV = RT )

3
=
2
× 8.314 × T = 12 .47 T Joules .

Average K.E. per mole 3 RT 3  R 

= = = KT  K = = Boltzmann constant 
N(Avogadro number ) 2 N 2  N 

This equation shows that K.E. of translation of a

gas depends only on the absolute temperature. This

is known as Maxwell generalisation. Thus average

K.E. ∝ T.

If T = 0K (i.e., − 273 .15 o C) then, average K.E. = 0.

Thus, absolute zero (0K) is the temperature at which

molecular motion ceases.

(5) Kinetic gas equation can be used to establish gas

laws.

Examples based on Kinetic molecular theory of gases

Example : 27 The kinetic energy for 14 grams of

nitrogen gas at 127 o C is nearly (mol. mass of nitrogen

= 28 and gas constant = 8.31 JK −1

mol −1
)

[CBSE PMT 1999]

(a) 1.0 J

(b) 4.15 J

(c) 2493 J

(d) 3.3 J

Solution: (c) K.E. = 32 RT mol −1

or K.E. = 32 nRT = 32 × 14
28
× 8.31 × 400 J = 2493 J

6.12 Molecular collisions.

(1) The closest distance between the centres of two

molecules taking part in a collision is called

molecular or collision diameter (σ). The molecular

diameter of all the gases is nearly same lying in the

order of 10 −8
cm .
 σ
Molecular diameter

(2) The number of collisions taking place in unit

time per unit volume, called collision frequency (z).

(i) The number of collision made by a single

molecule with other molecules per unit time are

given by,

Z A = 2πσ 2uav. n

where n is the number of molecules per unit

molar volume,

Avogadro number( N 0 ) 6.02 × 10 23 − 3

n= = m
Vm 0.0224
 (ii) The total number of bimolecular collision

per unit time are given by,

1
Z AA = πσ 2uav . n 2
2

(iii) If the collisions involve two unlike

molecules, the number of bimolecular collision are

given by,

1/ 2
 (M A + M B ) 
Z AB = σ 2
AB 8πRT 
 M AM B 

σ A +σB
where, σ AB =
2
and MA , MB are molecular

weights (M = mN 0 )

(iv) (a) At particular temperature; Z ∝ p2

(b) At particular pressure; Z ∝ T −3 / 2

 (c) At particular volume; Z ∝ T1/ 2

(3) During molecular collisions a molecule covers a

small distance before it gets deflected. The average

distance travelled by the gas molecules between two

successive collision is called mean free path (λ).

Average distance travelled per unit time( u av ) u av 1

λ= = =
No. of collisions made by single molecule per unit time (Z A ) 2πσ u avr. n
2
2πnσ 2

(4) Based on kinetic theory of gases mean free path,

T
λ∝
P
. Thus,

(i) Larger the size of the molecules, smaller the

1
mean free path, i.e., λ∝
(radius) 2
 (ii) Greater the number of molecules per unit

volume, smaller the mean free path.

(iii) Larger the temperature, larger the mean free

path.

(iv) Larger the pressure, smaller the mean free

path.

(5) Relation between collision frequency (Z) and

mean free path (λ) is given by,

urms
Z=
λ

6.13 Molecular speeds or velocities.

(1) At any particular time, in the given sample of gas

all the molecules do not possess same speed, due to

the frequent molecular collisions with the walls of

the container and also with one another, the

molecules move with ever changing speeds and also

with ever changing direction of motion.

(2) According to Maxwell, at a particular

temperature the distribution of speeds remains

constant and this distribution is referred to as the

Maxwell-Boltzmann distribution and given by the

following expression,

3/2
dn 0  M 
= 4π  .e − Mu
2

/ 2 RT
.u 2 dc
n  2πRT 

where, dn 0 = Number of molecules out of total

number of molecules n, having velocities between c

and c + dc , dn 0 / n = Fraction of the total number of

molecules, M = molecular weight, T = absolute

temperature. The exponential factor e − Mu

2
/ 2 RT
is called

Boltzmann factor.

(3) Maxwell gave distribution curves of molecular

speeds for CO 2 at different temperatures. Special

features of the curve are :

Ump

300 K (T1) T1<T2<T3

Ump
Uav
Fraction of molecules

Urms
Ump

1500 K (T2) 1800 K (T3)

Molecular speed

(i) Fraction of molecules with two high or two low

speeds is very small.

(ii) No molecules has zero velocity.

(iii) Initially the fraction of molecules increases in

velocity till the peak of the curve which pertains to

most probable velocity and thereafter it falls with

increase in velocity.

(4) Types of molecular speeds or Velocities :

(i) Root mean square velocity (urms) : It is the

square root of the mean of the squares of the

velocity of a large number of molecules of the same

gas.

u12 + u 22 + u 32 + ..... un2

urms =
n

3 PV 3 RT 3 RT 3kT 3P
urms = = = = =
(mN 0 ) = M (mN 0 ) = M M m d
 R
where k = Boltzmann constant =
N0

(a) For the same gas at two different

temperatures, the ratio of RMS velocities will be,

u1 T1
=
u2 T2

(b) For two different gases at the same temperature,

u1 M2
the ratio of RMS velocities will be, u2
=
M1

(c) RMS velocity at any temperature toC may

3 P(273 + t)
be related to its value at S.T.P. as, ut =
273 d
.

Note :  RMS velocity explained the non-existence

of gases in the atmosphere of moon.

 When temperature alone is given then,

T
urms = 1.58 × × 10 4 cm / sec .
M

 If P and T both are given, use equation in terms

3 RT 3 PV
of temperature, i.e., use urms =
M
and not M

(ii) Average velocity (vav ) : It is the average of

the various velocities possessed by the molecules.

v1 + v 2 + v 3 + ...... vn
vav =
n

8 RT 8kT
vav = =
πM πm

(iii) Most probable velocity (α mp ) : It is the

velocity possessed by maximum number of

molecules of a gas at a given temperature.

 2RT 2PV 2P
α mp = = =
M M d

(5) Relation between molecular speeds or

velocities,

(i) Relation between urms and vav : vav = 0.9213 × urms or

urms = 1.085 × vav

(ii) Relation between α mp and urms : α mp = 0.816 × urms

or urms = 1.224 × α mp

(iii) Relation between α mp and vav : vav = 1.128 × α mp

(iv) Relation between α mp , vav and urms :

α mp : vav :u rms

2RT 8 RT 3 RT
M
: πM
: M
 8
2 : π
: 3

1.414 : 1.595 : 1.732

1 : 1.128 : 1.224 i.e., α mp < vav < urms

Examples based on molecular speeds

Example : 28 The rms velocity of CO 2 at a temperature T (in kelvin)

velocity of nitrous oxide would be 4x

(a)16 T

(b)2 T

(c)4 T

(d)32 T

3 RT
Solution: (a) u=
M
∴ u CO 2
u N 2O
=
TCO 2
M CO 2
×
M N 2O
TN 2 O

x T 44 1 T
i.e., 4x
= ×
44 TN 2O
or 4
=
TN 2 O
or TN 2O = 16 T

Example : 29 The rms velocity of an ideal gas at 27 o C is 0.3 ms −1 . Its

(a)3.0

(b)2.4

(c)0.9

(d)0.6

3 RT
Solution: (d) u=
M

For the same gas at two different temperatures,

 u1 T1 0.3 300 1
u2
=
T2
; u2
=
1200
=
2
, u2 = 0.6 ms −1

Example : 30 The rms velocity of hydrogen is 7

times the rms velocity of nitrogen. If T is the

temperature of the gas

[IIT 2000]

(a) T(H 2) = T( N 2 )

(b) T(H 2) > T( N 2 )

(c) T(H 2) < T( N 2 )

(d) T(H 2) = 7 T( N 2 )

Solution: (c) u=
3 RT
M
; ∴ u (H 2 )
u (N 2 )
=
T (H 2 ) M ( N 2 )
×
M (H 2 ) T ( N 2 )
or

T(H 2 ) 28 T(H 2 ) T(H 2 ) 1

7 = ×
T( N 2 ) 2
or 7=
T( N 2 )
× 14 or =
T( N 2 ) 2
or T ( N 2 ) = 2 × T (H 2 ) i.e., T ( N 2 ) > T (H 2 )

Example : 31 If the average velocity of N2 molecules is 0.3 m/s at 27

(a)273 K

(b)927 K

(c)1000 K

(d)1200 K

Solution: (d) v = 0.921 u

∴ v1 u
= 1 =
v2 u2
T1
T2

∴ 0.3
0.6
=
300
T2
or 1
2
=
300
T2
or T2 = 300 × 4 = 1200 K

Example : 32 The temperature of an ideal gas is reduced from 927 o C

(a)Double the initial value

(b)Half of the initial value

(c)Four times the initial value

(d)Ten times the initial value

3 RT
Solution: (b) u=
M

∴ u1
u2
=
T1
T2
=
927 + 273
27 + 273
=
1200
300
= 4 =2

∴u 2 =
1
2
u1

6.14 Real and ideal gases.

(1) Gases which obey gas laws or ideal gas equation

(PV = nRT ) at all temperatures and pressures are called

ideal or perfect gases. Almost all gases deviate from

the ideal behaviour i.e., no gas is perfect and the

concept of perfect gas is only theoretical.

(2) Gases tend to show ideal behaviour more and

more as the temperature rises above the boiling

point of their liquefied forms and the pressure is

lowered. Such gases are known as real or non ideal

gases. Thus, a “real gas is that which obeys the gas

laws under low pressure or high temperature”.

(3) The deviations can be displayed, by plotting the

P-V isotherms of real gas and ideal gas.

 real gas

p
ideal gas

V
Plot of pressure against volume for
ideal and real gases

(4) It is difficult to determine quantitatively the

deviation of a real gas from ideal gas behaviour

from the P-V isotherm curve as shown above.

Compressibility factor Z defined by the equation,

PV = ZnRT or Z = PV / nRT = PVm / RT

is more suitable for a quantitative description of

the deviation from ideal gas behaviour.

(5) Greater is the departure of Z from unity, more is

the deviation from ideal behaviour. Thus, when

(i) Z =1 , the gas is ideal at all temperatures and

pressures. In case of N2 , the value of Z is close to 1

at 50 o C . This temperature at which a real gas exhibits

ideal behaviour, for considerable range of pressure,

is known as Boyle's temperature or Boyle's point

(TB ) .

(ii) Z >1 , the gas is less compressible than expected

from ideal behaviour and shows positive deviation,

usual at high P i.e. PV > RT .

(iii) Z<1 , the gas is more compressible than

expected from ideal behaviour and shows negative

deviation, usually at low P i.e. PV < RT .

(iv) Z >1 for H2 and He at all pressure i.e., always

shows positive deviation.

(v) The most easily liquefiable and highly soluble

gases ( NH 3 , SO 2 ) show larger deviations from ideal

behaviour i.e. Z << 1 .

(vi) Some gases like CO 2 show both negative and

positive deviation.

(6) Causes of deviations of real gases from ideal

behaviour : The ideal gas laws can be derived from

the kinetic theory of gases which is based on the

following two important assumptions,

(i) The volume occupied by the molecules is

negligible in comparison to the total volume of gas.

(ii) The molecules exert no forces of attraction upon

one another. It is because neither of these

assumptions can be regarded as applicable to real

gases that the latter show departure from the ideal

behaviour.

6.15 Vander Waal's equation.

(1) To rectify the errors caused by ignoring the

intermolecular forces of attraction and the volume

occupied by molecules, Vander Waal (in 1873)

modified the ideal gas equation by introducing two

corrections,
 (i) Volume correction

(ii) Pressure correction

(2) Vander Waal's equation is obeyed by the real

gases over wide range of temperatures and

pressures, hence it is called equation of state for the

real gases.

(3) The Vander Waal's equation for n moles of the

gas is,

 2 
P + a
n
[ V − nb] = nRT
 V 2 
 Volume correction for
Pressure correction finite size of molecules
for molecular attraction
 a and b are Vander Waal's constants whose values

depend on the nature of the gas. Normally for a gas

a >> b .

(i) Constant a : It is a indirect measure of

magnitude of attractive forces between the

molecules. Greater is the value of a, more easily the

gas can be liquefied. Thus the easily liquefiable

gases (like SO 2 > NH 3 > H 2 S > CO 2 ) have high values than

the permanent gases (like N 2 > O2 > H 2 > He) .

Units of 'a' are : atm. L 2

mol −2
or atm. m mol
6 −2
or

N m 4 mol −2
(S.I. unit).
 (ii) Constant b : Also called co-volume or

excluded volume,

 4 
b = 4 N 0 v = πr 3 
 3 

It's value gives an idea about the effective size

of gas molecules. Greater is the value of b, larger is

the size and smaller is the compressible volume. As

b is the effective volume of the gas molecules, the

constant value of b for any gas over a wide range of

temperature and pressure indicates that the gas

molecules are incompressible.

Units of 'b' are : L mol −1

or m 3 mol −1
(S.I. unit)

(iii) Vander Waal's constant for some gases are,

Name of a b

gas
atm litre2mol −2 Nm 4mol −2 litre mol −1
m3mol −1

Hydrogen 0.245 0.0266 0.0266 0.0266

Oxygen 1.360 0.1378 0.0318 0.0318

Nitrogen 1.390 0.1408 0.039 0.0391

Chlorine 6.493 0.6577 0.0562 0.0562

Carbon 3.590 0.3637 0.0428 0.0428

dioxide

Ammonia 4.170 0.4210 0.0371 0.0371

Sulphur 6.170 0.678 0.0564 0.0564

dioxide

Methane 2.253 0.0428

(iv) The two Vander Waal's constants and Boyle's

a
temperature (TB ) are related as, TB =
bR

(4) Vander Waal's equation at different

temperature and pressures :

(i) When pressure is extremely low : For one

mole of gas,

 a  a ab
 P + 2  (V − b) = RT or PV = RT − + Pb + 2
 V  V V
 (ii) When pressure is extremely high : For

one mole of gas,

PV Pb Pb
PV = RT + Pb ; RT
= 1+
RT
or Z = 1+
RT

where Z is compressibility factor.

(iii) When temperature is extremely high :

For one mole of gas,

PV = RT .

(iv) When pressure is low : For one mole of

gas,

 a  a ab
 P + 2  (V − b) = RT or PV = RT + Pb − + or
 V  V V2

PV a a
RT
= 1−
VRT
or Z = 1−
VRT
 (v) For hydrogen : Molecular mass of

hydrogen is small hence value of 'a' will be small

owing to smaller intermolecular force. Thus the

a ab
terms and may be ignored. Then Vander
V V2

Waal's equation becomes,

PV Pb Pb
PV = RT + Pb or RT
= 1+
RT
or Z = 1+
RT

In case of hydrogen, compressibility factor is

always greater than one.

(5) Merits of Vander Waal's equation :

(i) The Vander Waal's equation holds good for

real gases upto moderately high pressures.

 (ii) The equation represents the trend of the

isotherms representing the variation of PV with P

for various gases.

(iii) From the Vander Waal's equation it is

possible to obtain expressions of Boyle's

temperature, critical constants and inversion

temperature in terms of the Vander Waal's constants

'a' and 'b'.

(iv) Vander Waal's equation is useful in

obtaining a 'reduced equation of state' which being a

general equation of state has the advantage that a

single curve can be obtained for all gases when the

equation if graphically represented by plotting the

variables.

(6) Limitations of Vander Waal's equation :

(i) This equation shows appreciable deviations at

too low temperatures or too high pressures.

(ii) The values of Vander Waal's constants a

and b do not remain constant over the entire ranges

of T and P, hence this equation is valid only over

specific range of T and P.

(7) Other equations of state : In addition to Vander

Waal's equation, there are also equations of state

which have been used to explain real behaviour of

gases are,
  a 
(i) Clausius equation : P + 2
(V − b) = RT . Here
 T(V + c) 

'c' is another constant besides a, b and R.

 a 
(ii) Berthelot equation : P +  (V − b) = RT .
 TV 2 

RT a c
(iii) Wohl equation : P= − +
(V − b) V(V − b) V 2

RT
(iv) Dieterici equation : P=
V −b
.e −a / RTV . The

expression is derived on the basis of the concept that

molecules near the wall will have higher potential

energy than those in the bulk.

(v) Kammerlingh Onnes equation : It is the

most general or satisfactory expression as equation

expresses PV as a power series of P at a given

temperature.

PV = A + BP + CP 2 + DP 3 + ......

Here coefficients A, B, C etc. are known as first,

second and third etc. virial coefficients.

(a) Virial coefficients are different for different

gases.

(b) At very low pressure, first virial coefficient,

A = RT.

(c) At high pressure, other virial coefficients

also become important and must be considered.

6.16 The critical state.

(1) A state for every substance at which the vapour

and liquid states are indistinguishable is known as

critical state. It is defined by critical temperature and

critical pressure.

(2) Critical temperature (Tc) of a gas is that

temperature above which the gas cannot be liquified

however large pressure is applied. It is given by,

8a
Tc =
27 Rb

(3) Critical pressure (Pc) is the minimum pressure

which must be applied to a gas to liquify it at its

a
critical temperature. It is given by, Pc =
27b 2
(4) Critical volume (Vc) is the volume occupied by

one mole of the substance at its critical temperature

and critical pressure. It is given by, Vc = 3b

(5) Critical compressibility factor (Zc) is given by,

Pc Vc 3
Zc = = = 0.375
RTc 8

A gas behaves as a Vander Waal’s gas if its

critical compressibility factor ( Zc ) is equal to 0.375.

Note :  A substance in the gaseous state below Tc

is called vapour and above Tc is called gas.

6.17 The principle of corresponding states.

(1) In 1881, Vander Waal’s demonstrated that if the

pressure, volume and temperature of a gas are

expressed in terms of its Pc , Vc and Tc , then an

important generalization called the principle of

corresponding states would be obtained.

(2) According to this principle, “If two substances

are at the same reduced temperature (θ) and pressure

(π) they must have the same reduced volume (φ),”

 3 
i.e. π +  (3φ − 1) = 8θ
 φ 2 


where, φ = V / V or c V = φVc ; π = P / Pc or P = πPc ; θ = T /T

c

or T = θTc
 This equation is also called Vander Waal's

reduced equation of state. This equation is

applicable to all substances (liquid or gaseous)

irrespective of their nature, because it is not

involving neither of the characteristic constants.

(3) This principle has a great significance in the

study of the relationship between physical properties

and chemical constitution of various liquids.

6.18 Degrees of freedom of a gaseous molecule.

(1) The motion of atoms and molecules is generally

described in terms of the degree of freedom which

they possess.
(2) The degrees of freedom of a molecule are

defined as the independent number of parameters

required to describe the state of the molecule

completely.

(3) When a gaseous molecule is heated, the energy

supplied to it may bring about three kinds of motion

in it, these are,

(i) The translational motion

(ii) The rotational motion

(iii) The vibrational motion.

 This is expressed by saying that the molecule

possesses translational, rotational and vibrational

degrees of freedom.

(4) For a molecule made up of N atoms, total

degrees of freedom = 3N. Further split up of these is

as follows :

Translational Rotational Vibrational

For linear molecule :32 3N – 5

For non-linear molecule :3 3 3N – 6

6.19 Specific and Molar heat capacity of Gases.

(1) Specific heat (or specific heat capacity) of a

substance is the quantity of heat (in calories, joules,

kcal, or kilo joules) required to raise the temperature

of 1g of that substance through 1o C . It can be

measured at constant pressure (c p ) and at constant

volume (cv ) .

(2) Molar heat capacity of a substance is the

quantity of heat required to raise the temperature of

1 mole of the substance by 1o C .

∴ Molar heat capacity = Specific heat capacity ×

Molecular weight, i.e.,

Cv = cv × M and Cp = cp × M .

(3) Since gases upon heating show considerable

tendency towards expansion if heated under constant

pressure conditions, an additional energy has to be

supplied for raising its temperature by 1o C relative to

that required under constant volume conditions, i.e.,

C p > Cv or C p = Cv + Work done on expanson, P∆V(= R)

where, Cp = molar heat capacity at constant

pressure; Cv = molar heat capacity at constant

volume.

Note :  C p and Cv for solids and liquids are

practically equal. However, they differ considerable

in case of gas because appreciable change in volume

takes place with temperature.

(4) Some useful relations of Cp and Cv

 (i) C p − Cv = R = 2 calories = 8.314 J

3 3
(ii) Cv =
2
R (for monoatomic gas) and Cv =
2
+x (for

di and polyatomic gas), where x varies from gas to gas.

Cp
(iii) Cv
=γ (Ratio of molar capacities)

(iv) For monoatomic gas Cv = 3 calories whereas,

C p = Cv + R = 5calories

5
Cp R
(v) For monoatomic gas, (γ ) = = 2 = 1.66 .
Cv 3
R
2

7
Cp R
(vi) For diatomic gas (γ ) = = 2 = 1.40
Cv 5
R
2

Cp 8R
(vii) For triatomic gas (γ ) =
Cv
=
6R
= 1.33
 Values of Molar heat capacities of some gases,

Gas Cp Cv Cp– Cv Cp/Cv= γ Atomici

ty

He 5 3.01 1.99 1.661 1

N2 6.95 4.96 1.99 1.4 2

O2 6.82 4.83 1.99 1.4 2

CO 2 8.75 6.71 2.04 1.30 3

H 2S 8.62 6.53 2.09 1.32 3

6.20 Liquefaction of gases.

(1) A gas may be liquefied by cooling or by the

application of high pressure or by the combined

effect of both. The first successful attempt for

liquefying gases was made by Faraday (1823).

(2) Gases for which the intermolecular forces of

attraction are small such as H2 , N2 , Ar and O2 , have

low values of Tc and cannot be liquefied by the

application of pressure are known as “permanent

gases” while the gases for which the intermolecular

forces of attraction are large, such as polar

molecules NH 3 , SO 2 and H 2O have high values of Tc

and can be liquefied easily.

(3) Methods of liquefaction of gases : The modern

methods of cooling the gas to or below their Tc and

hence of liquefaction of gases are done by Linde's

method and Claude's method.

(i) Linde's method : This process is based upon

Joule-Thomson effect which states that “When a

gas is allowed to expend adiabatically from a region

of high pressure to a region of extremely low

pressure, it is accompained by cooling.”

(ii) Claude's method : This process is based

upon the principle that when a gas expands

adiabatically against an external pressure (as a

piston in an engine), it does some external work.

Since work is done by the molecules at the cost of

their kinetic energy, the temperature of the gas falls

causing cooling.

(iii) By adiabatic demagnetisation.

(4) Uses of liquefied gases : Liquefied and gases

compressed under a high pressure are of great

importance in industries.

(i) Liquid ammonia and liquid sulphur dioxide

are used as refrigerants.

(ii) Liquid carbon dioxide finds use in soda

fountains.

(iii) Liquid chlorine is used for bleaching and

disinfectant purposes.
 (iv) Liquid air is an important source of oxygen

in rockets and jet-propelled planes and bombs.

(v) Compressed oxygen is used for welding

purposes.

(vi) Compressed helium is used in airships.

(5) Joule-Thomson effect : When a real gas is

allowed to expand adiabatically through a porous

plug or a fine hole into a region of low pressure, it is

accompanied by cooling (except for hydrogen and

helium which get warmed up).

Cooling takes place because some work is done

to overcome the intermolecular forces of attraction.

As a result, the internal energy decreases and so

does the temperature.

Ideal gases do not show any cooling or heating

because there are no intermolecular forces of

attraction i.e., they do not show Joule-Thomson

effect.

During Joule-Thomson effect, enthalpy of the

system remains constant.

Joule-Thomson coefficient. µ = (∂T / ∂P) H . For

cooling, µ = +ve (because dT and dP will be − ve ) for

heating µ = −ve (because dT = +ve, dP = −ve) . For no heating

or cooling µ =0 (because dT = 0) .
(6) Inversion temperature : It is the temperature at

which gas shows neither cooling effect nor heating

effect i.e., Joule-Thomson coefficient µ =0. Below

this temperature, it shows cooling effect and above

this temperature, it shows heating effect.

Any gas like H 2 , He etc, whose inversion

temperature is low would show heating effect at

room temperature. However, if these gases are just

cooled below inversion temperature and then

subjected to Joule-Thomson effect, they will also

undergo cooling.
 “The branch of chemistry which deals with the

study of composition of atomic nucleus and the

nuclear trans- formations”

The discussion of nuclear science with special

emphasis on its chemical aspects is termed Nuclear

chemistry. It has become a very important and

fascinating branch of science due to the tremendous

amount of energy liberated during nuclear reaction,

which led to the discovery of atom bomb, hydrogen

bomb, etc. The controlled release of nuclear energy

promises to lead us into a new era, in which an

unlimited storehouse of energy is available to man.

It is rightly said that we are now living in the nuclear

age and the future of humanity is at the mercy of the

nuclear scientists. They can annihilate the whole

world within a few minutes. They are the hope of

human happiness and prosperity as well. In this

chapter we shall deal broadly with the various

aspects of nuclear chemistry

7.1 Nucleus.
 Nucleus is found to be a source of tremendous

amount of energy, which has been utilised for the

destructive as well as constructive purposes. Hence

the study of nucleus of an atom has become so

important that it is given a separate branch of

chemistry under the heading of nuclear chemistry.

According to an earlier hypothesis, the nucleus is

considered as being composed of two building

blocks, proton's and neutron's, which are

collectively called nucleons.

(1) Nuclear forces : Since the radius of

nucleus is very small ≈ 10 −15 m, two protons lying in

the nucleus are found to repel each other with an

electrostatic force of about 6 tonnes. The forces,

which hold the nucleons together means stronger

proton – proton, neutron – neutron and even proton

– neutron attractive forces, exist in the nucleus.

These attractive forces are called nuclear forces.

Unlike electrostatic forces which operate over long

ranges, but the nuclear forces operate only within

small distance of about 1 × 10 −15 m or 1 fermi (1 fermi =

10 −13 cm ) and drops rapidly to zero at a distance of

1 × 10 −13 cm. Hence these are referred to as short range

forces. Nuclear forces are nearly 10 21 times stronger

than electrostatic forces.

 (2) Nuclear stability : Nucleus of an atom

contains all the protons and neutrons in it while all

electrons are in the outer sphere. Nuclides can be

grouped on the basis of nuclear stability, i.e. stable

and unstable nucleus. The most acceptable theory

about the atomic nuclear stability is based upon the

fact that the observed atomic mass of all known

isotopes (except hydrogen) is always less from the

sum of the weights of protons and neutrons

(nucleons) present in it. Other less important (or

unusual) fundamental particles of the nucleus are

electron, antiproton, positron, neutrino, photon,

graviton, meson and γ - particles are considered as

created by stresses in which energy is converted into

mass or vice versa, e.g. an electron (β- particle)

from a radio active nucleus may be regarded as

derived from a neutron in the following way.

Neutron → Proton + Electron

Similarly, photons are produced from internal

stresses within the nucleus.

A list of elementary particles is given below :

 Name of Symbol Anti – Mass Spin Cha

particle particle rge

symbol

Photon hν – 0 1 0

Electron e– e+ 1 1/2 –1

Neutrino Ve Ve 0 1/2 0
LEPTONS

Muon µ− µ+ 207 1/2 –1

Vµ
Muon – Vµ 0 1/2 0

neutrino τ− τ+ 3500 1/2 –1

Tauon
HAR

π0 264 0 0
ME
 Pions π+ π− 273 0 +1

k+ k− 966 0 +1

Kaons k0 k0 974 0 0

Etameson n0 – 1074 0 0

Proton p p– 1836.6 1/2 +1

n–
BARYONS

Neutron n 1836.6 1/2 0

Lambda λ0 λ0 2183

hyperon
 Σ+ Σ+ 2328 1/2 0

Sigma Σ0 Σ0 2334 1/2 +1

hyperons 2343 1/2 0

Σ− Σ −1

1/2 –1

Xi hyperons 1.1, 1.1 – 2573 1/2 0

Omega Ω− Ω− 3273 3/2 –1

hyperons

Some common important elementary

particles are listed below :

Name Symbol Mass Charge Discoverer

Electron e− 9.1 × 10 −31 kg − 1.602 × 10 −19 C J.J. Thomson

(1896)

Proton p 1.673 × 10 −27 kg + 1.602 × 10 −19 C E. Goldstein

(1886)

Neutron n 1.675 × 10 −27 kg Zero J. Chadwick

(1932)

Neutrino V 3.64 × 10 −32 kg Zero Pauli

Mesons µ 275 – 300 times +ve, 0 or −ve Yukawa

mass of electron (1935)

Positron e+ 9.1 × 10 −31 kg +ve Anderson

 (1932)

The stability of nucleus may be discussed in

terms of any one of the following.

(i) Nuclear Binding Energy and Mass defect :

The mass of hydrogen atom is equal to the sum of

the masses of a proton and an electron. For other

atoms, the atomic mass is less than the sum of the

masses of protons, neutrons and electrons present.

This difference in mass termed as, mass defect, is a

measure of the binding energy of protons and

neutrons in the nucleus. The mass energy

relationship postulated by Einstein is expressed as :

 ∆E = ∆mc 2 , Where ∆E is the energy

liberated, ∆m the loss of mass and c is the speed of

light.

Consider the helium nucleus, which contains 2

protons and 2 neutrons; the mass of helium nucleus

on 12
C = 12mu , scale is 4.0017 mu . The masses of

individual isolated proton and neutron are 1.0073

and 1.0087 mu respectively. The total mass of 2

protons and 2 neutrons is (2 × 1.0073 ) + (2 × 1.0087 ) = 4.0320 m .

u

The loss in mass or mass defect for helium nucleus

is, 4.0320 mu − 4.0017 mu = 0.0303 mu

 1mu = 1.66057 × 10 −27 kg and c = 2.998 × 10 8 ms −1

 ∆E = 0.0303 × 1.66057 × 10 −27 × 6.02 × 10 23 × (2.998 × 10 8 ) 2 kg m 2 s−2 mol −1

= 2.727 × 10 12 J mol −1

Thus, the molar nuclear binding energy of

helium nucleus, 2 He 4 , is 2.73 × 10 12 J mol −1

. Binding

energy of a nucleus is generally quoted as energy in

million electron volts (MeV) per nucleon. One

million electron volts are equivalent to 9.6 × 10 10 J mol −1

.

Thus, the formation of helium nucleus results in the

release of 2.7 × 10 12 / 9.6 × 10 10 MeV = 28 MeV

(approximately). In comparing the binding energies

of different nuclei, it is more useful to consider the

binding energy per nucleon. For example, helium

nucleus contains 4 nucleons (2 protons and 2

neutrons), the binding energy per nucleon in this

case is 28/4 = 7 MeV.

Binding energies of the nuclei of other atoms

can be calculated in a similar manner. When we

plotted binding energies of the nuclei of atoms

against their respective mass number. Three features

may be noted. First, nuclei with mass number

around 60 have the highest binding energy per

nucleon. Second, species of mass numbers 4, 12,

and 16 have high binding energy per nucleon

implying that the nuclei 4

He, 12
C and 16
O , are

particularly stable. Third the binding energy per

nucleon decreases appreciably above mass number

100. The form of relationship between binding

energy per nucleon and mass number indicates that

heavy nuclei would release mass (and therefore

energy) on division (or fission) into two nuclei of

medium mass and that the light nuclei would release

mass (and therefore energy) on fusion to form

heavier nuclei. These processes called fission and

fusion are described later in this Unit.

• The average binding energy for most of the

nuclei is in the vicinity of 8 MeV. Nuclei having

binding energy per nucleon very near to 8 MeV are

more or less stable.

• Iron has the maximum average binding energy

(8.79 MeV) and thus its nucleus is

thermodynamically most stable.

• The isotopes with intermediate mass numbers 40

to 100 are most stable. The elements with Low

Mass numbers or High Mass numbers tend to

become stable by acquiring intermediate mass

number. Evidently, nuclei of lighter elements

combine together to form a heavier nucleus of

intermediate mass number (nuclear fusion); while

the nuclei of heavy elements split into two lighter

nuclei of intermediate mass numbers (nuclear

fission). In either case, energy is released and hence

the stability is enhanced.

Note :  Relation between different units of energy

1cal = 4.2 J ;1J= 10 7 ergs; 1eV = 1.622 × 10 −19

J

(ii) Relative stability of isotopes and binding

energy: Value of binding energy predicts the

relative stability of the different isotopes of an

element. If the value of binding energy is negative,

the product nucleus or nuclei will be less stable than

the reactant nucleus. Thus the relative stability of the

different isotopes of an element can be predicted by

the values of binding energy for each successive

addition of one neutron to the nucleus.

 2 He
3
+ 0 n1 → 2 He 4 + 20 .5 MeV ;

2 He
4
+ 0n1 → 2 He5 − 0.8 MeV

Therefore, 2 He 4 is more stable than 2 He 3 and 2 He 5 .

(iii) Packing fraction: The difference of

actual isotopic mass and the mass number in terms

of packing fraction is defined as:

Actual isotopic mass − Mass number

Packing fraction = × 10 4
Mass number

The value of packing fraction depends upon the

manner of packing of the nucleons with in the

nucleus. Its value can be negative, positive or even

zero.

Note :  Actual isotopic mass is not a whole

number whereas, mass number is a whole number.

(a) Zero packing fraction: Carbon12 has zero

packing fraction because it is taken as a reference on

the atomic scale and its actual isotopic mass (12) is

equal to its mass number (12).

(b) Negative packing fraction : Negative

value of the packing fraction means that the actual

isotopic mass is less to the mass number. This term

indicates that some mass has been transformed into

energy (binding energy) during formation of

nucleus. Such nuclei are, therefore more stable.

(c) Positive packing fraction : Positive

packing fraction should imply the opposite, i.e., the

nuclei of such isotopes should be unstable.

However, this generalisation is not strictly correct

especially for elements of Low Mass numbers. For

these elements, though packing fraction is positive,

yet they are stable. This is explained on the basis

that the actual masses of protons and neutrons (of

which the nuclei are composed) are slightly greater

than unity.
 In general, lower the packing fraction, greater is

the binding energy per nucleon and hence greater is

the stability the relatively low packing fraction of

He, C and O implies their exceptional stability

packing fraction is least for Fe (negative) and

highest for H (+78).

(iv) Meson theory of nuclear forces :

Neutron is found to play a leading role in binding

the nuclear particles. It has been established that

neutron proton attractions are stronger than the

proton-proton or neutron – neutron attraction. This

is evident by the fact that the deutron, 1H

2
having

one proton and one neutron, is quite stable.

 Yukawa in 1935, put forward a postulate that

neutrons and protons are held together by very rapid

exchange of nuclear particles called Pi-mesons (π-

mesons have mass equal to 275 times of the mass of

an electron and a charge equal to +1, 0 or –1. There

are designated as π+ π0 and π– respectively). The

nuclear force which is used in rapid exchange of Pi-

mesons between nucleons are also called exchange

forces.

• The binding forces between unlike nucleons (p

and n) are explained by the oscillation of a charged

(a) p1 + n2 n1 + π + + n2 n1 + p 2
π-meson (π+ or π )
−
(b) p1 + n2 n1 + π + p 2
−
n1 + p 2
• Binding forces between like nucleons (p - p or n

- n) result from the exchange of neutral mesons (π0)

as represented below.

(a) p1 p 2 + π 0 or p1 + π 0 p2
(b) n1 n2 + π 0 or n1 + π 0 n2

(v) Nuclear shell model : According to this theory,

nucleus of atom, like extra-nuclear electrons, also

has definite energy levels (shells). The shell

structure is supported by the existence of periodicity

in the nuclear properties. For example, elements

with even number of protons and neutrons are more

abundant, more stable and richer in isotopes.

Nuclides with odd number of protons and neutrons

are least abundant in nature (only 5 are known

1 H 2 , 5 B10 , 7 N 14 and 73 Ta 180 ).

Thus elements have a tendency to have even number

of both protons and neutrons. This suggests that like

electrons, nucleon particles in the nucleus are paired.

Magnetic fields of the two paired protons spinning

in opposite direction cancel each other and develop

attractive forces, which are sufficient to stabilize the

nucleus. Further nuclei with 2, 8, 20, 28, 50, 82 or

126 protons or neutrons have been found to be

particularly stable with a large number of isotopes.

These numbers, commonly known as Magic

numbers are defined as the number of nucleons

required for completion of the energy levels of the

nucleus. Nucleons are arranged in shells as two

protons or two neutrons (with paired spins) just like

electrons arranged in the extra-nuclear part. Thus the

following nuclei 2 He
4
, 8 O 16 , 20 Ca 40 and 82 Pb 208 containing

protons 2, 8, 20 and 82 respectively (all magic

numbers) and neutrons 2, 8, 20 and 126 respectively

(all magic numbers) are the most stable.

Magic numbers for protons : 2, 8, 20, 28,

50, 82, 114

Magic numbers for neutrons : 2, 8, 20, 28,

50, 126, 184, 196

When both the number of protons and number of

neutrons are magic numbers, the nucleus is very

stable. That is why most of the radioactive

disintegration series terminate into stable isotope of

lead (magic number for proton = 82, magic number

for neutron = 126). Nuclei with nucleons just above

the magic numbers are less stable and hence these

may emit some particles to attain magic numbers.

(vi) Nuclear fluid theory : According to this theory

the nucleus is considered to resemble a liquid drop.

Nucleons are believed to be present in the nucleus as

nuclear fluid of very high density equal to 130

trillion tonnes/m3, which is about 100 trillion times

the density of water. The density is uniform and

does not vary from atom to atom. Along with its

almost unbelievable high density nuclear fluid

possesses a correspondingly high surface tension

( = 9.3 × 10 19
Nm −1 , i.e., 1.24 × 10 18 times the surface tension

of water). A nuclear film attached to a wire one

centimetre long would support the mass of one

billion tonnes. This force of nuclear surface tension

is, in fact, responsible for keeping the nucleons

bound together against the forces of repulsion. This

is known as the Nuclear fluid theory of the stability

of the nuclei. Thus according to this theory the

nucleons are free to move with in the nucleus

whereas according to the nuclear shell structure

theory the nucleons exist in definite energy levels.

(vii) Neutron-proton ratio and nuclear stability

or causes of radioactivity : The nuclear stability is

found to be related to the neutron/proton (n/p) ratio.

If for different elements the number of neutrons is

plotted against the number of protons, it is found

that the elements with stable nuclei (non-radioactive

elements) lie within a region (belt) known as zone or

belt of stability.

130
n/p=1.5 200 Hg
120 80

110

100
Stability
belt
90
trons (n)

80 n/p=1.4 120 Sn
50
70
 (a) For elements with low atomic number (less

than 20), n/p ratio is 1, i.e., the number of protons is

equal to the number of neutrons. Remember that n/p

ratio of 1H
1
is zero as it has no neutron. Nuclide with

highest n/p ratio is 1H

3
(n/p = 2.0)

(b) With the increase in atomic number

although the number of protons increases but the

number of neutrons increases much more than the

number of protons with the result the n/p ratio goes

on increasing from 1 till it becomes nearly equal to

1.5 at the upper end of the belt.

(c) When the n/p ratio exceeds 1.52 as in

elements with atomic number 84 or higher, the

element becomes radioactive and undergoes

disintegration spontaneously. Note that these

elements lie outside the zone of stability.

The way an unstable nucleus disintegrates is

decided by its position with respect to the actual n/p

plot of stable nuclei (the zone of stability)

• Neutrons to proton (n/p) ratio too high. If

the n/p ratio is too high, i.e., when the nucleus

contains too many neutrons, it falls above the zone

of stability. The isotope would be unstable and

would tend to come within the stability zone by the

emission of a β-ray (electron). Electron, is produced

in the nucleus probably by the following type of

decay of a neutron.

0n
1
→ 1 H 1 + −1 e 0 (Beta particle)

The electron thus produced is emitted as a β-particle

and thus the neutron decay ultimately increases the

number of protons, with the result the n/p ratio

decreases and comes to the stable belt. Consider the

example of C 12 and C 14 . In C 12 , the n/p ratio (6/6) is 1,

hence its nucleus is quite stable. On the other hand,

in C 14 , the n/p ratio (8/6) is 1.3, hence it should be

unstable. In practice also it is found to be so and C 14

decays in he following way to give N 14 (n/p ratio =

1)

6C
14
→ 7N
14
+ −1 e 0 ;
n 8  n 7 
 p = 6 =1.33   p = 7 =1.0 
   

92U 238
→ 90Th 234
+ 2 He 4
 n 146   n 144 
 p = 92 =1.587   p = 90 =1.6 
   

• Neutron to proton ratio (n/p) too low, (i.e.,

when the nucleus contains excess protons) : There

are no naturally occurring nuclides with n/p ratio

less than 1, however there are many artificially

nuclides in such cases, the nucleus lies below the

zone of stability, it would again be unstable and

would tend to come within the zone of stability by

losing a positron.

6C
11
→ 5B
11
+ +1 e
0
; 7 N 13
→ 6 C 13 + +1 e0
n 5  n 6  n 5  n 7 
 = = 0.83   = =1.2   p = 6 = 0.83   = =1.16 
p 6    p 6 
p 5 

Such nuclides can increase n/p ratio by adopting

any one of the following three ways :

By emission of an alpha particle :

U
92
238
→ Th
90
234
+ 2 He 4
 n 146   n 144 
 = =1.58   = =1.60 
 p 92   p 90 

By emission of a positron : 13
7 N → 13
6
n 7
C + +1e0
n 6
 =   = 
p 7  p 6

By K-electron capture : 194

79 Au + −1 e0 → 194
78Pt
 n 115   n 116 
 =   = 
 p 79   p 78 
 α-emission is usually observed in natural

radioactive isotopes while emission of positron or

K-electron capture is observed in artificial

radioactive isotopes. The unstable nuclei continue to

emit α or β-particles. Until stable nuclei comes into

existence.

(3) Nuclear reactions : In a chemical reaction,

only electrons (extra-nuclear particle) of the atom

take part while the nucleus of the atom remains

unaffected. However, the reverse reactions (i.e.,

where only nuclei of atoms take part in reactions)

are also possible. Such reactions in which nucleus of

an atom itself undergoes spontaneous change or

interact with other nuclei of lighter particles

resulting new nuclei and one or more lighter

particles are called nuclear reactions.

(i) Some characteristics of nuclear reactions :

(a) Nuclear reactions are written like a chemical

reaction : As in a chemical reaction, reactants in a

nuclear reaction are written on the left hand side and

products on the right hand side with an arrow in

between them.

(b) Mass number and atomic number of the elements

are written in a nuclear reactions : Mass number and

atomic number of the element involved in a nuclear

reaction are inserted as superscripts and subscripts

respectively on the symbol of the element. For

example 27
13 Al or Al 1327 or 13 Al 27 stands for an atom of

aluminum with mass number 27 and atomic number

13.

(c) Mass number and atomic number are conserved :

In a nuclear reaction the total mass numbers and

total atomic numbers are balanced on the two sides

of the reaction (recall that in an ordinary reaction the

total number of atoms of the various elements are

balanced on the two sides)

(d) Energy involved in the nuclear reactions is

indicated in the product as +Q or –Q of reactions

accompanied by release or absorption of energy

respectively.

(e) Important projectiles are α-particles ( 2 He 4 ) ,

Proton (1 H 1 or p) , deutron ( 1H
2
or 1 D 2 ), neutron ( 0 n1 ) ,

electron (β-particle or −1 e0 or e–) and positron ( +1 e 0 ) .

(f) Representation of nuclear reactions : For

example, 7 N 14 + 2 He 4 → 8 O 17 + 1 H 1 + Q . Some times a short

hand notation is used, e.g., the above reaction can be

represented as below. 7 N 14 (α , p) 8 O 17

(ii) Nuclear reactions Vs chemical reactions :

(a) As per definition, chemical reactions depend

upon the number of extranuclear electrons while

nuclear reactions are independent upon the electrons

but depend upon the nature of the nucleus.

(b) Chemical reactions involve some loss, gain or

overlap of outer orbital electrons of the two-reactant

atoms. On the other hand, nuclear reactions involve

emission of some light particles (α, β, positron, etc.)

from the nucleus of the atom to form another

element.

(c) The chemical reactivity of the element is

dependent on the nature of the bond present in the

concerned compound. On the other hand, the nuclear

reactivity of the element is independent of its state

of chemical combination, e.g., radium, whether

present as such or in the form of its compound,

shows similar radioactivity.

(d) The energy change occuring in nuclear reactions

is very high as compared to that in chemical

reactions. Again in chemical reactions the energy is

expressed in kcal per mole while in nuclear

reactions the energy is expressed in MeV per

nucleus. Nuclear reactions, which liberate energy

are called exoergic reactions and which absorb

energy are called endoergic.

(e) A chemical reaction is balanced in terms of mass

only while a nuclear reaction must be balanced in

terms of both mass and energy. In endoergic

reactions, the mass of products is more than the

mass of reactants. While in exoergic reaction the

mass of products is less than the mass of reactants.

(f) The chemical reactions are dependent on

temperature and pressure while the nuclear reactions

are independent of external conditions.

(iii) Types of nuclear reactions : Nuclear reactions

may broadly be divided into two types :

(a) Natural nuclear reactions : In these reactions,

nucleus of a single atom undergoes a spontaneous

change itself.

(b) Artificial nuclear reactions : In these reactions,

two nuclei of different elements are brought to

interact artificially. Bombarding a relatively heavier

nucleus (non-radioactive) with a lighter nucleus, viz.

proton, deutron and helium, does this. Artificial

nuclear reactions are divided as follows :

• Projectile capture reactions : The bombarding

particle is absorbed with or without the emission of

γ-radiations.
 92 U
238
+ 0 n1 → 92 U 239 + γ ; 13 Al 27 + 0 n1 → 13 Al 28 + γ

• Particle-particle reactions : Majority of nuclear

reactions come under this category. In addition to

the product nucleus, an elementary particle is also

emitted.

11 Na 23 + 1 H 1 → 12 Mg 23 + 0 n1 ; 11 Na 23 + 1 H 2 → 11 Na 24 + 1 H 1

11 Na 23 + 2 He 4 → 12 Mg 26 + 1 H 1 ; 7 N 14 + 0 n1 → 6 C 14 + 1 H 1

• Spallation reactions : High speed projectiles

with energies approximately 40 MeV may chip

fragments from a heavy nucleus, leaving a smaller

nucleus.
 29 Cu 63 + 2 He 4 + 400 MeV → 17 Cl 37 + 14 1 H 1 + 16 0 n1

• Fission reactions : A reaction in which a heavy

nucleus is broken down into two or more medium

heavy fragments. The process is usually

accompanied with emission of neutrons and large

amount of energy.

92 U
235
+ 0 n1 → 56 Ba 141 + 36 Kr
92
+ 3 0 n1 + 200 MeV

• Fusion reactions : Light nuclei fuse together to

reproduce comparatively heavier nuclei. A fusion

reactions is the source of tremendous amount of

energy.

1H
2
+ 1 H 3 → 2 He 4 + 0 n1 + 17 .6 MeV
 •
U-235
Examples based on Binding energy

Example : 1 Sulphur-35 (34.96903 amu) emits a β-

particle but no γ-ray. The product is chlorine-35

(34.96885 amu). The maximum energy emitted by

the β-particle is

[CBSE 1999]

(a) 16.758 MeV

(b) 1.6758 MeV

(c) 0.16758 MeV

(d) 0.016758 MeV

Solution: (c) The mass converted into energy

= 34 .96903 amu − 34 .96885 amu = 1.8 × 10 −4 amu ( 1 amu = 931 .5 MeV )

 Energy produced = 1.8 × 10 −4

× 931 .5 = 0.16758 MeV

Example : 2 If the atomic masses of lithium,

helium and proton are 7.01823 amu, 4.00387 amu

and 1.00815 amu respectively, calculate the energy

that will be evolved in the reaction.

Li 7 + H 1 → 2He 4 + energy .(Given that 1 amu = 931 MeV)

(a) 17.3 MeV

(b) 17.8 MeV

(c) 17.2 MeV

(d) 17.0 MeV

Solution: (a) Total mass of the reacting species

(Li 7 and H 1
) = 7.01823 + 1.00815 = 8.02638 amu

The mass of the resulting species

(2 He 4 ) = 2 × 4.00387 = 8.00774 amu

Mass of reacting species converted

into energy, i.e., ∆m = 8.02638 − 8.00774 = 0.01864 amu

∴ Energy evolved in the

reaction = 0.01864 × 931 .5 = 17.363 MeV.

Example : 3 Calculate the mass defect and binding

energy per nucleon for 27 Co

59
. [The mass of

Co 59 = 58 .95 amu , mass of hydrogen atom = 1.008142

amu and mass of neutron = 1.008982 amu].

(a) 8.77 MeV

(b) 8.25 MeV

(c) 9.01 MeV

(d) 8.00 MeV

Solution: (a) Number of protons in 27 Co

59
= 27

∴ Number of neutrons = 59 – 27 =

32

∆m = (1.008142 × 27 + 1.008982 × 32) − 58 .95 = 0.556438 amu

The binding energy (E B ) per

∆m × 931 0.556438 × 931

nucleon = Mass of cobalt
=
59
MeV = 8.77 MeV
7.2 Radioactivity.

“Radioactivity is a process in which nuclei of certain

elements undergo spontaneous disintegration

without excitation by any external means.’’

• Henry Becquerel (1891) observed the

spontaneous emission of invisible, penetrating rays

from potassium uranyl sulphate K 2 UO 2 (SO 4 )2 , which

influenced photographic plate in dark and were able

to produce luminosity in substances like ZnS.

• Later on, Madam Marie Curie and her

husband P. Curie named this phenomenon of

spontaneous emission of penetrating rays as,

Radioactivity. They also pointed out that

radioactivity is a characteristic property of an

unstable or excited nucleus, i.e., a nuclear property

is independent of all the external conditions such as

pressure, temperature, nature of other atoms

associated with unstable atom but depends upon the

amount of unstable atom.

• Curies also discovered a new radioactive element

Radium from pitchblende (an ore of U i.e. U 3 O8 )

which is about 3 million times more radioactive than

uranium. Now a days about 42 radioactive elements

are known.
• The elements whose atoms disintegrate and emit

radiations are called radioactive elements.

• Radioactivity can be detected and measured by a

number of devices like ionisation chamber, Geiger

Muller counter, proportional counter, flow counter,

end window counter, scintillation counter, Wilson

cloud chamber, electroscope, etc. The proper device

depends upon the nature of the radioactive substance

and the type of radiation emitted. GM counter and

proportional counter are suitable for solids and

liquids, ionisation chamber is most suitable for

gases.
• Lightest radioactive isotope is tritium ( 1H 3 ) ; other

lighter radioactive nuclides are 14

C , 40
K and 99
Tc .

(1) Nature of radioactive emissions : The nature of

the radiations emitted from a radioactive substance

was investigated by Rutherford (1904) by applying

electric and magnetic fields to the radiation as

shown in figure.

Photographic plate Photographic plate

γ Magnet γ
α β Slit α β
Radioactive
substance

Block of Lead
(as Shiled)

Study of the nature of radiations emitted form a radioactive substance

It is observed that on applying the field, the rays

emitted from the radioactive substances are

separated into three types, called α, β, and γ-rays.

The α-rays are deflected in a direction which shows

that they carry positive charge; the β-rays are

deflected in the opposite direction showing that they

carry negative charge and the γ-rays are not

deflected at all showing that they carry no charge.

(2) Characteristics of radioactive rays :

Radioactive rays are characterised by the following

properties :

(i) They blacken photographic plates.

 (ii) They pass through thin metal foils.

(iii) They produce ionization in gases through

which they passes.

(iv) They produce luminescence in zinc

sulphide, barium platinocyanide, calcium tungstate,

etc.

Radioactive radiations are composed of three

important rays, namely α, β and γ − rays which differ

very much in their nature and properties, e.g.

penetrating power, ionising power and effect on

photographic plates. Remember that γ-rays are not

 produced simultaneously with α and β-rays but are

produced subsequently.

Comparison of α, β and γ-rays

α-Particle or α-Ray β-Particle or β-Ray γ-Ray

(1) Charge and mass : It carries 1 unit These are

It carries 2 units negative charge and no electromagnetic rays

positive charge and 4 mass. with very short

unit mass. wavelength (app. 0.05

Å)

(2) Nature : It is It is represented as It is represented as 0

γ0

represented as helium electron − 1e0 .

nucleus or helium ions

2 He
4
or He + + .

(3) Action of These are deflected to These are not

magnetic field : These anode. deflected.

are deflected towards

the cathode.

(4) Velocity : 2 × 10 9 cm / s 2.36 to 2.83 × 1010 cm / s (2.36 Same as that of light

or 2 × 10 7 m / sec (1/10th to to 2.83 × 10 8 m / s ) 3 × 1010 cm / s (3 × 10 8 m / s)

that of light)

(5) Ionizing power : Low nearly 100 times Very low.

Very high nearly 100 to that of γ-rays.

times to that of β-rays.

(6) Effect on ZnS Very little effect. Very little effect.

plate : They cause

luminescence.

(7) Penetrating power 100 times that of α- 10 times that of β-

: Low particles. particles.

(8) Range : Very small More that of α- More

(8-12 cm.) particles.

(9) Nature of product Product obtained by There is no change in

: Product obtained by the loss of 1 β-particle the atomic number as

the loss of 1 α-particle has atomic number well as in mass

has atomic number less more by 1 unit, number.

by 2 units and mass without any change in

number less by 4 units. mass number.

Note :  β-particles originates in the nucleus; they

are not orbital electrons.

 β-particles having their velocity almost equal to

velocity of light are known as hard β-particles and

the others having their velocity ≈ 1 × 10 10 cm sec −1 are

called soft β-particles.

 γ-radiation always accompany alpha or beta

emissions and thus are emitted after α- and β-decay.

 Only one kind of emission at a time is noticed.

No radioactive substance emits both α- and β-

particles simultaneously.

7.3 Theory of radioactive disintegration.

Rutherford and Soddy, in 1903, postulated that

radioactivity is a nuclear phenomenon and all the

radioactive changes are taking place in the nucleus

of the atom. They presented an interpretation of the

radioactive processes and the origin of radiations in

the form of a theory known as theory of radioactive

disintegration. The main points of this theory are as

follows :
• The atomic nuclei of the radioactive elements are

unstable and liable to disintegrate any moment.

• The disintegration is spontaneous, i.e., constantly

breaking. The rate of breaking is not affected by

external factors like temperature, pressure, chemical

combination etc.

• During disintegration, atoms of new elements

called daughter elements having different physical

and chemical properties than the parent elements

come into existence.

• During disintegration, either alpha or beta

particles are emitted from the nucleus.

The disintegration process may proceed in one of

the following two ways :

(1) α-particle emission : When an α-particle ( 2 He 4 )

is emitted from the nucleus of an atom of the parent

element, the nucleus of the new element, called

daughter element possesses atomic mass or atomic

mass number less by four units and nuclear charge

or atomic number less by 2 units because α-particle

has mass of 4 units and nuclear charge of two units.

Parent element α → Daughter element

 -
Atomic mass : W W−4
Atomic number : Z Z−2

Examples are:
 88 Ra
226
→ 86 Rn
222
+ 2 He 4 ; 92 U
238
→ 90 Th
234
+ 2 He 4
(Radium) (Radon) (Uranium) (Thorium)

83 Bi
213
→ 81 Tl
209
+ 2 He 4 ; 84 Po
215
→ 82 Pb
211
+ 2 He 4
(Bismuth) (Thallium) (Polonium) (Lead)

(2) β-particle emission : β-particle is merely an

electron which has negligible mass. Whenever a

beta particle is emitted from the nucleus of a

radioactive atom, the nucleus of the new element

formed possesses the same atomic mass but nuclear

charge or atomic number is increased by 1 unit than

the parent element. Beta particle emission is due to

the result of decay of neutron into proton and

electron.

0n
1
→ 1 p1 + −1 e
0
 The electron produced escapes as a beta-particle-

leaving proton in the nucleus.

-β
Parent element   → Daughter element
Atomic mass : W W
Atomic number : Z Z +1

Examples are:

82 Pb 214 → 83 Bi
214
+ −1 e
0
; 90 Th
234
→ + 91 Pa
234
+ −1 e 0 ;
(Lead) (Bismuth) (Thorium) ( protoactin ium)

83 Bi
213
→ 84 Po
213
+ −1 e
0

(Polonium)

Special case : If in a radioactive transformation 1

alpha and 2 beta-particles are emitted, the resulting

nucleus possesses the same atomic number but

atomic mass is less by 4 units. A radioactive

transformation of this type always produces an

isotope of the parent element.

−α W−4 −β W−4 −β W−4

Z AW →
 Z−2B →
 Z −1C →
 ZD

A and D are isotopes.

• γ-rays are emitted due to secondary effects. The

excess of energy is released in the form of γ-rays.

Thus γ-rays arise from energy re-arrangements in

the nucleus. As γ-rays are short wavelength

electromagnetic radiations with no charge and no

mass, their emission from a radioactive element

does not produce new element.

7.4 Group displacement law.

Soddy, Fajans and Russell (1911-1913) observed

that when an α-particle is lost, a new element with

atomic number less by 2 and mass number less by 4

is formed. Similarly, when β-particle is lost, new

element with atomic number greater by 1 is

obtained. The element emitting then α or β-particle

is called parent element and the new element

formed is called daughter element. The above

results have been summarized as Group

displacement laws as follows :

(1) When an α-particle is emitted, the new element

formed is displaced two positions to the left in the

periodic table than that of the parent element

(because the atomic number decreases by 2).

New element Original element

formed (daughter) (parent)

X
A–4
Y
A
Period
Z–2 Z

Two position left of

the original element By loss of α - particle

For example, when

92 U
238
→ 90 Th 234 + 2 He 4

(2) When a β-particle is emitted, the new element

formed is displaced one position to the right in the

periodic table than that of the parent element

(because atomic number increased by 1).

Original element New element

(parent) formed (daughter)

Y X
A A
Period
Z Z+1

By loss of α - particle One position right of

the original element
For example,

90 Th
234
→ 91 Pa 234 + −1 e
0
; 6C
14
→ 7 N 14 + −1 e
0

Hence, group displacement law should be applied

with great care especially in the case of elements of

lanthanide series (57 to 71), actinide series (89 to

103), VIII group (26 to 28; 44 to 46; 76 to 78), IA

and IIA groups. It is always beneficial to keep in

mind the setup and skeleton of the extended form of

periodic table.
I II II I V V VI VIII I II II IV V VI VI Ze

A A IB V B IB IB B B IA A A A IA ro

1 2 3 4 5 6 7 8 9 1 1 1 13 14 1 16 17 18

0 1 2 5

IA IIA IIIB IVB Zero

1 18

At. No. At. No.

1st period 1 – – – 2

2nd 3 – – – 10
period

3rd period 11 – – – 18

4th period 19 – – – 36

5th period 37 – – – 54

6th period 55 56 57*–71 72 86

7th period 87 88 89!–103 104

*Lanthanides, ! Actinides

Important tips

 α-Decay produces isodiapher i.e., the parent and daughter nuclide

formed by α-decay have same isotopic number, i.e., difference

between the number of neutrons and protons is same. For example,

226 222
88 Ra → 86 Rn
No. of neutrons 138 136
No. of protons 88 86
Difference 50 50

Thus note that an α-decay leads to

(i) Decrease in atomic weight, mass number and number of

nucleons by four units.

(ii) Decrease in number of protons, neutrons, nuclear charge

and atomic number by two units.

(iii) Increase in n/p ratio.

 β-Decay results in the formation of an isobaric element i.e.,

parent and daughter nuclide have different atomic numbers but same
mass number. For example,

40 40 0
19 K → 20 Ca + −1 e

Thus note that a β-decay leads to

(i) No change in atomic weights, mass number and number of

nucleons.

(ii) Decrease in number of neutrons by one unit.

(iii) Increase in nuclear charge, number of protons and atomic

number by one unit.

(iv) Decrease in n/p ratio.

It is important to note that although β-particle (electron) is not

present in the nucleus, even then it is emitted from the nucleus since
a neutron at first breaks down to a proton and electron.

1
0n → 1 p 1 + −1 e
0

The proton is retained by the nucleus while the electron is

emitted as a β-particle.

 Emission of 1 α-particle and 2 β-particles in succession produces

an isotope of the parent element. For example,

235 −α −β −β
92 U → 90 Th 231 
 → 91 Pa 231 
→ 92 U 231

 This law helps to fix the position of the radioelements in the

periodic table.

 To determine the number of α- and β- particles emitted during the

nuclear transformation. It can be done in following manner :

 a
cX → bd Y + x 42 He + y −1 e
0
,

a−b
a = b + 4x or x =
4
.......(i)

c = d + 2x − y ......(ii)

where x = no. of α-emitted, y = no. of β-emitted

substituting the value of x from eq. (i) in eq. (ii) we get

 a−b  a − b
c = d+
 4 
2−y ; y=d+
 2 
−c

•
U-235
Examples based on Group displacement law

Example : 4 Calculate the number of

neutrons in the remaining atom after emission of an

alpha particle from 238

92 U atom
 [Roorkee 1978]

(a) 146

(b) 145

(c) 144

(d) 143

Solution: (c) On account of emission of an alpha

particle, the atomic mass is decreased by 4 units and

atomic number by 2 units

So, Atomic mass of daughter element =

234

Atomic number of daughter element = 90

 Number of neutrons = Atomic mass –

Atomic number

= 234 – 90 = 144

Example : 5 Radioactive disintegration of

226
88 Ra takes place in the following manner into RaC

−α
Ra  −α
→ Rn  −α −β
→ RaB 
→ RaA  → RaC ,

Determine mass number and atomic number of RaC.

(a) 214 and 84

(b) 214 and 86

(c) 214 and 83

(d) 214 and 85

Solution: (c) Parent element is 226
88 Ra

Atomic mass = 226

Atomic number = 88

RaC is formed after the emission of 3

alpha particles. Mass of 3 alpha particles = 3 × 4 = 12

So Atomic mass of RaC

= (226 − 12) = 214

With emission of one α-particle,

atomic number is decreased by 2 and with emission

of β-particle, atomic number is increased by 1.

So Atomic number of RaC

= 88 − (3 × 2) + 1 = 83
Example : 6

(a) 2 and 6

(b) 4 and 2

(c) 2 and 4

(d) 6 and 2

Solution: (b) The change is; 90 Th

234
→ 84 Po
218
Parent End product

Decrease in mass = (234 − 218 ) = 16 amu

Mass of 1 α-particle = 4 amu

Therefore, number of α-particles

16
emitted =
4
=4
 Number of β-particles emitted

= 2 × No. of αparticles emitted − (atomic no. of parent − At. no. of product )

= 2 × 4 − (90 − 84 ) = 2

Hence number of α-particles = 4 and

number of β-particles = 2

Example : 7

resultant atom has atomic mass 212 and atomic

number 82. How many α-particles are emitted

during this process

[CBSE 1992]

(a) 5
(b) 6

(c) 7

(d) 8

Solution: (a) The decrease in atomic mass = (232 –

212) = 20

Decrease in mass occurs due to emission of α-

particles. Let x be the number of alpha particles

emitted.

Mass of 'x' α-particles = 4x

20
So 4 x = 20 or x=
4
=5
 Alternative method : This can also be

determined by the application of following equation

:No. of β-particles emitted = 2 × No. of α-particles

emitted −(Z Parent − Z End product )

2 = 2 × x – (90 – 82) or x = 5

Example : 8 An element X with atomic number 90

and mass number 232 loses one α- and two β-

particles successively to give a stable species Z.

What would be the atomic number and atomic

weight of Z

[CPMT 1990]

(a) 90 Z 228
(b) 91 Z 235

(c) 90 Z 235

(d) 91 Z 238

Solution: (a) At. no. and At. wt. of the element (Y)

produced by the loss of one α-particle ( 2 He 4 ) from

90 X 232 = 88 Y
228

At. no. and At.wt. of Z produced by the loss of 2

β-particles ( −1 e 0 ) from Y= 90 Z
228

Example : 9

(a) 6 and 4

(b) 8 and 4
(c) 9 and 6

(d) 2 and 4

Solution: (a)

Now since in one α-particle emission, at. wt. is

decreased by 4 amu, the number of α-emissions for

24 amu = 24/4 = 6

Atomic number after 6α-emissions = 90 –

12 = 78 ( α = 2 He 4 )

Increase in atomic number from 78 to the

given 82 = 82 – 78 = 4 ( β - particle = −1 e
0
)

∴ No. of β-particle emissions = 4

Example : 10 92 U
235
belongs to group III B of the periodic table. It los
Solution: Since loss of an α-particle decreases the

atomic number of the element by 2, the resulting

product should lie two groups to the left of the

parent group. However, in the present case the

element will remain in the same group of the

periodic table because it is an actinide element.

Example : 11 234
90 Th disintegrates to give 206
82 Pb as the final product. How

(a) 6

(b) 8

(c) 9

(d) 2
Solution: (a) 234
90 Th    →
Parent
206
82 Pb
End product

Decrease in mass = (234 – 206) = 28

Mass of α-particle = 4

So Number of α-particles emitted = 284 = 7

Number of beta particles emitted = 2 × No.

of α-particles – (At. no. of parent – At. no. of end

product)

= 2 × 7 – (90 – 82) = 6

7.5 Rate of radioactive decay.

“According to the law of radioactive decay, the

quantity of a radioelement which disappears in unit

time (rate of disintegration) is directly proportional

to the amount present.”

The law of radioactive decay may also be expressed

mathematically.

Suppose the number of atoms of the radioactive

element present at the commencement of

observation, i.e. when t=0 is N0 , and after time t, the

number of atoms remaining unchanged is Nt , then

dN t
the rate of decay of atoms is −
dt
(the word ‘d’

indicates a very-very small fraction; the negative

sign shows that the number of atoms Nt decreases as

time t increases)
Now since the change in number of atoms is

proportional to the total number of atoms N , the t

relation becomes −
dN t
dt
= λN t , where λ is a radioactive

constant or decay constant.

• Rate of decay of nuclide is independent of

temperature, so its energy of activation is zero.

• Since the rate of decay is directly proportional to

the amount of the radioactive nuclide present and as

the number of undecomposed atom decreases with

increase in time, the rate of decay also decreases

with the increase in time. Various forms of equation

for radioactive decay are,

 N0 λt
N t = N 0 e − λt ; log N 0 − log N t = 0.4343 λt ; log
Nt
=
2.303

2.303 N
λ= log 0
t Nt

where N0 = Initial number of atoms of the given

nuclide, i.e. at time 0

Nt = Number of atoms of that nuclide

present after time t.

λ= Decay constant

Note :  This equation is similar to that of first

order reaction, hence we can say that radioactive

disintegration are examples of first order reactions.

However, unlike first order rate constant (K), the

decay constant (λ) is independent of temperature.

Decay constant (λ) : The ratio between the number

of atoms disintegrating in unit time to the total

number of atoms present at that time is called the

decay constant of that nuclide.

Characteristics of decay constant (λ) :

• It is characteristic of a nuclide (not for an

element).

• Its units are time −1 .

• Its value is always less than one.

7.6 Half life and Average life period.

(1) Half-life period (T1/2 or t1/2) : Rutherford in

1904 introduced a constant known as half-life period

of the radioelement for evaluating its radioactivity or

for comparing its radioactivity with the activities of

other radioelements. The half-life period of a

radioelement is defined, as the time required by a

given amount of the element to decay to one-half of

its initial value.

0.693
Mathematically, t1 / 2 =
λ

Now since λ is a constant, we can conclude that

half-life period of a particular radioelement is

independent of the amount of the radioelement. In

other words, whatever might be the amount of the

radioactive element present at a time, it will always

decompose to its half at the end of one half-life

period.

Half-life period is a measure of the radioactivity of

the element since shorter the half-life period of an

element, greater is the number of the disintegrating

atoms and hence greater is its radioactivity. The

half-life periods or the half-lives of different

radioelements vary widely, ranging form a fraction

of a second to million of years.

Fraction and Percent of radioactive nuclides left

after n-Half-Lives
No. of half- Fraction of mass Percent of mass

lives passed Decayed Left Decayed Left

(n)

0 0 1.0 0 100

1 2 −1 1
2 = 0.293
2
= 0.707 29.3 79.7
2

1 1
1 2
= 0.50
2
= 0.50 50 50

3 1
2 4
= 0.75
4
= 0.25 75 25

7 1
3 8
= 0.875
8
= 0.125 87.5 12.5

15 1
4 16
= 0.9375
16
= 0.0625 93.75 6.25

31 1
5 32
= 0.96875
32
= 0.03125 96.75 3.125
∞ Total 0 100 0

Let the initial amount of a radioactive substance be

N0

After one half-life period (t1 / 2 ) it becomes = N0 / 2

After two half-life periods (2t1 / 2 ) it becomes = N0 / 4

After three half-life periods (3t1 / 2 ) it becomes

= N0 / 8

After n half life periods (nt1 / 2 ) it shall becomes

n
1
=   N0
 2
 Half life periods of some isotopes

Radio Half life Radio isotope Half life

isotope

238
92 U 4.5 × 10 9 years 32
15 P 14.3 days

230
90 Th 8.3 × 10 4 years 131
53 I 8.0 days

226
88 Ra 1.58 × 10 3 years 214
84 Po 1.5 × 10 −4 seconds

234
90 Th 24 days 14
6 C 5 × 10 3 years

59
26 Fe 44.3 days 222
86 Rn 3.82 days

Thus, for the total disintegration of a radioactive

substance an infinite time will be required.

Time (T) Amount of Amount of radioactive

radioactive substance decomposed (N0 – N)

substance (N)

0 (N 0 ) 0

1 1
1
1  1
t1 / 2 N0 =   N0 N 0 = 1 −  N 0
2  2 2  2

1 1
2
3  1
2t1 / 2 N0 =   N0 N 0 = 1 −  N 0
4  2 4  4 

1 1
3
7  1
3t1 / 2 N0 =   N0 N 0 = 1 −  N 0
8  2 8  8

1 1
4
15  1
4t1 / 2 N0 =   N0 N 0 = 1 − N0
16  2 16  16 

1
n
  1 n 
nt / 2   N0 1 −    N 0
 2   2  
Amount of radioactive substance left after n half-life

periods

n
1
N =   N0
 2

and Total time T = n × t1 / 2

where n is a whole number.

(2) Average-life period (T) : Since total decay

period of any element is infinity, it is meaningless to

use the term total decay period (total life period) for

radioelements. Thus the term average life is used

which the following relation determines.

Average life (T) = Sum of lives of the nuclei

Total number of nuclei
Relation between average life and half-life :

Average life (T) of an element is the inverse of its

decay constant, i.e., T=

1
λ
, Substituting the value of λ

in the above equation,

t1 / 2
T= = 1.44 t1 / 2
0.693

Thus, Average life (T) = 1.44 × Half life(T 1/ 2 ) = 2 × t1 / 2

Thus, the average life period of a radioisotope is

approximately under-root two times of its half life

period.

Note :  This is because greater the value of λ , i.e.,

faster is the disintegration, the smaller is the average

life (T).
 •
U-235 Examples based on Rate constant and Half-life period

Example : 12The isotopes 238

U and 235
U occur in

nature in the ratio of 140 : 1. Assuming that at the

time of earth formation, they were present in equal

ratio, make an estimation of the age of earth. The

half life period of 238

U and 235
U are 4.5 × 10 9 and 7.13 × 10 8

years respectively

[Roorkee 1983]

(a) 6.04 × 10 9 years

Solution: (a) Let the age of the earth be t years

N0U 238
For 238
U λ1 × t = 2.303 log
N U 238
......(i)
 N0U 235
For 235
U λ2 × t = 2.303 log
N U 235
......(ii)

Subtracting eq. (ii) from eq. (i)

 N U N U  N U NU 235
t(λ1 − λ 2 ) = 2.303 log 0 238 − log 0 235  = 2.303 log 0 238 ⋅
 N U 238 N U 235  N U 235 N U 238

 0.693 0.693  1
t −  = 2.303 log
 4.5 × 10 7.13 × 10 
9 8
140

= −(2.303 ) (2.1461 )

= −4.9425

t = 6.04 × 10 9 years

Example : 13Calculate the mass of 14

C (half life period = 5720 years

(a) 2.34 × 10 −4 g

(b) 2.24 × 10 −4 g
(c) 2.64 × 10 −4 g

(d) 2.64 × 10 −2 g

Solution: (a) Number of atoms in m g

m
of 14
C=
14
× 6.02 × 10 23

0.693 0.693
λ= = = 3.84 × 10 −12 sec −1
Half life 5720 × 365 × 24 × 60 × 60

dN t
We know that −
dt
= λ ⋅ Nt

i.e. Rate of disintegration

= λ × No. of atoms

0.693 m 3.84 × 10 −12 × m × 6.02 × 10 23

3.7 × 10 7 = × × 6.02 × 10 23 = = 2.24 × 10 − 4 g
5720 × 365 × 24 × 60 × 60 14 14

Example : 14Prove that time required for 99.9% decay of a radioact

 2.303 N0
Solution: We know that t=
λ
log
Nt

N 0 = 100 , N t = (100 − 99 .9) = 0.1

2.303 100
So, Time required for 99.9% decay t=
λ
log
0.1

2.303
=
λ
×3 ......(i)

0.693
Half life period =
λ

......(ii)

So
Time requird for 99.9% decay 2.303 × 3 λ
= × = 10
Half lifeperiod λ 0.693

Example : 151.0 g of 198

79 Au (t 1 / 2 = 65 hours) decay by β-emission to produce

(a) Write the nuclear reaction for the process.

(b) How much mercury will be present after 260

hours ?

Solution: (a) 198

79 Au → 198
80 Hg +
0
−1 e

(b) No. of half-lives in 260 hours = 260

65
=4

n
Amount of gold left after 4 half-lives =  12  =
1
  16

Amount of gold disintegrated = 1 − 161 = 15

16
g

15
So Amount of mercury formed =
16
= 0.9375 g

Example : 16A certain radio-isotope A

Z X
(Half life = 10 days) decays to A− 4
Z−2 Y . If 1 g of atoms

of A
Z X is kept in sealed vessel, how much helium will

accumulate in 20 days

[Roorkee 1986]

(a) 16800 mL

3
Solution: (a) A
Z X→ A− 4
Z−2 Y + 42 He In two half lives, 4
of

3
the isotope A
Z X has disintegrated, i.e., 4
g atom of

helium has been formed from 43 g atom of A

Z X

Volume of 1 g atom of helium =

22400 mL
 3
Thus, Volume of 4
g atom of

3
helium =
4
× 22400 mL = 16800 mL

Example : 17 210
84 Po decays with α-particle to

206
82 Pb with a half life period of 138.4 days. If 1g of

210
84 Po is placed in a sealed tube, how much helium

will be accumulated in 69.2 days ? Express the

answer in cm 3 at STP.

[Roorkee 1991]

Solution :

Amount of polonium left after 69.2 days can be

calculated by applying,
 n
1 69 .2 1
N = No   where n= =
 2 138 .4 2

1/ 2
1
= 1  = 0.7072 g
 2

Amount of polonium disintegrated = (1 – 0.7072) =

0.2928g

No. of atoms of polonium in 0.2928g = 6.023210× 10

23
× 0.2928

Thus, No. of atoms of helium formed

6.023 × 10 23 × 0.2928
=
210

Volume of helium collected

22400 22400 × 0.2928
= × No. of helium atoms = = 31 .23 cm 3
6.023 × 10 23 210

Example : 18 In nature a decay chain series starts

with 232
90 Th and finally terminates at 208
82 Pb. A thorium

ore sample was found to contain 8 × 10 −5 mL of helium

at STP and 5 × 10 −7 g of 232

Th. Find the age of the ore

sample assuming the source of helium to be only

decay of 232
Th . Also assume complete retention of

helium within the ore. (Half life of

232
Th = 1.39 × 10 10 years)

[Roorkee 1992]

(a) 6.89 × 10 9 years

(b) 4.89 × 10 9 years

(c) 3.69 × 10 9 years

(d) 6.893 × 10 10 years

 −5
× 10
Solution: (b) No. of moles of helium = 822400

232
90 Th → 208
82 Pb + 6 42 He

No. of 232
90 Th moles which have disintegrated

8 × 10 −5
=
6 × 22400

Mass of 232
90 Th which have disintegrated

8 × 10 −5 × 232
= = 1.3809 × 10 −7 g
6 × 22400

Mass of 232
Th left, ' N t ' = 5 × 10 −7 g

' N 0 ' = (5 × 10 −7 + 1.3809 × 10 −7 ) = 6.3809 × 10 −7 g

Applying

2.303 N0 2.303 6.3809 × 10 −7

t=
λ
log
Nt
=
0.693
× 1.39 × 10 10 log
5 × 10 −7
= 4.89 × 10 9 years

7.7 Radioactive disintegration series.

The phenomenon of natural radioactivity continues

till stable nuclei are formed. All the nuclei from the

initial element to the final stable element constitute a

series known as disintegration series. Further we

know that mass numbers change only when α-

particles are emitted (and not when β-particles are

emitted) causing the change in mass of 4 units at

each step. Hence the mass numbers of all elements

in a series will fit into one of the formulae.

4n, 4n + 1 , 4n + 2 and 4n + 3

Hence there can be only four disintegration series

Series 4n 4n + 1 4n + 2 4n + 3

n 58 59 59 58

Parent 90 Th
232
94 Pu 241 92 U
238
92 U
235

element

Half life 1.39 × 1010 10 years 4.5 × 10 9 years 7.07 × 10 8

years years

Prominent 90 Th
232
93 Np
237
92 U
238
89 Ac 227

element

Half life 1.39 × 1010 year 2.2 × 10 6 years 4.5 × 10 9 years 13.5 years

Name of Thorium Neptunium Uranium Actinium

series (Natural) (Artificial) (Natural) (Natural)

End 82 Pb
208
83 Bi 209 82 Pb
206
82 Pb
207

product

n 52 52 51 51

Number of α =6 α =8 α =8 α =7

lost β =4 β =5 β =6 β =4

particles

The numbers indicate that in a particular series the

mass numbers of all the members are either divisible

by 4 (in case of 4n) or divisible by 4 with remainder

of 1, 2 or 3 (in the rest three series), n being an

integer. In other words, the mass numbers of the

members of 4n, 4n + 1 , 4n + 2 and 4n + 3 series are

exactly divisible by 4, 4 + 1, 4 + 2 and 4 + 3

respectively.

Note :  4n + 1 series is an artificial series while

the rest three are natural.

 The end product in the 4n + 1 series is bismuth,

while in the rest three, a stable isotope of lead is the

end product.

 The 4n + 1 series starts from plutonium 94 Pu 241

but commonly known as neptunium series because

neptunium is the longest-lived member of the series.

 The 4n + 3 series actually starts from 92 U
235
.

7.8 Activity of population, Radioactive

equilibrium and Units of radioactivity.

(1) Activity of population or specific activity : It is

the measure of radioactivity of a radioactive

substance. It is defined as ' the number of

radioactive nuclei, which decay per second per gram

of radioactive isotope.' Mathematically, if 'm' is the

mass of radioactive isotope, then

Rate of decay λN Avogadro number

Specific activity = = =λ×
m m Atomic mass in g

where N is the number of radioactive nuclei which

undergoes disintegration.
(2) Radioactive equilibrium : Suppose a

radioactive element A disintegrates to form another

radioactive element B which in turn disintegrates to

still another element C.

A → B → C

In the starting, the amount of A (in term of atoms) is

large while that of B is very small. Hence the rate of

disintegration of A into B is high while that of B

into C is low. With the passage of time, A go on

disintegrating while more and more of B is formed.

As a result, the rate of disintegration of A to B goes

on decreasing while that of B to C goes on

increasing. Ultimately, a stage is reached when the

rate of disintegration of A to B is equal to that of B

to C with the result the amount of B remains

constant. Under these conditions B is said to be in

equilibrium with A. For a radioactive equilibrium to

be established half-life of the parent must be much

more than half-life of the daughter.

It is important to note that the term equilibrium is

used for reversible reactions but the radioactive

reactions are irreversible, hence it is preferred to say

that B is in a steady state rather than in equilibrium

state.

At a steady state,
 N A λ B TA  1
= = T = 
N B λ A TB  λ
, Where λA and λB are the

radioactive constants for the processes A→B and

B→C respectively. Where TA and TB are the average

life periods of A and B respectively.

N A (t1 / 2 ) A
In terms of half-life periods, =
N B (t1 / 2 ) B

Thus at a steady state (at radioactive equilibrium),

the amounts (number of atoms) of the different

radioelements present in the reaction series are

inversely proportional to their radioactive constants

or directly proportional to their half-life and also

average life periods.

It is important to note that the radioactive

equilibrium differs from ordinary chemical

equilibrium because in the former the amounts of

the different substances involved are not constant

and the changes are not reversible.

(3) Units of radioactivity : The standard unit in

radioactivity is curie (c) which is defined as that

amount of any radioactive material which gives

3.7 × 10 10 disintegration’s per second (dps), i.e.,

1c = Activity of 1g of Ra 226 = 3.7 × 10 10 dps

The millicurie (mc) and microcurie (µc) are equal to

10 −3 and 10 −6 curies i.e. 3.7 × 10 7 and 3.7 × 10 4 dps

respectively.

1c = 10 3 mc = 10 6 µc ; 1c = 3.7 × 10 10 dps ; 1mc = 3.7 × 10 7 dps ;

1µc = 3.7 × 10 4 dps

But now a day, the unit curie is replaced by

rutherford (rd) which is defined as the amount of a

radioactive substance which undergoes 10 6 dps. i.e.,

1 rd = 10 6 dps . The millicurie and microcurie

correspondingly rutherford units are

millirutherford (mrd) and microrutherford (µrd)

respectively.
 1 c = 3.7 × 10 10 dps = 37 × 10 3 rd ; 1 mc = 3.7 × 10 7 dps = 37 rd ;

1 µc = 3.7 × 10 4 dps = 37 mrd

However, is SI system the unit of radioactivity is

Becquerel (Bq)

1 Bq = 1 disintegration per second = 1 dps

= 1µrd

10 6 Bq = 1 rd

3.7 × 10 10 Bq = 1 c

(4) The Geiger-Nuttal relationship : It gives the

relationship between decay constant of an α-

radioactive substance and the range of the α-particle

emitted.

log λ = A + B log R

Where R is the range or the distance which an α-

particle travels from source before it ceases to have

ionizing power. A is a constant which varies from

one series to another and B is a constant for all

series. It is obvious that the greater the value of λ

the greater the range of the α-particle.

7.9 Artificial transmutation, Synthetic or

Transuranic elements and Artificial

radioactivity.
(1) Artificial transmutation or Nuclear

transformation or Nuclear transmutation : The

conversion of one element into another by artificial

means, i.e., by means of bombarding with some

fundamental particles, is known as artificial

transmutation. The phenomenon was first applied on

nitrogen whose nucleus was bombarded with α-

particles to produce oxygen.

7N
14
+ 2 He 4 → 8O
17
+ 1H1
Nitrogen isotope Alpha particle Oxygen isotope Proton

The element, which is produced, shows

radioactivity, the phenomenon is known as Induced

radioactivity. The fundamental particles which

have been used in the bombardment of different

elements are as follows :

(i) α-particle : Helium nucleus, represented as 2 He

4
.

(ii) Proton : Hydrogen nucleus, represented as 1H

1
.

(iii)Deutron : Deuterium nucleus, represented as 1H

2

or 1D
2
.

(iv) Neutron : A particle of mass number 1 but no

change, represented as 0n
1
.

Since α-particles, protons and deutrons carry

positive charge, they are repelled by the positively

charged nucleus and hence these are not good

projectiles. On the other hand, neutrons, which

carry no charge at all, are the best projectiles.

Further among α-particles, protons and deutrons; the

latter two carrying single positive charge are better

projectiles than the α-particles. However, the

positively charged α-particles, protons and deutrons

can be made much more effective if they are

imparted with high velocity. Cyclotron is the most

commonly used instrument for accelerating these

particles. The particles leave the instrument with a

velocity of about 25,000 miles per second. A more

recent accelerating instrument is called the

synchrotron or bevatron. It is important to note

that this instrument cannot accelerate the neutrons,

being neutral.

When a target element is bombarded with neutrons,

product depends upon the speed of neutrons. Slow

neutrons penetrate the nucleus while a high-speed

neutron passes through the nucleus.

92 U
238
+ 0n
1
→ 92 U 239 ; 92 U
238
+ 0n
1
→ 92 U 237 + 2 0 n1
slow speed high speed

Thus slow neutrons, also called thermal neutrons

are more effective in producing nuclear reactions

than high-speed neutrons.

Alchemy : The process of transforming one element

into other is known as alchemy and the person

involved in such experiments is called alchemist.

Although, gold can be prepared from lead by

alchemy, the gold obtained is radioactive and costs

very high than natural gold.

Some examples are given below for different

nuclear reactions :

(i) Transmutation by α-particles :

(a) α, n type

4 Be 9 (α , n) 6 C 12 i.e. 4 Be 9 + 2 He 4 → 6 C 12 + 0 n1 ; 94 Pu 239 (α , n) 96 Cm 242 i.e.

94 Pu 239 + 2 He 4 → 94 Cm 242 + 0 n1

(b) α, p type
 9 F 19 (α , p) 10 Ne 22 i.e. 9 F 19 + 2 He 4 → 10 Ne 22 + 1 H 1 ; 7 N 14 (α , p) 8 O 17

i.e., 7 N 14 + 2 He 4 → 8 O17 + 1 H 1

(c) α, β type

26 Fe59 (α , β ) 29 Cu 63 i.e., 26 Fe59 + 2 He 4 → 29 Cu 63 + −1 e 0

(ii) Transmutation by protons :

(a) p, n type

15 P 31 ( p, n) 16 S 31 i.e., 15 P 31 + 1 H 1 → 16 S 31 + 0 n1

(b) p, γ type

6 C 12 ( p, γ ) 7 N 13 i.e., 6 C 12 + 1 H 1 → N 13 + γ

(c) p, d type

4 Be 9 ( p, d) 4 Be 8 i.e., 4 Be 9 + 1 H 1 → 4 Be 8 + 1 H 2
 (d) p, α type

8 O 16 ( p,α ) 7 N 31 i.e., 8 O16 + 1 H 1 → 7 N 13 + 2 He 4

(iii)Transmutation by neutrons :

(a) n,p type

13 Al 27 (n, p) 12 Mg 27 i.e., 13 Al 27 + 0 n1 → 12 Mg 27 + 1 H 1

(b) n,α type

8 O16 (n, α ) 12 Mg 27 i.e., 8 O16 + 0 n1 → 6 C 13 + 2 He 4

(c) n, γ type

92 U 238 (n, λ ) 92 U 239 i.e., 92 U 238 + 0 n1 → 92 U 238 + λ

(d) n,β type

 8 O18 (n, β ) 9 F 19 i.e., 8 O18 + 0 n1 → 9 F 19 + −1 e 0

(iv) Transmutation by deutrons :

(a) d,p type

3 Li 6 (d, p) 3 Li 7 i.e., 3 Li 6 + 1 H 2 → 3 Li 7 + 1 H 1 ; 32 As75 (d, p) 32 As76

i.e., 32 As75 + 1 H 2 → 32 As76 + 1 H 1

(v) Transmutation by γ-radiations :

(a) γ, n type

4 Be 9 (γ , n) 4 Be 8 i.e., 4 Be 9 + γ → 4 Be 8 + 0 n1

(2) Synthetic elements : Elements with atomic

number greater than 92 i.e. the elements beyond

uranium in the periodic table are not found in nature

like other elements. All these elements are prepared

by artificial transmutation technique and are

therefore known as transuranic elements or

synthetic elements. The nuclear reactions for the

preparation of some transuranic elements are cited

below.

Elements 93 (neptunium) and 94 (plutonium) were

first discovered in 1940. Bombarding uranium-238

with neutrons produced them.

92 U
238
+ 0 n1 → 92 U 239 → 93 Np 239 + −1 e
0
; 94 Np 239 → 94 Pu 239 → −1 e 0
(Uranium) (Neptunium )

Elements with larger atomic numbers are normally

formed in small quantities in particle accelerators.

For example, curium-242 is formed when a

plutonium-239 target is struck with alpha particles.

94 Pu
239
+ 2 He 4 → 96 Cm 242 + 0 n1
Plutonium curium

(3) Artificial radioactivity or induced

radioactivity : In 1934, Irene Curie and F. Joliot

observed that when boron and aluminium were

bombarded by α-particles, neutrons, protons and

positrons were emitted.

Curie and Joliot explained this observation by

saying that during bombardment, a metastable

isotope is formed which behaves as a radioactive

element. This process was termed as artificial

radioactivty.

“The process in which a stable isotope is converted

into radioactive element by artificial transmutation

is called artificial radioactivity.”

When 27
13 Al is bombarded by α-particles, radioactive

isotope 30
15 P is formed.

Si + 1 H 1 (95 % of total conversion )

30
27
Al + 42 He 14

15 P + 0 n (5% of total conversion half lifeperiod of

13 30 * 1 30
15 P is 3.2 minutes)

30
14 Si + +1 e
0

Positron

In a similar manner, the artificial radioactivity was

observed when 10
5 B was bombarded by α-particles.
 C + 11 H
13
10
B + 42 He 6

N * + 0 n1
5 13
7

13
6 C + +1 e
0

The following are some of the nuclear reactions in

which radioactive isotope are fomed.

23
11 Na + 12 H → 11
24
Na * + 11 H 24
( 11 Na − β radioactiv e) ; 238
92 U + 10 n → 92
239
U * +γ

239
( 92 U − β radioactiv e)

12
6 C 7 N * + γ ( 7 N − positron radioactiv e)
+ 11 H → 13 13
;

25
12 Mg + 42 He → 13
28
Al * + 11 H ( 13
28
Al − β radioactiv e)

7.10 Nuclear fission and Nuclear fusion.

(1) Nuclear fission : The splitting of a heavier atom

like that of uranium – 235 into a number of

fragments of much smaller mass, by suitable

bombardment with sub-atomic particles with

liberation of huge amount of energy is called

Nuclear fission. Hahn and Startsman discovered

that when uranium-235 is bombarded with neutrons,

it splits up into two relatively lighter elements.

92 U
235
+ 0 n1 → 56 Ba
140
+ 36 Kr 93 + 2 − 3 0 n1 + Huge amount of

energy

Spallation reactions are similar to nuclear fission.

However, they differ by the fact that they are

brought by high energy bombarding particles or

photons.
Elements capable of undergoing nuclear fission and

their fission products. Among elements capable of

undergoing nuclear fission, uranium is the most

common. The natural uranium consists of three

isotopes, namely U 234 (0.006 %) , U 235 (0.7%) and U 238 (99 .3%) .

Of the three isomers of uranium, nuclear fission of

U 235 and U 238 are more important. Uranium-238

undergoes fission by fast moving neutrons while U 235

undergoes fission by slow moving neutrons; of these

two, U 235 fission is of much significance. Other

examples are Pu 239 and U 233 .

Uranium-238, the more abundant (99.3%) isotope of

uranium, although itself does not undergo nuclear

fission, is converted into plutonium-239.

92 U
238
+ 0 n1 → 92 U 239 ; 92 U
239
→ 93 Np 239 + −1 e
0
;

93 Np 238 → 94 Pu 239 + −1 e
0

Which when bombarded with neutrons undergo

fission to emit three neutrons per plutonium nucleus.

Such material like U-238 which themselves are non-

fissible but can be converted into fissible material

(Pu-239) are known as fertile materials.

Release of tremendous amount of energy : The

importance of nuclear fission lies in the release of

tremendous amount of energy during this process.

During the U 235 fission nearly 0.215 mass unit per

uranium nucleus is found to be converted into

energy.

U 235 + 0 n1 → Xe 139 + Sr 95 + 2 0 n1 + E
235 .124 138 .955 94 .945
 1.009 2× 
1.009
236 .133 235 .918

The released energy is due to difference in the total

sum of masses of the reactants and products, in

according to the Einsten's mass energy relation i.e.

E = mc 2 .

Alternatively, ∆m = 236 .133 − 235 .918 = 0.215 amu

 1 amu = 931 MeV

0.215 amu = 931 × 0.215 MeV = 198 MeV = 198 × 2.3 × 10 7 kcal
∴ Energy released by the fission of 1 g of

198 × 2.3 × 10 7
U 235 = = 1.9 × 10 7 kcal
235

Recall that the combustion of 1 g of carbon releases

only 94 .0 / 12 = 7.83 kcal of energy while the fission of 1 g

of U 235 releases 1.9 × 10 7 kcal . Hence nuclear fission

releases several million times higher energy than the

ordinary chemical combustion.

Release of neutrons : During U 235 fission it is

obvious that 2-3 neutrons per uranium molecule are

emitted. Some neutrons are ejected within an

Uranium

Neutron
E

3E

9E
extremely short interval and are called prompt

neutrons; fission products for an appreciable time

fraction of a second to several seconds emit the rest

after the fission. These are called delayed neutrons.

Note :  Each fission yields 3 neutrons each of

which can cause further fission to give 3 neutrons

goes on increasing in geometric progression 1, 3, 9,

27, 81, 243,.... and many geometric progression take

place in a very small fraction of a second.

Chain reaction : With a small lump of U 235 , most of

the neutrons emitted during fission escape but if the

amount of U 235 exceeds a few kilograms (critical

mass), neutrons emitted during fission are absorbed

by adjacent nuclei causing further fission and so

producing more neutrons. Now since each fission

releases a considerable amount of energy, vast

quantities of energy will be released during the

chain reaction caused by U 235 fission.

Atomic bomb : An atomic bomb is based upon the

process of that nuclear fission in which no

secondary neutron escapes the lump of a fissile

material for which the size of the fissile material

should not be less than a minimum size called the

critical size. There is accordingly a sudden release of

a tremendous amount of energy, which represents an

explosive force much greater than that of the most

powerful TNT bomb. In the world war II in 1945

two atom bombs were used against the Japanese

cities of Hiroshima and Nagasaki, the former

contained U-235 and the latter contained Pu-239.

Atomic pile or Nuclear reactor : It is a device to

obtain the nuclear energy in a controlled way to be

used for peaceful purposes. The most common

reactor consists of a large assembly of graphite (an

allotropic form of carbon) blocks having rods of

uranium metal (fuel). Many of the neutrons formed

by the fission of nuclei of 92 U

235
escape into the

graphite, where they are very much slow down

(from a speed of about 6000 or more miles/sec to a

mile/sec) and now when these low speed neutrons

come back into the uranium metal they are more

likely to cause additional fissions. Such a substance

likes graphite, which slow down the neutrons

without absorbing them is known as a moderator.

Heavy water, D2 O is another important moderator

where the nuclear reactor consists of rods of

uranium metal suspended in a big tank of heavy

water (swimming pool type reactor). Cadmium or

boron are used as control rods for absorbing excess

neutrons.

Plutonium from a nuclear reactor : For such

purposes the fissile material used in nuclear reactors

is the natural uranium which consists mainly

(99.3%) of U-238. In a nuclear reactor some of the

neutrons produced in U-235 (present in natural

uranium) fission converts U-238 to a long-lived

plutonium isotope, Pu-239 (another fissionable

material). Plutonium is an important nuclear fuel.

Such reactors in which neutrons produced from

fission are partly used to carry out further fission

and partly used to produce some other fissionable

material are called Breeder reactors.

Production of radioactive isotopes by

bombarding with neutrons from a nuclear

reactor : These radioactive isotopes are used in

medicine, industry and hospitals.

Nuclear reactors in India : India is equipped with

the five nuclear reactors, namely Apsara (1952),

Cirus (1960), Zerlina (1961), Purnima (1972) and R-

5. Purnima uses plutonium fuel while the others

utilize uranium as fuel.

Apsara the first nuclear reactor was completed on

14th August 1952 at Trombay under the guidance of

the late Dr. H.J. Bhabha. It is the swimming pool

reactor, which consists of a lattice of enriched

uranium (fuel) immersed in a large pool of water.

Water acts as a moderator, coolant and shield. This

reactor is simple, safe, flexible, easily accessible and

cheap.
(2) Nuclear fusion : “ Oposite to nuclear fission,

nuclear fusion is defined as a process in which

lighter nuclei fuse together to form a heavier nuclei.

However, such processes can take place at

reasonable rates only at very high temperatures of

the order of several million degrees, which exist

only in the interior of stars. Such processes are,

therefore, called Thermonuclear reactions

(temperature dependent reactions). Once a fusion

reaction initiates, the energy released in the process

is sufficient to maintain the temperature and to keep

the process going on.

 4 1 H 1 → 2 He 4 + 2 +1 e 0 + Energy
Hydrogen Helium Positron

This is not a simple reaction but involves a set of the

thermonuclear reactions, which take place in stars

including sun. In other words, energy of sun is

derived due to nuclear fission.

Calculation of energy released in nuclear fusion :

Let us write the reaction involving the fusion of four

hydrogen nuclei to form helium nucleus.

4 1H 1 → 2 He
4
+ 2 +1e0
Hydrogen Helium Positron
Mass: 4×1.008144 2×0.000558 =0.001116
4.003873


 
  
or = 4.032576 4.004989

∴ Loss is mass, ∆m = 4.032576 − 4.004989 = 0.027587 amu

∴ Energy released = 0.027587 × 931 MeV = 26.7 MeV

 ∴ Energy released/gm of hydrogen

consumed = 264.7 = 6.7 MeV = 6.7 × 2.3 × 10 7

kcal = 1.54 × 10 8 kcal

Controlled nuclear fusion : Unlike the fission

process, the fusion process could not be controlled.

Since there are estimated to be some 10 17 pounds of

deuterium ( 1H 2) in the water of the earth, and since

each pound is equivalent in energy to 2500 tonnes of

coal, a controlled fusion reactor would provide a

virtually inexhaustible supply of energy.

Comparision of nuclear fission and nuclear

fusion : Now let us compare the efficiency of the

energy conversion of the two processes, i.e. nuclear

fission and nuclear fusion

Nuclear fission reaction,

92 U
235
+ 0 n1 → 56 Ba 141 + 36 Kr
92
+ 2 − 3 0 n1 + 200 MeV

If one atom of uranium is fissioned by one neutron,

the percent efficiency in terms of mass converted

into energy (where 1 mass unit = 931 MeV) will be :

200 MeV
× 100 = 0.09 %
(235 + 1) mass units × 931

Nuclear fusion reaction, 1H

2
+ 1 H 3 → 2 He 4 + 0 n1 + 17 .8 MeV

The percent efficiency of the reaction =

17 .8 MeV
× 100 = 0.35 %
(2 + 3 mass units) × 931
Thus it indicates that for these two fission and fusion

reactions the percent efficiency is approximately

four times greater for the fusion reaction.

Hydrogen bomb : Hydrogen bomb is based on the

fusion of hydrogen nuclei into heavier ones by the

thermonuclear reactions with release of enormous

energy.

As mentioned earlier the above nuclear reactions can

take place only at very high temperatures. Therefore,

it is necessary to have an external source of energy

to provide the required high temperature. For this

purpose, the atom bomb, (i.e., fission bomb) is used

as a primer, which by exploding provides the high

temperature necessary for successful working of

hydrogen bomb (i.e., fusion bomb). In the

preparation of a hydrogen bomb, a suitable quantity

of deuterium or tritium or a mixture of both is

enclosed in a space surrounding an ordinary atomic

bomb. The first hydrogen bomb was exploded in

November 1952 in Marshall Islands; in 1953 Russia

exploded a powerful hydrogen bomb having power

of 1 million tonnes of TNT

A hydrogen bomb is far more powerful than an atom

bomb. Thus if it were possible to have sufficiently

high temperatures required for nuclear fusion, the

 deuterium present in sea (as D 2 O) sufficient to

provide all energy requirements of the world for

millions of years.

Note :  The first nuclear reactor was assembled by

Fermi in 1942.

Difference between Nuclear fission and fusion

Nuclear fission Nuclear fusion

The process occurs only in the The process occurs only in the

nuclei of heavy elements. nuclei of light elements.

The process involves the fission of The process involves the fission

the heavy nucleus to the lighter of the lighter nuclei to heavy

nuclei of comparable masses. nucleus.

The process can take place at The process takes place at

ordinary temperature. higher temperature 10 8 o C) .

The energy liberated during this The energy liberated during the

process is high (200 MeV per process is comparatively low (3

fission) to 24 MeV per fusion)

Percentage efficiency of the energy Percentage efficiency of the

conversion is comparatively less. energy conversion is high (four

times to that of the fission

process).

The process can be controlled for The process cannot be

useful purposes. controlled.

7.11 Isotopes, Isobars, Isotones, Isodiaphers,

Isoelectronic species, Isosters and Nuclear

isomers.

(1) Isotopes : Atoms of a given element which have

same atomic number (nuclear charge) but different

mass number are called isotopes. In other words,

isotopes are the atoms of the same element differing

in mass number. Thus isotopes have same number of

protons and electrons but different number of

neutrons. They have same position in the periodic

table, same chemical properties and same atomic

charge. The term was first coined by Soddy.

However, Aston using mass spectrometer first

separated isotopes ( Ne 20 and Ne 22 ) .

Examples :

(i) 1H
1
, 1H
2
, 1H
3

Hydrogen (Protium) Deuterium Triti um

( p = 1, e = 1, n = 0) ( p = 1, e = 1, n = 0) ( p = 1, e = 1, n = 0)

(ii) 6C
12
, 6 C 13 and 6C
14

(iii) 8O
16
, 8 O 17 , 8 O 18

(iv) 17 Cl
35
and 17 Cl
37

Of all the elements, tin has maximum number of

stable isotopes (ten).

The fractional atomic weight (35.5) of chlorine is

due to the fact that in the ordinary chlorine atom, Cl 35

and Cl 37 are present in the ratio of 3 : 1.

∴ Average atomic weight of Cl =

3 × 35 + 1 × 37
4
= 35 .5 amu

The percentage of a given isotope in the naturally

occurring sample of an element is called Isotopic

abundance. As the isotopic abundance of an

element is constant irrespective of its source, atomic

weight of an element is constant.

(2) Isobars : Isobars are the atoms of different

elements with the same mass number but different

atomic numbers. In other words, isobars have

different number of protons, neutrons and electrons

but the sum of protons and neutrons (i.e., number of

nucleons) is same.

Examples :

(i) 18 Ar 40 , 19 K 40 and 20 Ca
40

(ii) 52 Te
130
, 54 Xe 130 and 56 Ba 130 .

Since isobars are the atoms of different elements,

they will have different physical and chemical

properties.

(3) Isotones : Isotones are the atoms of different

elements with the same number of neutrons but

different mass numbers, e.g. 14 Si 30 , 15 P 31 and 16 S 32 .

Since the variable factor in isotones is the number of

protons (atomic number), they must have different

physical and chemical properties.

Examples :

(i) 14 Si 30 , 14 P 31 and 16 S 32

(ii) 19 K 39 and 20 Ca
40

(iii) 1H
3
and 2 He 4

(iv) 6C
13
and 7 N 14

(4) Isodiaphers : Atoms having same isotopic

number are called isodiaphers.

Mathematically, isotopic number (isotopic excess) =

(N – Z) or (A – 2Z)

Where, N = Number of neutrons; Z = Number of

protons

Examples :

(i) 92 U
235
and 90 Th
231

(ii) 19 K 39 and 9 F 19

(iii) 29 Cu
65
and 24 Cr
55

(5) Isoelectronic species : Species (atoms,

molecules or ions) having same number of electrons

are called isoelectronic.

Examples :
(i) N 3− , O 2− , F − , Ne, Na + , Mg 2+ , Al 3+ , CH 4 , NH 3 , H 2 O and HF have

10 electrons each.

(ii) P 3−
, S 2− , Cl − , Ar , K + and Ca 2+ have 18 electrons each.

(iii) H − , He, Li + and Be 2+ have 2 electrons each.

(iv) CO, CN − and N2 have 14 electrons each.

(v) N 2 O, CO 2 and CNO − have 22 electrons each.

(6) Isosters : Molecules having same number of

atoms and also same number of electrons are called

isosters.

Examples :

(i) N2 and CO
(ii) CO 2 and N 2 O

(iii) HCl and F2

(iv) CaO nad MgS

(v) C6 H 6 (benzene) and inorganic benzene B6 N 6 .

(7) Nuclear isomers : Nuclear isomers (isomeric

nuclei) are the atoms with the same atomic number

and same mass number but with different

radioactive properties. They have same number of

electrons, protons and neutrons. An example of

nuclear isomers is uranium-X (half-life 1.4 min) and

uranium-Z (half-life 6.7 hours). Otto Hahn

discovered nuclear isomers.

The reason for nuclear isomerism is the different

energy states of the two isomeric nuclei. One may

be in the ground state whereas the other should be in

an excited state. The nucleus in the excited state will

evidently have a different half-life.

Now-a-days as much as more than 70 pairs of

nuclear isomers have been found. Few examples

areas follows

(i) 69
Zn and 69
Zn
(T1 / 2 =13 .8 hour ) (T1 / 2 = 57 min)

(ii) 80
Br and 80
Br
(T1 / 2 = 4.4 hour ) (T1 / 2 =18 min)

•
U-235 Examples based on
Example : 19 Naturally occurring boron consists of

two isotopes whose atomic weights are 10.01 and

11.01. The atomic weight of natural boron is 10.81.

Calculate the percentage of each isotope in natural

boron

[IIT 1978, 82; MLNR 1994]

(a) 80

(b) 90

(c) 70

(d) 20

Solution: (a) Let the % of isotope with at. wt.

10.01 = x
 ∴ % of isotope with at. wt. 11.01 =

(100 – x)

x × 10 .01 + (100 − x) × 11 .01

Now since, At. wt. =
100

x × 10 .01 + (100 − x) × 11 .01

10 .81 =
100

x = 20

Hence, % of isotope with at. wt.

10.01 = 20

∴ % of isotope with at. wt. 11.01 =

100 – 20 = 80

7.12 Application of radioactivity and Hazards of

radiations.
Radioisotopes find numerous applications in a

variety of areas such as medicine, agriculture,

biology, chemistry, archeology, engineering and

industry. Some of the are given below :

(1) Age determination (carbon dating) :

Radioactive decay follows a very exact law, and is

virtually unaffected by heat, pressure, or the state of

chemical combination of the decaying nuclei, it can

be used as a very precise clock for dating past

events. For instance, the age of earth has been

determined by uranium dating technique as follows.

Samples of uranium ores are found to contain Pb 206

as a result of long series of α- and β-decays. Now if

it is assumed that the ore sample contained no lead

at the moment of its formation, and if none of the

lead formed from U 238 decay has been lost then the

measurement of the Pb 206 / U 238 ratio will give the value

of time t of the mineral.

No. of atoms of Pb 206

238
= e −λt −1 , where λ is the
No. of atoms of U left

decay constant of uranium-238

Alternatively,

2.303 Initial amount of U 238

t= log
λ Amount of U 238 in the mineral pr esent till date

Similarly, the less abundant isotope of uranium, U 235

eventually decays to Pb 207 ;Th 232 decays to Pb 208 and

thus the ratios of Pb 207 / U 235 and Pb 208 / Th 232 can be used

to determine the age of rocks and minerals. Many

ages have been determined this way to give result

from hundreds to thousands of million of years,.

Besides the above long-lived radioactive substances

viz. U 238 ,U 235 and Th 232 (which have been present on

earth since the elements were formed), several short-

lived radioactive species have been used to

determine the age of wood or animal fossils. One of

the most interesting substances is 6C

14
(half-life 5760

years) which was used by Willard Libby (Nobel

lauret) in determining the age of carbon-bearing

materials (e.g. wood, animal fossils, etc.) Carbon-14

is produced by the bombardment of nitrogen atoms

present in the upper atmosphere with neutrons (from

cosmic rays).

7 N 14 + 0 n1 → 6 C 14 + 1 H 1

Thus carbon-14 is oxidised to CO 2 and eventually

ingested by plants and animals. The death of plants

or animals puts an end to the intake of C 14 from the

atmosphere. After this the amount of C 14 in the dead

tissues starts decreasing due to its disintegration.

6C
14
→ 7 N 14 + −1 e
0

It has been observed that on an average, one gram of

radioactive carbon emits about 12 β-particles per

minute. Thus by knowing either the amount of C-14

or the number of β-particles emitted per minute per

gram of carbon at the initial and final (present)

stages, the age of carbon material can be determined

by using the following formulae.

2.303 N 2.303 N0
λ=
t
log 0
Nt
or t=
λ
log
Nt

where t = Age of the fossil, λ = Decay constant, N0 =

Initial radioactivity (in the fresh wood), Nt =

Radioactivity in the fossil

The above formula can be modified as

2.303 Initial ratio of C 14 / C 12 (in fresh wood)

t= log
λ C 14 / C 12 ratio in the old wood
 2.303 Initial amount of C 14 / C 12 (in fresh wood) 2.303 Radioactiv ity in fresh wood due to C 14
= log = log
λ Amount of C 14 in the old wood λ Radioactiv ity in old wood due to C 14

2.303 × T1 / 2 of C 14 counts min −1 g −1 of C 14 in fresh wood

= log
0.693 counts min −1 g −1 of C 14 in old wood

Similarly, tritium 1H
3
has been used for dating

purposes.

(2) Radioactive tracers (use of radio–isotopes) : A

radioactive isotope can be easily identified by its

radioactivity. Because of similar physical and

chemical properties of radioisotopes and non-

radioisotopes of an element, if a small quantity of

the former is mixed with normal isotope, then

chemical reactions can be studied by determining

the radioactivity of the radioisotope. The

radioactivity can, therefore act as a tag or label that

allows studying the behaviour of the element or

compounding which contains this isotope. An

isotope added for this purpose is known as isotopic

tracer. The radioactive tracer is also known as an

isotopic tracer. The radioactive tracer is also known

as an indicator because it indicates the reaction.

Radioisotopes of moderate half-life periods are used

for tracer work. The activity of radioisotopes can be

detected by means of electroscope, the electrometer

or the Geiger-Muller counter. Tracers have been

used in the following fields :

(i) In medicine : Radioisotopes are used to diagnose

many diseases. For example, Arsenic – 74 tracer is

used to detect the presence of tumours, Sodium –24

tracer is used to detect the presence of blood clots

and Iodine –131 tracer is used to study the activity

of the thyroid gland. It should be noted that the

radioactive isotopes used in medicine have very

short half-life periods.

(ii) In agriculture : The use of radioactive

phosphorus 32
P in fertilizers has revealed how
phosphorus is absorbed by plants. This study has

led to an improvement in the preparation of

fertilizers. 14
C is used to study the kinetics of photo

synthesis.

(iii) In industry : Radioisotopes are used in

industry to detect the leakage in underground oil

pipelines, gas pipelines and water pipes. Radioactive

isotopes are used to measure the thickness of

materials, to test the wear and tear inside a car

engine and the effectiveness of various lubricants.

Radioactive carbon has been used as a tracer in

studying mechanisms involved in many reactions of

industrial importance such as alkylation,

polymerization, catalytic synthesis etc.

(iv) Analytical Studies : Several analytical

procedures can be used employing radioisotopes as

tracers.

(a) Adsorption and occlusion studies : A small

amount of radioactive isotope is mixed with the

inactive substance and the activity is studied before

and after adsorption. Fall in activity gives the

amount of substance adsorbed.

(b) Solubility of sparingly soluble salt : The

solubility of lead sulphate in water may be estimated

by mixing a known amount of radioactive lead with

ordinary lead. This is dissolved in nitric acid and

precipitate as lead sulphate by adding sulphuric

acid. Insoluble lead sulphate is filtered and the

activity of the water is measured. From this, the

amount of PbSO 4 still present in water can be

estimated.

(c) Ion-exchange technique : Ion exchange process

of separation is readily followed by measuring

activity of successive fractions eluted from the

column.
(d) Reaction mechanism : By labelling oxygen of

the water, mechanism of ester hydrolysis has been

studied.

O O
*
R−C + H OH → R−C + R′OH
*
OR OH

(e) Study of efficiency of analytical separations :

The efficiency of analytical procedures may be

measured by adding a known amount of radio-

isotopes to the sample before analysis begins. After

the completion, the activity is again determined. The

comparison of activity tells about the efficiency of

separation.
(3) Use of γ − rays : γ − rays are used for disinfecting

food grains and for preserving food stuffs. Onions,

potatoes, fruits and fish etc., when irradiated with

γ − rays, can be preserved for long periods. High

yielding disease resistant varieties of wheat, rice,

groundnut, jute etc., can be developed by the

application of nuclear radiations. The γ − rays

radiations are used in the treatment of cancer. The

γ − radiations emitted by cobalt –60 can burn

cancerous cells. The γ − radiations are used to

sterilize medical instruments like syringes, blood

transfusion sets. etc. These radiations make the

rubber and plastics objects heat resistant.

Hazards of radiations : The increased pace of

synthesis and use of radio isotopes has led to

increased concern about the effect of radiations on

matter, particularly in biological systems. Although

the radioisotopes have found wide spread uses to

mankind such as atomic power generation, dating,

tracer technique, medicinal treatment, the use of

nuclear energy is an extremely controversial social

and political issue. You should ask yourself, how

you would feel about having a nuclear power plant

in your town. The accident of Chernobyl occurred in

1986 in USSR is no older when radioisotopes

caused a hazard there. The nuclear radiations (alpha,

beta, gamma as well as X-rays) possess energies far

in excess of ordinary bond energies and ionisation

energies. Consequently, these radiations are able to

break up and ionise the molecules present in living

organisms if they are exposed to such radiations.

This disrupts the normal functions of living

organisms. The damage caused by the radiations,

however, depends upon the radiations received. We,

therefore, conclude this chapter by examining the

health hazards associated with radioisotopes.

The resultant radiation damage to living system can

be classified as :
(i) Somatic or pathological damage : This affects

the organism during its own life time. It is a

permanent damage to living civilization produced in

body. Larger dose of radiations cause immediate

death whereas smaller doses can cause the

development of many diseases such as paralysis,

cancer, leukaemia, burns, fatigue, nausea, diarrhoea,

gastrointestinal problems etc. some of these diseases

are fatal.

Many scientists presently believe that the effect of

radiations is proportional to exposure, even down to

low exposures. This means that any amount of

radiation causes some finite risk to living

civilization.

(ii) Genetic damage : As the term implies,

radiations may develop genetic effect. This type of

damage is developed when radiations affect genes

and chromosomes, the body's reproductive material.

Genetic effects are more difficult to study than

somatic ones because they may not become apparent

for several generations.

5.4 Packing constituents in Crystals.

(1) Close packing in crystalline solids : In the

formation of crystals, the constituent particles

(atoms, ions or molecules) get closely packed

together. The closely packed arrangement is that in

which maximum available space is occupied. This

corresponds to a state of maximum density. The

closer the packing, the greater is the stability of the

packed system. It is of two types :

 1 1

4 2

Square close packing

(i) Close packing in two dimensions : The two

possible arrangement of close packing in two

dimensions.

(a) Square close packing : In which the spheres

in the adjacent row lie just one over the other and

show a horizontal as well as vertical alignment and

form square. Each sphere in this arrangement is in

contact with four spheres.

 11 2

6 3

5 4

Hexagonal close packing

(b) Hexagonal close packing : In which the

spheres in every second row are seated in the

depression between the spheres of first row. The

spheres in the third row are vertically aligned with

spheres in first row. The similar pattern is noticed

throughout the crystal structure. Each sphere in this

arrangement is in contact with six other spheres.

Note :  Hexagonal close packing is more dense

than square close packing.

 In hexagonal close packing about

60.4% of available space is occupied by

spheres. Whereas, square close packing

occupies only 52.4% of the space by

spheres.

 In square close packing the vacant

spaces (voids) are between four touching

spheres, whose centres lie at the corners of

a square are called square voids. While in

hexagonal close packing the vacant spaces

 (voids) are between three touching

spheres, whose centres lie at the corners of

an equilateral triangle are called

triangular voids.

a a aa a a

b b b
a a a a
c c c

a a a a a

Close packing in three dimensions

(ii) Close packing in three dimensions : In

order to develop three dimensional close packing, let

us retain the hexagonal close packing in the first

layer. For close packing each spheres in the second

layer rests in the hollow at the centre of three

touching spheres in the layer as shown in figure. The

spheres in the first layer are shown by solid lines

while those in second layer are shown by broken

lines. It may be noted that only half the

triangular voids in the first layer are occupied by

spheres in the second layer (i.e., either b or c).

The unoccupied hollows or voids in the first layer

are indicated by (c) in figure.

There are two alternative ways in which species

in third layer can be arranged over the second layer,

 (a) Hexagonal close packing : The third layer

lies vertically above the first and the spheres in third

layer rest in one set of hollows on the top of the

second layer. This arrangement is called ABAB ….

type and 74% of the available space is occupied by

spheres.

(b) Cubic close packing : The third layer is

different from the first and the spheres in the third

layer lie on the other set of hollows marked ‘C’ in

the first layer. This arrangement is called

ABCABC….. type and in this also 74% of the

available space is occupied by spheres. The cubic

close packing has face centred cubic (fcc) unit cell.

A
B
A A
A
B

A C B ≡ B

B B
C
A A
A

(a) AB AB – type close (b) ABC ABC – type

packing (hexagonal close (c) Hexagonal close packing (hcp) in three
close packing (cubic
packing). close packing). dimensions

This arrangement is found in Be, Mg, Zn, Cd,

Sc, Y, Ti, Zr.

 A
A

C C
≡
≡ B
B
A

A
Cubic close packing (ccp) ≡ face – centred cubic
Cubic close packing (ccp) in three
di i

This arrangement is found in Cu, Ag, Au, Ni, Pt,

Pd, Co, Rh, Ca, Sr.

(c) Body centred cubic (bcc) : This

arrangement of spheres (or atoms) is not exactly

close packed. This structure can be obtained if

spheres in the first layer (A) of close packing are

 A A A A A A
A A
B B B
B
A A A A
A
B B B
A A
A A A A A

Body centred cubic (bcc) close packing in three dimensions

slightly opened up. As a result none of these spheres

are in contact with each other. The second layer of

spheres (B) can be placed on top of the first layer so

that each sphere of the second layer is in contact

with four spheres of the layer below it. Successive

building of the third will be exactly like the first

layer. If this pattern of building layers is repeated

infinitely we get an arrangement as shown in figure.

 This arrangement is found in Li, Na, K, Rb, Ba, Cs,

V, Nb, Cr, Mo, Fe.

(2) Comparison of hcp, ccp and bcc

Property Hexagonal close Cubic close Body centred

packed (hcp) packed (ccp) cubic (bcc)

Arrangement Close packed Close packed Not close

of packing packed

Type of AB AB AB A….. ABC ABC AB AB AB

packing A…. A……

Available 74% 74% 68%

space occupied
Coordination 12 12 8

number

Malleability Less malleable, Malleable and

and ductility hard and brittle ductile

(3) Interstitial sites in close packed structures :

Even in the close packing of spheres, there is left

some empty space between the spheres. This empty

space in the crystal lattice is called site or void or

hole. Voids are of following types

(i) Trigonal void : This site is formed when

three spheres lie at the vertices of an equilateral

 Trigonal

Triogonal void

triangle. Size of the trigonal site is given by the

following relation.

r = 0.155 R

where, r = Radius of the spherical trigonal

site

R = Radius of closely packed spheres

(ii) Tetrahedral void : A tetrahedral void is

developed when triangular voids (made by

 Tetrahedral void

three spheres in one layer touching each other) have

contact with one sphere either in the upper layer or in

the lower layer. This type of void is surrounded by

four spheres and the centres of these spheres lie at the

apices of a regular tetrahedron, hence the name

tetrahedral site for this void.

In a close packed structure, there are two

tetrahedral voids associated with each sphere because

every void has four spheres around it and there are

eight voids around each sphere. So the number of

tetrahedral voids is double the number of spheres

in the crystal structure. The maximum radius of the

atoms which can fit in the tetrahedral voids relative

to the radius of the sphere is calculated to be 0.225:

1, i.e.,

where r is the radius of the tetrahedral void or atom

r
R
,
= 0.225 occupying tetrahedral void and R is the radius of
spheres forming tetrahedral void.

(a) Octahedral void : This type of void is

surrounded by six closely packed spheres, i.e. it is

formed by six spheres. Out of six spheres, four are

placed in the same plane touching each other, one

 Octahedral void

sphere is placed from above and the other from below

the plane of these spheres. These six spheres

surrounding the octahedral void are present at the

vertices of regular octahedron. Therefore, the

number of octahedral voids is equal to the number

of spheres. The ratio of the radius (r) of the atom or

ion which can exactly fit in the octahedral void

formed by spheres of radius R has been calculated to

be 0.414, i.e.

r
= 0.414
R

(b) Cubic void : This type of void is formed

between 8 closely packed spheres which occupy all

the eight corner of cube i.e. this site is surrounded

by eight spheres which touch each other. Here radius

ratio is calculated to be 0.732, i.e.

r
= 0.732
R
 Cubic void

Cubic void

Thus, the decreasing order of the size of the various

voids is Cubic > Octahedral > Tetrahedral >

Trigonal

Important Tips

 At the limiting value of radius ratio r+ /r− , the

forces of attraction & repulsion are equal.

 The most malleable metals (Cu, Ag, Au) have

cubic close packing.

 Cubic close packing has fcc (face centred

cubic) unit cell

 Number of octahedral voids = Number of

atoms present in the closed packed

arrangement.

 Number of tetrahedral voids = 2 × Number of

octahedral voids = 2 × Number of atoms.

5.5 Mathematical analysis of Cubic system.

 Simplest crystal system is to be studied in cubic

system. Three types of cubic systems are following

• Simple cubic (sc) : Atoms are arranged only at

the corners.

• Body centred cubic (bcc) : Atoms are

arranged at the corners and at the centre of the cube.

• Face centred cubic (fcc) : Atoms are arranged

at the corners and at the centre of each faces.

(1) Atomic radius : It is defined as the half of

the distance between nearest neighbouring atoms in

a crystal. It is expressed in terms of length of the

edge (a) of the unit cell of the crystal.

 (i) Simple cubic structure (sc) : Radius of

a
atom 'r' = 2

(ii) Face centred cubic structure (fcc) : 'r' =

a
2 2

r r

(iii) Body centred cubic structure (bcc) : 'r' =

3a
4

(2) Number of atoms per unit cell/Unit cell

contents : The total number of atoms contained in

the unit cell for a simple cubic called the unit cell

content.

(i) Simple cubic structure (sc) : Each corner

atom is shared by eight surrounding cubes.

1
Therefore, it contributes for 8
of an atom. ∴

1
Z=8×
8
=1 atom per unit cell in crystalline solid.

(ii) Face centered cubic structure (fcc) : The

1
eight corners atoms contribute for 8
of an atom and

thus one atom per unit cell. Each of six face centred

atoms is shared by two adjacent unit cells and

therefore one face centred atom contribute half of its

share. ∴ Z = 6 × 12 = 3 atom per unit cell.

So, total Z = 3 + 1 = 4 atoms per unit cell.

(iii) Body centered cubic structure (bcc) : Eight

corner atoms contribute one atom per unit cell.

Centre atom contribute one atom per unit cell.

1
So, total 1 + 1 = 2 atoms per unit cells. Z=8×
8
+1= 2

Note :  Number of atoms in unit cell : It can

nc n f ni
be determined by the simplest relation =
8
+ +
2 1

Where nc = Number of atoms at the

corners of the cube = 8

 nf = Number of atoms at six faces of the

cube = 6

ni = Number of atoms inside the cube = 1

Cubic unit cell nc nf ni Total atom

in per unit

cell

Simple cubic (sc) 8 0 0 1

body centered cubic 8 0 1 2

(bcc)
Face centered cubic 8 6 0 4

(fcc)

(3) Co-ordination number (C.N.) : It is defined

as the number of nearest neighbours or touching

particles with other particle present in a crystal is

called its co-ordination number. It depends upon

structure of the crystal.

(i) For simple cubic system C.N. = 6.

(ii) For body centred cubic system C.N. = 8

 (iii) For face centred cubic system C.N. = 12.

(4) Density of the unit cell : It is defined as the

ratio of mass per unit cell to the total volume of unit

cell.

Density of unit cell

mass of unit cell Number of particl es × mass of each particle

(ρ ) =
volume of unit cell
;ρ =
volume of the unit cell
or

Z× M
a3 × N 0

Where Z = Number of particles per unit cell, M

= Atomic mass or molecular mass, N0 = Avogadro

number (6.023 × 10 23 mol −1

) , a= Edge length of the unit

cell= a pm = a × 10 −10 cm , a3 = volume of the unit cell

 Z× M
i.e. ρ=
a × N 0 × 10 − 30
3
g / cm 3

The density of the substance is same as the

density of the unit cell.

(5) Packing fraction (P.F.) : It is defined as

ratio of the volume of the unit cell that is occupied

by spheres of the unit cell to the total volume of the

unit cell.

Let radius of the atom in the packing = r

Edge length of the cube = a

Volume of the cube V = a3

 4 3
Volume of the atom (spherical) ν =
3
πr , then

4 3
νZ πr Z
packing density =
V
= 3 3
a

(i) Simple cubic unit cell : Let the radius of

atom in packing is r. Atoms are present at the corner

of the cube, each of the eight atom present at the

eight corners shared amongst eight unit cells.

1
Hence number of atoms per unit cell = 8×
8
=1 ,

a
again r=
2

4 3
πr
∴ P.F. = 3 3 = 0.52 ; % P.F. = 52%, then % of void
(2r )

= 100 – 52 = 48%
 (ii) Body centred cubic unit cell : Number of

1 3a
atoms per unit cell = 8×
8
+1 = 2 , r=
4

4 3
2× πr
P.F. = 3 = 0.68 ; % P.F. = 68%, then % of void
3
 4r 
 
 3

= 100 – 68 = 32%

(iii) Face centred cubic unit cell : Number of

2a
atoms per unit cell = 4, r=
4

4 3
4× πr
P.F . = 3 = 0.74 ; % P.F. = 74 % , then % of void =
3
 4r 
 
 2

100 – 74=26%
 Structure r related to a Volume of the Packing

atom (ν) density

a 4  a
3 π
Simple r=
2 π 
3  2 6
= 0.52

cubic

a 3
Face- r= 4  a  2π
π = 0.74
2 2 3  2 2  6

centred

cubic

3π
3
Body- r=
3a 4  3a 
π = 0.68
4 3  4  8

centred

cubic
(6) Ionic radii : X-ray diffraction or electron

diffraction techniques provides the necessary

information regarding unit cell. From the

dimensions of the unit cell, it is possible to calculate

ionic radii.

Cl–

a/2

90°
Na+ Cl–

a/2

Radii of chloride ion

Let, cube of edge length 'a' having cations and

anions say NaCl structure.

Then, rc + ra = a / 2

where rc and ra are radius of cation and anion.

(a / 2) 2 + (a / 2) 2 a
Radius of Cl − =
2
=
4

3a
For body centred lattice say CsCl . rc + ra =
2

Radius ratio : Ionic compounds occur in

crystalline forms. Ionic compounds are made of

cations and anions. These ions are arranged in three

dimensional array to form an aggregate of the type

(A+B–)n . Since, the Coulombic forces are non-

directional, hence the structures of such crystals are

mainly governed by the ratio of the radius of cation

(r+ ) to that of anion (r− ). The ratio r+ to r− (r+ / r− ) is

called as radius ratio.

r+
Radius ratio =
r−

r+/r– > 0.414 to 0.732 r+/r– < 0.414

(b) (c)

r+/r– = 0.414 Unstable

r+/r– > 0.732 (a)

Coordination number Coordination number

increases from 6 to 8 decreases from 6 to 4

Effect of radius ratio on co-ordination

number

The influence of radius ratio on co-ordination

number may be explained as follows : Consider an

ideal case of octahedral voids in close packing of

anions with radius ratio 0.414 and co-ordination

number six. An increase in size of cation increases

the radius ratio from 0.414, then the anions move

apart so as to accommodate the larger cation. As the

radius ratio increases more and more beyond 0.732,

the anions move further and further apart till a stage

is obtained when more anions can be accommodated

and this cation occupies a bigger void i.e., cubic

void with co-ordination number eight.

When the radius ratio decreases from 0.414, the

six anions would not be able to touch the smaller

cation and in doing so, they overlap each other. This

causes the cation to occupy a smaller void i.e.,

 tetrahedral void leading to co-ordination number

four

Limiting Radius ratios and Structure

Limiting radius ratio C.N. Shape

(r+)/(r–)

< 0.155 2 Linear

0.155 – 0.225 3 Planar triangle

0.225 – 0.414 4 Tetrahedral

0.414 – 0.732 6 Octahedral

0.732 – 0.999 or 1 8 Body-centered cubic

 Characteristics of Some Typical Crystal

Structure

r+
Cryst Type of Example r−
C.N Number of

al unit cell . formula units of

(AB, or AB2) per

unit cell

CsBr Body- CsBr, TiCl 0.93 8 – 1

centred 8

NaCl Face- AgCl, MgO 0.52 6 – 4

centred 6

ZnS Face- ZnS 0.40 4 – 4

 centred 4

CaF2 Face- CaF2, SrF2, 0.73 8 – 4

centred CdF2, ThO2 4

Note :  The ionic radius increases as we move

from top to bottom in a group of periodic

table for example :

Na + < K + < Rb + < Cs+ and F − < Cl − < Br − < I −

 Along a period, usually iso-electronic ions

are obtained e.g. Na+ , Mg 2+ , Al 3 + (greater the nuclear

charge, smaller the size, Al 3 + < Mg 2 + < Na + )

 Examples based on Packing constituents in Crystals and
Mathematical analysis

Example : 3 A metallic element crystallizes into a

lattice containing a sequence of layers of

ABABAB ............ Any packing of spheres

leaves out voids in the lattice. The

percentage by volume of empty space of

this is

(a) 26%

(b) 21%

(c) 18%

(d) 16 %
Solution :(a) The hexagonal base consists of six

equilateral triangles, each with side 2r and altitude

2r sin 60°.

1 
Hence, area of base = 6  (2r ) (2r sin 60 o ) = 6 3 .r 2
2 

The height of the hexagonal is twice the

distance between closest packed layers.

The latter can be determined to a face

centred cubic lattice with unit cell length a. In such a

lattice, the distance between closest packed layers is

3a
one third of the body diagonal, i.e. 3
, Hence

 3a  2a
Height (h) = 2  =
 3  3
 Now, in the face centred lattice, atoms

touch one another along the face diagonal,

Thus, 4r = 2 . a

With this, the height of hexagonal

2  4r   2
becomes : Height (h) =   = 4  .r
3  2   3 

Volume of hexagonal unit is, V= (base

4 2 
area) × (height) = (6 3 r 2 )  . r  = 24 2. r 3
 3 

In one hexagonal unit cell, there are 6

atoms as described below :

• 3 atoms in the central layer which exclusively

belong to the unit cell.

• 1 atom from the centre of the base. There are

two atoms of this type and each is shared between

two hexagonal unit cells.

• 2 atoms from the corners. There are 12 such

atoms and each is shared amongst six hexagonal unit

cells.

Now, the volume occupied by atoms =

4 
6  πr 3 
3 

Fraction of volume occupied by atoms

4 
6 πr 3 
Volume occupied by atoms 3  = / 3 2 = 0.74 .
= = 3
π
Volume of hexagonal unit cell 24 2. r

Fraction of empty space = (1.00 − 0.74 ) = 0.26

 Percentage of empty space = 26%

Example : 4 Silver metal crystallises in a cubic

closest – packed arrangement with the edge of the

unit cell having a length a = 407 pm. . What is the radius

of silver atom.

(a) 143.9 pm (b) 15.6 pm (c)

11.59 pm (d) 13.61 pm

Solution :(a) AC 2 + AB 2 = BC 2

here AC = AB = a, BC = 4r

a 2 + a 2 = (4r ) 2
 C
r

407 pm 2r

r
B
A
407 pm

2a 2 = 16 r 2

a2
∴ r2 =
8

a 407
∴ r= = = 143 .9 pm .
2 2 2 2

Example : 5 From the fact that the length of the

side of a unit cell of lithium is 351 pm. Calculate its

atomic radius. Lithium forms body centred cubic

crystals.

(a) 152.69 pm
(b) 62.71 pm

(c) 151.98 pm

(d) 54.61 pm

Solution : (c) In (bcc) crystals, atoms touch each

other along the cross diagonal.

a 3 3
Hence, Atomic radius (R) =
4
= 351 ×
4
= 151 .98 pm

Example : 6 Atomic radius of silver is 144.5 pm.

The unit cell of silver is a face centred cube.

Calculate the density of silver.

(a) 10.50 g/cm3

(b) 16.50 g/cm3

(c) 12.30 g/cm3

(d) 15.50 g/cm3

Solution :(a) For (fcc) unit cell, atoms touch each

other along the face diagonal.

a 2
Hence, Atomic radius (R) =
4

4R 4
a= = × 144 .5 pm = 408 .70 pm = 408 .70 × 10 −10 cm
2 2

ZM
Density (D) =
VN 0
, V = a3

ZM
D = a3 N 0
; where Z for (fcc) unit cell = 4 ,

Avagadro’s number ( N 0 ) = 6.023 × 10 23 , Volume of cube

( V ) = (408 .70 × 10 −10 3

) cm 3 and M (Mol. wt.) of silver = 108,
 4 × 108
D =
(408 .70 × 10 −10 )3 × 6.023 × 10 23
= 10 .50 g / cm 3

Example : 7 Lithium borohydride (LiBH 4 ),

crystallises in an orthorhombic system with 4

molecules per unit cell. The unit cell dimensions are

: a = 6.81Å, b= 4.43Å, c=717Å. If the molar mass of

LiBH 4 is 21.76 g mol −1

. The density of the crystal is –

(a) 0.668 g cm −3

(b) 0.585 g cm 2

(c) 1.23 g cm −3

(d) None
Solution : (a) We know that,

ZM 4 × (21 .76 gmol −1 )

ρ= = = 0.668 g cm −3
N 0 V (6.023 × 10 mol −1 )(6.81 × 4.43 × 7.17 × 10 − 24 cm 3 )
23

Example : 8 A metallic elements exists as a cubic

lattice. Each edge of the unit cell is 2.88Å. The

density of the metal is 7.20 g cm −3 . How many unit

cells will be present in 100 gm of the metal.

(a) 5.82 × 10 23

(b) 6.33 × 10 23

(c) 7.49 × 10 24

(d) 6.9 × 10 24
Solution : (a) The volume of unit cell (V) = a3 =

(2.88Å)3 = 23 .9 × 10 −24 cm 3

Volume of 100 g of the metal =

Mass 100
= = 13 .9cm 2
Density 7.20

Number of unit cells in this volume =

13 .9cm 3
= 5.82 × 10 23
23 .9 × 10 − 24 cm 3

Example : 9 Silver crystallizes in a face centred

cubic system, 0.408 nm along each edge. The

density of silver is 10.6 g / cm 3 and the atomic mass is

107.9 g / mol . Calculate Avogadro's number.

(a) 6.00 × 10 23 atom/mol

(b) 9.31 × 10 23 atom/mol

(c) 6.23 × 10 23 atom/mol

(d) 9.61 × 10 23 atom/mol

Solution:(a) The unit cell has a volume of (0.408

× 10 −9 m)3 = 6.79 × 10 −29 m 3 per unit cell and contains four

atoms. The volume of 1 mole of silver is,

 (1 × 10 −2 m)3 
107 .9 g / mol  −5
 = 1.02 × 10 m / mol
3
; where
 10 . 6 g 

107.9 g/mol is the molecular mass of the silver

The number of unit cells per mol. is,

 1unit cell 
1.02 × 10 − 5 m 3 / mol  − 29
 = 1.50 × 10
23
unit cells
 6.79 × 10 m 
3

per mol.
 and the number of atoms per mol. is,

 4 atoms   1.50 × 10 unit cell 

23
   = 6.00 × 10
23
atom/mol.
 unit cell   mol 

Example: 10 Fraction of total volume occupied by

atoms in a simple cube is

π
(a) 2

3π
(b) 8

2π
(c) 6

π
(d) 6

Solution:(d) In a simple cubic system, number of

atoms a = 2r
 4 3 4 3
πr πr
Volume occupied by one atom π
∴ Packing fraction =
Volume of unit cell
= 3 3 = 3 3 =
a (2r ) 6

Example: 11 A solid AB has the NaCl structure. If

radius of cation A+ is 120 pm, calculate the

maximum possible value of the radius of the anion

B−

(a) 240 pm

(b) 280 pm

(c) 270 pm

(d) 290 pm

Solution:(d) We know that for the NaCl structure

 radius of cation/radius of anion = 0.414;
r A+ r A+ 120
rB−
= 0.414 ; rB− =
0.414
=
0.414
= 290 pm

Example: 12 CsBr has a (bcc) arrangement and its unit cell edge lengt

(a) 346.4 pm

(b) 643 pm

(c) 66.31 pm

(d) 431.5 pm

Solution:(a) The (bcc) structure of CsBr is given in

figure

The body diagonal AD = a 3 , where a is the length of

edge of unit cell

 C

A B

On the basis of figure

AD = 2(rCs+ + rCl − )

a 3 = 2(rCs+ + rCl − ) or

a 3 3
(rCs+ + rCl − ) = = 400 × = 200 × 1.732 = 346 .4 pm
2 2

5.6 Crystal structures and Method of

determination.

Ionic compounds consist of positive and negative

ions arranged in a manner so as to acquire minimum

potential energy (maximum stability). To achieve

the maximum stability, ions in a crystal should be

arranged in such a way that forces of attraction are

maximum and forces of repulsion are minimum.

Hence, for maximum stability the oppositely

charged ions should be as close as possible to one

another and similarly charged ions as far away as

possible from one another. Among the two ions

constituting the binary compounds, the larger ions

(usually anions) form a close-packed arrangement

(hcp or ccp) and the smaller ions (usually cations)

occupy the interstitial voids. Thus in every ionic

compound, positive ions are surrounded by negative

ions and vice versa. Normally each ions is

surrounded by the largest possible number of

oppositely charged ions. This number of oppositely

charged ions surrounding each ions is termed its

coordination number.

Classification of ionic structures : In the

following structures, a black circle would denote an

anion and a white circle would denote a cation. In

any solid of the type A x By the ratio of the coordination

number of A to that of B would be y:x .

(1) Rock salt structure : The NaCl structure is

composed of Na + and Cl − . The no. of Na + ions is equal

 =Na+
= Cl–

Na+ ion surrounded

Cl– ion surrounded
octahedrally octahedrally by six
Cl– ions octahedrally by six Na+ ions
Structure of NaCl (rock salt)

to that of Cl − . The radii of Na + and Cl − are 95 pm and

rNa + 95 pm
181 pm respectively =
rCl − 181 pm
= 0.524 . The radius

ratio of 0.524 for NaCl suggests an octahedral voids.

Chloride is forming a fcc unit cell in which Na + is in

the octahedral voids. The coordination number of

Na + is 6 and therefore that of Cl − would also be 6.

Moreover, there are 4 Na + ions and 4 Cl − ions per unit

cell. The formula is Na 4 Cl 4 i.e., NaCl. The other

substances having this kind of a structure are halides

of all alkali metals except cesium, halides and

oxides of all alkaline earth metals except berylium

oxide.

The zine sulphide crystals are composed of

equal no. of Zn +2 and S 2− ions. The radii of
two ions ( Zn +2 = 74 pm and S 2− = 184 pm )
led to the radius ratio ( r + / r − ) as 0.40 which
suggests a tetrahedral arrangement
rZn+2 74 pm
2−
= = 0.40
rS 184 pm
=Zn2+ ion
= S2– ion

Structure of ZnS (Zinc blende)

(2) Zinc blende structure : Sulphide ions are face

centred and zinc is present in alternate tetrahedral

voids. Formula is Zn4 S4 , i.e., ZnS. Coordination

number of Zn is 4 and that of sulphide is also 4.

Other substance that exists in this kind of a structure

is BeO.

(3) Fluorite structure : Calcium ions are face

centred and fluorite ions are present in all the

tetrahedral voids. There are four calcium ions and

eight fluoride ions per unit cell. Therefore the

formula is Ca 4 F8 , (i.e. CaF2 ). The coordination number

of fluoride ions is four (tetrahedral voids) and thus

the coordination number of calcium ions is eight.

Other substances which exist in this kind of

structure are UO2 and ThO 2 .

= Ca2+
=F–

Structure of CaF2 (Fluorite)

(4) Anti-fluorite structure : Oxide ions are face

centred and lithium ions are present in all the

tetrahedral voids. There are four oxide ions and

eight lithium ions per unit cell. As it can be seen,

this unit cell is just the reverse of fluorite structure,

in the sense that, the position of cations and anions

is interchanged. Other substances which exist in this

kind of a structure are Na 2 O , K 2O and Rb 2 O .

(5) Spinel and inverse spinel structure : Spinel is a

mineral (MgAl 2 O4 ) . Generally they can be represented

as M 2+ M 23+ O4 . Where M 2+ is present in one-eighth of

tetrahedral voids in a fcc lattice of oxide ions and

M 3+ present in half of the octahedral voids. M 2+ is

usually Mg, Fe, Co, Ni, Zn and Mn, M 3+ is generally

Al, Fe, Mn, Cr and Rh. e.g., ZnAl 2 O4 , Fe3 O4 , FeCr 2 O4 etc.
(6) Cesium halide structure : Chloride ions are

primitive cubic while the cesium ion occupies the

centre of the unit cell. There is one chloride ion and

one cesium ion per unit cell. Therefore the formula

is CsCl. The coordination number of cesium is eight

and that of chloride is ions is also eight. Other

substances which exist in this kind of a structure are

all halides of cesium.

The CsCl crystal is composed of equal no. of Cs + and

Cl − ions. The radii of two ions ( Cs +

= 160 pm and

Cl − = 181 pm ) led to radius ratio of rCs+ to rCl − as 0.884

rCs+ 160 pm
= = 0.884
rCl − 181 pm
Suggests a body centred cubic structure cubic

structure having a cubic hole.

Cs+ ion surrounded by 8 Cl– ions

Cl– ion surround by 8 Cs+ ions

= Cs+
= Cl–

Structure of caesium chloride

(7) Corundum structure : The general formula of

compounds crystallizing in corundum structure is

Al 2 O3 . The closest packing is that of anions (oxide) in

hexagonal primitive lattice and two-third of the

octahedral voids are filled with trivalent cations.

e.g., Fe2 O3 , Al 2 O3 and Cr 2 O3 .

(8) Pervoskite structure : The general formula is

ABO 3 . One of the cation is bivalent and the other is

tetravalent. e.g., CaTiO 3 , BaTiO 3 . The bivalent ions are

present in primitive cubic lattice with oxide ions on

the centres of all six square faces. The tetravalent

cation is in the centre of the unit cell occupying

octahedral void.

Note :  On applying high pressure, NaCl structure

having 6:6 coordination number changes to CsCl

structure having 8:8 coordination number similarly,

CsCl having 8:8 coordination number on heating to

760 K changes to NaCl structure having 6:6

coordination number.

NaCl Pressure
CsCl
Temp.
6 : 6 Co − orditnation number 8 : 8 Co − orditnation number

Depending upon the relative number of positive and

negative ions present in ionic compounds, it is

convenient to divide them into groups like AB, AB2,

AB3, etc. Ionic compounds of the type AB and AB2

are discussed below.

S. Crystal Brief description Examples Co- Num

No. Structu ordinati ber of

re on form

number ula

units

per

unit

cell

1. Type It has fcc Halides of Li, Na+ = 6 4

AB arrangement in Na, K, Rb,

Cl − = 6

Rock which Cl − ions AgF, AgBr,

salt occupy the corners NH4Cl, NH4Br,

 (NaCl) and face centres of NH4I etc.

type a cube while Na +

ions are present at

the body and edge

of centres.

2. Zinc It has ccp CuCl , CuBr , CuI , AgI , BeS Zn2+ = 4 4

blende arrangement in
S 2− = 4

(ZnS) which S2 − ions form

type fcc and each Zn2+ ion

is surrounded

tetrahedrally by

four S 2− ions and

 vice versa.

3. Type It has arrangement BaF2 , BaCl 2 , SrF2 Ca 2+ = 8 4

AB2 in which Ca 2+ ions SrCl 2 , CdF2 , PbF2

F− = 4

Fluorite form fcc with each

(CaF2) Ca 2+ ions surrounded

type by 8F − ions and

each F− ions by

4Ca2+ ions.

4. Antiflu Here negative ions Na2O Na + = 4 4

orite form the ccp

O 2− = 8

type arrangement so that

each positive ion is

 surrounded by 4

negative ions and

each negative ion

by 8 positive ions

CsCl , CsBr , CsI , CsCN ,

5. Caesiu It has the bcc Cs+ = 8 1
TlCl , TlBr , TlI and
m arrangement with
Cl − = 8
TlCN

chlorid Cs+ at the body

e centre and Cl − ions

(CsCl) at the corners of a

type cube or vice versa.

(iii) Crystal structure of some metals at room

temperature and pressure :

Li B
Body
N M Al
Face
K C Sc Ti V C M Fe C Ni C Z
Simple
R Sr Y Zr N M Tc R R P A C
Hexagonal
Cs B close

5.7 Experimental method of determining Crystal

structure.

X-ray diffraction and Bragg’s Equation :

Crystal structure has been obtained by studying on

the diffraction of X-rays by solids. A crystal, having

constituents particles arranged in planes at very

small distances in three dimension array, acts as

diffraction grating for X- rays which have

wavelengths of the same order as the spacing in

crystal.

When a beam of X-rays passes through a crystalline

solid, each atom in the beam scatters some of the

radiations. If waves are on same phase means if their

peak and trough coincides they add together to give

a wave of greater amplitude. This enhancement of

intensity is called constructive interference. If waves

are out of phase, they cancel. This cancellation is

called destructive interference.

Thus X- ray diffraction results from the scattering of

X-rays by a regular arrangement of atoms or ions.

Bragg’s equation : Study of internal structure

of crystal can be done with the help of X-rays. The

distance of the constituent particles can be

determined from diffraction value by Bragg’s

equation,.

nλ = 2d sinθ where, λ = Wave

length of X-rays, n = order of diffraction,

θ = Angle of

reflection, d = Distance between two parallel

surfaces
 The above equation is known as Bragg’s

equation or Bragg’s law. The reflection

corresponding to n = 1 (for a given family of planes)

is called first order reflection; the reflection

corresponding to n = 2 is the second order reflection

and so on. Thus by measuring n (the order of

reflection of the X-rays) and the incidence angle θ,

d n
we can know d/λ. λ
=
2 sin θ

From this, d can be calculated if λ is known and

vice versa. In X-ray reflections, n is generally set as

equal to 1. Thus Bragg’s equation may alternatively

be written as
 λ = 2 d sinθ = 2 dhkl sinθ

Where dhkl denotes the perpendicular distance

between adjacent planes with the indices hkl.

Examples based on X-ray diffraction and

Bragg’s equation

Example : 15 The first order reflection (n = 1) from

a crystal of the X-ray from a copper anode tube

(λ = 0.154 nm) occurs at an angle of 16.3°. What is the

distance between the set of planes causing the

diffraction.

(a) 0.374 nm
(b) 0.561 nm

(c) 0.274 nm

(d) 0.395 nm

Solution :(c) From Bragg’s equation, nλ = 2d sinθ ;

n× λ 1 × 0.154 0.154 nm
d= = = = 0.274 nm
2 sin θ 2(sin 16 .3) 2 × 0.281

Example : 16 The diffraction of barium with X-

radiation of wavelength 2.29Å gives a first – order

reflection at 30°. What is the distance between the

diffracted planes.

(a) 3.29 Å

(b) 4.39 Å
(c) 2.29 Å

(d) 6.29 Å

Solution :(c) Using Bragg's equation 2d sinθ = nλ

nλ
d=
2 sinθ
, where d is the distance between two

diffracted planes, θ the angle to have maximum

intensity of diffracted X-ray beam, n the order of

reflection and λ is the wavelength

1 × 2.29 Å  1
∴ d= = 2.29 Å  sin 30 = 
o

2 × sin 30 o  2

Example : 17 When an electron in an excited Mo

atom falls from L to the K shell, an X-ray is emitted.

These X-rays are diffracted at angle of 7.75 o by

planes with a separation of 2.64Å. What is the

difference in energy between K-shell and L-shell in

Mo assuming a first-order diffraction. (sin 7.75 o = 0.1349 )

(a) 36.88 × 10 −15 J

(b) 27 .88 × 10 −16 J

(c) 63.88 × 10 −17 J

(d) 64 .88 × 10 −16 J

Solution : (b) 2d sinθ = nλ

λ = 2d sinθ = 2 × 2.64 × 10 −10 × sin 7.75 o = 0.7123 × 10 −10 m

hc 6.62 × 10 −34 × 3 × 10 8
E= = = 27 .88 × 10 −16 J
λ 0.7123 × 10 −10

5.8 Defects or Imperfections in Solids.

 Any deviation from the perfectly ordered

arrangement constitutes a defect or imperfection.

These defects sometimes called thermodynamic

defects because the number of these defects depend

on the temperature. Crystals may also possess

additional defect due to the presence of impurities.

Imperfection not only modify the properties of

solids but also give rise to new properties. Any

departure from perfectly ordered arrangement of

atoms in crystals called imperfections or defects.

(1) Electronic imperfections : Generally, electrons

are present in fully occupied lowest energy states.

But at high temperatures, some of the electrons may

occupy higher energy state depending upon the

temperature. For example, in the crystals of pure Si

or Ge some electrons are released thermally from

the covalent bonds at temperature above 0 K. these

electrons are free to move in the crystal and are

responsible for electrical conductivity. This type of

conduction is known as intrinsic conduction. The

electron deficient bond formed by the release of an

electron is called a hole. In the presence of electric

field the positive holes move in a direction opposite

to that of the electrons and conduct electricity. The

electrons and holes in solids gives rise to electronic

imperfections.

(2) Atomic imperfections/point defects : When

deviations exist from the regular or periodic

arrangement around an atom or a group of atoms in

a crystalline substance, the defects are called point

defects. Point defect in a crystal may be classified

into following three types;

Point defects

(i) Stoichiometric defects (ii) Non-

stoichiometric defects (iii) Impurity defects

 (i) Stoichiometric defects : The compounds in

which the number of positive and negative ions are

exactly in the ratios indicated by their chemical

formulae are called stoichiometric compounds. The

defects do not disturb the stoichiometry (the ratio of

numbers of positive and negative ions) are called

stoichiometric defects. These are of following types

(a) Schottky defects : This type of defect when

equal number of cations and anions are missing

from their lattice sites so that the electrical neutrality

is maintained. This type of defect occurs in highly

ionic compounds which have high co-ordination

number and cations and anions of similar sizes. e.g.,

NaCl, KCl, CsCl and KBr etc.

(b) Interstitial defects : This type of defect is

caused due to the presence of ions in the normally

vacant interstitial sites in the crystals.

(c) Frenkel defects : This type of defect arises when

an ion is missing from its lattice site and occupies an

interstitial position. The crystal as a whole remains

electrically neutral because the number of anions

and cations remain same. Since cations are usually

smaller than anions, they occupy interstitial sites.

This type of defect occurs in the compounds which

have low co-ordination number and cations and

anions of different sizes. e.g., ZnS, AgCl and AgI

etc. Frenkel defect are not found in pure alkali metal

halides because the cations due to larger size cannot

get into the interstitial sites. In AgBr both Schottky

and Frenkel defects occurs simultaneously.

A+ B– A+ B– A+ B– A+ B– A+ B– A+ B–
A+
B– A+ B– A+ B+ A– A+ B– A+ B– A+

A+ B– A+ B– B– A+ B– B– A+ B–

Ideal Crystal Schottky defect Frenkel defect

 Consequences of Schottky and Frenkel

defects : Presence of large number of Schottky

defect lowers the density of the crystal. When

Frenkel defect alone is present, there is no decrease

in density. The closeness of the charge brought

about by Frenkel defect tends to increase the

dielectric constant of the crystal. Compounds having

such defect conduct electricity to a small extent.

When electric field is applied, an ion moves from its

lattice site to occupy a hole, it creates a new hole. In

this way, a hole moves from one end to the other.

Thus, it conducts electricity across the crystal. Due

to the presence of holes, stability (or the lattice

energy) of the crystal decreases.

(ii) Non-Stoichiometric defects : The defects which

disturb the stoichiometry of the compounds are

called non-stoichiometry defects. These defects are

either due to the presence of excess metal ions or

excess non-metal ions.

(a) Metal excess defects due to anion vacancies :

A compound may have excess metal anion if a

negative ion is absent from its lattice site, leaving a

‘hole’, which is occupied by electron to maintain

electrical neutrality. This type of defects are found

in crystals which are likely to possess Schottky

defects. Anion vacancies in alkali metal halides are

reduced by heating the alkali metal halides crystals

in an atmosphere of alkali metal vapours. The

‘holes’ occupy by electrons are called F-centres (or

colour centres).

(b) Metal excess defects due to interstitial cations

: Another way in which metal excess defects may

occur is, if an extra positive ion is present in an

interstitial site. Electrical neutrality is maintained by

the presence of an electron in the interstitial site.

This type of defects are exhibit by the crystals which

are likely to exhibit Frenkel defects e.g., when ZnO

is heated, it loses oxygen reversibly. The excess is

accommodated in interstitial sites, with electrons

trapped in the neighborhood. The yellow colour

and the electrical conductivity of the non-

stoichiometric ZnO is due to these trapped

electrons.

A+ B– A+ B– A+ B– A+ B–

A+
B– A+ B– A+ B– A+ B– A+

A+ B– A+ B– A+ e– A+ B–

Metal excess defect due to extra Metal excess defect due to anion vacancy
ti

Consequences of Metal excess defects :

• The crystals with metal excess defects are

generally coloured due to the presence of free

electrons in them.

• The crystals with metal excess defects conduct

electricity due to the presence of free electrons and

are semiconductors. As the electric transport is

mainly by “excess” electrons, these are called n-type

(n for negative) semiconductor.

• The crystals with metal excess defects are

generally paramagnetic due to the presence of

unpaired electrons at lattice sites.

Note :  Colour Centres : Crystals of pure alkali

metal halides such as NaCl, KCl, etc. are white.

However, alkali metal halides becomes coloured

on heating in excess of alkali metal vapour. For

example, sodium chloride becomes yellow on

heating in presence of sodium vapour. These

colours are produced due to the preferential

absorption of some component of visible

spectrum due to some imperfections called colour

centres introduced into the crystal.

When an alkali metal halide is heated in an

atmosphere containing an excess of alkali metal

vapour, the excess alkali metal atoms deposit on the

crystal surface. Halide ions then diffuse to the

surface where they combine with the metal atoms

which have becomes ionised by loosing valence

electrons. These electrons diffuse back into the

crystal and occupy the vacant sites created by the

halide ions. Each electron is shared by all the alkali

metal ions present around it and is thus a delocalized

electrons. When the crystal is irradiated with white

light, the trapped electron absorbs some component

of white light for excitation from ground state to the

excited state. This gives rise to colour. Such points

are called F-centres. (German word Farbe which

means colour) such excess ions are accompanied by

positive ion vacancies. These vacancies serve to trap

holes in the same way as the anion vacancies

trapped electrons. The colour centres thus produced

are called V-centres.

(c) Metal deficiency defect : These arise in two

ways

• By cation vacancy : in this a cation is missing

from its lattice site. To maintain electrical

neutrality, one of the nearest metal ion acquires two

positive charge. This type of defect occurs in

compounds where metal can exhibit variable

valency. e.g., Transition metal compounds like NiO,

FeO, FeS etc.

A+ B– A+ B–
Cation vacancy

B– B– A+

Metal having higher

charge
A+ B– A+2 B–

B– A+ B– A+

• By having extra anion occupying interstitial

site : In this, an extra anion is present in the

interstitial position. The extra negative charge is

balanced by one extra positive charge on the

adjacent metal ion. Since anions are usually larger it

could not occupy an interstitial site. Thus, this

structure has only a theoretical possibility. No

example is known so far.

Consequences of metal deficiency defects :

Due to the movement of electron, an ion A+ changes

to A+2 ions. Thus, the movement of an electron from

A+ ion is an apparent of positive hole and the

substances are called p-type semiconductor

• Impurity defect : These defects arise when

foreign atoms are present at the lattice site (in place

of host atoms) or at the vacant interstitial sites. In

the former case, we get substitutional solid solutions

while in the latter case, we get interstitial solid

solution. The formation of the former depends upon

the electronic structure of the impurity while that of

the later on the size of the impurity.

Important Tips

 Berthallides is a name given to non-

stoichiometric compounds.

 Solids containing F- centres are paramagnetic.

 When NaCl is dopped with MgCl2 the nature of

defect produced is schottky defect.

 AgBr has both Schottky & Frenkel defect.

5.9 Properties of Solids .

Some of the properties of solids which are useful in

electronic and magnetic devices such as, transistor,

computers, and telephones etc., are summarised

below :

(1) Electrical properties : Solids are classified into

following classes depending on the extent of

conducting nature.

(i) Conductors : The solids which allow the electric

current to pass through them are called conductors.

These are further of two types; Metallic conductors

and electrolytic conductors. In the metallic

conductors the current is carries by the mobile

electrons without any chemical change occurring in

the matter. In the electrolytic conductor like NaCl,

KCl, etc., the current is carried only in molten state

or in aqueous solution. This is because of the

movement of free ions. The electrical conductivity

of these solids is high in the range 10 4 − 10 6 ohm −1 cm −1 .

Their conductance decrease with increase in

temperature.

(ii) Insulators : The solids which do not allow

the current to pass through them are called

insulators. e.g., rubber, wood and plastic etc. the

electrical conductivity of these solids is very low

i.e., 10 −12 − 10 −22 ohm −1 cm −1 .

(iii) Semiconductors : The solids whose

electrical conductivity lies between those of

conductors and insulators are called semiconductors.

The conductivity of these solid is due to the

presence of impurities. e.g. Silicon and Germanium.

Their conductance increase with increase in

temperature. The electrical conductivity of these

solids is increased by adding impurity. This is called

Doping. When silicon is doped with P (or As,

group 15 elements), we get n-type semiconductor.

This is because P has five valence electrons. It forms

4 covalent bonds with silicon and the fifth electron

remains free and is loosely bound. This give rise to

n-type semiconductor because current is carried by

electrons when silicon is doped with Ga (or in In/Al,

group 13 elements) we get p-type semiconductors.

Conductivity of the solids may be due to the

movement of electrons, holes or ions.

• Due to presence of vacancies and other defects,

solids show slight conductivity which increases with

temperature.

• Metals show electronic conductivity.

• The conductivity of semiconductors and

insulators is mainly governed by impurities and

defects.

• Metal oxides and sulphides have metallic to

insulator behavior at different temperatures.

 Conductivity

Insulator like Insulator – to – Metal like

metal

FeO, Fe2O3 Ti 2 O 3 TiO

MnO, MnO 2 V2 O 3 VO

Cr 2 O3 VO 2 CrO2

CoO ReO3

NiO

CuO

V2O5
 (2) Superconductivity : When any material

loses its resistance for electric current, then it is

called superconductor, Kammerlingh Onnes (1913)

observed this phenomenon at 4K in mercury. The

materials offering no resistance to the flow of

current at very low temperature (2-5 K) are called

superconducting materials and phenomenon is

called superconductivity. e.g., Nb 3 Ge alloy (Before

1986), La1.25 Ba 0.15 CuO 4 (1986), YBa 2 Cu 3 O7 (1987) – super

conductive at a temperature up to 92 K.

Applications

(a) Electronics,
(b) Building supermagnets,

(c) Aviation transportation,

(d) Power transmission

“The temperature at which a material enters the

superconducting state is called the superconducting

transition temperature, (Tc ) ”. Superconductivity was

also observed in lead (Pb) at 7.2 K and in tin (Sn) at

3.7K. The phenomenon of superconductivity has

also been observed in other materials such as

polymers and organic crystals. Examples are

• (SN)x, polythiazyl, the subscript x indicates a

large number of variable size.

 • (TMTSF)2PF6, where TMTSF is tetra methyl

tetra selena fulvalene.

(3) Magnetic properties : Based on the

behavior of substances when placed in the magnetic

field, there are classified into five classes.

Magnetic properties of solids

Properti Description Alignment of Examples Applica

es Magnetic tions

Dipoles

Diamag Feebly repelled by All paired TiO2, Insulato

netic the magnetic fields. electrons V2O5, r

 Non-metallic NaCl, C6H6

elements (excepts (benzene)

O2, S) inert gases and

species with paired

electrons are

diamagnetic

Parama Attracted by the O2 , Cu 2+ , Fe3 + , TiO, Electron

gnetic magnetic field due to Ti 2O3 , VO, VO2 , ic

the presence of CuO applianc

permanent magnetic es
At least one
dipoles (unpaired
unpaired
electrons). In
 magnetic field, these electron

tend to orient

themselves parallel

to the direction of the

field and thus,

produce magnetism

in the substances.

Ferrom Permanent Dipoles are Fe, Ni, Co, CrO2 is

agnetic magnetism even in aligned in the CrO2 used in

the absence of same audio

magnetic field, direction and

Above a temperature video

 called Curie tapes

temperature, there is

no ferromagnetism.

Antiferr This arises when the MnO, –

omagne dipole alignment is MnO2,

tic zero due to equal and Mn2O,

opposite alignment. FeO,

Fe2O3;

NiO,

Cr2O3,

CoO,

Co3O4,
Ferrima This arises when Fe3O4, –

gnetic there is net dipole ferrites

moment

(4) Dielectric properties : When a non-

conducting material is placed in an electrical field,

the electrons and the nuclei in the atom or molecule

of that material are pulled in the opposite directions,

and negative and positive charges are separated and

dipoles are generated, In an electric field :

 (i) These dipoles may align themselves in the

same direction, so that there is net dipole moment in

the crystal.

(ii) These dipoles may align themselves in such

a manner that the net dipole moment in the crystal is

zero.

Based on these facts, dielectric properties of

crystals are summarised in table :

Dielectric properties of solids

Property Description Alignment Exa Applica

of electric mple tions

dipoles s

Piezoele When polar crystal is – Quart Record

ctricity subjected to a mechanical z, players,

stress, electricity is capacito

produced a case of rs,

Roch
piezoelectricity. transisto
elle
Reversely if electric field rs,
salt
is applied mechanical compute
BaTi
stress developed. r etc.
O3,
Piezoelectric crystal acts
as a mechanical electrical KH2P

transducer. O4,

• Piezoelectric crystals

with permanent dipoles PbZr

are said to have O3
ferroelectricity

• Piezoelectric crystals

with zero dipole are said

to have

antiferroelectricity
Pyroelec Small electric current is – Infrared

tricity produced due to heating detectors

of some of polar crystals –

a case of pyroelectricity

Important Tips

 Doping : Addition of small amount of foreign

impurity in the host crystal is termed as doping. It

increases the electrical conductivity.

 Ferromagnetic property decreases from iron to

nickel (Fe > Co > Ni ) because of decrease in the number of

unpaired electrons.
 Electrical conductivity of semiconductors and

electrolytic conductors increases with increase in

temperature, where as electrical conductivity of

super conductors and metallic conductors decreases

with increase in temperature.

5.10 Silicates.

These are the compounds with basic unit of (SiO4)4–

anion in which each Si atom is linked directly to

four oxygen atoms tetrahedrally. These tetrahedra

link themselves by corners and never by edges.

Which are of following types :

(1) Ortho silicates : In these discrete SiO 44 − tetrahedra

are present and there is no sharing of oxygen atoms

between adjacent tetrahedra e.g., Willamette

(Zn 2 Si 2 O 4 ) , Phenacite (Be 2 SiO 4 ) , Zircons (ZrSiO 4 ) and

Forestrite (Mg 2 SiO 4 ) .

(2) Pyrosilictes : In these silicates the two

tetrahedral units share one oxygen atom (corner)

between them containing basic unit of (Si 2 O7 )6 − anion

e.g., Thortveitite (Sc 2 Si 2 O7 ) and Hemimorphite

Zn 3 Si 2 O7 Zn(OH ) 2 H 2 O

(3) Cyclic or ring silicates : In these silicates the

two tetrahedral unit share two oxygen atoms (two

corners) per tetrahedron to form a closed ring

containing basic unit of (SiO 3 )n2n− e.g., Beryl

(Be 3 Al 2 Si 6 O18 ) and Wollastonite (Ca 3 Si 3 O9 ) .

(4) Chain silicates : The sharing of two oxygen

atoms (two corners) per tetrahedron leads to the

formation of a long chain e.g., pyroxenes and

Asbestos CaMg 3 O(Si 4 O11 ) and Spodumene LiAl (Si 2 O6 ) .

(5) Sheet silicates : In these silicates sharing of

three oxygen atoms (three corners) by each

tetrahedron unit results in an infinite two

dimensional sheet of primary unit (Si 2 O5 )n2n− . The

sheets are held together by electrostatic force of the

cations that lie between them e.g., [ Mg 3 (OH ) 2 (Si 4 O10 )] and

Kaolin, Al 2 (OH ) 4 (Si 2 O5 ) .

(6) Three dimensional or frame work silicates : In

these silicates all the four oxygen atoms (four

corners) of (SiO 4 ) 4 − tetrahedra are shared with other

tetrahedra, resulting in a three dimensinal network

with the general formula (SiO 2 )n e.g., Zeolites, Quartz.

Important Tips

 Beckmann thermometer : Cannot be used to

measure temperature. It is used only for the

measurement of small differences in temperatures.

It can and correctly upto 0.01o

 Anisotropic behaviour of graphite : The

thermal and electrical conductivities of graphite

along the two perpendicular axis in the plane

containing the hexagonal rings is 100 times more

than at right angle to this plane.

 Effect of pressure on melting point of ice : At

high pressure, several modifications of ice are

formed. Ordinary ice is ice –I. The stable high

pressure modifications of ice are designated as ice –

II, ice – III, ice- V, ice – VI and ice – VII. When ice

–I is compressed, its melting point decreases,

reaching − 22 o C at a pressure of about 2240 atm. A

further increase in pressure transforms ice – I into

ice – IIIs whose melting point increases with

pressure. Ice- VII, the extreme high-pressure

modification, melts to form water at about 100°C

and 20,000 atm pressure. The existence of ice-IV

has not been confirmed.

 Isotropic : The substances which show same

properties in all directions.

 Anisotropic : Magnitude of some of the

physical properties such as refractive index,

coefficient of thermal expansion, electrical and

thermal conductivities etc. is different in different

directions, with in the crystal

A solution is a homogenous mixture of two or more

substances, the composition of which may vary

within limits. “A solution is a special kind of

mixture in which substances are intermixed so

intimately that they can not be observed as separate

components”. The dispersed phase or the substance

which is to be dissolved is called solute, while the

dispersion medium in which the solute is dispersed

to get a homogenous mixture is called the solvent. A

solution is termed as binary, ternary and quartenary

if it consists of two, three and four components

respectively.

4.1 Solubility.

Solubility of as substance in the solvent is the

measure of the capacity of the latter to dissolve the

former at a given temperature and pressure.

“Solubility of a substance may be defined as the

amount of solute dissolved in 100gms of a solvent

to form a saturated solution at a given temperature”.

A saturated solution is a solution which contains at

a given temperature as much solute as it can hold in

presence of dissolveding solvent. Any solution may

contain less solute than would be necessary to to

saturate it. Such a solution is known as unsaturated

solution. When the solution contains more solute

than would be necessary to saturate it then it is

termed as supersaturated solution. It is metastable.

4.2 Kinds of solutions.

All the three states of matter (gas , liquid or

solid) may behave either as solvent or solute.

Depending on the state of solute or solvent, mainly

there may be following nine types of binary

solutions.
Solven Solute Example

Gas Gas Mixture of gases, air.

Gas Liquid Water vapours in air, mist.

Gas Solid Sublimation of a solid into a gas, smoke.

Liquid Gas CO2 gas dissolved in water (aerated drinks).

Liquid Liquid Mixture of miscible liquids, e.g., alcohol in

water.

Liquid Solid Salt in water, sugar in water.

Solid Gas Adsorption of gases over metals; hydrogen over

 palladium.

Solid Liquid Mercury in zinc, mercury in gold, CuSO4.5H2O.

Solid Solid Homogeneous mixture of two or more metals

(alloys), e.g., copper in gold, zinc in copper.

Among these solutions the most significant type

of solutions are those which are in liquid phase and

may be categorised as : (i) Solid in liquid solutions,

(ii) Liquid in liquid solutions and (iii) Gas in liquid

solutions.

(i) Solid in liquid solutions : For the solid in

liquid solutions the solid is referred to as solute. The

amount of solute that is dissolved in 100 g of a

solvent, to form a saturated solution at a particular

temperature is called solubility. The solubility of a

solid solute in liquid depends upon

(a) Nature of solute and solvent

(b) Temperature : Usually the solubility of the solute

increases with increase in temperature (e.g.,

KI , KNO 3 , NH 4 Br ) but in some cases increase in solubility

is negligible (e.g. NaCl ) and in cases of some salts

(e.g., NaOH , Na 2 SO 4 , CeSO 4 ) solubility decreases with

increase in temperature.

Cause of miscibility of solids in liquids : The

basic cause of solubility of solid solute in liquid

solvent can be summed up in one line, i.e., “Similia

similibus solvanter” meaning like dissolves like

which implies that polar solvents dissolve polar

solutes and non-polar solvents dissolve non-polar

solutes.

For ionic solutes, the solubility, in general, is

related to the magnitude of hydration (or salvation)

energy and lattice energy. In general if the

magnitude of hydration energy is greater than lattice

energy, the solute is soluble otherwise it is insoluble.

 (ii) Liquid in liquid solutions : When two

liquids are mixed, the mixture may be of the

following types :

(a) The two components may be almost

immiscible : In this case, one of the liquids is polar

while the other is of non-polar nature. For example,

benzene and water.

(b) The miscibility of the component may be

partial : If the intermolecular attraction of one liquid

is different from intramolecular attraction of the

other, there may be a partial miscibility of the two

liquids. For example, ether and water.

 (c) The two components may be completely

miscible : In this case, the two liquids are of the

same nature, i.e., they are either polar (like alcohol

and water) or non-polar (like benzene and hexane).

Cause of Miscibility of Liquids

(a) Chemically alike liquids dissolve in one

another more freely as compared to others, for

example, alkanes are miscible in all proportions with

one another. Alkanes are however, not miscible with

water because they cannot form H-bonds with water

molecules.
 (b) Dipole-Dipole interactions also play an

important role in forming liquid solutions.

(c) Molecular sizes of liquids which are

mutually soluble, are also approximately same.

(iii) Gas in Liquid solutions : Most of the gases

are soluble in water to some extent. The solubility of

gas in water generally depends upon the following

factors

(a) Nature of the gas : In general the gases which

are easily liquefiable are more soluble in water.

 (b) Temperature : The dissolution of gas in water

is exothermic process. Hence, the solubility of gas

decreases with rise in temperature.

(c) Pressure : Effect of pressure on the solubility of

gas is explained by “Henry’s law”. According to

Henry’s

law “mass of gas dissolved in a given volume of

solvent, at a constant temperature, is proportional to

the pressure of the gas with which it is in

equilibrium.”

Solubility ∝ Pressure; S = KP where K is Henry’s

constant.
Higher the value of K at given pressure, the lower is

the solubility of the gas in the liquid. Value of K

increases with increase in temperature while

solubility of gas decreases. It is due to this reason

that aquatic species are more comfortable in cold

water rather than hot water.

Applications of Henry's law : Henry's law finds

several applications in industry and explains some

biological phenomena. Notable among these are :

(i) To increase the solubility of CO 2 in soft drinks

and soda water, the bottle is sealed under high

pressure.
(ii) To minimise the painful effects accompanying

the decompression of deep sea divers, oxygen

diluted with less soluble helium gas is used as

breathing gas.

(iii) In lungs, where oxygen is present in air with

high partial pressure of oxygen to form

oxohaemoglobin. In tissues where partial pressure of

oxygen is low. Oxohaemoglobin releases oxygen for

utilization in cellular activities.

4.3 Methods of expressing concentration of

solution.
 Concentration of solution is the amount of solute

dissolved in a known amount of the solvent or

solution. The concentration of solution can be

expressed in various ways as discussed below.

(1) Percentage : It refers to the amount of the

solute per 100 parts of the solution. It can also be

called as parts per hundred (pph). It can be

expressed by any of following four methods :

(i) Weight to weight percent (% w/w)

Wt. of solute
= × 100
Wt. of solution
 e.g., 10% Na 2 CO 3 solution w/w means 10 g of

Na 2 CO 3 is dissolved in 100 g of the solution. (It means

10 g Na 2 CO 3 is dissolved in 90 g of H 2O )

(ii) Weight to volume percent (% w/v)

Wt. of solute
= × 100
Volume of solution

e.g., 10% Na 2 CO 3 (w/v) means 10 g Na 2 CO 3 is

dissolved in 100 cc of solution.

(iii) Volume to volume percent (% v/v)

Vol. of solute
= × 100
Vol. of solution

e.g., 10% ethanol (v/v) means 10 cc of ethanol

dissolved in 100 cc of solution.

 (iv) Volume to weight percent (% v/w)

Vol. of solute
= × 100
Wt. of solution

e.g., 10% ethanol (v/w) means 10 cc of ethanol

dissolved in 100 g of solution.

(2) Parts per million (ppm) and parts per

billion (ppb) : When a solute is present in trace

quantities, it is convenient to express the

concentration in parts per million and parts per

billion. It is the number of parts of solute per million

(10 6 ) or per billion (10 9 ) parts of the solution. It is

independent of the temperature.

 mass of solute component
ppm =
Total mass of solution
× 10 6 ;

mass of solute component

ppb = × 10 9
Total mass of solution

Examples based on percentage and parts

Example:115 g of methyl alcohol is dissolved in 35 g of water. The

(a) 30%

(b) 50%

(c) 70%

(d) 75%

Solution : (a)  Weight percentag e = Weight

Weight of solute 
× 100 
 of solution 
Total weight of solution = (15 + 35) g = 50 g

Weight percentage of methyl alcohol

Weight of methyl alcohol 15

= × 100 = × 100 = 30 %
Weight of solution 50

Example: 2Sea water contains 5.8 × 10 −3 g of dissolved oxygen per kilo

(a) 5.8 ppm

(b) 58 .5 ppm

(c) 0.58 ppm

(d) 0.05 ppm

Solution:(a)Partpermillion

Mass of solute 5.8 × 10 −3 g

= × 10 6 = × 10 6 = 5.8 ppm
Mass of solution 10 3 g
Example: 3 A 500 gm toothpaste sample has 0.2g fluoride concentration

(a) 250 ppm

(b) 200 ppm

(c) 400 ppm

(d) 1000 ppm

Mass of solute 0.2

Solution: (c) ppm of F− ions =
Mass of solution
× 10 6 =
500
× 10 6

= 400 ppm

(3) Strength : The strength of solution is defined as

the amount of solute in grams present in one litre (or

dm 3 ) of the solution. It is expressed in g/litre or

(g / dm 3 ) .
 Mass of solute in grams
Strength =
Volume of solution in litres

(4) Normality (N) : It is defined as the number of

gram equivalents (equivalent weight in grams) of a

solute present per litre of the solution. Unit of

normality is gram equivalents litre–1. Normality

changes with temperature since it involves volume.

When a solution is diluted x times, its normality also

decreases by x times. Solutions in term of normality

generally expressed as,

N= Normal solution; 5N = Penta normal, 10 N = Deca

normal; N/2= semi normal

N / 10 = Deci normal; N /5 = Penti normal

N / 100 or 0.01 N = centinormal, N / 1000 or 0.001=

millinormal

Mathematically normality can be calculated by

following formulas,

(i)
Number of g.eq. of solute Weight of solute in g.
Normality ( N ) = =
Volume of solution (l ) g. eq. weight of solute × Volume of solution (l )
Wt. of solute per litre of solution
(ii) N=
g eq. wt. of solute
,

Wt. of solute 1000

(iii) N= ×
g.eq. wt. of solute Vol. of solution in ml

of solute × 10
(iv) N = Percent
g eq. wt. of solute
,

Strength in g l -1 of solution
(v) N=
g eq. wt. of solute
 Wt% × density × 10
(vi) N=
Eq. wt.

(vii) If volume V1 and normality N1 is so changed

that new normality and volume N2 and V2 then,

N 1 V1 = N 2 V2 (Normality equation)

(viii) When two solutions of the same solute are

mixed then normality of mixture (N ) is

N 1 V1 + N 2 V2
N=
V1 + V2

(ix) Vol. of water to be added i.e., (V2 − V1 ) to get a

solution of normality N2 from V1 ml of normality N1

 N − N2 
V2 − V1 =  1  V1
 N2 
(x) If Wg of an acid is completely neutralised by V ml

of base of normality N

Wt. of acid VN
=
g eq. wt. of acid 1000
; Similarly,

Wt. of base Vol. of acid × N of acid

=
g eq. wt. of base 1000

(xi) When Va ml of acid of normality Na is mixed with

Vb ml of base of normality Nb

(a) If Va N a = Vb N b (Solution neutral)

(b) If Va N a > Vb N b (Solution is acidic)

(c) If Vb N b > Va N a (Solution is basic)

Va N a + Vb N b
(xii) Normality of the acidic mixture =
(Va + Vb )
 Vb N b + Va N a
(xiii) Normality of the basic mixture =
(Va + Vb )

No. of meq * of solute

(xiv) N=
Vol. of solution in ml
(* 1 equivalent = 1000

milliequivalent or meq.)

Examples based on

Example: 4Normality of a solution containing 9.8 g of H 2 SO 4 in 250 cm

[MP PMT 1995, 2003; CMC Vellore 1991;

JIPMER 1991]

(a) 0.8 N

(b) 1N

(c) 0.08 N

(d) 1.8 N
 Mol. mass of H 2 SO 4 98
Solution: (a) Eq. wt. of H 2 SO 4 =
Basicity of H 2 SO 4
=
2
= 49

Weight in g 9.8
∴ Number of g equivalent of H 2 SO 4 =
Eq. mass
=
49
= 0.2

250 cm 3 of solution contain H 2 SO 4 = 0.2g equivalent

0.2
∴ 1000 cm 3 of the solution contain H 2 SO 4 =
250
× 1000 g

equivalent = 0.8 g equivalent

Hence normality of the solution = 0.8 N

Example: 5 Amount of NaOH present in 200 ml of 0.5 N

solution is

[AIIMS 1992]

(a) 40 g

(b) 4 g
(c) 0.4 g

(d) 4.4 g

N × V × g eq. wt . 0.5 × 200 × 40

Solution: (b) Wt. of solute =
1000
=
1000
= 4g

Example: 6 50 ml of 10 N H 2 SO 4 , 25 ml of 12 N HCl and 40 ml of

5 N HNO 3 were mixed together and the volume of the

mixture was made 1000 ml by adding water. The

normality of the resulting solution will be

[MP PMT 1998, 2002, Kerala CET 2003]

(a) 1N

(b) 2N

(c) 3N
(d) 4N

Solution: (a) N 1 V1 + N 2 V2 + N 3 V3 = N 4 V4

50 × 10 + 25 × 12 + 40 × 5 = N 4 × 1000 or N 4 = 1N

Example: 7 100 ml of 0.3 N HCl is mixed with 200 ml of

0.6 N H 2 SO 4 . The final normality of the resulting

solution will be

[DPMT 1994]

(a) 0.1 N

(b) 0.2 N

(c) 0.3 N

(d) 0.5 N
Soltuion: (d) 100 ml of 0.3 N HCl contains HCl = 0.03 g eq.,

0.6
200 ml of 0.6 N H 2 SO 4 contains H 2 SO 4 =
1000
× 200 = 0.12 g eq.

Total g eq. = 0.15 , Total volume = 300 ml Finally

0.15
normality =
300
× 1000 = 0.5

Alternatively N 1 V1 + N 2 V2 = N 3 V3 i.e., 0.3 × 100 + 0.6 × 200 = N 3 × 300

or 0.3 + 1.2 = 3 N 3 or N 3 = 1.5 / 3 = 0.5

Example: 8An aqueous solution of 6.3 g oxalic acid dihydrate is mad

(a) 40 ml

(b) 20 ml

(c) 10 ml

(d) 4 ml
Solution: (a) Normality of oxalic acid solution
6.3 1000
= × = 0.4
63 250

N 1 V1 = N 2 V2

0.1 × V1 = 0.4 × 10 or V1 = 40 ml

Example: 9 10 .6 g of Na 2 CO 3 was exactly neutralised by 100 ml of H 2 SO 4 so

(a) 1 N

(b) 2 N

(c) 1.5 N

(d) 0.5 N

Solution: (b)Weight of base (w) = 10 .6 g ; g eq. wt. of base = 53; Vol. o

V× N 10 .6 100 × N 1000 × 10 .6
w
= ; 53
=
1000
; N=
100 × 53
=2
g eq. wt . 1000
 (4) Molarity (M) : Molarity of a solution is the

number of moles of the solute per litre of solution

(or number of millimoles per ml. of solution). Unit

of molarity is mol/litre or mol/dm3 For example, a

molar (1M ) solution of sugar means a solution

containing 1 mole of sugar (i.e., 342 g or 6.02 × 10 23

molecules of it) per litre of the solution. Solutions in

term of molarity generally expressed as,

M
1M = Molar solution, 2M = Molarity is two, 2
or

0.5 M = Semimolar solution,

M M
10
or 0.1 M = Decimolar solution, 100
or 0.01 M

= Centimolar solution
 M
1000
or 0.001 M = Millimolar solution

• Molarity is most common way of representing

the concentration of solution.

• Molarity is depend on temperature as,

1
Molarity ∝
Temperatur e

• When a solution is diluted (x times), its

molarity also decreases (by x times)

Mathematically molarity can be calculated by

following formulas,

No. of moles of solute (n)

(i) M=
Vol. of solution in litres
,
 Wt. of solute (in gm) per litre of solution
(ii) M=
Mol. wt. of solute

Wt. of solute (in gm) 1000

(iii) M=
Mol. wt. of solute
×
Vol. of solution in ml .

(iv) M = No.Vol.
of millimoles of solute
of solution in ml

Percent of solute × 10
(v) M=
Mol. wt. of solute

-1
(vi) M = Strength in gl of solution
Mol. wt. of solute

10 × Sp. gr. of the solution × Wt. % of the solute

(vii) M=
Mol. wt. of the solute

(viii) If molarity and volume of solution are

changed from M 1 , V1 to M 2 , V2 . Then,

M 1 V1 = M 2 V2 (Molarity equation)
 (ix) In balanced chemical equation, if n1 moles of

reactant one react with n2 moles of reactant two.

Then,

M 1 V1 M 2 V2
=
n1 n2

(x) If two solutions of the same solute are mixed

then molarity (M) of resulting solution.

M 1 V1 + M 2 V2
M=
(V1 + V2 )

(xi) Volume of water added to get a solution of

molarity M2 from V1 ml of molarity M1 is

 M − M2 
V2 − V1 =  1  V1
 M2 

Relation between molarity and normality

Normality of solution = molarity
Molecular mass
×
Equivalent mass

Normality × equivalent mass = molarity ×

molecular mass

Molecular mass
For an acid, Equivalent mass
= basicity

So, Normality of acid = molarity × basicity.

Molecular mass
For a base, Equivalent mass
= Acidity

So, Normality of base = Molarity × Acidity.

Examples based
Example:10 The molarity of pure water (d = 1 g / l ) is

[KCET 1993; CMC 1991, CPMT 1974, 88,90]

(a) 555 M

(b) 5.55 M

(c) 55.5 M

(d) None

Solution: (c)Consider 1000 ml of water

Mass of 1000 ml of water = 1000 × 1 = 1000 g

1000
Number of moles of water =
18
= 55 .5

No. of moles of water 55 .5

Molarity =
Volume in litre
=
1
= 55 .5 M
Example:11 The number of iodine atoms present in

1cm 3 of its 0.1M solution is

[Pb. CET 1990]

(a) 6.02 × 10 23

(b) 6.02 × 10 22

(c) 6.02 × 10 19

(d) 1.204 × 10 20

0.1
Solution: (d) 1 cc of 0.1M I 2 solution =
1000
= 10 − 4 mol

= 10 −4 × 6.02 × 10 23 molecules = 6.02 × 10 19 molecules

= 2 × 6.02 × 10 19 atoms = 1.204 × 10 20

Example:12Equal volumes of 0.1M AgNO 3 and 0.2M NaCl

are mixed. The concentration of NO 3− ions in the

mixture will be

[MP PMT 1996; CPMT 1991; Pb. PMT 1994;

BHU 1994]

(a) 0.1M

(b) 0.05 M

(c) 0.2 M

(d) 0.15 M

Solution: (b) AgNO 3 + NaCl → AgCl + NaNO 3

0.1 M 0.2 M

0.1M AgNO 3 reacts with 0.1M NaCl to produce

0.1M AgCl and 0.1M NaNO 3

0.1M
∴ NO 3− = = 0.05 M
2

[ when equal volumes are mixed dilution occurs]

Example:13 The molarity of H 2 SO 4 solution that has

a density of 1.84 g / cc at 35 o C and contains 98% by

weight is

[CPMT 1983, 2000; CBSE 1996, 2000; AIIMS

2001]

(a) 4.18 M

(b) 8.14 M

(c) 18 .4 M
(d) 18 M

Wt. of solute 1000

Solution: (c) Molarity =
Mol. wt.
×
Vol. of solution (in ml .)

98 1000
= × = 18 .4 M
98 54 .34

 mass 100 
 Vol. of solution = = = 54 .34 ml 
 density 1. 84 

Example:14Amount of oxalic acid ((COOH ) 2 .2H 2 O) in grams that is requ

(a) 17.25 g

(b) 17.00 g

(c) 15.75 g

(d) 15.00 g

Solution: (c) Molecular mass of oxalic acid = 126

1000 ml of 1M oxalic acid require oxalic acid = 126 g

∴ 250 ml of 1M oxalic acid will require oxalic acid

126
= × 250 = 31 .5 g
1000

M
Hence 250 ml of 2
oxalic acid will require oxalic acid

1
= 31 .5 × = 15 .75 g
2

∴ Mass of oxalic acid required = 15 .75 g .

Example:15Volume of 10 M HCl should be diluted with water to prepa

(a) 2L

(b) 1.5 L

(c) 1.00 L
(d) 0.5 L

Solution: (c) In dilution, the following equation is

applicable :

M 1 V1 = M 2 V2

10 M HCl 5 M HCl

10 × V1 = 5 × 2.00

5 × 2.00
V1 = L = 1.00 L
10

Example:16The volume of 95% H 2 SO 4 (density = 1.85 g cm −3 ) needed to p

(a) 5 cc

(b) 7.5 cc

(c) 9.4 cc
(d) 12 .4 cc

95 1
Solution: (c) Molarity of 95% H 2 SO 4 = ×
98 100 / 1.85
× 1000

= 17 .93 M

15 1
Molarity of 15% H 2 SO 4 = ×
98 100 / 1.10
× 1000 = 1.68 M

M 1 V1 = M 2 V2

(95% H 2 SO 4 ) (15% H 2 SO 4 )

17 .93 × V1 = 1.68 × 100 or V1 = 9.4 cm 3

Example:17 The molarity of a 0.2 N Na 2 CO 3 solution

will be

[MP PMT 1987]

(a) 0.05 M

(b) 0.2M

(c) 0.1M

(d) 0.4 M

molecular mass (M 2 )
Solution: (c) N=M×
Equivalent mass (E)

Equivalent mass (E)

So, M =N×
Molecular mass (M 2 )

Molecular mass
Equivalent mass of salt =
Total posi tive valency

M2
Equivalent mass of Na 2 CO 3 =
2

M2 / 2 0.2
M = 0.2 ×
M2
; M =
2
= 0.1M

Example:18If 20 ml of 0.4 N NaOH solution completely neutralises 40 ml o

 [EAMCET 1992; DPMT 1994; JIPMER 1994]

(a) 0.1M

(b) 0.2M

(b) 0.3 M

(d) 0.4 M

Solution: (a) We know N 1 V1 = N 2 V2

0.4 × 20 = N 2 × 40 ; N 2 = 0.2 N

Normality of acid
Molarity =
basicity
; Here acid solution is

0.2
dibasic, so M =
2
= 0.1M

(5) Molality (m) : It is the number of moles or gram

molecules of the solute per 1000 g of the solvent.

Unit of molality is mol / kg . For example, a 0.2 molal

(0.2m) solution of glucose means a solution obtained

by dissolving 0.2 mole of glucose in 1000 gm of water.

Molality (m) does not depend on temperature since

it involves measurement of weight of liquids. Molal

solutions are less concentrated than molar solution.

Mathematically molality can be calculated by

following formulas,

(i)

Number of moles of the solute Strength per 1000 grams of solvent

m= × 1000 =
Weight of the solvent in grams Molecular mass of solute

No. of gm moles of solute

(ii) m=
Wt. of solvent in kg
 Wt. of solute 1000
(iii) m= ×
Mol. wt. of solute Wt. of solvent in g

of millimoles of solute
(iv) m = No. Wt. of solvent in g

10 × solubility
(v) m=
Mol. wt. of solute

1000 × wt. % of solute (x)

(vi) m=
(100 − x) × mol. wt. of solute

1000 × Molarity
(vii) m=
(1000 × sp. gravity) − (Molarity × Mol. wt. of solute)

Relation between molarity (M) and molality

(m)
 Molarity
Molality (m) = Molarity × molecular mass
Density −
1000

Molality × density
Molarity (M) =
Molality × molecular mass
1+
1000

Examples based on

Example:19 H 2 SO 4 solution whose specific gravity is 1.98 g ml −1 and H 2 SO

(a) 7.412

(b) 8.412

(c) 9.412

(d) 10.412

Solution: (c) H 2 SO 4 is 95% by volume

 Wt. of H 2 SO 4 = 95 g

Vol. of solution = 100 ml

95
∴ moles of H 2 SO 4 =
98
and weight of solution

= 100 × 1.98 = 198 g

Weight of water = 198 − 95 = 103 g

95 × 1000
Molality =
98 × 103
= 9.412

Hence molality of H 2 SO 4 solution is 9.412

Example:20The density of H 2 SO 4 solution is 1.84 gm ml −1 . In 1 litre solut

(a) 9.42

(b) 10.42

(c) 11.42
(d) 12.42

Solution: (b) Given H 2 SO 4 is 93% by volume

Wt. of H 2 SO 4 = 93 g

mass
Volume of solution = 100 ml  Density =
volume

∴ mass = d × volume

∴ weight of solution = 100 × 1.84 g = 184 g

wt. of water = 184 − 93 = 91 g

Moles 93 × 1000
Molality =
wt. of water in kg
=
98 × 91
= 10 .42

(6) Formality (F) : Formality of a solution may

be defined as the number of gram formula masses of

the ionic solute dissolved per litre of the solution. It

is represented by F . Commonly, the term formality

is used to express the concentration of the ionic

solids which do not exist as molecules but exist as

network of ions. A solution containing one gram

formula mass of solute per litre of the solution has

formality equal to one and is called formal solution.

It may be mentioned here that the formality of a

solution changes with change in temperature.

Formality

of gram formula masses of solute

(F)= NumberVolume of solution in litres
=

Mass of ionic solute (g)

(gm. formula mass of solute) × (Volume of solution (l))

WB (g) WB (g) × 1000

Thus, F=
GFM × V(l )
or
GFM × V(ml )
(7) Mole fraction (X) : Mole fraction may be

defined as the ratio of number of moles of one

component to the total number of moles of all the

components (solvent and solute) present in the

solution. It is denoted by the letter X . It may be

noted that the mole fraction is independent of the

temperature. Mole fraction is dimensionless. Let us

suppose that a solution contains the components A

and B and suppose that WA g of A and WB g of B are

present in it.

WA
Number of moles of A is given by, nA =
MA
and the

WB
number of moles of B is given by, nB =
MB
where MA and MB are molecular masses of A and B

respectively.

nA
zMole fraction of A , XA =
n A + nB
; Mole fraction of B ,

nB
XB =
n A + nB

The sum of mole fractions of all the components in

the solution is always one.

nA nB
X A + XB = +
n A + nB n A + nB
=1 .

Thus, if we know the mole fraction of one

component of a binary solution, the mole fraction of

the other can be calculated.

 Relation between molality of solution (m) and

mole fraction of the solute (XA).

m
XA =
55 .5 + m

Examples based on

Example: 21 A solution contains 16 gm of methanol

and 10 gm of water, mole fraction of methanol is

[BHU 1981, 87; EAMCET 2003]

(a) 0.90

(b) 0.090

(c) 0.1
(d) 1.9

Solution: (b) Mass of methanol = 16 g , Mol. mass of

CH 3 OH = 32

16
∴ No. of moles of methanol =
32
= 0.5 moles

90
No. of moles of water = 18 = 5 moles

0.5
∴ Mole fraction of methanol =
5 + 0.5
= 0.090

Example: 22A solution has 25% of water, 25% ethanol and 50% ac

(a) 0.50, 0.3, 0.19

(b) 0.19, 0.3, 0.50

(c) 0.3, 0.19,

0.5

(d) 0.50, 0.19, 0.3

Solution: (d)Since 18 g of water = 1mole

25
25 g of water = 18
= 1.38 mole

Similarly, 46 g of ethanol = 1 mole

25
25 g of ethanol =
46
= 0.55 moles

Again, 60 g of acetic acid = 1 mole

50
50 g of acetic acid =
60
= 0.83 mole

1.38
∴ Mole fraction of water =
1.38 + 0.55 + 0.83
= 0.50
 Similarly, Mole fraction of ethanol
0.55
= = 0.19
1.38 + 0.55 + 0.83

Mole fraction of acetic acid

0.83
= = 0.3
1.38 + 0.55 + 0.83

(8) Mass fraction : Mass fraction of a

component in a solution is the mass of that

component divided by the total mass of the solution.

For a solution containing w A gm of A and w B gm of B

wA wB
Mass fraction of A =
w A + wB
; Mass fraction of B =
w A + wB

Note :  It may be noted that molality, mole

fraction, mass fraction etc. are preferred to molarity,

normality, etc. because the former involve the

weights of the solute and solvent where as later

involve volumes of solutions. Temperature has no

effect on weights but it has significant effect on

volumes.

(9) Demal unit (D) : The concentrations are also

expressed in “Demal unit”. One demal unit

represents one mole of solute present in one litre of

solution at 0o C .

4.4 Colligative properties.

Certain properties of dilute solutions containing

non-volatile solute do not depend upon the nature of

the solute dissolved but depend only upon the

concentration i.e., the number of particles of the

solute present in the solution. Such properties are

called colligative properties. The four well known

examples of the colligative properties are

(1) Lowering of vapour pressure of the solvent.

(2) Osmotic pressure of the solution.

(3) Elevation in boiling point of the solvent.

(4) Depression in freezing point of the solvent.

Since colligative properties depend upon the

number of solute particles present in the solution,

the simple case will be that when the solute is a non-

electrolyte. In case the solute is an electrolyte, it

may split to a number of ions each of which acts as a

particle and thus will affect the value of the

colligative property.

Each colligative property is exactly related to

any other and thus if one property is measured, the

other can be calculated. The study of colligative

properties is very useful in the calculation of

molecular weights of the solutes.

4.5 Lowering of vapour pressure.

The pressure exerted by the vapours above the

liquid surface in equilibrium with the liquid at a

given temperature is called vapour pressure of the

liquid. The vapour pressure of a liquid depends on

(1) Nature of liquid : Liquids, which have weak

intermolecular forces, are volatile and have greater

vapour pressure. For example, dimethyl ether has

greater vapour pressure than ethyl alcohol.

(2) Temperature : Vapour pressure increases

with increase in temperature. This is due to the

reason that with increase in temperature more

molecules of the liquid can go into vapour phase.

(3) Purity of liquid : Pure liquid always has a

vapour pressure greater than its solution.

 Raoult’s law : When a non-volatile substance is

dissolved in a liquid, the vapour pressure of the

liquid (solvent) is lowered. According to Raoult’s

law (1887), at any given temperature the partial

vapour pressure (pA) of any component of a solution

is equal to its mole fraction (XA) multiplied by the

vapour pressure of this component in the pure state

( p 0A ) . That is, p A = p 0A × X A

The vapour pressure of the solution (Ptotal ) is the

sum of the parital pressures of the components, i.e.,

for the solution of two volatile liquids with vapour

pressures pA and pB .
 Ptotal = p A + p B = ( p 0A × X A ) + ( p B0 × X B )

Alternatively, Raoult’s law may be stated as “the

relative lowering of vapour pressure of a solution

containing a non-volatile solute is equal to the mole

fraction of the solute in the solution.”

Relative lowering of vapour pressure is defined

as the ratio of lowering of vapour pressure to the

vapour pressure of the pure solvent. It is determined

by Ostwald-Walker method.

Mole fraction of the solute is defined as the ratio

of the number of moles of solute to the total numbr

of moles in solution.
 Thus according to Raoult’s law,

w
p0 − p n m
= =
p0 n+ N w W
+
m M

where, p= Vapour pressure of the solution;

p0 = Vapour pressure of the pure solvent

n= Number of moles of the solute; N=

Number of moles of the solvent

w and m= weight and mol. wt. of solute;

W and M= weight and mol. wt. of the solvent.

Limitations of Raoult’s law

• Raoult’s law is applicable only to very dilute

solutions.
 • Raoult’s law is applicable to solutions

containing non-volatile solute only.

• Raoult’s law is not applicable to solutes which

dissociate or associate in the particular solution.

Examples based on Relative

Example: 2334.2 g of canesugar is dissolved in 180 g of water. The

(a) 0.0099

(b) 1.1597

(c) 0.840

(d) 0.9901
Solution:(a)

PA0 − PA WB / M A 34 .2 / 342 0.1

= = = = 0.0099
P 0
A
WB / M B + WA / M A 34 .2 / 342 + 180 / 18 10 .1

Example: 24 Lowering in vapour pressure is the

highest for

[Roorkee 1989; BHU 1997]

(a) 0.2m urea

(b) 0.1 m glucose

(c) 0.1m MgSO 4

(d) 0.1m BaCl 2

PA0 − PA
Solution: (d) PA0
= Molality × (1 − αx + xα + γx)
 The value of PA0 − PA is maximum for BaCl 2 .

Example: 25 Vapour pressure of CCl 4 at 25 o C is 143 mm Hg 0.5 g of

(a) 141.93 mm

(b) 94.39 mm

(c) 199.34 mm

(d) 143.99 mm

PA0 − PA nB 143 − Ps 0.5 / 65

Solution: (a) P 0
=
nA
; 143
=
158 / 154
or Ps = 141 .93 mm
A

Example:26The vapour pressure of pure benzene

and toluene are 160 and 60 torr respectively. The

mole fraction of toluene in vapour pressure in

contact with equimolar solution of benzene and

toluene is

[Pb.CET1988]

(a) 0.50

(b) 0.6

(c) 0.27

(d) 0.73

Solution: (c) For equimolar solutions, X B = X T = 0.5

PB = X B × PB0 = 0.5 × 160 = 80 mm

PT = X T × PT0 = 0.5 × 60 = 30 mm

PTotal = 80 + 30 = 110 mm
 Mole fraction of toluene in vapour phase
30
= = 0.27
110

Example:27The vapour pressure of a solvent decreases by 10 mm o

vapour pressure is to be 20 mm of

mercury then the mole fraction of the

solvent is

[CBSE PMT 1998]

(a) 0.8

(b) 0.6

(c) 0.4

(d) None
Solution: (a) ∆P / P 0 = X 2

Hence ∆P / P0 = X 2 / X 21 i.e. 10 / 20 = 0.2 / X B or X B = 0.4

Mole fraction of solvent = 1 − 0.4 = 0.6

Example:28The vapour pressure of a solvent A is 0.80 atm. When a

(a)0.25

(b) 0.50

(c) 0.75

(d) 0.90

Solution: (a) ∆P / P 0 = X B or X B = 0.2 / 0.8 = 0.25

4.6 Ideal and Non-Ideal solution.

 (1) Ideal solution : An ideal solution may be

defined as the solution which obeys Raoult’s law

over the entire range of concentration and

temperature and during the formation of which no

change in enthalpy and no change in volume takes

place. So for ideal solutions the conditions are,

(i) It should obey Raoult’s law, i.e., PA = PA0 X A and

PB = PB0 X B .

(ii) ∆H mixing = 0

(iii) ∆Vmixing = 0

The solutions in which solvent-solvent and

solute-solute interactions are almost of the same

type as solvent-solute interactions, behave nearly as

ideal solutions.

This type of solutions are possible if molecules

of solute and solvent are almost of same size and

have identical polarity. For example, solutions of

following pairs almost behave as ideal solutions,

n-Heptane and n-hexane.; Chlorobenzene and

bromobenzene.

Benzene and toluene; Ethyl bromide and ethyl

iodide.

Ethylene bromide and ethylene chloride; Carbon

tetrachloride and silicon tetrachloride.

 For such solutions the vapour pressure of the

solution is always intermediate between the vapour

pressures of pure components A and B, i.e., PA0 and

PB0 .

(2) Non-Ideal solution : The solutions which do

not obey Raoult’s law and are accompanied by

change in enthalpy and change in volume during

their formation are called non-ideal solutions. so, for

non-ideal solutions the conditions are :

(i) It does not obey Raoult's law. PA ≠ PA0 X A ; PB ≠ PB0 X B

(ii) ∆H mixing ≠ 0

(iii) ∆Vmixing ≠ 0
 Either component of non-ideal binary solution do

not follow Raoult's law. The non-ideal solutions are

further divided into two types :

(a) Solutions showing positive deviations. (b)

Solutions showing negative deviations.

(a) Solutions showing positive deviation : In

this type of deviations, the partial vapour pressure of

each component (say A and B) of solution is greater

than the vapour pressure as expected according to

Raoult’s law. This type of deviations are shown by

the solutions in which solvent-solvent and solute-

 P=PA+PB

Vapour Pressure
PB

PA

XA = 1 Mole Fraction XA = 0
XB = 0 XB = 1
Partial and total vapour pressure
curves for solutions that show positive
deviations from Raoult’s law

solute interactions are stronger than solvent-

solute interactions.

For the non-ideal solutions exhibiting positive

deviation.

PA > PA0 X A , PB > PB0 X B ; ∆H mixing = + ve ; ∆Vmixing = + ve

e.g. of solutions showing positive deviations

(CH 3 )2 CO + CS 2 ; (CH 3 )2 CO + C2 H 5 OH

C6 H 6 + (CH 3 )2 CO ; CCl 4 + C6 H 6
 CCl 4 + CHCl 3 ; CCl 4 + C6 H 5 CH 3

H 2 O + CH 3 OH ; H 2 O + C2 H 5 OH

CH 3 CHO + CS 2 ; CHCl 3 + C2 H 5 OH

(b) Solutions showing negative deviation : In

this type of deviations the partial vapour pressure of

each component of solution is less than the vapour

pressure as expected according to Raoult’s law. This

type of deviations are shown by the solutions in

which solvent-solvent and solute-solute interactions

are weaker than solvent-solute interactions.

 Vapour Pressure
P=PA+PB

PB

PA
Mole Fraction
XA = 1 XA = 0
XB = 0 XB = 1

A vapour pressure curve showing

negative deviation (solid lines) from
ideal behaviour (dotted lines)

For non-ideal solution showing negative

deviation.

PA < PA0 X A , PB < PB0 X B ; ∆H mixing = − ve ; ∆Vmixing = − ve

e.g. of solutions showing negative deviations

CH 3 COOH + C5 H 5 N (pyridine)

CHCl 3 + (CH 3 ) 2 CO ; CHCl 3 + C6 H 6

CHCl 3 + (C 2 H 5 ) 2 O ; H 2 O + HCl

H 2 O + HNO 3 ; (CH 3 ) 2 CO + C6 H 5 NH 2
 Differences between ideal and non-ideal

solutions

Ideal solutions Solutions with Solutions with

positive deviations negative deviations

A……B interactions A……B interactions A……B interactions

are similar to are smaller than are greater than

A……A and B……B A……A and B……B A……A and B……B

interactions interactions interactions

PA = PA0 X A ; PB = PB0 X B PA > PA0 X A ; PB > PB0 X B PA < PA0 X A ; PB < PB0 X B

∆H sol. = 0 ∆H sol. > 0 ∆H sol. < 0

∆Vmix = 0 ∆Vmix > 0 ∆Vmix < 0

Do not form Exhibit minimum Exhibit maximum

azeotrope boiling point boiling azeotropy

azeotropy

4.7 Azeotropic mixture.

Azeotropes are defined as the mixtures of liquids

which boil at constant temperature like a pure liquid

and possess same composition of components in

liquid as well as in vapour phase. Azeotropes are

also called constant boiling mixtures because whole

of the azeotropes changes into vapour state at

constant temperature and their components can not

be separated by fractional distillation. Azeotropes

are of two types as described below :

(1) Minimum boiling azeotrope : For the

solutions with positive deviation there is an

intermediate composition for which the vapour

pressure of the solution is maximum and hence,

boiling point is minimum. At this composition the

solution distills at constant temperature without

change in composition. This type of solutions are

called minimum boiling azeotrope. e.g;

Components Mass % Boiling points (K)

fB
 A B A B Azeotr

ope

H 2O C 2 H 5 OH 95.57 373 351.3 351.1

H 2O C 2 H 5 CH 2 OH 71.69 373 370 350.72

CHCl 3 C 2 H 5 OH 67 334 351.3 332.3

(CH 3 ) 2 CO CS 2 6.8 329.25 320 312.2

(2) Maximum boiling azeotrope : For the

solutions with negative deviations there is an

intermediate composition for which the vapour

pressure of the solution is minimum and hence,

 boiling point is maximum. At this composition the

solution distill`s at constant temperature without the

change in composition. This type of solutions are

called maximum boiling azeotrope. e.g

Components Boiling points (K)

Mass %
A B A B Azeotr
of B
ope

H 2O HCl 20.3 373 188 383

H 2O HNO 3 58.0 373 359 393.5

H 2O HClO 4 71.6 373 383 476

4.8 Osmosis and Osmotic pressure of the solution.

The flow of solvent from pure solvent or from

solution of lower concentration into solution of

higher concentration through a semi-permeable

membrane is called Osmosis. Osmosis may be

divided in following types,

(1) Exo-Osmosis : The outward osmotic flow of

water from a cell containing an aqueous solution

through a semi-permeable membrane is called as

Exo-osmosis. For example, egg (after removing hard

shell) placed in conc. NaCl solutions, will shrink

due to exo-osmosis.
 (2) Endo-osmosis : The inward flow of water

into the cell containing an aqueous solution through

a semi-permeable membrane is called as endo-

osmosis. e.g., an egg placed in water swells up due

to endo-osmosis.

(3) Reverse osmosis : If a pressure higher than

osmotic pressure is applied on the solution, the

solvent will flow from the solution into the pure

solvent through the semi-permeable membrane.

Since here the flow of solvent is in the reverse

direction to that observed in the usual osmosis, the

process is called reverse osmosis.

 Differences between osmosis and diffusion

Osmosis Diffusion

In osmosis movement of In diffusion there is no role of

molecules takes place through a semi-permeable membrane.

semi-permeable membrane.

It involves movement of only It involves passage of solvent as

solvent molecules from one side well as solute molecules from

to the other. one region to the other.

Osmosis is limited to solutions Diffusion can take place in

only. liquids, gases and solutions.

Osmosis can be stopped or Diffusion can neither be stopped

reversed by applying additional nor reversed

pressure on the solution side.

Osmotic pressure (π) : Osmotic pressure may

be defined in following ways,

The osmotic pressure of a solution at a particular

temperature may be defined as the excess

hydrostatic pressure that builds up when the solution

is separated from the solvent by a semi-permeable

membrane. It is denoted by π.

Osmotic pressure may be defined as the excess

pressure which must be applied to a solution in order

to prevent flow of solvent into the solution through

the semi-permeable membrane.

Or

Osmotic pressure is the excess pressure which

must be applied to a given solution in order to

increase its vapour pressure until it becomes equal to

that of the solution.

Or

Osmotic pressure is the negative pressure which

must be applied to (i.e. the pressure which must be

withdrawn from) the pure solvent in order to

decrease its vapour pressure until it becomes equal

to that of the solution.

Measurements of osmotic pressure :

Following methods are used for the measurement of

osmotic pressure : (i) Pfeffer’s method, (ii) Morse

and Frazer’s method, (iii) Berkeley and Hartley’s

method, (iv) Townsend’s negative pressure method,

(v) De Vries plasmolytic method.

Determination of molecular mass of non-

volatile solute from osmotic pressure (π) :

According to Van’t Hoff equation,

 nB WB RT
π =
V
RT ; MB =
πV
where, WB = known mass

of solute in gm

This method is especially suitable for the

determination of molecular masses of

macromolecules such as proteins and polymers. This

is due to the reason that for these substances the

values of other colligative properties such as

elevation in boiling point or depression in freezing

point are too small to be measured. On the other

hand, osmotic pressure of such substances are

measurable. Conditions for getting accurate value of

molecular mass are,

 (i) The solute must be non-volatile.

(ii) The solution must be dilute.

(iii) The solute should not undergo dissociation

or association in the solution.

Van’t Hoff’s solution equation :

The osmotic pressure is a colligative property.

For a given solvent the osmotic pressure depends

only upon the molar concentration of solute but does

not depend upon its nature. Osmotic pressure is

related to the number of moles of the solute by the

following relation :
 πV = nRT or π =
n
V
RT ⇒ π = CRT ; here, C =

concentration of solution in moles per litre

R = gas constant; T = temperature; n =

number of moles of solute; V = volume of solution

Above eq. is called Van’t Hoff’s solution

equation

Relation of osmotic pressure with different

colligative properties : Osmotic pressure is related

to relative lowering of vapour pressure, elevation of

boiling point and depression of freezing point

according to the following relations.

  PAo − PA  dRT dRT
(1) π =  ×
 (2) π = ∆Tb × (3)
o
 PA  M B 1000 × K b

dRT
π = ∆Tf ×
1000 × K f

In the above relations, π = Osmotic pressure; d =

Density of solution at temperature T; R = Universal

gas constant; MB = Mol. Mass of solute; Kb = Molal

elevation constant of solvent; Kf = Molal depression

constant of solvent

Isotonic, Hypertonic and Hypotonic solutions

Isotonic or iso-osmotic solutions : Two

solutions of different substances having same

osmotic pressure at same temperature are known as

isotonic solutions.

For isotonic solutions, π1 = π 2 Primary

Condition …..(i)

Also, C1 = C 2

Secondary
n1 n2 Conditions
or =
V1 V2

w1 w2
or =
m1 V1 m2 V2

…..(ii)

Eq. (ii) holds good only for those solutes which

neither possess the tendency to get associate nor

dissociate in solution, e.g.,

 (a) Urea and glucose are isotonic then,

π1 = π 2 and C1 = C 2

(b) Urea and NaCl

(dissociate)
are isotonic then,

π1 = π 2 but C1 ≠ C 2

(c) Urea and Benzoic acid

(associate)
are isotonic then,

π1 = π 2 but C1 ≠ C 2

Hypertonic and Hypotonic Solution : The

solution which has more osmotic pressure than the

other solution is called as hypertonic solution and

the solution which has lesser osmotic pressure than

the other is called as hypotonic solution.

 The flow of solvent is always from lower

osmotic pressure to higher osmotic pressure i.e.

from hypotonic to hypertonic solution.

Examples based on

Example: 29 Osmotic pressure is 0.0821 atm at a

temperature of 300 K. find concentration in

mole/litre

[Roorkee 1990]

(a) 0.033

(b) 0.066
(c) 0.33 × 10 −2

(d) 3

P 0.0821 1
Solution:(c) C= = =
RT 0.0821 × 300 300
= 0.33 × 10 − 2 mole / litre

Example: 30The osmotic pressure of 5% (mass-

volume) solution of cane sugar at 150 o C (mol. mass of

sugar = 342) is

[BHU 1995]

(a) 4 atm

(b) 5.07 atm

(c) 3.55 atm

(d) 2.45 atm

 5 1 50
Solution:(b) C = 342 ×
100
× 1000 =
342
M

50
P= × 0.082 × 423 = 5.07 atm
342

4.9 Elevation in boiling point of the solvent

(Ebullioscopy).

Boiling point of a liquid may be defined as the

temperature at which its vapour pressure becomes

equal to atmospheric pressure, i.e., 760 mm. Since

the addition of a non-volatile solute lowers the

vapour pressure of the solvent, solution always has

lower vapour pressure than the solvent and hence it

must be heated to a higher temperature to make its

vapour pressure equal to atmospheric pressure with

the result the solution boils at a higher temperature

than the pure solvent. Thus sea water boils at a

higher temperature than distilled water. If Tb is the

boiling point of the solvent and T is the boiling point

of the solution, the difference in the boiling point

(∆T or ∆ Tb) is called the elevation of boiling point.

T − Tb = ∆Tb or ∆T

Elevation in boiling point is determined by

Landsberger’s method and Cottrell’s method. Study

of elevation in boiling point of a liquid in which a

non-volatile solute is dissolved is called as

ebullioscopy.

Important relations concerning elevation in

boiling point

(i) The elevation of boiling point is directly

proportional to the lowering of vapour pressure, i.e.,

∆Tb ∝ p 0 − p

(ii) ∆Tb = K b × m

where Kb = molal elevation constant or

ebullioscopic constant of the solvent; m= Molality

of the solution, i.e., number of moles of solute per

1000 g of the solvent; ∆Tb = Elevation in boiling point

 1000 × K b × w 1000 × K b × w
(iii) ∆Tb =
m×W
or m=
∆Tb × W

where, Kb is molal elevation constant and

defined as the elevation in b.p. produced when 1

mole of the solute is dissolved in 1 kg of the solvent.

Sometimes the value of Kb is given per 0.1kg ( 100 g ), in

such case the expression becomes

100 × K b × w
m=
∆Tb × W

Where w and W are the weights of solute and

solvent and m is the molecular weight of the solute.

0.002(T0 ) 2
(iv) Kb =
lV
 where T0 = Normal boiling point of the pure

solvent; lV = Latent heat of evaporation in cal / g of

pure solvent; Kb for water is 0.52 deg − kg mol −1

Examples based on Elevation in

b ili i t

Example: 31A solution containing 3.3 g of a substance in 125 g of b

(a) 127.20

(b) 131.20

(c) 137.12

(d) 142.72

1000 × Kb × w 1000 × 3.28 × 3.3

Solution: (b) M2 =
W × ∆Tb
=
125 × 0.66
= 131 .2
Example: 32 The molal b.p. constant for water is

0.513 o C kg mol −1
. When 0.1 mole of sugar is dissolved in

200 g of water, the solution boils under a pressure of

1 atm at

[AIIMS 1991]

(a) 100 .513 o C

(b) 100 .0513 o C

(c) 100 .256 o C

(d) 101 .025 o C

 0.1 
Solution: (c) ∆Tb = K b × m = 0.513  × 1000  = 0.2565 ;
 200 

∆Tb = 100 .2565 o C

Example: 33An aqueous solution containing 1 g of urea boils at 100 .2

(a) 100 .75 o C

(b) 100 .5 o C

(c) 100 o C

(d) 100 .25 o C

3
Solution: (d) 1 g urea = 601 mol , 3 g glucose = 180 =
1
60
mol .

Hence it will boil at the same temperature

4.10 Depression in freezing point of the solvent

(Cryoscopy).

Freezing point is the temperature at which the liquid

and the solid states of a substance are in equilibrium

with each other or it may be defined as the

temperature at which the liquid and the solid states

of a substance have the same vapour pressure. It is

observed that the freezing point of a solution is

always less than the freezing point of the pure

solvent. Thus the freezing point of sea water is low

than that of pure water. The depression in freezing

point (∆T or ∆Tf ) of a solvent is the difference in the

freezing point of the pure solvent (Ts ) and the

solution (Tsol . ) .

Ts − Tsol = ∆Tf or ∆T
NaCl or CaCl 2 (anhydrous) are used to clear snow on

roads. They depress the freezing point of water and

thus reduce the temperature of the formation of ice.

Depression in freezing point is determined by

Beckmann’s method and Rast’s camphor method.

Study of depression in freezing point of a liquid in

which a non-volatile solute is dissolved in it is called

as cryoscopy.

Important relations concerning depression in

freezing point.

(i) Depression in freezing point is directly

proportional to the lowering of vapour pressure.

∆Tf ∝ p 0 − p

(ii) ∆Tf = K f × m

where Kf = molal depression constant or cryoscopic

constant; m= Molality of the solution (i.e., no. of

moles of solute per 1000 g of the solvent);

∆Tf = Depression in freezing point

1000 × K f × w 1000 × K f × w
(iii) ∆Tf =
m×W
or m=
∆Tf × W

where Kf is molal depression constant and defined as

the depression in freezing point produced when 1

mole of the solute is dissolved in 1kg of the solvent.

Sometimes the value of Kf is given per 0.1kg (100 g) , in

such case the expression becomes

100 × K f × w
m=
∆Tf × W

where w and W are the weights of solute and

solvent and m is the molecular weight of the solute.

R(T0 ) 2 0.002(T0 ) 2
(iv) Kf =
l f 1000
=
lf

where T0 = Normal freezing point of the solvent;

lf = Latent heat of fusion/g of solvent; Kf for water is

1.86 deg − kg mol −1

 Relative lowering of vapour pressure, elevation

in boiling point and depression in freezing point are

directly proportional to osmotic pressure.

Examples based on depression in

freezing point

Example: 34 Solution of sucrose (Mol. Mass = 342)

is prepared by dissolving 34.2 gm. of it in 1000 gm.

of water. freezing point of the solution is (K f for

water is 1.86 K kg mol −1

)

[AIEEE 2003]

(a) 272.814 K
(b) 278.1 K

(c) 273.15 K

(d) 270 K

Solution: (a) Molality of the solution = 34

342
.2
= 0.1

∆T f = K f × m = 1.86 × 0.1 = 0.186 K

Freezing point of solution = 273 − 0.186 = 272 .814 K

Example: 35 An aqueous solution of a weak

monobasic acid containing 0.1 g in 21.7 g

of water freezes at 272.817K. If the value

of Kf for water is 1.86 K kg mol −1

, the

molecular mass of the acid is

 [AMU 2002]

(a) 46.0

(b) 48.6

(c) 48.8

(d) 46.8

Solution: (d) Mass of solvent (WA ) = 21 .7 g

Mass of solute (W ) = 0.1 g B

Depression in freezing point,

(∆Tf ) = 273 − 272 .817 = 0.183 K

WB 1000
∆T f = K f × m = K f . ×
WA MB
 K f × WB × 1000 1.86 × 0.1 × 1000
MB = = = 46 .8
WA × ∆T f 21 .7 × 0.183

Example: 36What is the molality of solution of a certain solute in a

(a) 0.01

(b) 1

(c) 0.001

(d) 100

∆T f 0.184
Solution: (a) ∆T f = K f × m or m=
Kf
=
18 .4
= 0.01

Example: 37 A solution containing 6.8 g of a

nonionic solute in 100 g of water was found to

freeze at − 0.93 o C . The freezing point depression

constant of water is 1.86. Calculate the molecular

weight of the solute

[Pb. PMT 1994; ISM Dhanbad 1994]

(a) 13.6

(b) 34

(c) 68

(d) 136

1000 × K f × WB 1000 × 1.86 × 6.8

Solution: (d) MB =
∆T f × WA
=
100 × 0.93
= 136

Example: 38The molar freezing point constant for water is 1.86 o C / mole

(a) − 1.86 o C

(b) 1.86 o C
(c) − 3.92 o C

(d) 2.42 o C

 342 
Solution: (a) ∆T f = 1.86   = 1.86
 342 

∆T f = −1.86 o C

4.11 Colligative properties of electrolytes.

The colligative properties of solutions, viz. lowering

of vapour pressure, osmotic pressure, elevation in

b.p. and depression in freezing point, depend solely

on the total number of solute particles present in

solution. Since the electrolytes ionise and give more

than one particle per formula unit in solution, the

colligative effect of an electrolyte solution is always

greater than that of a non-electrolyte of the same

molar concentration. All colligative properties are

used for calculating molecular masses of non-

volatile solutes. However osmotic pressure is the

best colligative property for determining molecular

mass of a non-volatile substance.

Points to remember

(i) Colligative properties ∝ Number of particles

∝ Number of molecules (in case

of non-electrolytes)
 ∝ Number of ions (In case of

electrolytes)

∝ Number of moles of solute

∝ Mole fraction of solute

(ii) For different solutes of same molar

concentration, the magnitude of the colligative

properties is more for that solution which gives

more number of particles on ionisation.

(iii) For different solutions of same molar

concentration of different non-electrolyte solutes,

the magnitude of the colligative properties will be

same for all.

 (iv) For different molar concentrations of the

same solute, the magnitude of colligative properties

is more for the more concentrated solution.

(v) For solutions of different solutes but of same

percent strength, the magnitude of colligative

property is more for the solute with least molecular

weight.

(vi) For solutions of different solutes of the same

percent strength, the magnitude of colligative

property is more for that solute which gives more

number of particles, which can be known by the

knowledge of molecular weight and its ionisation

behaviour.

4.12 Abnormal molecular masses.

Molecular masses can be calculated by

measuring any of the colligative properties. The

relation between colligative properties and

molecular mass of the solute is based on following

assumptions.

(1) The solution is dilute, so that Raoult’s law is

obeyed.

(2) The solute neither undergoes dissociation nor

association in solution.
 In case of solutions where above assumptions

are not valid we find discrepencies between

observed and calculated values of colligative

properties. These anomalies are primarily due to

(i) Association of solute molecules.

(ii) Dissociation of solute molecules.

(i) Association of solute molecules : Certain

solutes in solution are found to associate. This

eventually leads to a decrease in the number of

molecular particles in the solutions. Thus, it results

in a decrease in the values of colligative properties.

As already discussed, the colligative properties are

inversely related to the molecular mass,

1
colligative property ∝ molecular mass of solute
, therefore,

higher values are obtained for molecular masses

than normal values for unassociated molecules.

(ii) Dissociation of solute molecules : A

number of electrolytes dissociate in solution to give

two or more particles (ions). Therefore, the number

of solute particles, in solutions of such substances, is

more than the expected value. Accordingly, such

solutions exhibit higher values of colligative

properties. Since colligative properties are inversely

proportional to molecular masses, therefore,

molecular masses of such substances as calculated

from colligative properties will be less than their

normal values.

Van’t Hoff’s factor (i) : In 1886, Van’t Hoff

introduced a factor ‘i’ called Van’t Hoff’s factor, to

express the extent of association or dissociation of

solutes in solution. It is ratio of the normal and

observed molecular masses of the solute, i.e.,

Normal molecular mass

i=
Observed molecular mass

In case of association, observed molecular mass

being more than the normal, the factor i has a value

less than 1. But in case of dissociation, the Van’t

Hoff’s factor is more than 1 because the observed

molecular mass has a lesser value than the normal

molecular mass. In case there is no dissociation the

value of ‘i’ becomes equal to one.

Since colligative properties are inversely

proportional to molecular masses, the Van’t Hoff’s

factor may also be written as :

Observed value of colligative property

i=
Calculated value of colligative property assuming no associatio n or dissociati on

No. of particl es after associatio n or dissociati on

i=
No. of particl es before associatio n or dissociati on
 Introduction of the Van’t Hoff factor modifies

the equations for the colligative properties as

follows :

o
− PA
Relative lowering of vapour pressure = P A
= i XB
PAo

Elevation of boiling point, ∆Tb = ikb m

Depression in freezing point, ∆T f = ik f m

inRT
Osmotic pressure, π=
V
; π = iCRT

From the value of “i”, it is possible to calculate

degree of dissociation or degree of association of

substance.
 Degree of dissociation (α) : It is defined as the

fraction of total molecules which dissociate into

simpler molecules or ions.

i −1
α=
m−1
; m= number of particles in

solution

Degree of association (α) : It is defined as the

fraction of the total number of molecules which

associate or combine together resulting in the

formation of a bigger molecules.

i −1
α=
1/ m −1
; m = number of particles in

solution
 Examples based on Van’t
Hoff factor

Example: 39 The molal freezing point constant for

water is 1.86 o C / m . Therefore, the freezing point of 0.1

M NaCl solution in water is expected to be

[MLNR 1994]

(a) − 1.86 o C

(b) − 0.186 o C

(c) − 0.372 o C

(d) + 0.372 o C

Solution: (c) ∆T f = iK f m = 2 × 1.86 × 0.1 = 0.372

 T f = −0.372 o C

Example: 40The depression in freezing point of 0.01 M aqueous so

(a) 1 : 1 : 1

(b) 1 : 2 : 3

(c) 1 : 2 : 4

(d) 2 : 2 : 3

Solution: (b) Concentration of particles of 0.01 M

urea, NaCl and Na 2 SO 4 = 0.01 M , 0.02 M , 0.03

respectively i.e., they are in the ratio 1 : 2 :

3. Hence, depression in freezing point will

be in the same ratio.

Example: 41 The Van't Hoff factor for 0.1 M Ba(NO 3 ) 2

solution is 2.74. The degree of dissociation is

[IIT 1999]

(a) 91.3%

(b) 87%

(c) 100%

(d) 74%

Solution: (b) Ba( NO 3 ) 2

Initial 0.1
⇌ Ba + + + 2 NO 3−
0 0
At. eq. (0.1− x ) xM 2 xm

(0.1 − x) + x + 2 x 0.1 + 2 x
i= = = 2.74 = 0.1 + 2 x = 0.274
0.1 0.1

0.174
or x=
2
= 0.087