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SOME BASIC CONCEPTS OF
CHEMISTRY
PHYSICAL QUANTITIES AND SI UNITS
The 11th general conference of weights and measures in 1960 recommended the use of
international system of units. Abbreviated as SI Units (after the French expression La System
International de units).

FUNDAMENTAL UNITS
The SI system has seven basic units of physical quantities as follows:

Physical Quantity Abbreviation Name of unit Symbol

time t second s

mass m kilogram kg

length l metre m

temperature T kelvin K

electric current I ampere A

light intensity Iv candela Cd

amount of substance n mole mol

DERIVED UNITS
The units obtained by combination of basic units are known as derived units e.g. velocity is
expressed as distance/time. Hence unit is m/s or ms–1. Some common derived units are:
 Physical Quantity Definition SI Unit

volume length cube m3

area length square m2

ms–1
speed distance travelled
per unit time

ms–2
acceleration speed changed
per unit time

density mass per unit volume kg m–3

pressure force per unit area kgm–1s–2 or Nm–2 (pressure = Pa)

force mass times acceleration of object kgms–2 (Newton N)

energy force times distance travelled kgm2s–2(Joule J)

frequency cycles per second s–1 (hertz = Hz)

kgm2s–3 or Js–1
power energy per second
(Watt = W)

electric charge ampere times second As (coloumb = C)

electric potential energy per unit JA–1s–1 or kgm2s–3

difference charge A–1 (volt = V)

SOME NON-SI UNITS IN COMMON USE

Quantity Unit Symbol SI definition SI Name

Length angstrom Å 10–10 m 0.1 nanometers (nm)

Volume litre L 10–3 m3 1 decimeter (dm3)

Energy calorie cal kg m2s–2 4.184 Joule (J)

STANDARD PREFIXES FOR EXPRESSING THE DECIMAL FRACTIONS

OR MULTIPLES OF FUNDAMENTAL UNITS
 Fraction Prefix Symbol Multiple Prefix Symbol

10–1 deci d 101 Deka da

10–2 centi c 102 Hecta h

10–3 milli m 103 kilo k

10–6 micro m 106 Mega M

10–9 nano n 109 Giga G

10–12 pico p 1012 Tera T

10–15 femto f 1015 Peta P

10–18 atto a 1018 Exa E

PRECISION AND ACCURACY

Precision : It is the closeness of various measurements for the same quantity.
Accuracy : It is the agreement of a particular value to the true value.

Example : Let the true weight of a substance be 3.00g. The measurement reported by three students
are as follows

Case of A student : It is precision but no accuracy since measurements one close but not accurate.
Case of B student : Measurements are close (precision) and accurate (Accuracy)
Case of C student : Measurement are not close (no precision) and not accurate (no accuracy)

STOICHIOMETRY
Stoichiometry : It is calculation of masses or volumes of reactants and products involved in a
chemically balanced reaction. Consider the formation of ammonia.
N2 (g) + 3H2 (g) 2NH3(g)
All are gases indicated by letter (g) and coefficients 3 for H2 and 2 for NH3 are called stoichiometric
coefficients. The formation of ammonia can be interpreted in many ways:
 One mole of N2(g) reacts with three moles of H2(g) to give two moles of NH3(g).
 28g of N2(g) reacts with 6g at H2(g) to give 34g of NH3(g).
 22.4L of N2(g) reacts with 67.2L of H2(g) to give 44.8L of NH3(g)

SIGNIFICANT FIGURES
The weight 7.52 gm of a substance indicates that it is reliable to the nearest hundredth of a gram
and may be expressed as 7.52 ± 0.01. It means slightest variation may occur at the second place of
decimal or we can say that uncertainty is ± 0.01 g.

Now consider the weight 6.4234 g. It may correctly be expressed as 6.4234 ± 0.001 g.
In the first case the weight contains three significant figures and in the second case weight contains
five significant figures.
1. Significance of zero : If zero is used to locate the decimal point it is not considered as
significant figure. Thus in 0.0072 there are only two significant figures whereas in 70.40, there are
four significant figures since zero is after 4. Again in 0.0070 there are two significant figures, since
zero after 7 is significant for it has a meaning when written in exponentials. If we compare 7.0 × 10–3
and 7 × 10–3, the first term has uncertainty of one in seventy and second has uncertainty of one in
seven. The exponential term does not add to number of significant figures.
2. Addition and subtraction of quantities : In this case the uncertainty in the result is equal to
the sum of the uncertainties of the individual quantities.
3. Multiplication and division : In this case the uncertainty in the result is equal to the sum of
the percentage of individual uncertainties.
4. Rounding off : The following rules are observed.
1. If the digit after the last digit to be retained is less than 5, the last digit is retained as
such. e.g. 1.752 = 1.75 (2 is less than 5).
2. If the digit after the last digit to be retained is more than 5, the digit to be retained is
increased by 1. e.g. 1.756 = 1.76 (6 is more than 5).
3. If the digit after the last digit to be retained is equal to 5, the last digit is retained as
such if it is even and increased by 1 if odd.
5. Calculations involving addition and subtraction : In case of addition and subtraction the
final result should be reported to the same number of decimal places as the number with the
minimum number of decimal places .
6. Calculations involving multiplication and division : In this case the final result should be
reported having same number of significant digits as that of the number having least significant
digits.

MATTER
Anything which occupies space, possesses mass and can be felt is called matter.

CLASSIFICATION OF MATTER
ELEMENT
Pure substance consisting of one type of particles in the form of atoms eg. Cu, Na, Fe or molecules
eg. H2, O2 etc.

COMPOUND
Pure substance consisting of molecules formed by the combination of atoms of different elements
eg. CO2, H2O etc.

MIXTURES
Mixtures are substances made of two or more elements or compounds in any proportion. They may
be homogeneous or heterogeneous.

SEPARATION OF MIXTURES

Mixtures can be separated into constituents by following methods:

1. Filtration can separate those mixtures whose one component is soluble in a particular
solvent and other is not.
2. Distillation can be used to separate constituents of mixtures having different boiling points.
3. Extraction dissolves one out of several components of mixture.
4. Crystallisation is a process of separating solids having different solubilities in a particular
solvent.
5. Sublimation separates volatile solids which sublime on heating from non-volatile solids.
6. Chromatography is the technique of separating constituents of a mixture which utilises the
property of difference of adsorption on a particular adsorbent.
7. Gravity separation separates constituents having different densities.
8. Magnetic separation can separate magnetic components from non magnetic ones.

PHYSICAL AND CHEMICAL CHANGES

A change which does not affect chemical composition and molecular structure is a physical change
and the one that involves alteration of chemical composition and molecular structure is a chemical
change.
1. Chemical Combination is reaction between two or more elements or compounds to form a
single substance.
H2 + I2 2HI
2. Displacement means replacement of one element of compound by another.
3. Decomposition involves splitting of a compound to form two or more substances.

4. Combustion is a complete and fast oxidation of a substance.

5. Neutralisation is the reaction between acid and base to form a salt.

6. Polymerisation is the combination of molecules of same or different substances to form a

single molecule called polymer

7. Photochemical changes occur in presence of visible or ultraviolet light.

8. Double decomposition or metathesis is the exchange of oppositely charged ion on mixing
two salt solutions.
9. Hydrolysis involves reaction of salts with water to form acidic or basic solutions.

LAWS OF CHEMICAL COMBINATIONS

1. Law of conservation of mass : This law was given by French chemist A. Lavoisier (1774)
which states that "during any physical or chemical change, the total mass of products is equal to the
total mass of reactants". It is also called law of indistinctibility. It does not hold good for nuclear
reaction.
2. Law of definite proportions : This law was given by Proust (1799) and states that "a
chemical compound always contains some elements combined together in same proportion by
mass". For example different samples of pure CO2 always have carbon and oxygen in 3 : 8 ratio by
mass.
3. Law of multiple proportions : This law was given by John Dalton (1803) and states that
"when two elements combine to form two or more compounds, the different mass of one of the
elements and the fixed mass of the one with which it combines always form a whole number ratio".
This law explains the concept of formation of more than one compound by two elements.
4. Law of reciprocal proportions : This was given by Richter (1792) and states that "when
two elements combine separately with a fixed mass of third, the ratio of masses in which they do so
is same or whole number multiple of the ratio in which they combine with each other." This law is
also called law of equivalent proportions and is helpful in determining equivalent weights.
5. Gay Lussac's law of combining volumes : This law states that when gases react with
each other, their volumes bear a simple whole no. ratio to one another and to volume of products (if
gases) and similar conditions of pressure and temperature.
6. Dalton's atomic theory :
o Proposed by John Dalton in 1808. Main points are :
o Matter is made up, by indivisible particles called atoms
o Atoms of same elements are identical in physical and chemical properties.
o Atoms of different substances are different in every respect
o Atoms always combine in whole numbers to form compounds
o Atoms of resultant compounds possess similar properties
Drawbacks of Dalton's theory :
 Does not explain structure of atom.
 Fails to explain binding forces between atoms in compounds.
 Does not explain Gay Lussac's law.
 Does not differentiate between atom and molecule.
7. Avogadro's law :
It states that "equal volumes of all gases, under similar conditions of temperature and pressure
contain equal number of molecules". Applications are:
 Deducing atomicity of elementary gases
 Deriving relationship between molecular mass and vapour density
 Deriving formula of substances
 Determining molecular wt. of a gas
 Deducing the gram molecular volume.

ATOM
Atom is the smallest particle of element which might not be able to exist independently.

MOLECULE
Molecule is the smallest particle of the substance which can exist independently. It can be
subdivided as
1. Homoatomic molecules are molecules of same element and can be further divided as
monoatomic, diatomic and polyatomic molecules depending upon number of atoms. eg: He, O2, P4
etc.
2. Heteroatomic molecules are molecules of compound. They can be diatomic and polyatomic.
eg: H2O, PCl5, H2SO4, NO etc.

ATOMIC MASS UNIT (A.M.U.)

It is the unit of representing atomic masses. 1 a.m.u. = th the mass of C-12.

MOLE
It is a unit which represents 6.023 × 1023 particles. The number 6.023 × 1023 is called Avogadro's
number and is represented by N0 or NA. Avogadro's number of gas molecules occupy a volume of
22400 cm3 at N.T.P. Number of molecules in 1 cm3 of gas at NTP is Loschmidt N0. With value
2.688 × 1019.

ATOMIC MASS
"It is the number of times the atom of the element is heavier than H atom" was the first proposed
definition. Later on oxygen was preferred as standard. In 1961 C-12 was chosen as standard and
thus "the number of times the atom of an element is heavier than 12th part of C-12 is called atomic
mass of the element.
Atomic mass =

AVERAGE ATOMIC MASS

It is the mass of each isotope determined separately and then combined in ratio of their occurrence.
Suppose a and b are two isotopes of an element with their occurence ratio p : q then

Average atomic mass =

DETERMINATION OF ATOMIC MASS

1. Dulong and petit's rule : It is based on experimental facts. "At ordinary temperature,
product of atomic mass and specific heat for solid elements is approximately 6.4 and this product is
known as atomic heat of the element"
Atomic mass × specific heat = 6.4
The law is valid for solid elements except Be, B, Si and C.
Correct At. mass = Eq. mass × valency

2. Specific heat method : This method is for gases. , where Cp = specific heat at
constant pressure and Cv = specific heat at constant volume. the ratio g is a constant = 1.66 for
monoatomic, 1.40 for diatomic, 1.33 for triatomic gas and atomic mass of gaseous element

=.
3. Chloride formation method : This method converts the element (whose mass is to be
determined) into volatile chloride whose vapour density is found by Victor Mayer method.
Molecular mass = 2 × V.D.
4. Vapour density method is suitable for elements having volatile chlorides.
Atomic mass = Eq. mass of metal × valency.
5. Mitscherlich's law of isomorphism : It states that isomorphous substances have similar
chemical constitution. Isomorphous substances form crystals of same shape and valencies of
elements forming isomorphous salts are also same. eg: ZnSO4. 7H2O, MgSO4.7H2O and
FeSO4.7H2O are isomorphous.

GRAM ATOMIC MASS (GAM)

Is the mass of an atom expressed in gms.

No. of Gm-atoms of element =

MOLECULAR MASS :
It is the average relative mass of the molecule as compared with mass of C-12 atom.

Molecular mass =

CALCULATION OF MOLECULAR MASS :

1. Graham's law of diffusion : It states that rate of diffusion of two gases is inversely
proportional to the square root of ratio of their molecular weights.

2. Victor meyer method : This method can determine the molecular mass as

Molecular mass = × 22400

where W is the mass of liquid in gm. occupying a volume V ml at STP.
3. Vapour density method : Vapour density is the ratio of volume of a gas to the mass of same
volume of hydrogen under identical conditions.

or
Thus molecular mass = 2 × V.D.
4. Colligative properties method : This method can be helpful in determining molecular mass
as

elevation in boiling point

Where Tb is elevation in b.p., Kb is molal elevation constant w is wt. of solute W is wt. of solvent

Depression in freezing point

GRAM MOLECULAR MASS OR MOLAR MASS :

That amount of substance whose mass in grams is equal to its molecular mass or the equivalently
molecular mass of a substance expressed in grams is called gram molecular mass. Gram molecular
mass is also called one gram molecule. thus

No. of gm molecules =

EQUIVALENT MASS :
It is the number of parts by weight of the substance that combines or displaces, directly or indirectly,
1.008 parts by mass of hydrogen or 8 parts by mass of oxygen or 35.5 parts by mass of chlorine. It
can be calculated as-
 Equivalent mass for elements =

 Equivalent mass for acids =

 Equivalent mass for bases =

 Equivalent mass for salts =

 Equivalent mass for oxidising agents =

 Equivalent mass for reducing agents =

 Equivalent weight of radicals =

FORMULA MASS :
It is obtained by adding atomic masses of various atoms present in the formula and this term
replaces molecular mass in ionic compounds.

ACIDITY :
It is the number of OH– ions that can be displaced from one molecule of a substance.

BASICITY :
It is the number of H+ ions that can be displaced from one molecule of a substance.

GRAM EQUIVALENT MASS (GEM) :

It is the mass of a substance expressed in grams or equivalently the quantity of substance whose
mass in grams is equal to its equivalent mass is called one gram equivalent or gram equivalent
mass.

No. of gm equivalents = .

METHODS OF DETERMINING EQUIVALENT MASSES :

1. Hydrogen displacement method : It is for metals which can displace H2 from acids.
Equivalent mass of metal

=
2. Metal displacement method : It utilises the fact that one GEM of a more electropositive

metal displaces one GEM of a less electropositive metal from its salt .
3. Conversion method : When one compound of a metal is converted to another compound of
similar metal then

where E is the eqv. mass of the metal.

4. Electrolytic method :
It states that the quantity of substance that reacts at electrode when Faraday of electricity is passed
is equal to its GEM.
GEM = Electrochemical equivalent × 96500
and ratio of weights deposited by equal amount of electricity is in ratio of their equivalent masses.
5. Oxide method :

Equivalent mass of metal =

6. Double decomposition :

7. Neutralisation method for acids and bases :

Equivalent mass of acid (base)

=
8. Silver salt is method commonly used for organic acids.

Eqv. mass of acid =

Mol. mass of acid = Eqv. mass of acid × Basicity
9. Platinichloride method for bases :
Eqv. mass of base

=
Mol. mass of base = Eqv. mass of base × Acidity
10. Chloride method :
Eqv. mass of metal =

11. Volatile chloride method :

Valency of metal

CHEMICAL EQUATION :
It is the equation representing chemical change in terms of formula of reactants and products.
1. An equation which has not been equalised in terms of number of atoms of reactants and
products is called a skeleton equation.
2. An equation having equal number of atoms of various kinds on both sides is a balanced
equation.

EMPIRICAL FORMULA :
It is the simplest formula of a compound giving simplest whole number ratio of atoms present in one
molecule. e.g. CH is empirical formula of benzene.

MOLECULAR FORMULA :
It is the actual formula of a compound showing the total number of atoms of constituent elements
e.g. C6H6 is molecular formula of benzene.
Molecular formula = n × empirical formula, where n is simple whole number.

SOLUTION :
It is a homogenous mixture of two or more substances. The component of solution having larger
proportion is solvent and others are solute.

MOLE FRACTION :
It is the ratio of moles of a constituent to the total number of moles in a solution.
Let A be solute & B is solvent then mole fraction of solute (xA)

= , where n is the number of moles.

Mole fraction of solution

MASS PERCENTAGE :
It is the number of parts by mass of solute per hundred parts by mass of solution. If WA is mass of
solute and WB the mass of solvent, then

Mass percentage of A = .

VOLUME PERCENTAGE :
It is the number of parts by volume of solute per hundred parts by volume of solution. If VA is volume
of solute and VB is the volume of solvent then

Volume percentage of A =

PARTS PER MILLION (PPM) :

It is the mass of solute present in one million parts by mass of solution.

NORMALITY :
It is the number of gram equivalents of a solute present in one litre of solution.

Normality depends on temperature. Also if strength is given in normalities, N1 of A & N2 of B

Then N1V1 = N2V2.

MOLARITY :
It is the number of moles of solute present in one litre of solution.

and millimoles = M × V(in ml).

Molarity and mass percentage have the relation M

= , where d = density
If a solution of molarity M1 and volume V1 adds up with a solvent to a final volume V2, then molarity
M2 is given by

If two different solutions (M1, V1) and (M2, V2) are mixed then molarity of resulting solution is
M=
Also, Molarity × GMM of solute = Normality × GEM of solute

MOLALITY :
It is the number of moles of solute in 1 kg of solvent.

Molality (m) =

Molality is independent of temperature.

FORMALITY (F) :
It is the number of gram formula mass of ionic solute dissolved in 1 litre of solution.

Formality =

LIMITING REAGENT :
It is the reactant which is completely consumed during the reaction.

STRUCTURE OF ATOM
ATOM
John Dalton proposed in 1808 that atom is the smallest indivisible particle of matter.

ATOMIC RADII
Atomic radii are of the order of 10 cm (1Å) and radii of nuclei are nearly 10 cm.
–8 –13

Radius of the nucleus is thus th of the radius of atom.

Radius of atom Radius of nucleus

ELECTRON
1. It was discovered through the study of Cathode rays (discovered by Zulius Plucker) and
the name was proposed by Stoney.
2. Charge : It was determined by Mullikan by oil drop method as –1.602 × 10 coulombs or
–19

4.803 × 10 e.s.u.
–10

3. Mass : It was found by J. J. Thomson as

9.11 × 10 g.
–28

4. Specific charge : e/m ratio is called specific charge and was determined by Thomson
as 1.76 × 10 coulombs/gm.
8

5. Radius : It is of the order 10 cm.

–15

6. Density : 2.17 × 10 g/cc. 17

7. Mass of electron at speed v is m =

8. Atomic mass unit : It is 0.0005486 amu.
9. Mass of one mole of electron : It is 0.55 mg.

CATHODE RAYS
Originate from cathode. Electrons were discovered by cathode ray experiment.

SOME PROPERTIES OF CATHODE RAYS

1. They cast shadow of the object in their path
2. Rotate a mica wheel
3. Deflected by electric and magnetic fields in a direction showing negative charge.

PROTON (H ) +

Discovered by Goldstein (1886) through perforated cathode rays experiment which showed the
presence of anode or canal rays.
1. Mass : It was found to be 1.672 × 10 g or 1.672 × 10 kg or 1.00728 amu. It is about
–24 –27

1837 times heavier than an electron.

2. Charge : It carries unit positive charge 1.602 × 10 coulombs or 4.803 × 10 esu.
–19 –10

3. Specific charge : It is 9.58 × 10 coulomb/gm. It varies with nature of gas and is

4

maximum if H is used.2

4. Charge on 1 mole of proton is 96500 coulomb or 1 Faraday.

5. Volume : The volume for proton is approximately 1.5 × 10 cm . –38 3

NEUTRON ( N ) 0
1

Discovered by Chadwick by bombarding Be or B atoms (sheet) with high speed -particles

1. Mass : Its mass is 1.675 × 10 gm or 1.675 × 10 kg or 1.00866 amu.

–24 –27

2. It is heavier than proton by 0.18%.

3. Density : Its density is 1.5 × 10 g/cm . 14 3

4. Specific Charge : It is zero.

5. Stability : It is least stable of all elementary particles present in an atom.
6. Disintegration : Isolated neutron is unstable and disintegrates into electron, proton and
neutrino.
7. Among all elementary particles neutron is the heaviest and least stable.

OTHER SUBATOMIC PARTICLES

1. Positron (Positive electron e ). Discovered by Dirac (1930) and C. D. Anderson (1932).
+1
0

They are highly unstable and produce -rays on combining with electrons.
2. Neutrino and Antineutrino are particles of small mass and no charge as stated by
Fermi (1934). Anti-neutrino spin clockwise and neutrino spin anticlockwise.
3. Meson : They are unstable particles and include pions ( ,
+ –
or ) Kaons (K , K , K ,
0 + – 0

K ) and eta meson ( ).

–0

Mass : They have mass intermediate of electron and proton.

Discovery : By Yukawa (1935) and Kemmer.
4. Anti proton ( p ) : Negative proton produced by Segre and Weigland (1955) by proton-
–1
1

proton and proton-neutron collisions.

5. v-particles : They may be positive, negative or neutral. Discovered by G. D. Rochester
and C C. Butler v and v are 2200 times heavier than electron. Heavier disintegrate into
– 0

pions and lighter into mesons.

THOMSON'S ATOMIC MODEL

Atom is a sphere of positive electricity with a number of electrons distributed within the sphere.

RUTHERFORD'S NUCLEAR MODEL

It is based upon -particles scattering experiment. Only a few (one in 10,000) -particles were
returned back from the Au-foil (10 mm thick). –4

Conclusion - Atom consists of two parts - (a) Nucleus (b) Extra nuclear part.
Drawbacks - Model fails to explain the stability of the atoms and line spectrum of hydrogen.

NUCLEUS
1. Nucleus : It is small heavy and positively charged material located in the centre of atom
and electrons are distributed in extra nuclear part of atom and revolve around the nucleus.
2. Radius : It is of the order 1.5 × 10 cm to –13

6.5 × 10 cm (1.5 – 6.5 Fermi). In general

–13

Where r is a proportionality constant with value 1.4 × 10 cm. and A is mass number.
0
–13

3. Volume : It is about 10 cm . and that of atom is 10 cm

–39 3 –24 3

4. Density : It is about 10 g/cm .

14 3

5. Diameter : It is about 10 m or 1 fm (1 fm = 10 m)
–15 –15

6. Nucleus contains neutrons and protons, collectively known as nucleons.

ATOMIC NUMBER/MOSELEY'S POSTULATES
The number of protons present in an atom is called the atomic number, denoted by Z. Moseley
postulated that the frequency of X-rays produced when beam of strong electrons fall on metal
target, called anti-cathode is related to the charge present on the nucleus of an atom of the
element used as anti cathode. Mathematically
; where = frequency of X-rays, Z = nuclear charge, a and b = constants

MASS NUMBER
It is sum of number of protons and neutrons present in the nucleus (nucleons as a whole) and
denoted by A. It is always a whole number.

AVERAGE ATOMIC MASS

It is the average mass of all existing isotopes and not necessarily a whole number.

ISOTOPES
Isotopes are atoms of the same element having same atomic number but different mass
number. e.g. O , O and O . They were discovered by Soddy (1911).
8
16
8
17
8
18

ISOBARS
Atoms of different elements having same mass number but different atomic numbers e.g. K , 19
40

Ca .
20
40

ISOTONES
Atoms of different elements with different atomic and mass numbers but same number of
neutrons e.g. Si , P , S .
14
30
15
31
16
32

ISODIAPHERS
Atoms having same Isotopic number.

ISOELECTRONIC SPECIES
Species having same number of electrons e.g. CO and CN (both contain 14 electrons each) Na – +

and Ne (both contain 10 electrons each).

The ionic size decreases with increasing effective nuclear charge of iso-electronic species.

Ionic size of isoelectronic species depend on (effective nuclear charge).

Ionic size

Species C N O4– 3– 2–
Nuclear Charge 6 7 8 9
Total electrons 10 10 10 10

.6 .7 .8 .9
Ionic Radius (Å) 2.60 1.70 1.40 1.36
Species Na Mg Al Si
+ 2+ 3+ 4+

Nuclear Charge 11 12 13 14
Total electrons 10 10 10 10

(effective
Nuclear charge) 1.1 1.2 1.3 1.4
Ionic radius (Å) 0.95 0.65 0.50 0.41

FAILURE OF RUTHERFORD'S MODEL

According to classical theory of electromagnetism whenever a charge is subjected to an
acceleration around an opposite charge, it emits radiations continuously. Therefore the electron
while moving around nucleus in circular path must lose energy, go into spiral motion and
ultimately fall into the nucleus. Practically it does not happen.

PLANCK QUANTUM THEORY

According to Max Planck (1901) radiant energy is emitted or absorbed only in discrete units in
form of bundle or packets of energy called photon (quantum). Photon is not a material body. It is
massless bundle of energy

Energy associated with each photon (quantum) :

E = h =h
h = Planck's constant = 6.626 × 10 Js in S.I. units
–34

(or 6.6726 × 10 ergs in c.g.s. units).

–27

= frequency of radiation (each photon).

c = velocity of light,
= wavelength of radiation.

Thus, a body can radiate energy in multiples of quantum h , 2h , 3h .... nh where n is an

integer.

INTENSITY OF LIGHT
It is defined as number of photons falling per unit area per sec. and depends upon wavelength
of photons.
or
It is defined as amount of energy falling per unit area per sec and depends upon wavelength of
photons.
ELECTROMAGNETIC RADIATION
Electromagnetic radiation by James maxwell (1870). An electrically charged particles moving
under acceleration produces alternating electrical and magnetic fields mutually perpendicular to
each other. These fields are transmitted in the form of waves having same wavelengths,
frequency, speed and amplitude and are called electromagnetic waves or electromagnetic
radiations. In vacuum all types of electromagnetic radiations travel at the same speed (3.0 × 10 8

ms ) regardless of wavelengths.
–1

WAVELENGTH
It is the distance between two neighbouring crests or troughs of wave.

FREQUENCY
It is the number of waves which pass through a particular point in one second. Unit is Hertz (Hz)
or cycles per second. 1 Cps = 1 Hz.

VELOCITY
It is the distance travelled by wave in one second. Unit is
m sec and denoted by c.
–1

c= .

WAVE NUMBER
It is the number of wavelengths per cm. It is equal to the inverse of wavelength. Unit is cm and
–1

is denoted by .

AMPLITUDE
It is the height of crest or trough. Square of amplitude determines the amount of energy carried
by the wave.

ELECTROMAGNETIC SPECTRUM
Arrangement of all electromagnetic radiations in the increasing order of their wavelengths or
decreasing order of frequencies is called electromagnetic spectrum.

Rays Wavelength ( in Å) Frequency ( in Hz)

Cosmic Rays 3×10 to infinity
21

Rays 0.01 3×10 to 3×10

19 20

X Rays 1.0 2×10 to 3×10

16 19

UV Rays 150 7.9×10 to 2×10 14 16

Visible Light 3800 3.9×10 to 7.9×10 14 14

Infra Red 7600 1×10 to 3.95×10

11 14

Micro Waves 6×10 1×10 to 5×10

6 9 11
Radio Waves 3×10 1×10 to 1×10
9 5 9

ATOMIC SPECTRUM
Atoms of different elements emit electromagnetic radiations of definite frequencies when excited
by heating, passing current or electric discharge. Arrangement of these radiations in decreasing
order of frequencies is called atomic spectrum.

DISPERSION
Phenomenon of splitting of beam of light into radiations of different frequencies after passing
through a prism is called dispersion.

CONTINUOUS SPECTRUM
It is obtained by passing sunlight (white light) through a prism. The light is dispersed or resolved
into continuous spectra of colours from Violet to Red. It contains radiations of all the
frequencies.

LINE SPECTRUM
It is an atomic spectrum of an element which consists of a number of bright lines separated by
dark bands. Atomic Spectra of most elements is line spectrum.

ABSORPTION SPECTRUM
It is obtained by passing white light through solutions or vapours of chemical substance and
then is analysed by spectroscope. It has few dark lines in otherwise continuous spectrum.

EMISSION SPECTRUM
It is obtained by passing radiations from the atoms through prism. It has few bright lines against
a dark background.

HYDROGEN SPECTRUM
It is obtained by passing light being emitted from discharge tube containing hydrogen at low
pressure through spectrograph.

Hydrogen Spectrum has five Series

Spectral Line Region n n 1 2

Lyman Series U.V. 1 2, 3, 4.....

Balmer Series Visible 2 3, 4, 5.....
Paschen Series I.R. 3 4, 5, 6.....
Brackett Series I.R. 4 5, 6, 7....
Pfund Series I.R. 5 6, 7, 8....
Wavelength of line in spectrum is given by the expression

R = Rydberg Constant, Z = charge on nucleus,

H

n , n = electronic levels involved in transition,

1 2 = Wave number

also for hydrogen where is frequency.

1. For calculation of longest wavelength line use n nearest and for shortest wavelength line
2

use n infinity e.g. value of longest wavelength in Balmer Series of hydrogen spectrum use n = 2
2 1

and n = 3.
2

2. Last line of spectrum is called Series limit. Last line is the line of shortest wavelength
and high energy when n = we get last wavelength
2

(series limit) = ,
3. Number of Lines in a Transition : Mathematical formula for number of lines is follows
as

No. of lines =

BLACK BODY RADIATION

The radiation emitted by a body when heated is called black body radiation. The frequency of
radiation increases with temperature. At a given temperature the intensity of radiation emitted
increases with decrease of wavelength, reaches a maximum value and then starts decreasing
with further decrease of wavelength. A black body can emit and absorb all frequencies.

PHOTOELECTRIC EFFECT
Phenomenon of ejection of electrons from the surface of a metal when light of suitable
frequency strikes on it is called photoelectric effect.
1. Threshold frequency (v ) : The minimum frequency of incident radiation to cause the
0

photoelectric effect is called threshold frequency.

2. Work function : A part of the photons energy that is absorbed by the metal surface to
release the electron is known as work function of the surface denoted by . The remaining part
of the energy of photons goes into the Kinetic energy of the electron emitted.
If 0 is the threshold frequency and the frequency of incident light then and E = h .

Note:
 K.E. is independent of the intensity of light.
 Number of photoelectrons Intensity of light
 K.E. is directly proportional to frequency of incident light.
 is known as Einstein's photoelectric equation.
 Energy required to stop the ejection of electrons is given by eV where e is the electric
0

charge and V is stopping potential.

0

BOHR’S MODEL OF ATOM

Proposed by Niel Bohr to overcome the drawbacks of Rutherford’s model.
1. Electrons revolve around nucleus only in certain selected circular orbits. These orbits are
associated with definite energies and are called energy shells or levels.
2. Electrons can move only in those circular orbits where angular momentum is a whole

number and multiple of h/2 . i.e. mvr =. or simply an integral number of wavelengths
should fit in given electron orbit of radius r i.e. n =2 r.
3. Electrons energy in a particular orbit is constant.
4. Lowest energy state is called ground state and when electron absorbs energy and
jumps to higher state, it is called excited state
5. Electronic energy is negative because at infinite distance there is no interaction
between electron and nucleus thus energy is zero. While when close to nucleus, attraction takes
place, energy is released and it becomes negative as it was already zero. The energy of
electron increases with the value of n, but the difference of energy between two successive
orbits decreases. Thus
E – E > E – E > E – E .......... etc.
2 1 3 2 4 3

6. Energy of electron in n orbit th

where m = Mass of the electron,

e = Charge on the electron,
h = Planck's constant
n = Principal quantum number,
k = A universal constant = 9.0 × 10 J.m/C 9 2

The constant k is inverse of permitivity factor 4 of the medium . The numerical value of
0

permitivity factor is 4 = 1.11264 × 10 C N m . In C.G.S. system k = 1.

0
–10 2 –1 –2

7. Radius of nth orbit

r =
n Å
8. Velocity of electron in n orbit, th
 cm/sec.

The velocity of electron in first orbit of hydrogen is of the velocity of light.

9. Kinetic energy of electron in n orbit, th

10. Potential energy of electron in n orbit, th

11. Total energy of electron in n orbit, th

12. Number of revolutions per second in n orbit, th

13. Angular velocity

14. Angular momentum = mvr

15. Number of spectral lines when electron jumps from the n to ground level = th

16. The electrons energy is generally expressed in kcal or kJ mol or in electron volts eV. –1

1 erg mol = 1.44×10 kcal mol = 6.022×10 kJ mol

–1 13 –1 13 –1

1eV = 1.602×10 J –19

17. Some important values :

In c.g.s. system,
m = 9.109×10 g –28

e = 4.803×10 esu, –10

h = 6.626×10 ergs, –27

k=1

R H

In S I system,
m = 9.109×10 kg –31

e = 1.602×10 C, –19

h = 6.626×10 J.s, –34

k = 9.0 × 10 Jm/C 9 2

R =
H
In SI system the charge e is replaced by

LIMITATIONS OF BOHR’S MODEL

1. Explains the spectrum of elements having only one electron
2. Does not explain splitting of spectral lines under magnetic field (Zeeman effect) and
electric field (stark effect)
3. Does not explain quantisation of angular momentum.
4. It goes against the Heisenberg’s uncertainity principle.

SOMMERFIELD MODEL
1. Motion of electrons is in closed elliptical paths of definite energy levels having nucleus
on either of the focii.
2. Angular momentum is quantized

3. where k = 1, 2 ---------n.
4. It does not explain distribution of electrons in extranuclear part of atom and also does
not explain for de Broglie concept.

QUANTUM MECHANICS
It was developed independently by Warner Heisenberg and Erwin Schrodinges and takes into
account the dual behaviour (particle and wave nature) of matter proposed by de Broglie.
Planck’s Quantum theory successfully explains.
1. Photoelectric effect
2. Black-body radiation
3. Line spectra of H-atom
4. Variation of heat capacity of solids with temperature.

DE- BROGLIE PRINCIPLE (1924)

1. Proposes that just as radiations have particle nature, the material particles are also
associated with wave nature.

2. de Broglie wavelength is h = Planck’s constant m = mass of object ; v=

velocity and this equation is called the de Broglie equation.

DAVISSON AND GERMER’S EXPERIMENT

Confirms the wave nature of electrons.

SCINTILLATION METHOD AND PHOTOELECTRIC EFFECT

Confirm the particle nature.

HEISENBERG’S UNCERTAINITY PRINCIPLE

“It is not possible to determine simultaneously the position and momentum of small moving sub-
atomic e.g., particle , such as electron with entire certainty”.
1. Mathematically

where, x = uncertainity in position

p = uncertainity in momentum and h = Planck’s constant
2. As the mass of particle increases, the uncertainity decreases

QUANTUM MECHANICAL MODEL OF ATOM

1. Based on de Broglie's and Heisenberg’s principle.
2. Put forward by Schrodinger (1920). Behaviour of electron was described in terms of
equation known as Schrodinger wave equation

where is amplitude of electron wave and is also called

wave function. x, y, z, are space coordinates, m is mass of electron, h is Planck’s constant, E is
total energy and V is potential energy of the electron.
3. Many solutions for this equation are possible for hydrogen but only certain solutions are
permissible and are called eigen values

4. The solution must be single valued, should satisfy the relation and must be
finite and continuous.

5. has no physical significance but gives intensity of electrons and thus gives
probability of electron in a particular region.

ORBITALS
Orbitals are the regions in space around nucleus where probability of finding the electron is
maximum.
1. Probability does not become zero even at infinity and is given by .
2. Electron orbitals in atoms are called atomic orbitals while those in molecules are called
molecular orbitals.
3. Orbitals have definite energy and momentum and are quantized. i.e, E = –E /n thus
n 1
2

Bohr’s concept of well defined orbits is ruled out.

QUANTUM NUMBERS
1. Four quantum numbers (n, l, m, s) help in providing complete information about an
electron in an atom.
2. Principal quantum number (n) determines the energy and average distance of
electron. It has whole number values also denoted as K, L, M, N. etc. As n increases, distance
of electron from nucleus increases and energy increases.
3. Azimuthal quantum number (l) determines angular momentum of the electron. It also
determines the shape of orbitals and it may have all possible whole number values from 0 to n–
1 for each principal energy level. The sublevels are:
Value of l 0 1 2 3
Sub-shell s p d f

Magnitude of angular momentum of an electron in orbital, mvr =

Angular momentum of an electron in any orbit,

mvr
4. Magnetic quantum number (m) defines the orientation of electrons cloud in a particular
sub shell. Values of m are the number of orbitals associated with a particular sub shell in
main shell. Values of m lie from 0 to l. Total values of ‘m’ for a given n is n . Total values
2

of ‘m’ for a given l is 2l +1. The table shows a clear relation between quantum numbers.
Shell (n) Sub -shells (l) Orbitals (m)
n=1K shell l= 0 1s m = 0
n=2L shell l= 0 2s m = 0
l= 1 2p m = –1,0, +1

n=3 M shell l= 0 3s m = 0
l= 1 3p m = –1, 0, +1
l= 2 3d m = –2, –1, 0,+1, +2

5. Spin quantum number (s) tells the spin of the electron. It can have two value

(clockwise) and (anticlockwise). Mathematically where s is amplitude

of spin quantum angular momentum.

SHAPE OF ORBITALS
1. s orbitals are spherically symmetrical.
2. p orbitals are dumbbell shaped.
3. d orbitals have five different orientation. Three of them d , d , d are identical in shape
xy yz xz

but have different orientation.

4. The plane passing through nucleus where probability of finding the electron is zero is
called a nodal plane. Number of nodal planes in an orbital = l. Number of nodal planes
increases with increasing value of n. e.g. 1s has no nodal plane. 2s has one nodal plane. For
e.g. : s orbitals (l=0) have no nodal plane, p orbital (l=1) have one nodal plane, d orbitals (l=2)
have two nodal planes.
Nodal plane = n-l-1
5. Orbitals of a sub shell having same energy are called degenerated orbitals.
6. Spherical surface within an orbital where probability of finding an electron is zero is
called spherical or radial node. Number of spherical nodes = (n–l–1). Angular or non
spherical nodes = (l). Thus total nodes = (n – 1).
Shape of s-orbital :

Shape of p-orbital :

for and for ,

Shape of d-orbitals :

PAULI’S EXCLUSION PRINCIPLE

No two electrons in an atom can have same values for all the four quantum numbers.
1. It is not possible to accomodate more than two electrons in an orbital. In other words. s
sub shell can have maximum of 2 electrons p sub shell can have maximum of 6 electrons. Thus
max. no. of electrons in a shell can be 2n .
2
2. Maximum number of electrons in a sub shell can be 2, 6, 10, 14 in s, p, d, f respectively
and max. electrons in an atomic orbital can be 2.
Maximum number of electrons in a sub shell is equal to
where

Note : Maximum numbers of electrons in an orbital = 2

AUFBAU’S RULE
Electrons are added to orbitals in increasing order of energies. The order of energies for orbitals
is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s.
1. The order of energies can be calculated by (n + l) rule. i.e. orbitals are filled in order of
increasing (n+l) values the one with lower n value is filled first.
2. The energy of atomic orbitals for H-atom depends on the value of n only.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f

HUND’S RULE OF MAXIMUM MULTIPLICITY

The pairing of electrons in orbitals of a subshell does not take place until all orbitals of sub shell
are singly occupied.
1. This arrangement leads to lower energy level.
2. Singly occupied orbitals should have same spins giving rise to lower energies.

RADIAL PROBABILITY DISTRIBUTION CURVES

The electron density is directly proportional to . The larger the value of more is the
probability of finding the electrons. Schrodinger wave equation may be separated into a product
of three functions dependent on

R (r) = Radial wave function, it may be 0, or

R = Radial density in per unit volume of spherical shell.
2

It is always positive.
Radial probability. It is defined as maximum density of electrons in the volume of
spherical shell having small thickness dr.
Note : is the volume of spherical shell having small thickness dr.
In case of s orbitals the number of peaks is equal to n,
In case of p orbitals the number of peaks is equal to (n–1),
In case of d, orbitals the number of peaks is equal to (n–2)
The point at which the probability of finding the electrons is zero is called nodal point.
The distance of maximum probability increases with increase in the value of n. hence 2s, 2p
electrons are greater distance than 1s. and have greater energy also.

ANGULAR PROBABILITY DISTRIBUTION CURVES

The total angular ( ). ( ) depends only on the direction and remain independent of the
distance electrons from the nucleus

Angular probability distribution curves for s and p orbitals. The length of the line OP is
proportional to the probability of finding the electrons. The length of the line OP is the same in
all directions for s orbital Hence there are equal chances for finding electrons in all directions
from the nucleus.

The length of line decreases with increasing in the value of angle . Hence there are more
chances for finding the electrons along the axes for p orbitals.

RITZ. COMBINATION PRINCIPLE

It states that the wave number (reciprocal of wavelength) of any line in hydrogen spectrum of
a particular series can be represented as a difference of two terms, one of which is constant and
other varies throughout the series. Mathematically, .

R = Rydberg constant
H
COMPTON EFFECT
The decrease in energy (or increase in wavelength) of X-rays after the scattering from the
surface of carbon or light element is known as Compton effect.

CLASSIFICATION OF ELEMENTS
AND PERIODICITY IN PROPERTIES
THE PERIODIC TABLE OF THE ELEMENTS

PERIODIC TABLE
It is a table of elements in which the elements with similar properties are placed together.

DOBEREINER’S LAW OF TRIADS

This was the classification of elements into groups of three elements each with similar properties
such that the atomic weight of the middle element was the arithmetic mean of the other two e.g.
Ca, Sr, Ba; Cl, Br, I etc.
The difference between atomic weights of any two successive elements is nearly constant.
NEWLAND’S LAW OF OCTAVES
This was an arrangement of elements in order of increasing atomic weights in which it was
observed that every eighth element had properties similar to those of the first just like the eight
node of an octave of music.

Prouts Hypothesis : Atomic weight of an element is simple multiple of atomic weight of

hydrogen.

MENDELEEV’S PERIODIC TABLE

This is based upon Mendeleev’s periodic law which states that the physical and chemical
properties of the elements are a periodic function of their atomic weights.

Mendeleev named Gallium and Germanium elements as eka-aluminium and eka-silicon

respectively.

STRUCTURAL FEATURES OF THE MENDELEEV’S PERIODIC TABLE

1. Mendeleev’s original periodic table consists eight vertical columns are called groups I-
VIII & seven horizontal rows are called periods 1-7. But modified Mendeleev’s periodic table
contains nine groups, i.e., I-VIII and zero (of noble gases).
2. All groups except VII and zero have been further divided into two sub-groups called A
and B. A groups of left hand side consist of normal elements while groups B of right hand side
consist of transition elements.
3. Elements of group IA are called alkali metals while those of group IB (i.e, Cu, Ag, Au)
are called coinage metals.

MODERN PERIODIC LAW

Moseley formed the basis of the modern periodic law. He discovered that the square root of the
frequency of the more prominent X-rays emitted by a metal was proportional to the atomic
number and not the atomic weight of the atom of the metal. Hence atomic number should be the
basis of classification of the elements.

Modern periodic law states, “that the physical and chemical properties of the elements are a
periodic function of their atomic number.”

It was observed that the elements with similar properties reoccurred at regular intervals of 2, 8, 8,
18 or 32. These numbers (2, 8, 8, 18 and 32) are called magic numbers, and cause of periodicity
in properties.

STRUCTURAL FEATURES OF THE LONG FORM OF THE PERIODIC TABLE

1. GROUPS -
a. The 18 vertical columns, of the periodic table, are called groups
b. Elements of groups 1, 2, 13-17 are called normal or representative elements.
c. Elements of groups 3-12 are called transition elements
d. The elements belonging to a particular group is known as a family and is usually
named after the first element. For example, Boron family (group 13). In addition
to this, some groups have typical names. For example,
Elements of group 1 are called alkali metals
Elements of group 2 are called alkaline earth metals
Elements of group 3 are called pnicogens
Elements of group 16 are called chalcogens
Elements of group 17 are called halogens
Elements of group 18 are called noble gases

2. PERIODS - The 7 horizontal columns (or rows) are called periods. The seven periods of
periodic table are
Shortest period - 1st period (1H 2He) contains 2 elements. It is the shortest period.
Short periods - 2nd period (3Li 10Ne) and 3rd period (11Na 18Ar) contains 8 elements
each. These are short periods.
Long periods - 4th period (19K 36Kr) and 5th period (37Rb 54Xe) contain 18 elements each
and are called long periods.
Longest period - 6th period (55Cs – 86Rn) contains 32 elements and is the longest period.
Incomplete period - 7th period (87Fr –) is, however, incomplete and contains at present only 26
elements.

3. BLOCKS - The periodic table is divided into four main blocks (s, p, d and f) depending
upon the subshell to which the valence electron enters into.
a. s-Block - Elements of group 1 and 2 constitute s-block.
b. p-Block - Elements of group 13 to 18 constitute p-block.
c. d-Block - Elements of group 3 to 12 constitute d-block.
d. There are three complete series and one incomplete series of d-block elements.
These are:
1st or 3d-transition series which contains ten elements with atomic number 21-30 (21Sc–30Zn).
2nd or 4d-transition series which contains ten elements with atomic number 39–48 (39Y–48Cd).
3rd or 5d-transition series which also contains ten elements with atomic n umber 57 and 72-80
(57La, 72Hf–80Hg).
4th or 6d-transition series which contains only ten elements.
e. The f-block elements comprise two horizontal rows placed at the bottom of the periodic
table to avoid its un-necessary expansion and make the symmetrical nature of periodic table. The
two series of f-block elements containing 14 elements each. Lanthanides - The 14 elements
from 58Ce–71Lu in which 4f-subshell is being progressively filled up are called lanthanides or
rare earth elements. Actinides - Similarly, the 14 elements from 90Th –103Lr in which 5f-
subshell is being progressively filled up are called actinides.
 f. Elements of s and p-blocks are called normal or representative elements, those of d-
block are called transition elements while the f-block elements are called inner
transition elements.
g. The 11 elements with Z = 93–103 (93Np – 103Lr) which occur in the periodic table after
uranium and have been prepared by artificial means are called transuranics. These are
all radioactive elements.

NOMENCLATURE OF ELEMENTS WITH ATOMIC NUMBER > 100

According to IUPAC the nomenclature can be derived using numerical roots for 0 and numbers
1-9 for atomic numbers of elements.

The roots are put together in order of digits which make the atomic number and ‘ium’ is added at
the end. Use the following table

Example : Name the IUPAC name of the element of atomic number 108 : Name will be
Unniloctium and symbol - UnO

Example – Name the element with atomic number 115.

Name will be - Ununpentium and symbol UuP

DIAGONAL RELATIONSHIP
Certain elements of 2nd period i.e., Li, Be, B. show similarity with their diagonal elements in the
3rd period i.e., Mg, Al, Si, as shown below:

This is called diagonal relationship and is due to the reason that these pairs of elements have
almost identical ionic radii and polarizing power. (i.e. charge/size ratio).

PERIODIC PROPERTIES
Properties which show a regular gradation when we move from left to right in a period or from
top to bottom in a group are called periodic properties. These properties are atomic size,
ionisation energy electron affinity etc.

ATOMIC SIZE
It refers to the distance between the centre of nucleus of atom to its outermost shell of electrons.
The absolute value of atomic radius cannot be determined because
 It is not possible to locate the exact position of electrons in an atom as an orbital has no
sharp boundaries.
 It is not possible to isolate an individual atom.
 In a group of atoms, the probability distribution of electrons is influenced by the presence
of neighbouring atoms.
Since absolute value of atomic size cannot be determined, it is expressed in terms of the
operational definitions such as covalent radius, vander waal’s radius, ionic radius and metallic
radius.

Covalent radius : It is half of the distance between the nuclei of two like atoms bonded together
by a single covalent bond, hence it is also known as single bond covalent radius (SBCR). Thus,
covalent radius .

where d = internuclear distance between two covalently bonded like atoms.

Van-der Waal’s radius : It is one-half of the distance between the nuclei of two adjacent atoms
belonging to two neighbouring molecules of an element in the solid state.
The covalent radius is always smaller than the corresponding van der waal’s radius.

Metallic radius : It is half of the distance between two successive nuclei of two adjacent metal
atoms in the metallic closed packed crystal lattice. Metallic radius of an element is always
greater than its covalent radius.

Ionic radius : It is the effective distance from the nucleus of the ion upto the electrons in the
outer shell to which it can influence the ionic bond.
An atom can be changed into a cation (by loss of electron) which is always much smaller than
the corresponding atom, or to an anion (by gaining of electrons) which is always larger than the
corresponding atom.
FACTORS INFLUENCING COVALENT RADIUS
1. Multiplicity of bond : Covalent radii depends on the multiplicity of bonds. e.g.,
Bond length Radius of C-atom

1.54Å

1.34Å
2. Percentage of ionic character : Covalent radius of H in HCl, HBr and HI are different.
3. Effective nuclear charge : Greater the effective nuclear charge, more tightly is the hold
with nucleus and hence smaller the radius.

PERIODIC VARIATION OF ATOMIC RADII

1. On moving down the group the valence shells become far away from the nucleus and
thus the atomic radius increases.
2. On moving along the period, the effective nuclear charge increases and thus the electron
cloud is attracted more strongly towards the nucleus resulting in the contraction of atomic radius.

ISOELECTRONIC IONS OR SPECIES

These are ions of the different elements which have the same number of electrons but different
magnitude of the nuclear charge. The size of isoelectronic ions decreases with the increase in the
nuclear charge.

IONISATION ENERGY (I.E.)

The amount of energy (work) required to remove an electron from the last orbit of an isolated
(free) atom in gaseous state is known as ionisation potential or energy or better first ionisation
potential of the element, i.e.,
1. The amount of energies required to remove the subsequent electrons (2nd, 3rd, ...) from
the monovalent gaseous cation of the element one after the other are collectively called
successive ionisation energies. These are designated as I.E1, I.E2, I.E3, I.E4 and so on. It may be
noted that. I.E4 > I.E3 > I.E2> I.E1 (for a particular element)
IE is expressed in eV/atom or kcal mol–1 or kJ mol–1
Note that eV atom–1 = 23.06 kcal mol–1 = 96.3 kJ mol–1
2. In general, the first I.E. increases along the period from left to right. However there are
some exceptions to the general trend -
a. I.E. decreases from elements of group 2 3.
b. I.E. decreases from elements of group 15 16.
3. In a group of the periodic table, the ionisation energy decreases from top to bottom.
4. The factors which affect the ionisation energy are
a. Atomic size or radius : I.E. decreases as the atomic size increases so the
attractive force decreases.
b. Number of electrons in the inner shell (screening effect) : On moving down a
group, the number of inner shells increases which increase the screening effect
and hence the ionisation potential tends to decrease.
c. Nuclear charge : On moving along the period, effective nuclear charge increases
due to addition of electrons in same valence shell and hence ionisation energy
increases.
d. Stable configuration : Half filled or completely filled subshells possess extra
stable nature and thus it is more difficult to remove electron and hence more is
I.E.
e. Penetration effect : More penetrating (i.e. more closes) are subshells of a shell to
the nucleus, more tightly the electrons are held towards the nucleus and more is
I.E.
I.E. : s > p > d > f for a given shell
Penetration power Surface area of a subshell
 5. In second period elements, the correct increasing order of ionisation energies is
IE1 : Li < B < Be < C < O < N < F < Ne
IE2 : Be < C < B < N < F < O < Ne < Li
6. In third period elements, the correct increasing order of ionisation is
IE1 : Na < Al < Mg < Si < S < P < Cl < Ar
IE2 : Mg < Si < Al < P < S < Cl < Ar < Na

ELECTRON AFFINITY (EA)

It is the amount of energy released when a gaseous atom accepts the electron to form gaseous
anion .

1. EA values are expressed in eV/atom or kcal/mol or kJ/mol.

2. The energy change accompanying the addition of first, second, third etc. electrons to
neutral isolated gaseous atoms are called successive electron affinities and are designated as EA 1,
EA2, EA3 etc.
3. The first EA is always taken as positive. However, the addition of second electron to the
negatively charged ion is opposed by coulombic repulsion and hence required (absorbed) energy
for the addition of second electron. Thus, second electron affinity (EA2) of an element is taken as
negative. For example,

(Exothermic)
(Endothermic)
4. Electron affinity increases in moving along the period from left to right due to increase in
charge. But the values are unexpectedly low in elements of group 2, 15 and 18 due to
stable electronic configurations of exactly half-filled and completely filled orbitals.
5. Within a group of the periodic table the electron affinities decreases from top to bottom.
6. In general, electron affinity follows the following trend:
Halogens > Oxygen family > Nitrogen family > Metals of groups 1 and 13 and Non-metals
of group 14 > Metals of group 2.
7. The electron affinities are indirectly measured with the help of Born-Haber Cycle, i.e.,

Where, S, D, IE, EA and U are the heat of sublimation, bond dissociation energy, ionization
energy, electron affinity and lattice energy respectively.
8. Electron affinity depends upon:-
a. Effective nuclear charge : Greater the effective nuclear charge, more is the
attraction of nucleus towards the electron and hence higher will be the value of
E.A.
b. Atomic size : Greater the atomic radius of the atom, less will be the attraction of
the nucleus to the electron to be added and hence lower will be the value of E.A.
 c. Penetrating power : Due to penetrating power, E.A. for addition of electron
show the order s > p > d > f
d. Electronic configuration : Half filled and fully filled subshell are extra stable
and thus oppose the addition of electron which leads to lower, E.A. value e.g. EA,
of C > EA, of N.

ELECTRONEGATIVITY (EN)

It is the tendency of an atom in a molecule to attract the bonded shared pair of electrons, towards
itself
1. There are several electronegativity scales:-
a. Mulliken scale : On the Mulliken scale, electronegativity X is taken as average of
IE and EA, i.e.,

where IE and EA are expressed in electron volts

or where IE and EA are expressed in kJ mol–1

or where IE and EA are expressed in kcal mol–1

b. Pauling scale : This is the most widely used scale and is based upon bond energy data.
According to Pauling, the difference in electronegativity of two atoms A and B is given by the
relationship as

where XA and XB are electronegativities of the atoms A and B respectively while.

where EA–B, EA–A and EB–B represent bond dissociation energies of the bonds A-B, A-A and B-B
respectively. The Pauling and the Mulliken scales are related to each other by the relation,

2. In a period, EN increases from left to right due to decrease in size and increase in nuclear
charge of atoms.
3. In a group, EN decreases from top to bottom due to increase in atomic size.
4. Electronegativity depends on:
 Atomic size
 Nuclear charge
 Shielding effect
 Oxidation state - EN increases as the positive oxidation state increases.
 Hybridization - Greater is the s-character in a hybrid orbital more is electronegativity.
5. If electronegativity difference is greater than 1.7 the bond is ionic otherwise covalent.
6. In general, greater is difference of EN between two atoms smaller is the bond length.
 7. Smaller the electronegativity, larger is the atomic size.

VALENCY
Valency of an element is the number of electrons gained or lost or shared with other atoms in the
formation of compounds.

Valency of group 1 and 2 elements is equal to the number of electrons in the outermost shell,
while that for groups 13 to 14 is group number -minus 10 and that for group 15–18 is 8 -minus
the number of electrons in the outermost shell.

ATOMIC VOLUME
It may be defined as the volume occupied by one mole atoms of the element at its melting point
in solid state.
1. It is obtained by dividing the gram atomic mass of the element by its density.
2. It decreases along the period, reaches a minimum in the middle and then starts increasing,
because of different packing arrangement of atoms in different elements in the solid state, i.e., P 4,
S8 etc.
3. In moving down the group atomic volume goes on increasing gradually

ACID-BASE BEHAVIOUR OF OXIDES AND HYDROXIDES

The oxides or hydroxide of an element may act either as base or an acid depending upon its
ionization energy.
1. If the IE is low, it acts as a base and if the IE is high, it acts as an acid.
2. The IE of alkali metals is the lowest, therefore, their oxides and hydroxides are the
strongest bases. The basic character of their hydroxides increases in the order:
CsOH > RbOH > KOH > NaOH > LiOH
3. The IE of halogens is quite high, therefore, their oxides are the strongest acids. The acidic
character of their oxides and hydroxides decreases in the order:
HClO4 > HBrO4 > HIO4
4. Within a period, the ionization energies of the elements usually increase and hence their
oxides and hydroxides show a gradual variation from strongly basic through amphoteric
to strongly acidic character.
5. The non-metallic character, oxidising character and acidic nature of oxides of the
elements increases from left to right in a period and decrease from top to bottom in a
group. The stability of the metal increases and activity decreases from left to right in a
period whereas the stability decreases and activity increases down the group.
CHEMICAL BONDING AND
MOLECULAR STRUCTURE
CHEMICAL BOND
A chemical bond is a sort of attraction which keeps the two atoms together.
Thus depending upon the variety of force, there may be variety of chemical
bonds.

REASONS FOR THE FORMATION OF A CHEMICAL BOND

1. Energy concept : When two atoms approach each other, the
attractive and repulsive forces operate between them. The distance at which
the attractive forces overweigh the repulsive forces is known as the bond
distance, the potential energy of the system is minimum and the bond is said
to be formed.

2. Lewis and Langmuir (Octet Rule) : Concept of stable electronic

configuration.
Atoms enter into chemical bonding to acquire the stable inert gas
electronic configuration. They can do so by losing, gaining or sharing of
electrons.

Lewis symbols : The electrons present in the outermost energy level

of an atoms and known as valence electrons. Only valence electrons
are involved in the combination of two atoms. The representation of
valence electrons on an atom called Lewis Symbol eg-

TYPES OF CHEMICAL BOND : (BY KOSSEL AND LEWIS)

Depending upon the mode of acquiring the stable electronic configuration,
the chemical bonds may be
 Ionic or electrovalent bond
 Covalent bond
 Coordinate or dative bond
 Metallic bond
 Hydrogen bond
 Weak van der waal's forces of attraction

IONIC BOND (BY KOSSEL AND LEWIS)

Ionic bond is formed by the complete transference of one or more valence
electrons of one atom to the valence shell of the other atom. Both atoms are
converted into ions and have the electronic configuration of nearest noble
gases. The electrostatic attraction between these oppositely charged ions,
which always tends to decrease the potential energy of the system is known
as the ionic bond. Consider the formation of KCl. The electronic configuration
of K, Cl and their ions (K+ and Cl–) are given below

K (19) 1s2, 2s2, 2p6, 3s2, 3p6, 4s1

K+(18) 1s2, 2s2, 2p6, 3s2, 3p6 Inert gas (Ar) configuration

Cl (17) 1s2, 2s2, 2p6, 3s2, 3p5

Cl– (18) 1s2, 2s2, 2p6, 3s2, 3p6 Inert gas (Ar) configuration

K+ +Cl– KCl

The number of electrons lost or gained by an atom represent the

electrovalency of the atom.

FACTORS AFFECTING THE FORMATION OF IONIC BOND

There are three main factors
1. Ionisation energy (I) : The lower the value of the ionisation energy
of an atom greater will be the ease of formation of cation from it.
Note: the size of the cation is always smaller than the atom from which it is
derived
2. Electron affinity (E) : The higher the electron affinity of an atom the
greater will be the ease of formation of anion from it.
The size of the anion is always larger than the atom from which it is
derived.
 3. Lattice structure : The electrostatic field of cations and anions
extends in all directions, their union is not limited to form a single
molecule, rather a cluster of ions, having three dimensional orderly
arrangement, known as the lattice structure is formed.
4. Lattice energy (U) : The amount of heat evolved when one mole of
ionic compound is formed from positive and negative ions in the
crystalline form is known as the lattice energy.

BORN HABER CYCLE

The formation of ionic compounds in terms of energy can be seen by Born
Haber cycle eg. formation of NaCl is as follows

where S = Heat of sublimation of Na metal

I = Ionisation energy of Na

D = Heat of dissociation of molecular chlorine

E = Electron affinity of chlorine atom

U = Lattice energy of NaCl

The amount of heat liberated (Q) in the overall reaction is the heat of
formation of NaCl.

Thus Q = S + I + 1/2 D – E – U

(The negative sign indicates heat is evolved or liberated)

The important energy terms are I, E and U. The more the negative value of
Q, the greater will be the stability of ionic compound. Hence formation of
ionic compound is favoured by:-
1. Low ionisation energy (I) of the metal
2. High electron affinity (E) of the non-metal.
3. Higher lattice energy (U) of the compound
In general the alkali metals have low values of ionisation energy and
halogens have high values of electron affinity. Hence they form the stable
ionic compounds.

FACTORS AFFECTING LATTICE ENERGY (U)

The force of attraction between two oppositely charged ions is given by well

known Coulomb's law as ,

Where q1 and q2 are the charges of ions in coulombs, is the permittivity

factor and r is the distance between ions. Hence lattice energy depends upon
1. Charge on ions : The higher the charge on ions, the greater will be
the force of attraction between them and greater will be the lattice energy.
The order of lattice energy for different solids is as follows
bi - bivalent > uni - bivalent > uni - univalent
solids solids solids
MgO > CaCl2 > NaCl
2. Size of ions : The smaller the size of the ions, the lesser will be
distance between them, the greater will be the force of attraction and
so greater will be the lattice energy.

FAJAN’S RULE
This rule is for covalent character of an ionic bond. Covalent character of an
ionic bond is favoured by
1. Small positive ion
2. Large negative ion
3. Large charge on ions

Thus for a fixed cation, the larger the size of anion, the more the magnitude
of the charge, the more is covalent character eg. covalent character of
sodium halides follows the order
NaI > NaBr > NaCl > NaF
For fixed anion, the smaller the size of cation, the more the magnitude of the
charge, the more is the covalent character eg.
BeCl2 > MgCl2 > CaCl2 > SrCl2 > BaCl2

It has been observed that a cation having 18 (s 2p6d10) electrons in outermost

shell (pseudo noble gas configuration) can polarise the anion more than
cation having 8 (s2p6) noble gas electronic configuration. Hence CuCl is more
covalent than NaCl. Similarly AgCl is more covalent than KCl.

POLARISING POWER OF CATION

It is generally represented by and also known as ionic potential charge
density. It can be represented as

POLARISATION
When cation and anion come closer to each other, the electron cloud of
anion is attracted towards the cation, some partial sharing of electrons take
place, the anion is distorted and the effect is known as polarisation.

More the effect of polarisation, more is the sharing of electrons and the more
is covalent character of ionic bond.

PROPERTIES OF IONIC COMPOUNDS

The important properties are as follows
1. Crystal structure : The crystalline ionic compounds have well defined
crystal structure or crystal lattice eg in NaCl each Na + is surrounded by six Cl-
ions and vice versa

2. Melting and boiling points : Ionic compounds have high m.pt and
b.pt due to powerful electrostatic force between ions.
3. Solubility : They are generally soluble in polar solvents (having high
value of dielectric constant). The solubility of ionic compounds
decreases with increase in covalent character of ionic compounds. It is
also governed by
 a. Lattice energy : More the lattice energy, lesser is the
solubility, eg. sulphates and phosphates of Ba and Sr are
insoluble in water due to high lattice energy.
b. Heat of hydration : More the heat of hydration, more is the
solubility. eg AlCl3 though covalent in nature is soluble in water
due to high value of heat of hydration.
4. Electrical conductivity : In solid state they do not conduct electricity
since there is no free movement of electrons but in molten state and in
solution they conduct electricity.
5. Isomorphism : NaF and MgO are isomorphous due to similar
electronic structure

Similarly K2S and CaCl2 are isomorphous

K+ S2- K+ Cl- Ca++ Cl-
2,8,8 2,8,8 2,8,8 2,8,8 2,8,8 2,8,8

VARIABLE ELECTROVALENCY
It is due to unstable atomic core and inert pair effect. When valence
electrons from a metal atom are removed it leaves behind the atomic core or
atomic kernel. The latter with 2 or 8 electrons are stable. In case of transition
elements the atomic cores are not very stable. They may lose one or more
electrons thus exhibiting variable electrovalency eg. iron and copper etc.

Fe (2, 8, 14, 2) 1s2, 2s2p6, 3s2p6 d6, 4s2

Fe++ (2, 8, 14) 1s2, 2s2p6, 3s2p6 d6

Fe+++ (2, 8, 13) 1s2, 2s2p6, 3s2p6 d5

The energy difference between 4s and 3d subshell is not very large.

INERT PAIR EFFECT

The reluctance of s electron pair of some heavy elements
(p - block elements present at the bottom of group) to take part in bonding is
known as inert pair effect. Thus Tl (6s2, 6p1) show +1 electrovalence.
Similarly Sn(5s2p2) and Pb (6s2p2) show + 2 oxidation state commonly. In
such elements the lower oxidation state is more stable than higher oxidation
state.

COVALENT BOND : (BY LEWIS AND LANGLEY)

According to G. N. Lewis atoms may also combine by sharing of electrons
present in their outermost shells and attain noble gas electronic
configuration. One shared pair of electrons constitute a single bond, two
electron pairs constitute a double bond and so on. The bonds thus formed
ore known as covalent bonds.

COVALENCY
It is the number of electron pairs shared by one atom of the element in
combination with other atoms in a molecule.

Variable Covalency

Generally the covalency of an element is equal to the total number of

unpaired electrons in s– and p– orbitals of the valence shell. For example

covalency of carbon = 4

covalency of oxygen = 2

The variable covalency is shown by elements having vacant d-orbitals in

their valence shell. The unpairing of the s- and p- electrons is possible by
promoting them to d- orbitals. For example

Ground state Covalency of sulphur = 2

First excited state Covalency of sulphur = 4

Second excited state Covalency of sulphur = 6

Similarly, other than fluorine, the halogens have high covalencies equal to 3,
5 and 7. Phosphorous shows covalencies equal to 3 and 5.

The elements having no d-orbitals do not exhibit variable covalency

EXAMPLES OF COVALENT COMPOUNDS

1. Chlorine (Cl2)

2. Carbon dioxide (CO2)

3. Nitrogen (N2)

NATURE OF COVALENT BOND

The nature of covalent bond is explained by

(i) Heitler - london theory Valence bond theory

(ii) Pauling - slater theory

(iii) Hund - mulliken theory } Molecular orbital theory

VALENCE BOND THEORY

A covalent bond is formed by the overlapping between two half filled atomic
orbitals having electrons with opposite spin.
1. Sigma bond (σ - bond) - The following overlappings result in the
formation of sigma bond
a. s - s overlapping
b. s - p overlapping
c. p - p head on overlapping
2. pi - bond ( - bond) - It is formed by the sidewise or lateral overlapping
between unhybridised p - atomic orbitals
p - p side wise or lateral overlapping.
 π-bond is a weaker bond than σ - bond.
 The strength of bond depends upon the extent of overlapping between
atomic orbitals. Greater the overlapping stronger the σ - bond is. It follows
the following order
s–s>s–p>p–p
 Single bond is always σ bond.
 In multiple bonds only one is σ bond, others are π - bonds
 π- bond is not formed by hybrid orbitals.

LIMITATIONS OF VALENCE BOND THEORY

1. It fails to explain the magnetic properties of some molecules

2. Bonding in electron deficient compounds.

MOLECULAR ORBITAL THEORY OR HUND- MULLIKEN THEORY

According to this theory the atomic orbitals combine to form the molecular
orbitals. The number of molecular orbitals formed are equal to the number of
atomic orbitals involved and they belong to the molecule.
1. The molecular orbitals are formed by LCAO method (linear combination
of atomic orbitals) i.e. by addition or subtraction of wave functions of
individual orbitals thus
MO = A B

b = A + B

a = A – B

2. Molecular orbital of lower energy is known as bonding molecular orbital

and of higher energy is known as antibonding molecular orbital.
3. Molecular orbitals are characterised by a set of quantum numbers.
4. Aufbau rule, Pauli's exclusion principle and Hund's rule are applicable
to molecular orbitals.
5. Their shape is governed by the shape of atomic orbitals eg by s - s and
p - p overlapping we have

a.

b. and overlap to form bond.

c. form bond and their combination is according to inter-
nuclear distance.

ENERGY LEVEL DIAGRAM

When two atoms A and B are brought nearer to one another, the atomic
orbitals present in atom A undergo overlapping with atomic orbitals present
in atom B, having the same energy and molecular orbitals are formed. There
are two types of energy level diagrams
1. for molecules upto N2 (here the energy difference between 2s and 2p
orbitals is small)
2. for molecules after N2 (here the energy difference between 2s and 2p
orbitals is large and they cannot interact)
Simply we can write

ELECTRONIC CONFIGURATION / BOND ORDER OF SIMPLE DIATOMIC

MOLECULES
The electronic configuration and the bond order in case of simple diatomic
molecules can be obtained by filling the molecular orbitals by applying
Aufbau principle and Hund's rule
Bond order [Number of bonding electrons - Number of antibonding
electrons]

The magnetic properties of molecules can also be ascertained

BONDING IN SOME DIATOMIC MOLECULES AND IONS

1. Hydrogen molecule (H2) - Total number of electrons = 2, filling in
molecular orbitals we have

Bond order =
Hence there is a single bond between two hydrogen atoms (H - H). Since
there is no unpaired electron, H2 is diamagnetic
2. Helium molecule (He2) - The total number of electrons = 4 and filling
in molecular orbitals we have

Bond order
Hence He2 molecule cannot exist
3. Nitrogen molecule (N2) - The total number of electrons = 14 and
filling in molecular orbitals we have

Bond order
4. Oxygen molecule (O2) - Total number of electrons = 16 and
electronic configuration is

Bond order =
As shown by electronic configuration the O 2 molecule contains two unpaired
electrons, hence it is paramagnetic in nature

5. - Total number of electrons (16 – 1) = 15.

Electronic configuration

Bond order
It is paramagnetic
 6. (Super-oxide ion) Total number of electrons .
Electronic configuration

Bond order
It is paramagnetic

7. Peroxide ion - Total number of electrons .

The electronic configuration is

Bond order
It is diamagnetic
8. Carbon monoxide (CO) - Total number of electrons = (6 + 8) = 14

The electronic configuration is

Bond order
It is diamagnetic
9. Nitric Oxide (NO) - Total number of electrons = (7 + 8) = 15

Bond order
It is paramagnetic.

IONIC CHARACTER OF A COVALENT BOND

1. By electronegativity difference - It is determined by the
electronegativity difference of the participating atoms. The higher the
electronegativity difference between the two atoms, more is the percentage
ionic character of a covalent bond. The mathematical equations for
calculating, the % ionic character are
a. Pauling equation % ionic character

b. Hannay and smith equation

= 16 (xA – xB) + 3.5 (xA –xB)2
where xA and xB are the electronegativities of atoms
Percentage ionic character and the electronegativity difference
xA - xB value % ionic character xA - xB value % ionic character
0.1 0.5 1.7 51.0
0.4 4.0 2.0 63.0
0.7 12.0 2.3 74.0
1.0 22.0 2.6 82.0
1.4 39.0 2.9 88.0
2. By dipole moment - By dipole moment the % ionic character of a
covalent bond can be obtained from the following equation

% ionic character

CHARACTERISTICS OF COVALENT COMPOUNDS

1. Physical state - They may be gases, liquids or solids
2. Crystal structure - They may exist as simple molecules held together
by weak forces, giant molecules united by covalent link eg diamond, silicon
carbide, alumina, aluminium nitride etc and can have layer structure. eg
graphite.
3. Solubility - Generally soluble in non polar solvents.
4. Melting/ boiling points - Low as compared to ionic compounds.
5. Electrical conductivity - Being non electrolytes they do not conduct
electricity, graphite does due to presence of free electrons.
6. Stereo-isomerism - They exhibit structural and stereo-isomerism
both

HYBRIDISATION
Hybridisation is the redistribution of energy levels at the time of formation of
molecules. It may also be defined as intermixing of atomic orbitals of nearly
the same energy and resulting in the formation of new atomic orbitals same
in number and identical in all respects (shape, energy and size). The new
atomic orbitals are known as hybrid atomic orbitals.

The completely filled or half filled atomic orbitals can take part in
hybridisation and hybrid atomic orbitals form stronger bonds.

METHOD FOR FINDING THE TYPE OF HYBRIDISATION

Apply the following formula to find the hybridisation of central atom.

Value of z 2 3 4 5 6 7

Hybridisation sp sp2 sp3 sp3d sp3d2 sp3d3

Examples :
1. Hybridisation of NH3 = [5 + 3 + 0 - 0] = 4; sp3
2. Hybridisation of H2O = [6 + 2 + 0 - 0] = 4; sp3
3. Hybridisation of SO3 = [6 + 0 + 0 - 0] = 3; sp2
4. Hybridisation of SO42– = [6 + 0 + 2 - 0] = 4; sp3
5. Hybridisation of CO32– = [4 + 0 + 2 - 0] = 3; sp2
6. Hybridisation of PCl5 = [5 +5 + 0 - 0] = 5; sp3d
7. Hybridisation of SF6 = [6 + 6 + 0 - 0] = 6; sp3d2
Note : Species having same hybridisation are isostructral in nature.

VSEPR THEORY VALENCE SHELL ELECTRON PAIR REPULSION

THEORY
The following types of repulsions between different pair of electrons change
the regular geometry of the molecule.
Lone pair - lone pair repulsion > Lone pair - bond pair repulsion > Bond pair -
bond pair repulsion or lp - lp > lp - bp > bp - bp eg:
1. Shape of H2O molecule - The hybridisation of oxygen is sp 3 and
angle should be 109º 28’. But actually the HOH angle is 104.5º. The VSEPR
theory explains this fact

All types of repulsions (lp–lp, lp–bp, bp–bp) are present in H 2O.

2. Shape of NH3 molecule - The hybridisation of nitrogen is sp3. The H–
N–H angle is 107.5º instead of 109º28’. Due to lp–bp and bp–bp
repulsions the value of angle change
 Pyramidal
3. Structure of PCl5 - The phosphorus is in sp3d hybridised form. The
five hybrid orbitals are not equivalent. The bonds pointing towards the
three corners of equilateral triangle are known as equatorial bonds
making an angle of 120° between them. The remaining two bonds are
at right angle to the plane of three make an angle of 90° and are called
axial bonds. The axial bonds are slightly longer and weaker than
equatorial bonds. Since they suffer more repulsive interaction from the
later. Consequently PCl5 is very reactive molecule.

COORDINATE COVALENT BOND OR DATIVE BOND

When both the electrons for sharing between two atoms are contributed by
one atom only the bond formed is known as coordinate bond or dative bond.

In terms of orbital theory the coordinate covalent bond is formed by

overlapping between empty and completely filled atomic orbitals.

The atom donating the pair of electrons is called donor and the atom which
accepts the pair of electrons is called acceptor. The compounds containing
coordinate bonds are known as coordination compounds. The bond is
represented by an arrow ( ) pointing head towards the acceptor.

Once the coordinate bond is formed it is indistinguishable from a covalent

bond. Examples
1. Formation of SO2

or
2. Formation of SO3

or
 3. Formation of Hydroxonium ion

or or
4. NH3 and BF3 form addition product by Coordinate covalent bond

CHARACTERISTICS OF COORDINATE COMPOUNDS

Coordinate compounds have volatile character in between ionic and covalent
compounds. Other properties like solubility, electrical conductivity and
stereo-isomerism are similar to covalent compounds.

HYDROGEN BOND
It may be defined as the force of attraction existing between hydrogen atom
covalently bonded to highly electronegative atom (N, O or F) and the
electronegative atom belonging to another molecule of the same or different
substance. It is represented by dotted lines

H–F ............ H–F ............ H–F

The chains possess a Zig-Zag structure

Hydrogen bond is purely electrostatic in nature. It is a weak bond, the

strength of the strongest being about 5 - 10 kcal per mole. The more the
electronegativity of atom involved in H - bonding, the more is the bond
strength eg.

> >

10 kcal/mole > 7 kcal/mole > 2.0 kcal/mole

TYPES OF HYDROGEN BONDS

Hydrogen bond is of two types

1. Intermolecular H-bonding (Association). H–bonding involving two or
more molecules.
2. Intramolecular H-bonding (Chelation). H–bonding taking place within
single molecule.

APPLICATIONS OF INTERMOLECULAR H-BONDING

1. Water - Water has the lowest molecular weight among the hydrides of
group 16 elements yet it has the highest melting and boiling points
H2O H2S H2Se H2Te
Melting point 0ºC -85.5ºC -66ºC -51.2ºC
Boiling point 100ºC -60.4ºC -41.5ºC +2ºC
It is due to intermolecular H - bonding through which water molecules
associate

2. Ice has less density than water - In crystal structure of ice every
water molecule is associated with four other water molecules by H-
bonding in a tetrahedral fashion

It gives rise to cage likes tetrahedral structure of ice with large empty
spaces. On melting the ice H-bonds are broken and space between water
molecules decreases and density of water increases upto 4ºC. Above 4ºC
more H - bonds are broken, the water molecules move apart from each other
and the density again decreases. Thus water has maximum density at 4ºC.
3. Alcohols - The marked difference between the melting and boiling
points of alcohols and corresponding mercaptans is also due to
association.

CH3OH C2H5OH C3H7OH C4H9OH

Boiling point 64.4ºC 78ºC 97ºC 117ºC
CH3SH C2H5SH C3H7SH C4H9SH
Boiling point 5.8ºC 37ºC 67ºC 97ºC

4. Amides - Amides associate and have higher melting and boiling points
 5. Amines - Primary and secondary amines are associated and have
higher boiling points than isomeric tertiary amines.
6. Fatty acids - In organic solvents, fatty acids form a dimer. It is
confirmed by electron diffraction method.

APPLICATIONS OF INTRAMOLECULAR H - BONDING

When the H - bonding takes place within a single molecule this is known as
intramolecular H - bonding. It also affects the physical and chemical
properties of compound.
1. Volatile character of nitrophenols - o-nitrophenol is more volatile
(b.pt 214ºC) as compared to meta (b.pt 290ºC) and para (b.pt 279ºC). It is
due to chelation

In meta and para isomer chelation is not possible due to the formation of
desired size of ring. They therefore associate to some extent and have
higher B.P
2. Salicylic acid is stronger acid than o - methoxy benzoic acid

H-bonding in salicylate ion No-H-bonding in o-methoxy benzoate ion

3. Ethyl aceto acetate - It exists in two forms

Enolic form is more volatile due to chelation

4. Maleic acid is stronger acid than fumaric acid

Maleic acid Chelation in maleate ion
5. Acid character of nitrophenols. It follows the following order
p - nitrophenol > o - nitrophenol > m - nitrophenol
Acid character of o - nitrophenol is suppressed by chelation

6. Other compounds showing intramolecular H – bonding

o-Chlorophenol o-hydroxy benzaldehyde

o-hydroxy benzoic acid

METALLIC BOND
It has been found that metals have generally low ionisation energies
indicating that valence electrons are weakly bound to the atomic kernel (or
core).

Metals contain few valence electrons and valence orbitals which are empty.
Thus valence electrons are completely delocalised and are frequently
exchanged between atoms. The atoms thus acquire a positive charge and
are arranged in a regular fashion (lattice structure).
The valence electrons form an “electron gas” or "sea of electrons". The
attractive interaction between the mobile electrons and a number of ions
constitutes a weak bond known as metallic bond.

CONSEQUENCES OF METALLIC BOND

1. Electrical conductivity - It is due to presence of mobile valence

electrons.
2. Thermal conductivity - On heating one part of metal, the K.E. of
electrons is increased and they conduct heat to the other parts of the metal.
3. Metallic lustre - The mobile electrons are promoted to excited states
by absorption of light and on coming back from the excited state light of all
wavelengths in the visible region is emitted. The surface, therefore emits
metallic lustre.
4. Malleability - Metals can be made thin sheets
5. Ductility - Metals can be drawn into wires since metal kernels can
easily be shifted.
6. Electrical conductivity decreases with temperature - It is due to
random motion of mobile electrons which increases with increase of
temperature.

VAN DER WAAL'S FORCES

Attractive forces between uncharged molecules are known as van der Waals
forces. These forces may be divided into three groups
1. Dispersion or London forces. These are due to transient polarisation.
2. Dipole-dipole attraction. These are due to permanent polarisation.
3. Dipole-induced dipole forces

LONDON FORCES

The negative electrons in a neutral molecule are balanced by the positive

charges on the nucleus. Since the electrons are in motion the centre of
density of the electrons does not coincide continuously with the centre of
density of positively charged nuclei, the molecules acquire an electric dipole.
Polarised molecules exert an attraction for other molecules having a dipole.
Consider the case of helium.
 The greater the polarizability of a molecule, the stronger are the
London forces.
 The polarizability increases with number of electrons and their distance
from the nucleus.
 These forces are operative over a very short range.
 The inert gases have weak van der Waals forces of attraction
 The straight chain hydrocarbons boil at higher temperature than
isomeric branched chain hydrocarbons due to greater magnitude of van der
Waal's forces of attraction.

DIPOLE-DIPOLE ATTRACTION

It is the attraction between the positive end of the one molecule and
negative end of the another molecule

or

This type of interaction is called dipole - dipole interaction. The force of

dipole - dipole attraction is inversely proportional to fourth power of their

separation of distance r. . The dipole dipole attractions in gaseous

molecules are particularly small since the gas molecules are in continuous
motion. This attraction increases the m.pt. and b.pt. of substances and
makes their liquefaction easy.

DIPOLE-INDUCED DIPOLE ATTRACTION

The attractive forces operate between polar molecules having permanent

dipole and non-polar molecules. The polarity in the non-polar molecules is
induced by the polar molecule

DIPOLE MOMENT
If a covalent bond is formed between two dissimilar atoms, eg. A and B, one
of the atoms (A or B) must be more electronegative than the other. If A is
more electronegative than the shared pair of electrons is drawn near A
leaving a positive charge on B and hence making the molecule dipolar (A –B+).
The percentage of polar character is given in terms of dipole moment ( ).

The dipole moment is defined as the product of electric charge q

and the distance r between the two atoms of a polar molecule. ( =
e × d) Dipole moment is a vector quantity with direction same as that of the
line joining positive and negative centres.

Thus molecules having dipole moment ( = 0) are called non polar

molecules and molecules with > 0 are polar. Greater is , greater is the
polarity.

For polyatomic molecules with two or more bonds, net dipole moment is the
resultant of vector addition of individual moments. For e.g. in the figure
shown, the resultant dipole moment,

While expressing dipole moments, generally charge is given in electrostatic

units (esu) and distance in angstrom units (1Aº =10 –10 m). Thus dipole
moment of an electron separated from unit positive charge by a distance 1Aº
would be (4.80 × 10–10 esu) × (10-8 cm) = 4.8 × 10–18 esu cm = 4.8 Debye.

APPLICATIONS OF DIPOLE MOMENT

1. Dipole moment is helpful in predicting the geometry of the molecule.

2. Dipole moment helps in determining the polarity.
3. Dipole moment can distinguish between symmetrical and non
symmetrical molecules. eg. CO2 has 0 dipole moment as it is symmetrical
whereas H2O has a dipole moment of 1.85D.

4. Cis and trans isomers can be distinguished by dipole moments, usually

cis isomers have higher dipole moment and hence higher polarity e.g.
Cis trans
5. Dipole moment is greatest for ortho isomer, zero for para isomer and
less than that of ortho for meta isomer. o > m > p. e.g.

ortho meta para

6. Ionic character can be determined by using dipole moment

For e.g. experimental dipole moment for HCl is 1.03 and

as r = 1.26 and, e = 4.8 × 10-10 esu,
= 6.05 Debye.
Thus the ionic character
Thus we can say % ionic character

7. Hybridisation can be determined by dipole moment for eg.

a. If a molecule AB2 has =0, the s orbitals used by

A (z < 21) must be sp hybridised e.g. BeF2
b. If a molecule AB3 has =0, the s orbitals used by
A (z < 21) must be sp2 hybridised e.g. BF3
c. If a molecule AB4 has =0, the s orbitals used by
A (z < 21) must be sp3 hybridised e.g. CCl4

BOND LENGTH
It is the distance between the nuclei of two atoms between which the bond is
formed. Other names for bond length are interatomic distance or bond
distance. It is usually expressed in angstrom unit (1Å=10 -10m). Pauling’s rule
states that for covalently bonded atoms, bond length is sum of covalent
radii. Thus for a covalent compound AB, the bond length is r A + rB. where rA
and rB are covalent radii of A and B

BOND LENGTH DEPENDS ON

1. Bond order - Bond length decreases with bond order. For e.g. C - C
length in CH3 - CH3 is 1.54 Å, C = C length in CH2 = CH2 is 1.34 Å and CC
length in CHCH is 1.20 Å. Larger the s character, smaller is bond length.
2. Electronegativity - If one of the atoms is more electronegative than
other, the bond length is found to be smaller than expected value. The
relation that holds true for most compounds is
rAB = rA + rB - 0.09 (xA - xB)
where xA and xB are electronegativities of A and B
3. Hybridisation - Larger is s character, shorter is orbital and hence
shorter is the length of bond formed by it.
4. Resonance and delocalisation - C-C bond length is 1.54Å and C = C
bond length is 1.34 Å but in benzene, due to resonance, the carbon-
carbon bond is neither single nor double but intermediate between
single and double and same holds for bond length and is equal to 1.39
Å.

BOND ENERGY
Bond strength or bond energy is the amount of energy required to break a
bond in one gram mole of a substance in gaseous state. Bond energy is also
called bond dissociation energy. Its units are kJmol –1. Bond dissociation
energy and (average) bond energy are same in diatomic molecules as they
have only one bond. But in molecules having many bonds, bond dissociation
energy of the bonds are different and bond energy is the average value of
bond dissociation energy

FACTORS AFFECTING THE BOND ENERGY

1. Atomic size - Strength of shorter bond is more e.g. atomic size of Cl,
Br, I has the order Cl < Br < I and their bond energies, Cl - Cl (243 kJ mol -1) >
Br - Br (192 kJ mol–1)
> I - I(151 kJmol–1)
2. Bond order - Higher bond order implies higher energy e.g. bond
energies for and are 347.2, 610.0 and 835.1 kJ mol-1 respectively.
3. Electronegativity - Larger the difference in electronegativities of
bonded atoms, more is the attraction, shorter is bond length and hence
higher is bond energy.
4. Hybridisation - Due to directional character of hybridised orbitals,
extent of overlapping increases and hence stronger bonds are formed.
5. Type or extent of overlapping - Coaxial overlappings (s-s, s-p, p-p)
have higher extents and hence are stronger than collateral overlappings.
Thus sigma bond (coaxial overlapping) is stronger than pi bond (collateral
overlapping).As p orbitals are more directional, p - p coaxial overlapping
gives stronger bond in comparison to s - s overlapping.
6. Repulsion between lone pair - In a bonding atom having lone pair
the bond formed is weaker due to non localisation of lone pair. Mutual
repulsion takes place between lone pair clouds of two atoms, decrease the
strength and hence the bond energy. For e.g. as lone pair at each C - C is 0,
N - N is one, O - O is two, so values of their bond energies are in order C - C
> N - N >O - O.

DETERMINATION OF BOND ENERGY

Bond energy is determined by thermochemical methods by determining

either the heat of atomisation i.e. heat required to break the molecule into
its atoms or by the heat of formation of compound.

BOND ANGLE
Bond angle is the angle between two adjacent bonds in a molecule.

Thus bond angles in CO2 and H2O are 180º and 105º.

FACTORS AFFECTING BOND ANGLE

1. Electronegativity - Cl - O- Cl bond angle in Cl2O is more than F - O - F

bond angle in OF2 because in Cl2O, O atom is more electronegative compared
to Cl atom due to which shared electrons are attracted towards O. This
makes bonded electrons of two Cl-O bonds to come close and hence more
repulsion resulting in wider bond angle. Whereas in OF 2, F is more
electronegative than O thus bonded electrons of F-O bond are closer to F
atom. This makes bonded electrons of two O - F bonds to go apart, feeling
less repulsion and hence a lower value for bond angle.
2. Hybridisation - sp3 hybridisation at central atom implies a bond angle
of 109º 28¢ each e.g. CH4, CH3CH3 etc. sp2 hybridisation leads to 120º bond
angle as in BF3. sp hybridisation makes angle 180º e.g. BeCl2.
3. Lone pair repulsions - Presence of lone pair at central atom results
in repulsion of shared pair of electrons. Thus bonds at central atom are
displaced inside making the value of bond angle smaller e.g. bond angle in
ammonia is 107º even though hybridisation at nitrogen is sp 3. It is due to
presence of lone pair of electrons at nitrogen atom which causes more
repulsion between N and H and hence decreasing the bond angle. Bond
angle can be measured by X-ray techniques or by I.R. spectroscopy.
Baeyer’s strain theory states that any shift in normal bond angle causes
strain over the molecule making it less stable and more reactive. Thus CH 4,
C2H6 are quite stable while ethylene is less stable (bond angle 120º).

OCTET RULE
During formation of a covalent bond, the atoms attain an inert gas electronic
configuration (ns2p6 configuration). This is known as Octet rule.

EXCEPTIONS OF OCTET RULE

1. Incomplete octet : Consider the following molecules

2. Expansion of octet : Consider the following molecules

EXPLANATION FOR THE FAILURE OF OCTET RULE

The concepts given below explain the failure of the octet rule :
1. Sidwick's rule of maximum covalency : The maximum covalency of
an element depends on the period to which it belongs and octet can be
exceeded for n = 1 it is 2, for n = 2 it is 4, for n = 3 it is 6 and for n > 4 it is
8.
2. Sugden's view of singlet linkage : According to Sugden the octet
rule is never violated. There can be one electron bond known as Singlet
linkage, Singlet or half bond is formed by sharing of one electron between
two atoms.
It is represented by half arrow ( ). Thus SF6 and PCl5 have the structures:

STATES OF MATTER
STATES OF MATTER
The three important states of the matter are (i) Solid state (ii) Liquid state (iii) Gaseous state,
which can exist together at a particular temperature and pressure e.g. water has three states in
equilibrium at 4.58 mm and 0.0098ºC.

PLASMA STATE : It is the gaseous mixture of electrons and positive ions existing at extremely high
temperatures (in the interior of stars) or internal electrical fields in discharge tubes.

SINGLE SUPER ATOM STATE : At extremely low temperature, all atoms lose their identity and get
condensed into a single entity behaving like a single super atom.

MEASURABLE PROPERTIES OF GASES

Four measurable properties are:
1. Mass : It is expressed in grams or kg. 1 kg=103 g moles of

gas =
2. Volume : It is equal to the volume of the container and is expressed in terms of litres (L),
millilitres (ml), cubic centimeters , cubic meters (m3) or cubic decimeters (dm3).

3. Pressure : It is equal to force per unit area and expressed in the units such as atmosphere,
millimetres (mm), centimetres (cm), torr, bar etc. SI unit of pressure is pascal (Pa) or
kilopascal (kPa)

4. Temperature : It is measured in celsius scale (°C)or in Kelvin scale (K). SI unit of

temperature is Kelvin (K) or absolute degree T (K) =

GAS LAWS

BOYLE’S LAW

The volume of a given mass of a gas is inversely proportional to its pressure at constant
temperature.

, a constant
Value of k depends on mass, temperature and nature of gas.
When mass and temperature are the same we have

ISOTHERMS
Graphs of V vs P or PV vs P at constant temperature are known as Isotherm.
Graphical representation of Boyle's law

CHARLE’S LAW

The volume of the given mass of a gas increases or decreases by of its volume at 0°C for
each degree rise or fall of temperature at constant pressure.

or

The volume of a given mass of a gas is directly proportional to the absolute temperature at constant
pressure.

ABSOLUTE ZERO
If in the above equation we put the value of t as –273.15 ºC the volume of the gas will be zero. It
means gas will not exist, which is not possible. In fact all gases get liquified before this temperature
is reached. This hypothetical or imaginary temperature at which the gases occupy zero volume is
called absolute zero.

ISOBARS
A graph of V vs T at constant pressure is known as Isobar.

GRAPHICAL REPRESENTATION OF CHARLE’S LAW

GAY LUSSAC’S LAW : (AMANTON’S LAW)

The pressure of a given mass, of gas increases or decreases by of its pressure at 0°C for
each degree rise or fall of temperature at constant volume.

or
The pressure of a given mass of a gas at constant volume is directly proportional to absolute
temperature
ISOCHORES
A graph of P vs T at constant volume is known as Isochore

GRAPHICAL REPRESENTATION OF GAY LUSSAC’S LAW

AVOGADRO’S LAW
The volume of a gas is directly proportional to number of molecules or moles at constant
temperature and pressure.

at constant T and P

GRAPHICAL REPRESENTATION OF AVOGADRO’S LAW

IDEAL GAS EQUATION

.
This is known as ideal gas equation. R is known as universal gas constant.

IDEAL GAS

The gas which obeys the equation at every temperature and pressure range strictly.

REAL OR NON-IDEAL GASES

Since none of the gases present in universe strictly obey the equation , hence they are
known as real or non ideal gases. Real gases behave ideally at low P and high T.

DENSITY OF A GAS

We have ,

Further,
The above equation shows that density of a gas depends on P and T.
Unit of density of gas :
It is usually expressed in gm/ litre

VAPOUR DENSITY (V.D.)

It is the ratio under similar conditions of P and T

Unit of vapour density : It is a ratio and has no unit.

NATURE OF GAS CONSTANT, (R)

= Work done per degree per mole

Deviation from ideal behaviour in terms of compressibility factor Z

Deviation from ideal behaviour in terms of PV-P curve

NUMERICAL VALUE OF R

As the work can be expressed in different systems of units, R will have different values.
1. In litre - atmosphere :
At NTP, P = 1atm, V=22.4 litre and T= 273.15K

2. In cgs system :
P = 1 atm = 1×76×13.6×980 dyne cm-2; V = 22400 cm3;
T = 273.15 K

3. In mks or SI units :
Unit of R is JouleK–1
107 ergs = 1 Joule or R = 8.314 Joule K–1

NTP OR STP AND SATP

Normal or standard temperature & pressure means 0°C or 273.15 K and 1 atm pressure.
Normal boiling : At 1 atm pressure the boiling temperature is called Normal boiling point.
Standard boiling point : At 1 bar pressure the boiling temperature is called standard boiling point.
Normal boiling point of water is 100 °C (373.13 K)
Standard boiling point of water is 99.6 °C (372.6K)

Standard temperature and pressure (STP)

273.15 K(0 °C) temperature
1 bar (105 pascal) pressure
Molar volume at STP = 22.71098 L mol–1

Normal temperature and pressure (NTP)

273.15 K(0 °C) temperature
1 atom (1.01325 pascal) pressure
Molar volume at NTP = 22.413996 L mol–1

Standard ambient temperature and pressure (SATP)

298.15 K (25 °C) temperature
1 bar (105 pascal) pressure
Molar volume at SATP = 22.784 L mol–1

BOLTZMANN CONSTANT (k)

It is the gas constant per molecule thus ; Where R=gas constant., N0= Avogadro number.
Value of

DALTON’S LAW OF PARTIAL PRESSURE

At constant temperature the total pressure, exerted by a mixture of non reacting gases, is the sum of
partial pressure of each gas

Partial pressure p of a gas = mole fraction of the gas × total pressure.

For a gas A, pA = xA × P
If n1,n2,and n3 are moles of non reacting gases filled in a vessel of volume V at temperature T.
The total pressure P is given by
This is the equation of state of a gaseous mixture.

RELATIONSHIP BETWEEN TOTAL PRESSURE AND INDIVIDUAL PRESSURE

On mixing of gases at constant temperature. If a gas A at pressure P 1 and volume V1 is mixed with
gas B at pressure p2 and volume V2 at same temperature, then

Total pressure,

AQUEOUS TENSION

It is the pressure exerted by water vapour at a particular temperature. It depends upon temperature.

PRESSURE OF A DRY GAS

When a gas is collected over water, its observed pressure is equal to the sum of the pressure of dry
gas and the pressure of water vapour (aqueous tension), then
Pressure of dry gas = pressure of moist gas – aqueous tension

DIFFUSION

The tendency of every gaseous substance to distribute itself uniformly throughout the available
space is known as diffusion. It also takes place through a porous vessel.

EFFUSION

The movement of a gas through a small hole when it is subjected to pressure is known as effusion.

GRAHAM’S LAW OF DIFFUSION (OR EFFUSION)

At constant temperature and pressure, the rate of diffusion or effusion of a gas is inversely
proportional to the square root of its density.

Rate of diffusion ∝
If and are rates of diffusion of two gases and and their respective densities then,
Rate of diffusion

If volume diffused is same

If time of diffusion is same

Effect of pressure on the rate of diffusion.

Rate of diffusion ∝ pressure, therefore,

APPLICATIONS OF GRAHAM’S LAW OF DIFFUSION

1. Determination of densities and molecular masses of unknown gases.

2. Separating the gases having different densities.
3. Separation of Isotopes

ATMOLYSIS

The phenomenon of separation of a mixture of gases due to difference in their rates of diffusion is
called atmolysis.

KINETIC THEORY OF GASES

Postulates of kinetic theory of gases.
1. A gas consists of large number of tiny particles called molecules.
2. Volume occupied by gas molecules, is negligible as compared to the total volume of gas.
3. There is continuous rapid random motion of gas molecules. The molecules collide with each
other and against walls of container.
4. The molecules are perfectly elastic bodies and there is no loss of kinetic energy during
collisions.
5. There are no attractive forces between the molecules of gas.
6. The pressure exerted by a gas is due to bombardment of gas molecules against the walls of
the container.
7. The different molecules possess different velocities and hence different energies. The
average K.E. is directly proportional to absolute temperature.

KINETIC GAS EQUATION

Based upon the postulates of Kinetic theory of gases, the kinetic gas equation is

where m = mass of a gas molecule, N= number of molecules,

U= Root mean square velocity.

KINETIC ENERGY OF GAS

It can be obtained from kinetic gas equation

KE of one molecule

of a gas
 KE of n moles of gas = 3/2 nRT
 At absolute zero, KE is zero

MAXWELL’S GENERALISATION

Kinetic Energy of translation of ideal gas is directly proportional to absolute temperature of gas or its
pressure and is independent of the nature of gas.

THERMAL MOTION

The molecular velocity of a gas is proportional to square root of the absolute temperature. The
molecular motion is called thermal motion of molecules.

CALCULATION OF MOLECULAR VELOCITIES OF GASES

1. Calculation of velocity when temperature alone is given :

From Kinetic gas equation,

2. Calculation of velocity at NTP

It is given by the formula,

AT NTP, P=dynes cm-2, (molar volume)

3. Calculation of velocity when pressure and density are given.
It is given by the following formula,

= ( )
4. Calulation of velocity when pressure and temperature are given but are not the same
as NTP

; In such case molecular volume (22400ml) is converted into the volume under given

conditions of T and P using relation,

MAXWELL’S DISTRIBUTION OF VELOCITIES

The molecules present in a given sample of gas move with different velocities in all possible
directions. Velocities and directions of molecules keep on changing due to intermolecular collisions.
Hence it is impossible to find out the individual velocity of each molecule. It is however possible to
predict fraction ( ) of the total number of molecules having specific velocities at a particular
temperature. As shown by the curve,

The gases show ideal behavior at low presence/large volume. Since the volume of molecules can be
neglected and at high temperature since intermolecular forces decrease.

Fraction of molecules having very small or very high velocities is very low. No molecule has zero
velocity. Fraction of molecules possessing a particular velocity at a particular temperature is
constant. The different velocities possessed by gas molecules are:
1. Most probable velocity ( ) : It is the velocity possessed by maximum fraction of gas
molecules at a particular temperature

Mathematically,
 2. Average velocity ( ) : This is the average of the different velocities of all the molecules.

where c1,c2,c3 etc. are individual velocities of n1,n2,n3 molecules.

Mathematically, =
3. Root mean square velocity (U) : It is the square root of the mean of the square of the
different velocities of the molecules

Mathematically, U =

RELATIONSHIP BETWEEN DIFFERENT TYPES OF VELOCITIES :

=
= =

Calculation of root mean square velocity (Urms) : As already discussed, the Urms can be calculated by
any of the following relations:

Urms =

Ratio of Urms for two different gases at the same temperature

Ratio of Urms for the same gas at different temperature

EFFECT OF TEMPERATURE ON DISTRIBUTION OF MOLECULAR VELOCITIES

Most probable velocity increases with the rise in temperature but fraction of molecules possessing
such velocity decreases.

Deviation from ideal behaviour of gas :

At high pressure and low temperature the gases deviate considerably from the ideal behaviour.

Deviation can be expressed in terms of compressibility factor (Z), expressed as

In case of ideal gas,

In case of real gas,

Negative deviation
In such case, Z < 1, gas is more compressible.

Positive deviation
In such case, Z >1, gas is less compressible.

Factors affecting the deviation :

The factors affecting the deviation are:
1. Nature of the gas : In general, the most easily liquefiable and highly soluble gases show
larger deviation.
2. Pressure : The deviation is more at high pressure. CO2 and N2 show negative deviation at
low pressure and positive deviation at high pressure.
3. Temperature : The deviation is more at low temperature. H2 and He always show positive
deviations at 0°C

BOYLE’S TEMPERATURE

Temperature at which a real gas exhibits ideal behaviour for considerable range of pressure is
called Boyle’s temperature. Mathematically,

, where a and b are Van der Waal’s constants

1. Boyle temperature is different for different gases
2. Below Boyle’s temperature a gas shows negative deviation.
3. Above Boyle’s temperature a gas shows positive deviation

CAUSE OF DEVIATION FROM THE IDEAL BEHAVIOUR

It is due to two faulty assumptions of Kinetic theory of gases particularly not valid at high pressure
and low temperature.
1. Volume occupied by the gas molecules is negligible as compared to the total volume of gas.
2. There are no attractive forces between the gas molecules.

VAN DER WAAL'S EQUATION

After volume & pressure correction, van der Waals obtained the following equation for n moles of a
gas

, For one mole

Excluded volume or co-volume, (b)
The constant b in van der Waal's equation is known as excluded volume or co-volume. It is nearly
four times the actual volume occupied by the gas molecules.
Excluded or co-volume (b) = 4 × actual volume of gas molecules.

Magnitude of attractive forces between gas molecules (a)

It is given by van der Waals constant ‘a’. Different gases have different value for ‘a’.
(i) The greater the value of ‘a’, the greater the strength of van der Waals forces.
(ii) The greater the value of ‘a’, the greater is the ease with which a gas can be liquefied.
Units for Van Der Waal's constant:
Pressure correction,

Volume correction,

DISCUSSION OF VAN DER WAAL’S EQUATION

Van der Waal’s equation for one mole of gas

1. At low pressure and ordinary temperature : V is very large and b can be neglected then

or ;
Therefore Z is less than 1.
Hence at low pressure the gases show negative deviation.
2. At high pressure and ordinary temperature : At high pressure, volume V will be quite

small. The quantity become negligible but ‘b’ cannot be ignored.

or ; Therefore Z is more than 1.

At high pressure the gases show positive deviation
Note : At some intermediate range of pressure and ordinary temperature the gas shows the ideal
behaviour.

3. At low pressure and high temperature : The effect of and b is negligible. We have

or
Therefore Z = 1. Hence gas shows ideal behaviour.
4. Exceptional behaviour of Hydrogen and Helium :

Due to their small size, the attractive forces between the molecules are too small, is

negligible, then
i.
Hence they always show positive deviation.
LIMITATION OF VAN DER WAAL’S EQUATION

There is specific range of temperature and pressure, to apply the equation. It deviates at too high
pressure and too low temperature.
Other equations of states :

1. Dieterici equation :

2. Berthelot’s equation :

3. Clausius equation :
Where c is a new constant
4. Kammerling onne's equation (virial equation):

a. The coefficients A,B,C,D, etc are known as first, second, third, fourth virial coefficients
b. At low pressure only A (which is equal to RT) is important, the others cancel out.
c. A is always positive and increases with rise of temperature.
d. At Boyle temperature B=0

e. Relation between B and van der Waals constant is

CRITICAL PHENOMENON AND LIQUEFACTION OF GASES

Increase of pressure and decrease of temperature tend to cause liquefaction of gases. The effect of
temperature is, however more important.

CRITICAL TEMPERATURE (TC)

It may be defined as the temperature above which no gas can be liquefied howsoever high the
pressure may be, critical temperature of CO2 is 31.1°C.
Critical temperature (Tc) of some gases,
He 5.2 CO2 304.1 CH4 190.2
H2 33.2 N2O 309.6 HCl 324.5
N2 126.0 NH3 405.5 H2S 373.5
CO 134.4 Cl2 417.1 Ar 150.7
O2 154.3 SO2 430.3

CRITICAL PRESSURE (PC)

At critical temperature the pressure needed to liquefy a gas is known as critical pressure.

CRITICAL VOLUME (VC)

The volume occupied by one mole of a gas at critical temperature and critical pressure is known as
critical volume.

Relationship between critical constants and van der Waal’s constant:

Relationship between boiling point and critical temperature:

Boiling point = critical temperature.

Compressibility for 1 mole of gas at critical state:

, almost constant.

JOULE THOMSON EFFECT

When a gas under high pressure is allowed to expand adiabatically into a region of extremely low
pressure, it suffers change of temperature. The phenomenon is known as Joule -Thomson effect.

CONDITION FOR JOULE-THOMSON EFFECT (INVERSION TEMPERATURE)

In Joule -Thomson effect, cooling is observed only if the gas is present below certain temperature
known as inversion temperature, Ti. It is characteristic of each gas and related to Van der Waal’s
constant a and b as,

At exact inversion temperature there is no Joule-Thomson effect. Above inversion temperature,

there is heating during Joule-Thomson effect. Below inversion temperature there is cooling during
Joule-Thomson effect.

Inversion temperature for hydrogen = –80°C and for He = –240°C. Joule-Thomson effect is zero in
an ideal gas and enthalpy remains constant. When an ideal gas expands in vacuum, it does no work
i.e. W=0 ; (Adiabatic condition). Hence internal energy of a given quantity of an ideal gas at
constant temperature is independent of its volume.

(for an ideal gas) ; This quantity is called internal pressure and is positive for real
gases.
Thermodynamically an ideal gas may be defined by following the equations.
1. PV = constant, at constant temperature.

2.

JOULE-THOMSON COEFFICIENT ( ):

The temperature change produced per atmosphere drop in pressure under constant enthalpy
conditions on passing a gas through the porous plug is called Joule-Thomson coefficient
The quantity is called Joule -Thomson coefficient.

1. Joule Thomson Coefficient is positive for real gases, (cooling)

Or Joule Thomson Coefficient will be positive when

2. When Joule Thomson Coefficient is negative, (heating)

Or Joule Thomson Coefficient will be negative when

3. When Joule Thomson Coefficient is zero, (no heating or cooling)

Or Joule Thomson Coefficient will be zero when

Since a, b and R are constants, the sign of Joule-Thomson Coefficient will depend only upon the
temperature at which the gas is being allowed to expand. The temperature at which the Joule-
Thomson Coefficient changes sign is known as the inversion temperature.

LAW OF CORRESPONDING STATES

When the values of pressure, volume and temperature are expressed as fractions of the

corresponding critical values we have.

where , and are termed, the reduced pressure, the reduced volume and the reduced temperature
respectively. If we replace P,V and T by Pc, Vc and Tc in van der Waal’s equation and put the values
of Pc, Vc and Tc terms of a, b and R we get,

If the two substances have the same reduced temperature and the same reduced pressure, they will
have the same reduced volume. The statement is known as the law of corresponding states.

HEAT CAPACITY OF SYSTEM

For gases it can be at constant volume or at constant pressure.
1. Heat capacity at constant volume (CV) is defined as the increase in internal energy of a gas
per degree rise of temperature.
 2. Heat capacity at constant pressure (Cp) is defined as increase in enthalpy of a gas per
degree rise of temperature.

For one mole of gas, the heat capacities at constant volume and constant pressure are denoted by
Cv and Cp and are termed as molar heat capacities.

RELATION BETWEEN CP AND CV

Cp– Cv = R
R = 1.987 cal or 8.314 Joule
R= PΔV = Work done by one mole of an ideal gas in expansion at constant pressure when heated
through 1°C.

MOLAR HEAT CAPACITIES FOR POLYATOMIC GASES

The values and are for monoatomic gases like He, Ar etc. where the energy
supplied increases translational kinetic energy only. In polyatomic gases heat supplied is utilised to
increase vibrational and rotational energy also. Thus we have

For monoatomic gas, x = 0,

for diatomic gases, x = R,

for triatomic gases, ,

COLLISION PROPERTIES
1. Molecular diameter or collision diameter : The distance between the centers of the
molecules at the point of their closest approach.
 2. Collision frequency (Z) : The number of collisions experienced by molecules per cc of a

gas per second is known as collision frequency of gas,

= average velocity
N = number of molecules per cm3
= collision diameter

At constant pressure,
At constant temperature,
3. Collision number (Z1) : Number of collisions undergone by a molecule with other molecules
per second present in 1cm3.

Z1 = Collision number =
= diameter of molecules, = Average velocity,
N = Number of molecules per unit volume of the gas
4. Mean free path (l) : The average distance travelled by the molecule between two successive
collisions

At constant pressure,

At constant temperature, l

VOLUME COEFFICIENT
It is defined as the ratio of the increase in volume of the gas at constant pressure per degree rise of
temperature to its volume at 0°C

V0 =Volume of a given mass of a gas at 0°C

Vt= Volume of a given mass of a gas at t°C

The value of v is found be 1/273 for all gases (charle's law)

Therefore,

PRESSURE COEFFICIENT ( )
It is defined as the ratio of the increase in pressure of the gas at constant volume per degree rise of
temperature to its pressure at 0°C

P0=Pressure of given mass of gas at 0°C

Pt=Pressure of given mass of gas at
The value found by Ragnault & Gay Lussac was in the vicinity of for all gases and hence

AMAGAT LAW OF PARTIAL VOLUME

The total volume of a mixture of non reacting gases at constant temperature and pressure is equal to
the sum of the individual partial volumes of the constituents

V(total)= V1+V2+V3+.....+Vn

LOSCHMIDT NUMBER
It is the number of molecules present in 1cc of a gas or vapour at STP. Its value is 2.617×1019 per
cc.

AVERAGE MOLECULAR WEIGHT OF A GASEOUS MIXTURE

Mmix=
ni= number of moles
Mi= molecular weight of each component

BAROMETRIC FORMULA
The decrease in the atmospheric pressure with increase in altitude given by the following expression
is called barometric formula.

ln
P0=Pressure at the sea level
P = Pressure at height h
= Average molecular mass of air,
g = acceleration due to gravity, 9.8 ms-2
R = gas constant ( 8.314 JK-1 mol-1)
T= Temperature in kelvin

ESCAPE VELOCITY
Velocity required by an object to escape from the gravitational field of a body. It is given by

AVERAGE KINETIC ENERGY

It is KE of a single molecule, and , where k= Boltzmann constant

Total KE =N (average KE), N ( ) =

LIQUEFACTION OF GASES
Liquefaction of gas can be achieved by
1. Increasing pressure : It increases attraction among molecules.
2. Decreasing temperature : It decrease Kinetic energy of molecules. The temperature of gas
must be lower than its critical temperature, TC.

Liquefaction is further based on the following principles

 Cooling by freezing mixture : eg NaCl & ice (-22°C), CaCl2 & ice(-55°C), KOH & ice (-
65°C)
 Cooling by adiabatic expansion (Claude’s Method) : The gas in this process suffers a
loss in temperature. Work is done by the gas at the cost of internal energy and temperature is
lowered.
 Cooling by Joule-Thomson effect ( Linde’s method) : Expansion of a gas through a small
jet under adiabatic conditions results in cooling and liquefaction of gas

LIQUID STATE
1. Liquid state of the matter is the intermediate state between the gaseous and the solid state.
2. In liquids the molecules of the matter are held together by strong intermolecular forces in
comparison to those in gases.
3. On the basis of kinetic molecular model, the liquid state is described as follow:
a. A liquid is composed of small molecules.
b. The molecules of the liquid are held closer by some kind of intermolecular forces.
c. The intermolecular forces are not very strong and thus the molecules are always in
constant random motion.
d. The average kinetic energy of molecules of a liquid is directly proportional to their
absolute temperature.
4. Properties of the liquid :
Most of the physical properties of liquids are controlled by the strength of intermolecular attractive
forces existing between molecules of a liquid. These intermolecular forces arranged in order of their
increasing strength are
London forces/induced dipole<dipole attraction< Hydrogen bonding
a. Shape: Liquids have no definite shape of their own. It acquires the shape of the container in
which it is put.
b. Volume: Liquids have a definite volume.
c. Density: The densities of liquids are nearly 1000 times more than the densities of the gases
under identical conditions.
d. Compressibility: Liquids are very less compressible compared to gases.
 e. Diffusion: Liquids diffuse like gases but the process of diffusion (also known as intermixing)
is much slower.
f. Evaporation: The process of conversion of a liquid into its vapours (i.e.) gaseous state) at
room temperature is known as evaporation.

VAPOUR PRESSURE
At equilibrium state the pressure exerted by vapour phase is called vapour pressure at a specific
temperature.
 The magnitude of vapour pressure depends upon the following two factors.
 The liquids having weak intermolecular attraction have greater tendency of escaping
from the liquid surface in comparison to liquids having stronger forces of intermolecular attraction.
For example, the vapour pressure of ether and acetone is more than that of water or acetic acid at
any specific temperature.
 The vapour pressure of a liquid increases with the increase in temperature.
 The vapour pressures of a given liquid at two different temperatures may be compared using
Clausius Clapeyron equation

where P1and P2 are the vapour pressures at temperature T1 and T2 ΔH is the heat of vapourisation
and R is molar gas constant.
 The temperature at which the vapour pressure of liquid becomes equal to atmospheric
pressure (or the external pressure) is termed as the boiling point of liquid. For example at 1
atmospheric pressure acetone boils at 56°C. benzene at 80°C, ethyl alcohol at 78.4°C and water at
100°C.
 The temperature at which the solid state and the liquid form of a substance are in equilibrium
at one atmospheric pressure is known as freezing point

SURFACE TENSION
 The surface tension is defined as the force per cm acting perpendicular to the tangential line
on the surface of the liquid which tend to compress the surface area.
 The units of surface tension are force per unit length i.e. dynes cm–1 or Nm–1 (in SI units)
 Stronger the forces of intermolecular attraction (cohesive forces) greater is the surface
tension.
 The surface tension decreases with rise in temperature or surface tension in inversely
proportional to temperature.Surface tension 1/Temperature
 Measurement of surface tension of a liquid by the drop number method is the most
convenient method.

VISCOSITY
 Viscosity may be defined as the force of friction between two layers of a liquid moving past
one another with different velocities.
 The viscosities of liquids are compared in terms of coefficient of viscosity which is defined as
the force per unit area needed to maintain a unit difference in velocities between two consecutive
parallel layers which are one cm. apart.
 The units of viscosity are poise (P) where 1P = g cm–1 sec–1. In SI units of viscosity 1P = 0.1
N sec m–2.
 The liquid having stronger forces of attraction has a higher viscosity.
 With the rise in temperature, viscosity of a liquid decreases because the intermolecular
attractive force between consecutive layers decrease as temperature increases.

THERMODYNAMICS
It is the branch of chemistry which deals with the energy changes taking
place during physical and chemical changes.

SYSTEM
A system is that part of universe which is under investigation .

SURROUNDINGS
The part of the universe other than the system is known as surroundings.
Thus, Universe = System + Surroundings
In simple case surroundings implies air or water both.

TYPES OF SYSTEM
1. Open system - A system which can exchange matter as well as
energy with surroundings.
2. Closed system – A system which can exchange energy and not
matter with surroundings.
3. Isolated system - A system which can exchange neither matter nor
energy with surroundings.
4. Homogeneous system – A system consisting of one phase only e.g.
pure solid, a liquid or a mixture of gases.
5. Heterogeneous system – It may consists of two or more phases e.g.
a solid in contact with liquid etc.

STATE OF SYSTEM
The condition of existence of a system when its macroscopic properties
have definite values is known as state of system e.g. at 1 atm pressure H 2O
is (a) Solid below 0°C, (b) liquid between 0°C - 100°C and (c) gas above
100°C.

MACROSCOPIC PROPERTIES
The properties which arise out of collective behaviour of large number of
chemical entities e.g. pressure, volume, temperature, composition,
colour, refractive index etc.

EXTENSIVE PROPERTIES
The properties which depend upon the quantity of the substance or
substances present in the system e.g. volume, enthalpy, free energy,
entropy, heat capacity.

INTENSIVE PROPERTIES
The properties which are independent of the quantity of the substance
present in the system e.g. density, molar volume, temperature, melting
point, boiling point, freezing point etc.
Note – Any extensive property if expressed as per mole or per gm becomes
intensive property e.g. mass and volume are extensive properties but
density is an intensive property.

STATE VARIABLES AND STATE FUNCTIONS

These are the macroscopic properties of the system which change with the
change in the state of system. They depend upon the initial and final state
of system. They are temperature, pressure, volume, chemical composition,
energy, entropy, free energy.

INTERNAL ENERGY, INHERENT ENERGY OR HIDDEN ENERGY (IE)

It is the sum of all types of energies (as given below) associated with a
system or substance.

 Translational energy of the molecules, Et

 Rotational energy, Er
 Vibrational energy, Ev
 Electronic energy, Ee
 Nuclear energy, En
 Interaction energy of molecules, Ei
E = Et + E r + E v + E e + E n + E i
It is a state function, depends upon chemical nature of the substance,
amount, temperature, pressure etc. Its absolute value cannot be determined
but change during a chemical process can be determined.

+ve change is endothermic

 - ve change is exothermic
Internal energy depends on temperature, pressure, volume and quantity of
matter. In most stable form the internal energy of an element is zero.

INTERNAL ENERGY CHANGE ( E)

It is the amount of heat evolved or absorbed when a chemical reaction is

carried out at constant volume and constant temperature. It is measured in
bomb calorimeter.

Where, C= Heat capacity of calorimeter

T = Rise in temperature
M = Molecular mass of the substance
W = Mass of the substance taken

MODES OF THE TRANSFER OF ENERGY

Exchange of energy between system and surroundings can take place by
(a) Heat (b) Work
(c) Electrical Energy (d) Radiations

EXPRESSION FOR PV WORK

The mathematical expression for pressure-volume work is

SIGN CONVENTIONS :

 Heat absorbed by the system is positive +ve

 Heat evolved by the system is negative –ve
 Work done on the system is positive +ve
 Work done by the system is negative –ve

PROCESSES AND THEIR TYPES

1. Process - The operation by which a system changes from one state to
another state is called process
2. Reversible process - If the driving force is only infinitesimally greater
than the opposing force and process can be reversed at any instant, it is
known as reversible process.
3. Irreversible process - It does not take place infinitesimally slow.

THERMODYNAMIC PROCESSES
1. Isothermal process ( T = 0) : During each stage of process, the
temperature remains constant. If the process is exothermic heat is given out
to surroundings, If the process is endothermic heat is absorbed from
surroundings.
2. Adiabatic process (dq=0) : No heat leaves or enter the system,
temperature of a system rises in exothermic process, temperature falls in
endothermic process.
3. Isobaric process : Pressure remains constant, only volume
changes.
volume decreases
volume increases
4. Isochoric process : Volume remains constant but pressure
changes.
pressure decreases
pressure increases
5. Cyclic process : After undergoing a number of changes, the
system returns to its original state. In cyclic process

THERMODYNAMIC EQUILIBRIUM
When there is no change in macroscopic properties with time. The types
are :
1. Thermal equilibrium - The temperature of the system remains
constant throughout and no heat flows from one part to another part of
system.
2. Mechanical equilibrium - The pressure remains constant and no
mechanical work is done by one part of system on another part.
3. Chemical equilibrium - The composition of various phases remains
the same.

FIRST LAW OF THERMODYNAMICS

1. Law of equivalence of different forms of energies
2. Energy can neither be created nor destroyed but can be transformed
from one form to another.
3. Total energy of universe is conserved (fixed, constant)

MATHEMATICAL EXPRESSION OF FIRST LAW

If q is the amount of heat absorbed by the system and w is the work done
on the system, the change in internal energy,
If volume remains constant, no work is done then
Note :- q and w are not state functions but the sum of the two (q + w) which
represents is a state function

DISCUSSION OF EQUATION

(i) when
If heat is absorbed by system, internal energy increases.
If heat is lost by system, internal energy decreases.
(ii) when
If work is done on the system, internal energy increases.
If work is done by the system, internal energy decreases.
In adiabatic process work is done by the system at the expense of internal
energy.
(iii) when
Heat absorbed by the system is equal to work done by the system
If we write w = - q
If work is done on the system (when ) heat flows from system to
surroundings.
(iv) Cyclic process, E = 0, q = –w
Work done by the system is equal to heat absorbed.

SIGNIFICANCE OF E

It represents the heat change taking place during the process occurring at
constant volume and constant temperature.
qv = ΔE

ENTHALPY (H) AND ENTHALPY CHANGE ( H)

Enthalpy is the heat content of the system and related to internal energy as
follows.
H = E + PV
We can measure change in enthalpy and not absolute value of enthalpy. It is
a state function.
Hproducts – H Reactants= HP – HR
If HP > HR, the change is endothermic. If HR > HP, the change is exothermic.

SIGNIFICANCE OF H

The enthalpy H is given by

H = E + PV
the change in enthalpy is given by when pressure is kept constant
P = 0,
; (From first law of thermodynamics)
The enthalpy change represents the heat change taking place during the
process occurring at constant pressure and constant temperature.

FACTORS AFFECTING THE H

 Physical state of reactants and products

 Quantities of reactants and products
 Allotropic forms
 Temperature
 Conditions of constant P and Constant V at a particular temperature.

KIRCHOFF’S EQUATION
If reaction takes place at constant pressure, the variation of with
temperature is given by this equation

Cp = Difference in the heat capacities of products and the reactants at

constant pressure.
If the reaction takes place at constant volume.

=Difference in the heat capacities of products and the reactants at

constant volume.

STANDARD ENTHALPY
The enthalpy change at the standard conditions i.e. at 1 atm pressure and
298K temperature is called standard enthalpy of the reaction and is denoted
by

RELATION BETWEEN H AND E:

It is given by , where
n = (Number of moles of products - number of moles of reactants) gaseous
only.

E AND H FOR MONOATOMIC GAS :

For such a gas

Internal Energy = per mole and

Enthalpy

APPLICATIONS OF FIRST LAW OF THERMODYNAMICS

HESS’S LAW OF CONSTANT HEAT SUMMATION

Law is based upon the first law of thermodynamics and states that if a
chemical change can be made to take place in two or more ways involving
one or more steps, the net amount of heat change in the complete process is
the same regardless of the method employed.

APPLICATIONS OF HESS’S LAW

 Calculation of heats of reactions

 Determination of heat changes of slow reactions
 Calculation of enthalpies of formation
 Calculation of bond energies

WORK DONE IN ISOTHERMAL REVERSIBLE EXPANSION (MAXIMUM WORK)

It is given by the expression

WORK DONE IN ADIABATIC REVERSIBLE EXPANSION

It is given by the expression

equal to and Cp – Cv = R
If we put the value of g we get the expression for workdone

Relation between temperature, volume and pressure in reversible

adiabatic expansion

or T .
P1– = const.

WORK DONE IN ADIABATIC IRREVERSIBLE EXPANSION

During expansion in vacuum
Pext = 0, work done = 0, also
If i.e. expansion work or work done by system.
If then Wirr is +ve i.e. compression work or work done on the system.

HEAT CAPACITY OF A SYSTEM

It is the amount of heat required to raise the temperature of the system by 1
degree (K or °C)

.
In case of single substance, when m=1 g, C is the specific heat of system;
when m = Mg or 1 mole, it is molar heat capacity. Since heat capacity
varies with temperature its true value is given by

Heat capacity at constant volume

Heat capacity at constant pressure

where are specific heats at constant pressure and constant volume

respectively
Cp and Cv are molar heat capacities at constant pressure and constant
volume respectively

Dulong and Petit’s rule : Atomic mass × specific heat = 6.4

The rule is valid for solid elements except Be, B, Si and C.
Units : In SI units the specific heat or molar heat is expressed in terms of
Joules ( 1 Cal = 4.184 J)

Molar heat capacity of a monoatomic gas at constant volume

Molar heat capacity of a monoatomic gas at constant pressure :

Molar heat capacity for polyatomic gas at constant volume :

Molar heat capacity for polyatomic gas at constant pressure :

For monoatomic gas X=0, for diatomic gas X=R and for triatomic gas

LIMITATION OF FIRST LAW OF THERMODYNAMICS

It fails to predict the feasibility and the direction of the change.

SPONTANEOUS PROCESS
A process which has an urge or a natural tendency to occur either of its own
or after proper initiation under a given set of conditions. It is irreversible
process and may only be reversed by some external agents.
1. Spontaneous processes that need no initiation
a. Evaporation of water H2O (l) H2O (g)
b. Dissolution of sugar

c. Intermixing of gases
4. Spontaneous processes that need initiation

c.
d. Electrolysis of water
It requires continuous supply of energy.

SECOND LAW OF THERMODYNAMICS

The entropy of the universe increases in every spontaneous (natural)
change. The entropy of the universe is continuously increasing.

Other statements of second law of thermodynamics

 Clausius : Heat cannot itself pass from a colder body to a hotter
body.
 Kelvin : It is impossible to get a continuous supply of work from a
body or engine which can transfer heat from a single heat reservoir.
 Planck : It is impossible to construct a device which will work in a
single complete cycle and convert heat into work without producing any
change in the surroundings.
 All natural and spontaneous processes take place in one direction and
thus are irreversible in nature.
 In a reversible process the entropy of the universe is constant. In an
irreversible process the entropy of the universe increases.

Entropy (S)
It is a measure of degree of disorder or randomness in a system. More the
disorder or randomness, the more is entropy.Heat added to a system
increases randomness and hence the entropy. Heat added to a system at
lower temperature causes greater randomness than the system at higher
temperature. At higher temperature the system already has higher
randomness. Thus entropy change is inversely proportional to temperature.

S=
For a spontaneous process
STotal = Ssystem + Ssurr > 0
Or Suniverse >0

Units of entropy :
Jmol-1K-1; It is a state function. The change in entropy is represented by
S = (Sfinal – Sinitial) = qrev / T
qrev is the heat absorbed by the system in a reversible manner and
isothermally.

ENTROPY CHANGE FOR AN IDEAL GAS UNDER DIFFERENT CONDITIONS:

WITH CHANGE IN P, V AND T

(when T and V are two variables)

(when T and P are two variables)

For isothermal process

For isobaric process

For isochoric process

GIBB’S FREE ENERGY (G)
It is the maximum amount of energy which can be converted into the useful
work (other than PV work). It is related to enthalpy (H) and entropy (S) as
follows.
and change is given by
Useful work

HELMHOLTZ FREE ENERGY (WORK FUNCTION) (A)

The maximum work obtainable from a system is given by this energy.
A = E - TS ; E= Internal energy, S = Entropy, T= Temperature

CRITERIA FOR FEASIBILITY OR SPONTANEITY OF A PROCESS

Enthalpy or entropy alone cannot predict the spontaneity of a change. Gibb’s

free energy is very useful factor for this
G = H – TS
G = H – T S (at constant T)
STotal = Ssys + Ssurr > 0

Ssurr =

Since, Heat lost by system = Heat gained by surroundings and vice

versa.

STotal = Ssys +
T STotal = T Ssys – Hsys
= –( Hsys – T Ssys)
= –( G)
Hence,
1. If is negative, the process is spontaneous
2. If is zero, the process is in equilibrium
3. If is Positive the process does not occur

STANDARD FREE ENERGY CHANGE ( AND EQUILIBRIUM CONSTANT (K)

They are related as follows 2.303 RT log K

FREE ENERGY CHANGE AND CELL POTENTIAL

nFEº
VARIATION OF FREE ENERGY WITH TEMPERATURE AND PRESSURE IN A
REVERSIBLE PROCESS

The equation is called the total differential equation.

(a) If temperature is kept constant dT=0 we have

(b) If pressure is kept constant dP = 0 we have

CHANGE IN FREE ENERGY FOR ISOTHERMAL PROCESS

CRITERIA OF FEASIBILITY OR SPONTANEITY IN TERMS OF :

1. Entropy :
, the process is reversible and system is in equilibrium when internal
energy and volume are kept constant.
the process is irreversible and if , the process is
reversible.
2. Internal energy : When entropy and volume kept constant

If , the process is irreversible and if , the process is

reversible.
3. Enthalpy (H) : When entropy and pressure are kept constant
, the process is irreversible and if , the process is
reversible.
4. Work function (A) : When temperature and volume are kept constant
, the process is irreversible and if , the process is
reversible.
5. Free energy (G) : When pressure and temperature are kept constant
, the process is irreversible and if , the process is
reversible.
Note : Criteria of feasibility or spontaneity in terms of free energy is most
important since most of the processes are carried out at constant
temperature and pressure.

ZEROTH LAW OF THERMODYNAMICS

If two bodies have separately equality of temperature with a third body,
they also have equality of temperature with each other.

THIRD LAW OF THERMODYNAMICS

At absolute zero temperature, the entropy of a perfectly crystalline
substance is taken as zero. This law was formulated by Nernst in 1906.

Calculation of absolute value of entropy:

Let S0 be the entropy of substance at 0 K and S be its entropy at T K.

Where Cp is the heat capacity of the substance at constant pressure.

According to the third law

.
The value of the integral can be obtained from a plot of
CP / T Vs T. The area under the curve between 0 and T K gives the value of
the integral and hence of S at temperature T.

CLAPEYRON - CLAUSIUS EQUATION

It gives the change in pressure dP accompanying change in temperature dT
or vice versa for a system containing two phases of a pure substance in
equilibrium, q is heat exchanged reversibly per mole of the substance during
the phase transformation at temperature T.

1. For water (liquid ) = water (vapour) we have

;
ΔHV = Molar heat of vaporisation
2. For water (Solid, Ice) = water (liquid)

;
ΔHf = Molar heat of fusion of ice
3. For solid = vapour equilibrium

;
ΔHs = Molar heat of sublimation

INTEGRATED FORM OF CLAPEYRON - CLAUSIUS EQUATION

For Liquid = gas system in Equilibrium

log

APPLICATIONS OF CLAPEYRON CLAUSIUS EQUATION

1. Calculation of molar heat of vaporisation

2. Effect of temperature on vapour pressure of a liquid
3. Effect of pressure on boiling point
4. Calculation of molal elevation constant (kb) and molal depression
constant (kf) of a solvent.

lv= latent heat of vaporisation per gram of solvent

T= boiling point of pure solvent

T= freezing point of solvent

lf = latent heat of fusion per gram of solvent

HEAT ENGINE
Machine which converts heat into work is called heat engine.

EFFICIENCY OF HEAT ENGINE

The fraction of the heat absorbed, converted into work is called the efficiency
of machine.

CARNOT CYCLE
It is a process where a system after undergoing a number of successive
changes returns to its original state. It consists of four different operations.
1. Isothermal expansion
2. Adiabatic expansion
3. Isothermal compression
4. Adiabatic compression

EFFICIENCY OF CARNOT CYCLE OR ENGINE

Since is always less than unity, hence efficiency is always less than
unity

CARNOT THEOREM

Efficiency of reversible heat engine is independent of the nature of working

substance and depends upon the temperature of source and sink.

or

All machines working reversibly between the same temperature of source

and sink have same efficiency.

RESONANCE ENERGY

(Expected value of ) – (Observed value of )

Example - Calculate the resonance energy of N2O from the following data
of N2O = 82 kJ mol–1, Bond energies of NN, N=N, O=O and N=O bands are
946, 418, 498 and 607 kJ mol–1 respectively
Sol. Calculated value of
CALORIFIC VALUE
The heat liberated on burning unit mass of a fuel is called calorific value.

The more the calorific value the more the efficient is the fuel. Oxygen atoms
present in a molecule reduce the calorific value.
The more the number of hydrogen atoms per carbon atom, the more is the
calorific value.

TYPES OF REACTIONS AND CORRESPONDING ENTHALPY CHANGES

1. Heat of reaction at constant volume and certain temperature
It is defined as the change in internal energy ( ) of the system when
requisite number of molecules of reactants react to form the products. ( )
= = heat of reaction at constant volume
2. Heat of reaction at constant pressure and certain temperature
It is defined as the difference in enthalpies ( ) of products and reactants
heat of reaction at constant pressure
3. Relation between heat of reaction at constant volume ( ) and
at constant pressure ( )

4. Sign of and : Negative sign of or shows that heat is

evolved and reaction is exothermic while a positive sign of and
shows that heat is absorbed and reaction is endothermic.
5. Factors affecting the heat of reaction
a. Physical state of the reactants and products
b. Amount of the reactants
c. Temperature
d. Pressure
6. Thermochemical equation
Stoichiometrically balanced, mentioning the physical state of the reactants
and products and showing the values of and equation is called
thermochemical equation
 7. Heat of formation ( ) : It is defined as the enthalpy change
accompanying the formation of one mole of the compound from its
elements.

8. Standard heat of formation : It is the enthalpy change

accompanying the formation of one mole of a compound from its
elements. All substances being in their standard states. The condition
of standard state is 25ºC and 1 atm pressure.
9. Heat of combustion : It is the change in enthalpy of the system,
when 1 gram mole of the substance is completely oxidized

The combustion is always exothermic process.

10. Application of heat of combustion
a. Calorific value of fuel
b. Calculation of heat of formation
c. Constitution of organic compounds
11. Heat of neutralization : It is defined as the enthalpy change ( )
accompanying the neutralization of one gram equivalent of the acid by
a base in dilute solution at that temperature.

Heat of neutralization of every strong acid by a strong base is identical.

When acid or alkali is weak the heat of neutralization is different because the
reaction involves the dissociation of the weak acid or the weak alkali.
Heat of neutralization of weak acids with NaOH at 25°C
12. Heat of solution : The enthalpy change per mole of solute when it is
dissolved in large excess of solvent (generally H2O) so that further
dilution of the solution produces no heat exchange.

13. Heat of dilution : The enthalpy change when a solution containing

one mole of a solute is diluted from one concentration to another.
14. Heat of hydration : The enthalpy change when one mole of a
substance combines with the required number of moles of water to
form a specified hydrate.
Heat of hydration = Heat of solution of the hydrated compound – Heat of
solution of the unhydrated compound
15. Heat of precipitation : The enthalpy change when one mole of a
sparingly soluble substance precipitates on mixing dilute solutions of
stable electrolytes is called heat of precipitation.
 16. Bond enthalpy : It is defined as the average amount of energy
required to break all the bonds of a particular type in one mole of the
substance. It is also known as bond energy and expressed in kJ mol –1.
In a diatomic molecule the bond energy and bond dissociation energy are
the same.
In polyatomic molecules the bond dissociation energy is not the same for
successive bonds though the bonds are of the same type.
;
;

17. Use of bond enthalpy :

a. Calculating standard enthalpy of reactions
H =[sum of bond energies of reactants] – [sum of bond energies of
products]
= [ Total energy required for breaking the bonds] – [Energy given out
in forming the bonds]
b. Calculation of bond energy of some specific bond in the molecule

LAWS OF THERMOCHEMISTRY
1. Lavosier and Laplace law : The heat evolved or absorbed in the
course of a chemical reaction is equal to the heat absorbed or evolved when

the reaction is reversed.

2. Hess’s law of constant heat summation

TROUTON’S RULE
Fredrick Trouton (1884) found that for many liquids molar heat of
vaporization in calories per mole divided by the normal boiling point in
degree kelvin is a constant.
The quantity is also called entropy of vaporization Sv.

ENDOTHERMIC COMPOUNDS
The compounds having positive values of formation are called endothermic
compounds. Ozone is an example.