Ge CH 11

PREFACE
In a bid to standardize higher education in the country, the University Grants

Commission (UGC) has introduced Choice Based Credit System (CBCS) based on five
types of courses viz. core, discipline specific, generic elective, ability and skill
enhancement for graduate students of all programmes at Honours level. This brings in
the semester pattern, which finds efficacy in sync with credit system, credit transfer,
comprehensive continuous assessments and a graded pattern of evaluation. The objective
is to offer learners ample flexibility to choose from a wide gamut of courses, as also to
provide them lateral mobility between various educational institutions in the country where
they can carry their acquired credits. I am happy to note that the university has been
recently accredited by National Assessment and Accreditation Council of India (NAAC)
with grade "A".
UGC (Open and Distance Learning Programmes and Online Programmes) Regulations,
2020 have mandated compliance with CBCS for U.G. programmes for all the HEIs in
this mode. Welcoming this paradigm shift in higher education, Netaji Subhas Open University
(NSOU) has resolved to adopt CBCS from the academic session 2021-22 at the Under
Graduate Degree Programme level. The present syllabus, framed in the spirit of syllabi
recommended by UGC, lays due stress on all aspects envisaged in the curricular framework
of the apex body on higher education. It will be imparted to learners over the six semesters
of the Programme.
Self Learning Materials (SLMs) are the mainstay of Student Support Services (SSS)
of an Open University. From a logistic point of view, NSOU has embarked upon CBCS
presently with SLMs in English / Bengali. Eventually, the English version SLMs will be
translated into Bengali too, for the benefit of learners. As always, all of our teaching
faculties contributed in this process. In addition to this we have also requisitioned the
services of best academics in each domain in preparation of the new SLMs. I am sure
they will be of commendable academic support. We look forward to proactive feedback
from all stakeholders who will participate in the teaching-learning based on these study
materials. It has been a very challenging task well executed, and I congratulate all
concerned in the preparation of these SLMs.
I wish the venture a grand success.
Professor (Dr.) Subha Sankar Sarkar

1 Vice-Chancellor
Under-Graduate : Chemistry
Choice Based Credit System (CBCS)
Subject : Honours in Chemistry (HCH)
Course Title: Basic Physical Chemistry
Course Code: GE -CH-11
First Print — June, 2021
Printed in accordance with the regulations of the Distance Education

Bureau of the University Grants Commission.
Netaji Subhas Open University
Under-Graduate Degree Programme
Choice Based Credit System (CBCS)
Subject : Honours in Chemistry (HCH)
Course Title: Basic Physical Chemistry
Course Code: GE -CH-11
: Board of Studies :
Members
Professor Kajal De (Chairperson) Professor Ashok Prasun Chattopadhyay
Director, School of Sciences Professor of Chemistry
Netaji Subhas Open University University of Kalyani
Dr. Sanjay Roy Dr. Sukanya Chakraborty
Associate Professor of Chemistry Associate Professor of Chemistry
Netaji Subhas Open University Lady Brabourne College
Dr. Asimesh Dutta Gupta Dr. Urmila Ukil
Associate Professor of Chemistry Principal
Netaji Subhas Open University Sarojini Naidu College for Women
Dr. Gautam Kumar Mukherjee Professor Chitta Ranjan Sinha
Associate Professor of Chemistry Professor of Chemistry
Netaji Subhas Open University Jadavpur University
Dr. Sintu Ganai Dr. Paritosh Biswas
Assistant Professor of Chemistry Associate Professor of Chemistry
Netaji Subhas Open University Chakdah College
Dr. Puspal Mukherjee
Assistant Professor of Chemistry
Netaji Subhas Open University
: Course Writer : : Course Editor :
Dr. Simanta Kundu Dr. Sanjay Roy
Assistant Professor Associate Professor
Shibpur Dinobundhoo Netaji Subhas Open
Institution (College) University, Kolkata
: Format Editor :
Dr. Sanjay Roy, NSOU
All rights reserved. No part of this Study material be reproduced in any form without
permission in writing from Netaji Subhas Open University.
Kishore Sengupta
3 Registrar
Netaji Subhas UG : CHEMISTRY
(HCH)
Open University
Course : Basic Physical Chemistry

Course Code : GE-CH-11
Unit – 1 Chemical Energetic 7-21
Unit – 2 Chemical Equilibrium 22-33
Unit – 3 Ionic Equilibrium 34-54
Unit – 4 Kinetic Theory of Gases 55-73
Unit – 5 Liquids 74-84
Unit – 6 Solids 85-104
Unit – 7 Solutions 105-124
Unit – 8 Chemical Kinetics 125-151
5
Unit 1  Chemical Energetic
Contents
1.0. Objectives
1.1. Introduction
1.2. Brief review of thermodynamics and the Laws of Thermodynamics
1.2.1. System and surrounding
1.2.2. State of a system
1.2.3. Properties of a system:
1.2.4. Types of processes
1.2.5. Work, heat and heat capacity
1.2.6. The Zeroth law of thermodynamics
1.2.7. The First law of thermodynamics
1.2.8. Internal energy
1.2.9. Enthalpy
1.3. Important principles and definitions of thermochemistry
1.3.1. Energy changes accompanying chemical reactions
1.3.2. Thermochemical equations
1.3.3. Standard enthalpy of reactions
1.3.4. Hess's law of constant heat summation
1.4. Standard enthalpies of formations
1.5. Enthalpies of solution and dilution
1.6. Bond energy, bond dissociation energy and resonance energy
1.7. Variation of enthalpy of a reaction with temperature - Kirchhoff's equation
1.8. Third Law of thermodynamics and calculation absolute entropies of substances
1.9. Summary
1.10. Questions
8  NSOU  GE-CH-11
1.0 Objectives
After reading this unit, we will be able to:
 define the commonly used terms in thermodynamics and laws of
thermodynamics;
 state important principles of thermochemistry;
 explain standard state and standard enthalpies of formations;
 explain enthalpies of solution and dilution;
 solve numerical problems based on the enthalpy changes;
 define bond enthalpy and bond dissociation enthalpy and resonance energy;
 variation of enthalpy of a reaction with temperature – Kirchhoff’s equation;
 state the third law of thermodynamics and calculate the absolute entropies of
substances.
1.1 Introduction
When a chemical reaction occurs, it is accompanied by an energy change which may
take any of several different forms. For example, the energy change involved in the combustion
of fuels like kerosene, coal, wood, natural gas, etc., takes the form of heat and light.
Electrical energy is obtained from chemical reactions in batteries. The formation of glucose,
C6H12O6 by the process of photosynthesis requires the absorption of light energy from the
sun. Thus, various forms of energy are interrelated and under certain conditions, these may
be transformed from one form into another. The study of these energy transformations
forms the subject matter of thermodynamics. In this unit we will review some of the
fundamental concepts of energy and heat and the relation between them. We will begin the
study of thermodynamics, which treats the energetic aspects of change in general, and will
finally apply this specifically to chemical change.
1.2. Brief review of thermodynamics and the Laws of

Thermodynamics
In this lesson we would come across some frequently used terms. Let us understand
the meaning of these terms first.
NSOU  GE-CH-11  9
1.2.1 System and surrounding

System is the part of the physical universe which is under study, while the rest of the
universe is surroundings. The system and surroundings are separated by a boundary. The
system can be of three different types – open, closed and isolated system. An open system
is a system which can exchange both energy and matter with surroundings. A closed
system is a system which can exchange energy but not matter with the surroundings. An
isolated system is a system which can exchange neither matter nor energy with the
surroundings.
1.2.2 State of a system

We describe the state of a system by its measurable properties. For example, we can
describe the state of a gas by specifying its pressure, volume, temperature etc. These
variable properties are called state variables or state functions. Their values depend only
on the initial and final state of the system and not on the path taken by the system during
the change. When the state of a system changes, the change depends only on the initial and
the final state of the system
1.2.3 Properties of a system

The measurable properties of a system are called state variables. They may be further
divided into two main types – extensive properties and intensive properties. Extensive
properties are those whose value depends upon the size or mass of the system. Examples
of extensive properties are energy, enthalpy, entropy, heat capacity etc. Intensive properties
are those whose value is independent of the size or mass of the system, like temperature,
refractive index, density, solubility etc., are the examples of intensive property.
1.2.4 Types of processes

The method of bringing about a change in state is called process. Processes could be
of different types. The different types of processes are explained below.
a) Isothermal process: When the temperature of the system remains constant
during various operations, then the process is said to be isothermal. This is
attained either by removing heat from the system or by supplying heat to the
system.
b) Adiabatic Process: In an adiabatic process there is no exchange of heat between

the system and the surroundings. Thus, in adiabatic processes there is always a
change in temperature.
c) Isobaric process: It is a process in which the pressure of the system remains
constant. Heating of water in an open vessel is an example of isobaric process.
d) Isochoric process: It is a process in which the volume of the system remains
constant.
e) Reversible and irreversible Process: A process or change is said to be
reversible, if a change is brought out in such a way that the process could, at
any moment, be reversed by an infinitesimal change. A reversible process proceeds
infinitely slowly by a series of equilibrium states such that system and the
surroundings are always in near equilibrium with each other. Processes other
than reversible processes are known as irreversible processes.
1.2.5 Work, heat and heat capacity

Heat and work are both measured in energy units, so they must both represent energy.
How do they differ from each other?
Work is a quantity of energy that flows across the boundary of a system by means of
a force during a change in its state and is completely convertible into lifting of a mass in
the surroundings. So, work appears in only at the boundary of the system and it appears
only during change in the state of the system. The SI unit of work is joule (J).
Heat is a form of energy that is exchanged at the boundary between a system and its
surroundings by virtue of a difference in temperature between them and flows from a point
of higher to a point of lower temperature and causes a change in the state of the system.
Since heat is also a form of energy, so its SI unit is joule (J). Heat is said to be positive
when energy is transferred to a system from its surroundings and negative when energy is
transferred from system to surroundings.
Heat Capacity (C) is defined as the amount of energy as heat needed to raise the
temperature of the system by 1 oC. So, SI unit of heat capacity is joule per Kelvin
(J K-1). Heat capacity is proportional to the amount of substance. So the molar heat capacity
or specific heat capacity is defined as the quantity of the heat required to raise the temperature
of one unit mass of the substance. Now, the transfer of heat to system can be done under
different condition. If the transfer of heat is done under the conditions of constant volume,
the associated heat capacity is called as the heat capacity at constant volume (Cv) and if
the transfer of heat is done under the conditions of constant pressure, the associated heat
capacity is called as the heat capacity at constant pressure (Cp). The values of Cp and Cv
for a given solid or liquid systems are not much different. However for gaseous systems
the difference in their values is significant and for an ideal gas it is given by the following
expression
C p – Cv = R
where R is the gas constant.
1.2.6 The Zeroth law of thermodynamics

The Zeroth law of thermodynamics is states that, if two thermodynamic systems, A and
B are in thermal equilibrium with a third thermodynamic system, C then the two thermodynamic
system (A and B) are also in thermal equilibrium with each other.
1.2.7 The First law of thermodynamics

You know that we cannot create or destroy energy. Energy only changes from one
form to another. This is the observation made by many scientists over the years. This
observation has taken the form of first law of thermodynamics. It has been found valid for
various situations. We state this law as follows:
Energy can neither be created nor destroyed. The total energy of the universe or an
isolated system is constant.
Mathematically the first law of thermodynamics is stated as:
ΔU = q + w
where ΔU = change in internal energy, q = heat absorbed by the system, and w =
work done on the system.
1.2.8 Internal energy (U)

Every system has a definite amount of energy. This amount is different for different
substances. It includes translational, vibrational and rotational energies of molecules, energy
of electrons and nuclei. The internal energy may be defined as the sum of the energies of
all the atoms, molecules or ions contained in the system. It is a state variable. It is not
possible to measure the absolute values of internal energy. However, we can calculate the
change in internal energy. If the internal energy of the system in the initial state is U1 and
that in the final state is U2, then change in internal energy ΔU is independent of the path
taken from the initial to the final state. We can write this change as:
Δ U = U 2 – U1
The internal energy of the system can be changed in two ways:
(i) either by allowing heat to flow into the system or out of the system; and
(ii) by work done on the system or by the system.
1.2.9 Enthalpy (H)

For measuring heat lost or gained at constant pressure, we define a new state function
called enthalpy. It is denoted by the symbol H and is given by
H=U+pV
Where, U is the internal energy, p is the pressure and V is the volume of the system.
Enthalpy change, ΔH, is given by
ΔH = ΔU + p ΔV (at constant pressure) = q (at constant pressure)
We denote q at constant pressure by qp hence
ΔH = qp
So, by measuring heat lost or gained at constant pressure by the system, we can
measure enthalpy change for any process.
1.3. Important Principles and Definitions of

Thermochemistry
1.3.1 Energy changes accompanying chemical reactions
Majority of chemical reaction are performed under the conditions of constant pressure,
so the measured heat changes refer to the enthalpy change for the reaction. Such an
enthalpy change associated with a given chemical reaction is termed as the enthalpy of
reaction (ΔrH). Let as denote total enthalpy of reactants as Hreactants and total enthalpy of
products as Hproducts. The difference between these enthalpies, ΔrH, is the enthalpy of the
reaction
ΔrH = Hproducts – Hreactants
When Hproducts is greater than Hreactants then ΔrH is positive and heat is absorbed in the
reaction, and the reaction will be endothermic. For example,
H2(g) + I2(g) → 2HI (g); ΔrH = 52.5 kJ
When Hproducts is less than Hreactants then ΔrH is negative and heat is evolved in the
reaction, and the reaction will be exothermic. For example,
CH4(g) + 2O2(g) → CO2(g) + 2H2O (l); ΔrH = – 890.4 kJ
Enthalpy of a reaction changes with pressure and temperature.
1.3.2 Thermochemical equations

You are familiar with equations for chemical reactions as the symbolic representation
of a given reaction that consists of chemical formulae of the reactant(s) and product(s) and
the reaction condition. If we write the chemical equations which will specify heat energy
changes and states of the reactants and products. These are called the thermochemical
equations. For writing these equations, we follow the conventions listed below:
(i) The heat evolved or absorbed in a reaction is affected by the physical state of the
reacting substances. Therefore, gaseous, liquid and solid states are represented by putting
symbols (g), (l), and (s) alongside the chemical formulae respectively. For example, to
represent burning of methane in oxygen, we write
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) + heat
(ii) In writing thermochemical reactions, we denote the amount of heat evolved or
absorbed by a symbol ΔrH. The amount of heat evolved or absorbed is written after the
equation followed by semicolon. ΔrH is negative for exothermic reactions and it is positive
for endothermic reactions. For example:
An exothermic reaction is written as
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) ; ΔrH = – 891 kJ
Whereas an endothermic reaction is written as
H2 (g) + I2 (g) → 2HI (g) ; ΔrH = 52.2 kJ
(iii) Thermochemical equations may be balanced even by using fractional coefficients,

if so required. The coefficients of the substances of the chemical equation indicate the
number of moles of each substance involved in the reaction and the ΔrH values given
correspond to these quantities of substances.
(iv) In case, if the coefficients are multiplied or divided by a factor, ΔrH value must
also be multiplied or divided by the same factor. In such cases, the ΔrH value will depend
upon the coefficients. For example, in equation
H2 (g) + 1/2O2 (g) → H2O (g) ; ΔrH = – 242 kJ
If coefficients are multiplied by 2, we would write the equation
2H2 (g) + O2 (g) → 2H2O (g) ; ΔrH = 2 (– 242) = – 484 kJ
(v) When a chemical equation is reversed, the value of ΔrH is reversed in sign. This
is known as Lavoisier – Laplace law. For example
N2(g) + 3H2 (g) → 2NH3 (g); ΔrH = – 91.8 kJ
2NH3(g) → N2(g) + 3H2 (g); ΔrH = + 91.8 kJ
1.3.3 Standard enthalpy of reactions

Enthalpy of a reaction depends on the conditions under which a reaction is carried out.
It is, therefore, necessary that we must specify some standard conditions. The standard
enthalpy of reaction is the enthalpy change for a reaction when all the participating substances
are in their standard states. It is denoted by ΔrH0. The standard state of a substance at
a specified temperature is its pure form at 1 bar. For example, the standard state of liquid
ethanol at 298 K is pure liquid ethanol at 1 bar; standard state of solid iron at 500 K is
pure iron at 1 bar. Usually data are taken at 298 K.
1.3.4 Hess’s law of constant heat summation

Hess’s law can be stated as follows:
The standard enthalpy change for a reaction is the sum of standard enthalpies of a
sequence of reactions (at the same temperature and pressure); the overall reaction should
be capable of being represented by the given sequence of reactions.
Hess’s law is a direct consequence of the law of conservation of energy i.e. first law
of thermodynamics. It is not necessary that every reaction in the given sequence should be
conducted in a laboratory. A particular reaction can also be imaginary. The only requirement
is that the individual chemical reactions in the sequence must balance and add up to the
equation for a particular reaction. Also Hess’s law enables arithmetic operations of chemical
equations. This law is helpful in calculating enthalpies of reactions which cannot be
experimentally determined; what is required is to select a correct sequence of reactions.
We give below the use of Hess’s law in calculating the enthalpy of conversion of graphite
to diamond which is very difficult to determine.
C (graphite) + O2 (g) → CO2 (g); ΔrH1 = – 393.5 kJ
C (diamond) + O2 (g) → CO2 (g); ΔrH2 = –395.4 kJ
Then subtracting, we get
C (graphite) – C (diamond) = ΔrH3 = ΔrH1 – ΔrH2 = –393.5 kJ – (–395.4 kJ) =
1.9 kJ
Hence, we can write
C (graphite) → C(Diamond) ΔrH3 = 1.9 kJ
1.4. Standard enthalpies of formations

The enthalpy change when one mole of a pure compound is formed from its elements
in their most stable states is called the enthalpy of formation and is denoted by ΔfH0.
When the reacting elements and the products formed are all in their standard states,
the enthalpy change accompanying the chemical reaction is called the standard enthalpy of
formation and is denoted by ΔfH0. By convention, we take the standard enthalpy of
formation of an element in its most stable state as zero. For example:
C(Graphite) + O2(g) → CO2 (g) ; Δf H0 = – 393.5 kJ
This means that carbon dioxide is formed from its elements in their most stable states,
carbon in the form of graphite at room temperature and gaseous O2 and CO2 being at 1
bar.
1.5. Enthalpies of solution and dilution

Enthalpy of solution of a substance is the enthalpy change when one mole of it dissolves
in a specified amount of solvent. The enthalpy of solution at infinite dilution is the enthalpy
change observed on dissolving the substance in an infinite amount of solvent when the
interactions between the ions (or solute molecules) are negligible.
When an ionic compound dissolves in a solvent, the ions leave their ordered positions
on the crystal lattice. These ions are now more free in solution. But solvation of these ions
(hydration in case solvent is water) also occurs at the same time. This is shown
diagrammatically, for an ionic compound, AB (s)
The enthalpy of solution of AB(s), ΔsolH0, in water is, therefore, determined by the
selective values of the lattice enthalpy, ΔlatticeH0 and enthalpy of hydration of ions, ΔhydH0
as
Δsol H 0
= ΔlatticeH 0 + ΔhydH 0
For most of the ionic compounds, ΔsolH0 is positive and the dissociation process is
endothermic. Therefore the solubility of most salts in water increases with rise of temperature.
If the lattice enthalpy is very high, the dissolution of the compound may not take place at
all.
It is known that enthalpy of solution is the enthalpy change associated with the addition
of a specified amount of solute to the specified amount of solvent at a constant temperature
and pressure. This argument can be applied to any solvent with slight modification. Enthalpy
change for dissolving one mole of gaseous hydrogen chloride in 10 mol of water can be
represented by the following equation. For convenience we will use the symbol aq. For
water
HCl (g) + 10 aq. → HCl.10 aq. ΔH = –69.01 kJ / mol
Let us consider the following set of enthalpy changes:
(S-1) HCl (g) + 25 aq. → HCl.25 aq. ΔH = –72.03 kJ / mol
(S-2) HCl (g) + 40 aq. → HCl.40 aq. ΔH = –72.79 kJ / mol
(S-3) HCl (g) +  aq. → HCl.  aq. ΔH = –74.85 kJ / mol
The values of ΔH show general dependence of the enthalpy of solution on amount of

solvent. As more and more solvent is used, the enthalpy of solution approaches a limiting
value, i.e, the value in infinitely dilute solution. For hydrochloric acid this value of ΔH is
given above in equation (S-3).
If we subtract the first equation (equation S-1) from the second equation (equation S-
2) in the above set of equations, we obtain–
HCl.25 aq. + 15 aq. → HCl.40 aq. ΔH = [ –72.79 – (–72.03)] kJ / mol
= – 0.76 kJ / mol
This value (–0.76 kJ/mol) of ΔH is enthalpy of dilution. It is the heat withdrawn from
the surroundings when additional solvent is added to the solution. The enthalpy of dilution
of a solution is dependent on the original concentration of the solution and the amount of
solvent added.
1.6. Bond energy, bond dissociation energy and resonance

energy
In a chemical reaction, we have seen that energy is either absorbed or evolved. The
origin of this energy changes in a chemical reaction are a result of energy changes in
breaking and forming of bonds. Let us consider the gaseous reactions, because in these,
we encounter the energy changes due to breaking and forming of bonds only. At high
temperature, hydrogen molecules dissociate into atoms as
H2 (g) → H (g) + H (g); ΔrH0 = 435 kJ/mol
The heat absorbed in this reaction is used to break the chemical bonds holding the
hydrogen atoms together in the H2 molecules. For a diatomic molecule like H2(g), we
define bond dissociation energy as the enthalpy change of the reaction in which one mole
of the gaseous molecules are dissociated into gaseous atoms.
Now, let us consider a polyatomic molecule like CH4 (g). The dissociation may involve
fragmenting the molecules into an atom and a group of atoms, called a radical, as in
CH4 (g) → CH3 (g) + H (g); ΔrH0 = 431.8 kJ/mol
CH3 (g) → CH2 (g) + H (g); ΔrH0 = 471.1 kJ/mol
CH2 (g) → CH (g) + H (g); ΔrH0 = 421.7 kJ/mol
CH (g) → C (g) + H (g); ΔrH0 = 338.8 kJ/mol
We can observe here that each of these equation represent the dissociation of C-H
bond but the energies required for them are different. Though all the C-H bond in CH4 are
equivalent, the dissociation energies are not same. This is due to the fact that once a C-
H bond dissociated, the remaining species has different electronic distributions.
We can add these four equations to get
CH4 (g) → C (g) + 4H (g); ΔrH0 = 1663.4 kJ/mol
In this reaction the methane molecule has got converted into its constituent atoms
therefore the enthalpy change is called enthalpy of atomization of methane. If we divide the
enthalpy of atomization of methane by 4, we get an average value (1663.4/4 = 415.9 kJ/
mol) for the bond enthalpy for C-H bond.
Now if we want to determine the bond enthalpy in ethane (C2H6), here two types of
bond exist, C-H and C-C. We assume that the bond enthalpy for C-H bond in ethane is
same as that of methane. The atomization of ethane is given by the expression
C2H6 (g) → 2C (g) + 6H (g); ΔrH0 = 2842.4 kJ/mol
The enthalpy of atomization of ethane would be equal to the bond enthalpies of six C-
H bond and one C-C bond. If we subtract the bond enthalpies of six C-H bonds from
the enthalpy of atomization we can get the bond enthalpy for C-C bond. Thus, bond
enthalpy for a given bond refers to the average bond dissociation energy for the same bond
in a number of molecules having the said bond. Using Hess’s law, bond enthalpies can be
calculated. Again bond enthalpy data can be used to calculate ΔrH for a chemical reaction
occurring in gaseous state by making use of difference in energy absorbed in breaking the
bonds in reactants and energy released in formation of bonds in products.
ΔrH = Σ B.E. (reactants) – Σ B.E. (products).
Using bond energy and enthalpy of formation data resonance energy in a molecule can
be calculated. When a compound shows resonance, there is considerable difference between
the heat of formation as calculated from bond energies and that determined experimentally.
Resonance energy = Experimental or actual heat of formation - Calculated heat of
formation.
For example the resonance energy of N2O can be calculated if observed ΔfHo (N2O)
is 82 kJ mol–1, B.E of N ad N is 946 kJ mol–1, B.E of N  N is 418 kJ mol–1, B.E of
O = O is 498 kJ mol–1; B.E of N = 0 is 607 kJ mol–1.
1
So we can write, N 2 (g)  O 2 (g)  N 2O
2
1
In another way we can write, N  N  O  O  N  N  O
2
So, calculated ΔfHo (N2O) = [B.E (Na=N)
+ B.E (O = O)
] – [B.E (N=N)
+ B.E (N=O)
]
 498 
= 946  – [418 + 607] = + 170 kJ/mole
 2 
Hence, Resonance energy = observed ΔfHo – calculated ΔfHo

= 82 – 170 = – 88 kJ/mol
1.7. Variation of enthalpy of a reaction with temperature

– Kirchhoff’s equation
We have learnt that the enthalpy of different types of reactions can be calculated with
the help of enthalpy of formation of different compounds. However, most of the data
available on enthalpy of reaction or enthalpy of formation of compounds are at 298 K. If
the enthalpy of reaction required at some other temperature, we need to know the temperature
dependence of the enthalpy of reaction. The enthalpy of reaction at a desired temperature
can be obtained from the enthalpy of reaction at some other temperature with the help of
Kirchhoff’s equation. Let us derive Kirchhoff’s equation.
We know that: ΔrH0 = H0(products) –H0(reactants)
Differentiating with respect to temperature we get,
d
dT
 
r H 0 
d 0
dT
H (products) 
d 0
dT
H (reactants)
d 0
As H  C0p we can write
dT
d
dT
 
r H 0  C0p (products)  C0p (reactants)
d
dT

r H 0   C0p 
Writing the equation in differential form
 
d r H 0   C0p dT
Integrating the equation between temperature T1 and T2,
T2
0 0

T1 d  r H  T1  CpdT
2 T
r H0 (T2 )  r H 0 (T1 )   C0p  T2  T1 
Rearranging,
r H0 (T2 )  r H0 (T1 )   C0p  T2  T1 
This is the Kirchhoff’s equation that gives the temperature dependence of enthalpy
change for a reaction.
1.8. Third Law of thermodynamics and calculation

absolute entropies of substances
The entropy of any pure crystalline substance approaches zero as the temperature
approaches absolute zero. This is called third law of thermodynamics. This is so because
there is perfect order in a crystal at absolute zero. The statement is confined to pure
crystalline solids because theoretical arguments and practical evidences have shown that
entropy of solutions and super cooled liquids is not zero at 0 K. The importance of the
third law lies in the fact that it permits the calculation of absolute values of entropy of pure
substance from thermal data alone. For a pure substance, this can be done by summing
qrev/T increments from 0 K to 298 K. Standard entropies can be used to calculate standard
entropy changes by a Hess’s law type of calculation.
1.9. Summary
In this unit we have started our discussion by revisiting the important terms and laws
of thermodynamics. Then we have focused our discussion on thermochemistry – the study

of the heat changes associated with chemical reactions. We have discussed about important
principles and definitions of thermochemistry. We have highlighted the concept of standard
state and standard enthalpies of formations, enthalpies of solution and dilution. We have
shown how to calculate bond energy, bond dissociation energy and resonance energy from
thermochemical data. Variation of enthalpy of a reaction with temperature is discussed and
Kirchhoff’s equation was derived. Finally third law of thermodynamics was stated and
calculation absolute entropies of substances were discussed.
1.10. Questions
1. What is standard enthalpy of a reaction?
2. Why the formation enthalpy of Graphite is taken as zero?
3. What is an exothermic and endothermic reaction?
4. Describe Hess’s law and explain.
5. Derive the Kirchhoff’s equation relating to the effect of temperature on the
reaction enthalpy of a reaction.
6. Calculate ΔrHo for the reaction C (graphite) + O2 (g) → CO (g) at 298 K.,
using the following thermochemical equations:
C (graphite) + O2 (g) → CO2 (g); ΔrHo = – 393.5 kJ
CO (g) + 1/2O2 (g) → CO2 (g); ΔrHo = – 283.5 kJ
(Ans. -110 kJ)
Unit 2  Chemical Equilibrium
Contents
2.0. Objectives
2.1. Introduction
2.2. Free energy change in a chemical reaction
2.3. Law of mass action
2.4. Thermodynamic derivation of the law of chemical equilibrium
2.5. Distinction between ΔG and ΔG0
2.6. Relationships between Kp, Kc and Kx for reactions involving ideal gases
2.7. Le Chatelier's principal
2.7.1. Effect of change of concentration
2.7.2. Effect of change of pressure
2.7.3. Effect of change of temperature
2.7.4. Effect of catalyst
2.8. Summary
2.9. Questions
2.0. Objectives
After going through this unit, we will be able to know about
 reversible and irreversible reactions.
 free energy change in a chemical reaction.
 law of mass action.
 relation between free energy and equilibrium constant
 express the equilibrium constant in different ways
 Le Chatelier’s principle and its applications.
2.1. Introduction
In general, chemical reactions can be divided into two types - reversible and irreversible.
Irreversible reactions are said to go to completion, implying thereby that the reaction
proceeds until at least one of the reactants is completely used up. So in the irreversible
reactions, the same reactants cannot be formed back from the products under normal set
of experimental conditions. On the other hand, all those reactions which appear not to
proceed beyond a certain stage after sometime even when the reactants are still available
are reversible reactions. This stage of the system is the dynamic equilibrium and the rates
of the forward and reverse reactions become equal. It is due to this dynamic equilibrium
stage that there is no change in the concentrations of various species in the reaction
mixture. The present unit discusses the meaning of this state of equilibrium and how the
equilibrium composition of the reactants and products are correlated with change in Gibb’s
free energy.
2.2. Free energy change in a chemical reaction

While discussing about the criteria for reversible and irreversible reactions in
thermodynamics, it was concluded that if the free energy change of a chemical reaction is
negative, the reaction can take place spontaneously, that is it is feasible. If the free energy
change is zero, the reaction is in a state of equilibrium and if the free energy change is
positive, the reaction would not proceed. By definition, G = H - TS so that, at constant
temperature,
ΔG = ΔH – TΔS (1)
where, ΔG is the change in free energy of the reaction, ΔH is the change in enthalpy of
the reaction and ΔS is the change in entropy of the reaction.
From the above equation it is evident that the spontaneity of the reaction is dependent
on the overall value of the two factors - energy factor ÄH and the entropy factor, TΔS.
For a reaction to be spontaneous, ΔG value should be negative. For this, ΔH should be
negative and TΔS should be positive. When both factors are favourable then the value of
ΔG will have large negative value, and the reaction will be highly feasible.
Now suppose the energy factor is favourable, i.e., ΔH is negative, but the entropy
factor is not favourable i.e., TΔS is also negative. In such case, the feasibility of the reaction
will be determined by the factor which predominates. So if the numerical value of ΔH is
greater than TΔS, then the reaction is feasible.
Again, if the energy factor does not favour, i.e., ΔH has a positive value but the
entropy factor favours the reaction, i.e., TΔS is positive then the reaction will occur if TΔS
is numerically greater than ΔH.
If neither energy factor nor entropy factor predominates then ΔH is numerically equal
to TΔS. Then the value of ΔG will be zero. Under these circumstances, the reaction will
be in a state of equilibrium, i.e., no net reaction will occur in any direction.
Standard free energy change (Δ ΔGo): The standard free energy change of a reaction
is defined as the free energy change of a reaction when the reactants and products are in
their standard states (25 oC, 1 atm pressure). At this condition the equation 1 may be
written as
ΔGo = ΔHo – TΔSo (2)
where ΔHo is the standard enthalpy change of the reaction and ΔSo is the standard entropy
change of the reaction at the temperature T.
2.3. Law of mass action

Our experimental observations tell us that most of the chemical reactions when carried
out in closed vessels do not go to completion. The reactants may still be present but they
do not appear to change into products. In this situation the rate of the back reaction
becomes equal to the rate of the forward reaction. The composition of the reaction mixture
at a given temperature is the same irrespective of the initial state of the system, i.e.,
irrespective of the fact whether we start with the reactants or the products. The reaction
is said to be in a state of equilibrium. The attainment of equilibrium can be recognised by
noting constancy of observable properties such as pressure, concentration, density or
whichever may be suitable in a given case. The relationship between the quantities of the
reacting substances and the products formed can be correlated readily with the help of the
law of mass action.
The law of mass action may be stated as follows:
The rate at which a substance reacts is proportional to its active mass and the rate of
a chemical reaction is directly proportional to the product of the active masses of the
reacting substances.
If we consider a general chemical reaction
aA + bB  mM + nN
According to the law of mass action, assuming that active masses are equivalent to the
molar concentration,
the rate of the forward reaction, rf  [A]a [B]b i.e. rf  k f [A]a [B]b
and the rate of the reverse reaction, rr   M m [N]n i.e, rr  k r [M]m [N]n
where kf and kr are proportionality constants and square brackets represent the molar
concentration of the entities enclosed. The constant k-f is rate constant of the forward
reaction and kr is the rate constant of the reverse or backward reaction. Now at equilibrium,
the rate of forward reaction is equal to the rate of the reverse reaction, that is,
k f [A]a [B]b  k r [M]m [N]n
kf [M]m [N]n
  K eq  (3)
kr [A]a [B]b
The constant Keq is called the equilibrium constant of the reaction. Equilibrium constant
being the ratio of the concentrations raise to the stoichiometric coefficients. Therefore, the
n
unit of the equilibrium constant =  Mole L1  .
where, Δn = (sum of stoichiometric coefficients of products – sum of stoichiometric

coefficients of reactants)
Equation 3 represents the law of chemical equilibrium.
The equilibrium concentrations in equation 3 can be written in terms of activities (ai),
partial pressure (pi), molar concentrations (ci) or mole fraction (xi) of the species involved
in the reaction. Consequently, Keq will have different numerical values for a given chemical
reaction.
Example 1: Calculate Kc for the reaction, H2 (g) + I2 ↔ 2HI (g), if the reaction had
been started with 1 mole of H2 (s) and 3 mole of I2 (g). At the equilibrium the moles of
HI formed is 1.5 moles. The volume of the reaction vessel is 2 litre.
Solution:
H2(g) + I2 ↔ 2HI(g)
Initially moles 2 3 0
Moles at eqm. 2 – x 3 – x 2x
Conc. of eqm.
From question, 2x = 1.5
x = 0.75
[H2] = (2–x)/2 =1.25/2

[I2] = (3–x)/2 = 2.25/2
[HI] = 1.5/2
Therefore Kc for the reaction = [HI]2 / [H2].[I2]
By putting the values we get Kc = 0.8
2.4. Thermodynamic Derivation of the Law of Chemical

Equilibrium
Consider once again the general reversible chemical reaction
aA + bB mM + nN
where the reactants and the products are assumed to be ideal gases.
We know that chemical potential (i.e., Gibbs free energy) of reactants consisting of a
moles of A and b moles of B is given by the expression
Greactants = aμA + bμB (4)
where μA and μB are the chemical potentials of the species A and B, respectively. Similarly,
for the products we have
Gproducts = mμM + nμN (5)
In each case, pressure and temperature are constant. The free energy of the reaction
is equal to the difference between the free energy of the products and that of the reactants.
So
(ΔG)reaction = Greactants – Gproducts
= (mμM + nμN) – (aμA + bμB) (6)
Now at equilibrium, the free energy change ΔG = 0. So the equation 6 becomes
(mμM + nμN) – (aμA + bμB)= 0 (7)
The chemical potential of the ith species in the gaseous state is given by
i  i0  RT ln pi (8)
where, pi is the partial pressure of the ith component and the i0 is its standard chemical
potential (i.e., when the partial pressure of the ith component is unity). So from equation
7 and 8 we can obtain

M M N  
 m 0  RT ln p  n 0  RT ln p  
 N 
 
 A A B  
a 0  RT ln p  b 0  RT ln p   0
B 
  (9)
pm n
or RT ln M pN
paA p B
b 
   
   m0M  n0N  a0A  b0B 

   G 0products  G 0reactant 
 

  G 0 reaction (10)
pm n
M pN
0
or,  e G RT (11)
paA p B
b
Since ΔG0 depends only on temperature and R is the gas constant, hence the right
hand side of equation 11 is a constant at constant temperature. Thus
pm n
M pN  constant  K p (12)
paA p B
b
This is the law of chemical equilibrium.

It can be easily shown that if the chemical potentials of the various species are expressed
in terms of mole fractions (xi), then
i  i0  RT ln x i (13)
So we obtain similar equation like equation 12
xm n
M xN  Kx (14)
x aA x B
b
If the chemical potentials of the various species are expressed in terms of molar
concentrations (ci), then
i  i0  RT ln ci (15)
From which we obtain the following expression
cm n
M cN  Kc (16)
caA cB
b
Equation 12, 14 and 16 are the expressions of Kp, Kx, and Kc respectively.
van’t Hoff reaction isotherm:
From equation 11 and 12 we can have
0
K eq  eG RT (17)
or G 0   RT ln K eq (18)
The equation 18 is called van’t Hoff reaction isotherm. It may be used to calculate the
change in free energy of a reaction in the standard condition (ÄG0) from the equilibrium
constant and vice-versa.
2.5. Distinction between ΔG and ΔG0

For a reaction ΔG0 is the difference in the free energy of products and reactants when
all of them are in their standard states. This does not refer to the actual reaction at
equilibrium. ΔG, however, refers to the difference in the free energy of products and
reactants at the actual measured concentrations (or partial pressures) of the components.
When ΔG=0, the reaction is at equilibrium and the concentrations (or the partial pressures)
of the components are those which appear in the equilibrium constant expression.
2.6. Relationships between Kp, Kc and Kx for reactions

involving ideal gases
Relation between Kp and Kc:
For an ideal gaseous mixture we can write
piV = niRT
n
pi  i RT  ci RT
V
Where, ci (=ni/V) is the molar concentration of the ith component in the mixture of
total volume V.
For the reaction
aA + bB mM + nN
We can write, pA = cART, pB = cBRT, pM = cMRT, pN = cNRT
So from equation 12 we get
m n
pm n
MpN  c M RT   c N RT  m n
cM cN
Kp    (RT)(m  n)  (a  b)
p aA p B
b
 cA RT a  cBRT b caA cB
b
= KcRTΔn
where Δn = (m + n) – (a + b)
Relation between Kp and Kx:
In an ideal gaseous mixture, each component obeys Dalton’s law of partial pressure,
i.e.,
where, P is the total pressure and pi is the partial pressure of the ith component with
mole fraction xi in the mixture.
For the reaction
aA + bB  mM + nN
we have pA = xAP, pB = xBP, pM = xMP, pN = xNP
m n
pm n
MpN  x M P   cN P  xm xn
Kp    M N (P)(m  n)  (a  b)  K x P n (20)
paA pB
b
 x A P a  c B P  b x aA x B
b
where Δn = (m + n) – (a + b)
So from equation 19 and 20 we can write
K p  K c RT n  K x P n (21)
This is the relation between different equilibrium constants.

If Δn = 0, (m + n) = (a + b) (i.e., the number of moles of products equals to the
number of moles of reactants), then
Kp = Kc = Kx
2.7. Le Chatelier’s principal

The equilibrium expressions derived so far are very useful to perform numerical
computations to check the effects of change in pressure, temperature or volume for a
system under equilibrium. We can find out the effect of such factors on the system under
equilibrium with the help of expressions such as, Eq. 12, 14 and 16. However, often one
is more interested in predicting qualitatively the results of a change brought about by
external forces on the system under equilibrium. The effect of concentration, temperature
and pressure on a system in equilibrium can be predicted with the help of a generalization
first proposed by a French chemist Le-Chetelier in 1884. After his name, this generalization
is known as Le-Chatelier’s principle. It states as follows:
If a stress is applied to any system under equilibrium, the system would tend to
shift in such a way so as to neutralise the effect of that stress (if possible).
The stress for a chemical reaction could be in the form of a change in pressure,
temperature or concentration at equilibrium. According to the above principle then, the
equilibrium would shift in such a direction so that the effect of these, changes is neutralised.
We shall consider the effect of each one of these factors on equilibrium.
2.7.1 Effect of change of concentration

Let us consider the following reaction at equilibrium,
H2 (g) + I2 (g) 2HI (g)
Now, if we add some H2 to the equilibrium mixture, it will disturb the equilibrium.
According to Le Chatelier’s principle, the equilibrium would shift in such a way so as to
oppose the effect of this excess H2. It can do so by using up this excess H2 to react with
more I2 to give more of HI. We describe this process by saying that the final position of
equilibrium has shifted to the right of the equation. In this final state of equilibrium, then,
more amount of HI is formed as compared to earlier equilibrium state. Just the opposite
would be the fate of the reaction if, instead of H2 some HI is added to the system under
equilibrium. In short, by changing the concentration at equilibrium, the reaction will move
forward or in the reverse direction so that the value of the equilibrium constant remains the
same.
2.7.2 Effect of change of pressure

If we consider the above reaction again and suppose that the pressure of the system
is increased by reducing the volume of the container, the system should react in such a way
so as to reduce the effect of the increase in pressure. However there is no way - by which
this can be achieved. The forward reaction or the reverse reaction will not be favoured by
pressure change since the total number of moles of the reactants is the same as the total
number of moles of the products.
However, the situation changes if we consider the synthesis of ammonia:
N2 (g) + 3H2 (g)  2NH3 (g)
If the pressure of the system is increased at the equilibrium as was done in the previous
example, the effect of this increase could be eliminated by the formation of more ammonia.
This becomes obvious if you realise that the total number of moles of the reactants is four
as compared to the moles of product which is two. Four moles will exert greater pressure
than two moles, so, if the system wants to reduce the extra pressure, it can do so by
moving in the forward direction. On the other hand, if we decrease the external pressure
on the system, more of ammonia will decompose to give nitrogen and hydrogen. Thus, if
we want to produce ammonia in the industry, it is preferable to carry out the reaction at
high pressures.
Comparing the two reactions given above, we can conclude that changes in pressure
at equilibrium will affect the amounts of products formed for only those reactions where the
total numbers of moles of the reactants are different from the total number of moles of the
products.
2.7.3 Effect of change of temperature

Consider once again the synthesis of ammonia from nitrogen and hydrogen which is
an exothermic reaction.
N2 (g) + 3H2 (g)  2NH3 (g) ΔH = – 92.38 kJ

If the temperature of the system is increased at equilibrium then according to Le
Chatelier’s principle, the system should react in such a way so as to neutralise this effect.
Let us see how this is possible. We know that the formation of ammonia is an exothermic
reaction and, therefore, the reverse reaction of decomposition of ammonia will be endothermic.
Thus, the excess heat supplied by raising the temperature of the system can be absorbed
by the system if the reaction goes more towards left. This will increase the amounts of N2
and H2 and decrease the amount of NH3 at equilibrium.
We can generalise this observation as with the increase of the temperature of the
system the amount of the products will decrease and the amount of the reactants will
increase for an exothermic reaction. Just the opposite will be true for all endothermic
reactions. The effect of these factors gains special importance for the production of a
substance on large scale. In any industrial production of a substance it is imperative to
know the optimum conditions of temperature, pressure and concentrations in order to get
the maximum yield at a minimum cost. For instance, in the production of ammonia we know
from Le Chatelier’s principle that high pressure and high concentration of N2 and H2 will
favour the reaction. Similarly, the above principle also predicts that the reaction would be
more favourable at low temperatures since it is exothermic. However, we cannot carry out
the reaction at a very low temperature because the rate of the reaction becomes too slow
at lower temperatures. Hence the reaction is performed at pressures of several megapascals
and at a optimum temperatures between 650 and 750 K in presence of finely divided iron
as catalyst.
2.7.4 Effect of catalyst

There is no effect on addition of a catalyst on the equilibrium state. This is because
catalyst increases the rate of forward reaction as well as rate of backward reaction to the
same extent. It simply helps to achieve the equilibrium quickly. It may be further noted that
catalyst has no effect on the equilibrium concentration of a reaction mixture.
2.8. Summary
In this unit we have discussed reversible and irreversible reaction and the free energy
change in a chemical reaction. Then we have discussed the meaning of chemical equilibrium
and the law of mass action. A general expression for the equilibrium constant was derived
from the basic principles of thermodynamics. Different forms of the general expression
were then utilised in understanding the equilibrium. We then learnt Le Chatelier’s principle
and its use in predicting the shift in the position of equilibrium by the changes brought about
in concentration, temperature and pressure in the system.
2.9. Questions
1. Describe the Law of mass action.
2. Derive the relation between Kp and Kc.
3. Write a short note on Le Chatelier’s principal.
4. Explain the effect of pressure and temperature in the following reaction
N2 (g) + O2 (g)  2NO (g); ΔH = – 43.2 kJ
5. At 20 oC the Kp of the reaction 2NO (g) + Cl2 (g)  2NOCl (g) is 1.9 ×
10-3 atm-1. Calculate the value of K-c at that temperature.
(Ans. 45649.4 L mol-1)
6. At equilibrium, the concentrations of N2 = 3.0 × 10–3 M, O2 = 4.2 × 10–3 M and
NO = 2.8 × 10–3 M in a sealed vessel at 800 K. What will be Kc for the
reaction
N2 (g) + O2 (g)  2NO (g) (Ans. 0.622)
Unit 3  Ionic Equilibrium
Contents
3.0. Objectives
3.1. Introduction
3.2. Strong and weak electrolytes
3.3. Degree of ionization
3.4. Ionization of weak acids and bases
3.5. Ionization constant and ionic product of water
3.6. pH scale
3.7. Common ion effect
3.8. Salt hydrolysis - hydrolysis constant, degree of hydrolysis and pH for different
salts
3.9. Buffer solutions
3.10. Solubility and solubility product of sparingly soluble salts
3.11. Summary
3.12. Questions
3.0. Objectives
After going through this unit, we will be able to know about
 Strong and weak electrolytes.
 Degree of ionization.
 Ionic product of water.
 pH scale and pH calculation.
 Common ion effect and its applications.
 Salt hydrolysis.
 Buffer solution and buffer action.
 Solubility and solubility product of sparingly soluble salts.

 Application of solubility product in precipitation reaction.
3.1. Introduction
There are numerous equilibria that involve ions only. In the following sections we will
study the equilibrium involving ions. It is well known that the aqueous solution of sugar
does not conduct electricity. However, when common salt (NaCl) is added to water it
conducts electricity. Also, the conductance of electricity increases with increase in
concentration of common salt. Michael Faraday classified the substances into two categories
based on their ability to conduct electricity. One category of substances conduct electricity
in their aqueous solutions and are called electrolytes while the other do not conduct
electricity are, referred to as non electrolytes. Faraday further classified electrolytes into
strong and weak electrolytes. Strong electrolytes on dissolution in water are ionized almost
completely, while the weak electrolytes are only partially dissociated. For example, an
aqueous solution of sodium chloride is comprised entirely of sodium ions and chloride
ions, while that of acetic acid mainly contains unionized acetic acid molecules and only
some acetate ions and hydronium ions. This is because 100% ionization in case of sodium
chloride as compared to less than 5% ionization of acetic acid which is a weak electrolyte.
It should be noted that in weak electrolytes, equilibrium is established between ions and
unionized molecules. This type of equilibrium involving ions in aqueous solution is called
ionic equilibrium.
3.2. Strong and weak electrolytes

An electrolyte is defined as a compound whose aqueous solution or molten state
conducts electricity. On the other hand, a compound whose aqueous solution or molten
state does not conduct electricity is called a non electrolyte. The conductance by an
electrolyte is due to the presence of ions produced by the dissociation of the substance.
However, different electrolytes dissociate to different extents. Acids, bases and salts come
under the category of electrolytes.
Depending upon the degree of dissociation or ionization, the electrolytes are divided
into two categories, called ‘strong electrolytes’ and ‘weak electrolytes’.
Strong Electrolytes: These are the substances which dissociate almost completely
into ions in aqueous solution and hence are a very good conductor of electricity.
Examples:
Acid: HCl, HNO3, H2SO4 etc.
Base: NaOH, KOH, Ba(OH)2 etc.
Salt: NaCl, KCl, CaCl2, KNO3, CuSO4 etc.
Weak Electrolytes: These are the substances which dissociate to a small extent in
aqueous solution and hence conduct electricity also to a small extent.
Examples:
Acids: H2CO3, CH3COOH, HCN etc.
Base: NH4OH, Al(OH)3, Zn(OH)2 etc.
Salt: MgCO3, PbCl2, BaCO3 etc.
3.3. Degree of ionization

As we know that the weak electrolytes do not ionize completely, so an equilibrium will
reach between the ionized and unionized species in the solution. The degree of ionisation
may be defined as the fraction of total amount of a weak electrolyte that exists in the
ionized form. It is denoted by a Greek letter ‘α’.
Number of molecules dissociated at equilibrium

So,   (1)
Total number of molecules taken
Consider a weak electrolyte AB, which dissociates in water and forms A+ and B-. So
an equilibrium will be established in solution.
Let the initial concentration of the weak electrolyte, AB is c mol/L and α is the degree
of dissociation. Then at equilibrium the concentration of A+ and B- will be αc mol/L and
concentration of AB will be (c- αc) mol/L.
AB  A+ + B-
Initial concentration: c 0 0
Equilibrium concentration: c(1–α) αc αc
So according to the law of mass action the equilibrium constant can be written
as
 A    B 
K      where K is the dissociation constant or ionization constant.
 AB
c  c  2c
So, K  (2)
c(1   ) 1  
As for a weak electrolyte α << 1; we can take (1 – α) = 1.
K
K   2c or,   (3)
c
So if we know the value of the dissociation constant of the weak electrolyte and
the concentration of the weak electrolyte we can find its degree of dissociation or
ionization.
Factors affecting degree of ionization:

The degree of ionization of a weak electrolyte depends on the following factors:
1. Nature of electrolytes: The degree of ionization depends upon the nature of
electrolytes. Strong electrolytes have a high degree of ionization (value of á is
equal to 1) while weak electrolytes have a low degree of ionization.
2. Nature of solvent: The ionizing power of the solvent depends upon its dielectric
constant. The greater the value of the dielectric constant greater will be ionizing
power of solvent and the greater will be the degree of ionization.
3. Dilution: From equation 3, we can observe that degree of ionization is inversely
1
proportional to the concentration i.e.   . This is known as the Ostwald’s
c
dilution law. So, the degree of ionization increases with an increase in
dilution. At infinite dilution, even the weak electrolytes are almost completely
ionized.
4. Temperature: The degree of ionization increases with the increase in
temperature.
5. Common ion effect: Due to the common ion effect, the degree of ionization of
weak electrolytes is decreased or suppressed. The suppression of degree of
ionization of weak electrolyte by the addition of strong electrolyte having common
ion is called common ion effect.
3.4. Ionization of weak acids and bases

Ionization of weak acid:
Weak acids are dissociated to a very small extent in the solution and the ions produced
on dissociation are in equilibrium with the undissociated molecules in solution
If HA represents any weak acid, we can write the dissociation reaction as,
HA  H+ + A–
and the corresponding dissociation constant expression as,
H   A  
Ka      (4)
 HA 
Ka is the dissociation constant of the acid. If the initial concentration of the
acid is c and α is the degree of dissociation, then the equilibrium concentrations would
be,
HA  H+ + A–
Equilibrium concentration: c(1–α) αc αc
Substituting these values in equation 4, we get
 2c
Ka  (5)
1 
for a weak acid á << 1; we can take (1 – α) = 1.
Ka
 (6)
c
From this equation we can calculate the degree of dissociation of a weak acid.
Now the concentration of H+ ion in the solution can be calculated using equation 6
 H    c  K a  c  K c (7)
  a
c
Ionization of weak base:

Similarly for a weak base BOH, we can write the dissociation reaction as,
BOH  B+ + OH-
and the corresponding dissociation constant expression as,
 B   OH  
Kb     
(8)
 BOH 
Kb is the dissociation constant of the weak base. If the initial concentration of the
base is c and α is the degree of dissociation, then the equilibrium concentrations would
be,
BOH  B+ + OH-
Equilibrium concentration: c(1-α) αc αc
Substituting these values in equation 8, we get
 2c
Kb  (9)
1 
for a weak base α << 1; we can take (1 – α) = 1.
Kb
 (10)
c
From this equation we can calculate the degree of dissociation of a weak base.
Now the concentration of OH- ion in the solution can be calculated using equation 10
OH    c  K b  c  K c (11)
  b
c
3.5. Ionization constant and ionic product of water

Pure water is poor conductor of electricity. This shows that water is weak electrolyte
i.e., it is ionized to a very small extent as
H2O  H+ + OH– (12)
or 2H2O  H3O+ + OH– (13)
Although eqs. 12 and 13 are representations of the same equilibrium, eq. 13 is a
better representation in the sense that a free proton having a high charge density and
extremely small size is incapable of free existence in solution and, therefore, gets attached
to a molecule of water. However, since our calculations on equilibrium constant will not
be different in case of either representation, for simplicity sake, we represent the water
equilibrium by eq 12.
Applying law of chemical equilibrium, its dissociation constant K, is given by
 H   OH  
K  
(14
 H 2O 
K[H2O] = [H+] [OH–] (15)
In pure water the concentration of H2O molecules is approximately 55.4 M and since
the dissociation of H2O is negligibly small in comparison with its concentration, we can
safely assume that the concentration of H2O at equilibrium is a constant quantity. Thus, K
[H2O] in eq. 15 can be replaced by a new constant.
Kw = [H+] [OH–] (16)
where Kw is called the dissociation constant of water or, more commonly, the ionic product
of water. Hence ionic product of water may be defined as the product of the molar
concentration of H+ and OH- ions.
The value of Kw at 298 K (25 0C) is experimentally determined as Kw = 1.0 ×
10-14.
Hence, [H+] [OH–] = 1.0 × 10–14 (17)
Since the amount of H+ and OH- produced by the dissociation of pure water is equal,
concentration of each ion in solution is given by
 H   OH    K  1.0  107 (for pure water (18)

   w
Like any equilibrium constant, Kw also depends on temperature as with increase of

temperature degree of dissociation of water increases. So the concentration of H+ and OH-
also increases. The following table shows the variation of Kw with temperature.
T(oC) Kw (mol2 dm6)

0 0.114 × 1014
25 1.008 × 1014
50 5.476 × 1014
100 51.3 × 1014
3.6. pH scale
From the above discussion we have seen that the equilibrium of water is given by
equation 14
 H   OH  
K  
 2 
H O
Now suppose that we add a small quantity of an acid to water, thereby increasing
the concentration of H’ ions at equilibrium. The equilibrium will immediately shift back to
oppose the effect of this increase by the combination of the added H+ ions with some
OH- ions to form undissociated water till eq.14 is satisfied. Once the equilibrium is re-
established, the concentration of the hydrogen ion will be more than the concentration of
the hydroxyl ion in solution. Hence, at 298 K, whenever the concentration of hydrogen
ion in water is greater than 1.0 × 10-7 M, we call the solution to be acidic and whenever
it is less than 1.0× 10-7 M, we call it a basic solution. It is quite inconvenient to express
these concentrations by using powers of 10. In 1909 a Danish botanist S.P.L. Sorensen
proposed a logarithmic scale (called pH scale) for expressing the concentrations of H+
ions. He defined pH as the negative logarithm of the molar concentration of hydrogen
ions. That is,
pH = – log10 [H+] (19)
[H+] = 10–pH (20)

where H+ ion concentration is expressed in mol dm-3. The concept of negative logarithm
can be used for defining the concentration of other ions also. For example, pOH represents
the concentration of OH- ion in solution and pM represents the concentration of the metal
ion, M, in solution.
Pure water, where H+ ion and OH- ion concentration are both equal to 1.0 ×
10-7 (at 298 K), will thus have a pH value of 7. An acidic solution means that the pH
should be less than 7 and a basic solution should have pH greater than 7.
Let us consider a few simple calculations to see quantitatively as to what happens
to the self-ionisation equilibrium of water when we add a small quantity of a strong acid
to it. Consider a solution containing 0.010 mole of HCl in one dm3 of water. The
concentration of hydrogen ion due to HCl will be 1.0 × 10-2 M. This addition of acid
will disturb the water equilibrium and this equilibrium will shift to left so that dissociation
of water is suppressed. Thus, the concentration of H+ ions produced by the self-ionisation
of water (  10–7 M) is negligible in comparison with the H+ ion produced by the added
acid (10–2 M). Hence, the contribution due to water dissociation can be neglected in
such a case and the pH of the solution will be 2. The concentration of OH– will then
be given by,
14
OH    K w  1 10  11012
  [H] 1 107
or pOH = 12
We can state this in a different way that, in 10-2 M acid solution, the concentration
of OH- ion (10–12 M in the above example) is less than the concentration of H+ ion
(10–2 M) and, the product of the two is always constant, and is equal to 1.0 × 10–14.This
can be expressed as,
pH + pOH = 14 = – log Kw (21)
Thus, in pure water or a dilute solution of an acid or a base, we can express the
concentration of H+ or OH- by simply stating the pH of the solution. We have also studied
that the contribution due to self-ionisation of water is negligible in cases of solution of
strong acids and bases as well as of moderately concentrated solutions of weak acids
and weak bases. However, dealing with very dilute solutions of weak acids and bases,
we cannot neglect the contributions due to self-ionisation equilibrium of water.
3.7. Common ion effect

In the previous unit we have learnt about Le Chatelier’s principle. According to this
principle the presence of common ions in a solution of a weak acid or a base will affect
its dissociation. This in fact would suppress the dissociation of the acid or base.
Let us consider the dissociation of a weak acid such as acetic acid,
CH3COOH  H+ + CH3COO–
the equilibrium constant for which can be represented as,
 H   CH COO 
3
Ka     
(22)
 CH3COOH 
 H    K  CH3COOH 
  a
or, CH COO  (23)
 3 
Now, suppose that we add some acetate ions in the form of solid sodium acetate
to the above solution. Sodium acetate is added in the solid form so as not to cause any
change in the volume of the solution. Sodium acetate being a strong electrolyte will
dissociate almost completely to give Na+ ions and CH3COO– ions in solution. The acetate
ions so added will disturb the equilibrium of acetic acid. The equilibrium will, therefore,
shift to left producing more of undissociated acetic acid in order to counteract the effect
of added acetate ions according to Le Chatelier’s principle. The net result is that the
dissociation of the acid has been suppressed by the addition of a common ion (acetate
ion in this case) at equilibrium. Thus any ion which is involved in a chemical equilibrium
and comes from two different sources in solution is known as ‘common ion’ and its effect
finds great use in the study of buffer solutions and the solubility of sparingly soluble salts
which we will discuss in the next few sections.
3.8. Salt Hydrolysis - Hydrolysis Constant, Degree of

Hydrolysis and pH for Different Salts
The aqueous solutions of certain salts also behave as acids or bases. They do so
because of the hydrolysis of the cation or anion or both. As you know, hydrolysis is a
reaction with water. Depending on the behaviour towards hydrolysis there are four different
types of salts.
(i) Salt of strong acid and strong base (eg. HCl + NaOH) NaCl
(ii) Salt of strong acid and weak base (e.g. HCl + NH4OH) NH4Cl
(iii) Salt of weak acid and strong base (e.g. CH3COOH + NaOH)
CH3COONa
(iv) Salt of weak acid and weak base (e.g. CH3COOH + NH4OH)
CH3COONH4
Let us consider the acid base behaviour of the different type of salts.
(i) Salt of strong acid and strong base: The cations of the strong bases and the
anions of the strong acids do not get hydrolysed. Therefore the salts of this category do
not show any acid-base behaviour and are neutral.
(ii) Salt of strong acid and weak base: the salts of this type dissociate in aqueous
solutions to give a cation of a weak base and the anion belonging to strong acid. For
example,
NH4Cl dissociates as:
NH4Cl (aq) → NH4+ (aq) Cl– (aq)
The anion from the strong acid does not get hydrolysed but the cation get hydrolysed
as per the following equation:
NH4+ (aq) + H2O (l) NH4OH + H+ (aq)
which produces a weak base and excess of hydrogen ions in solution, thus rendering the
solution acidic. Hence, we can say that the salt of a weak base and a strong acid will
produce an acidic solution.
Let c mol/litre is concentration of the NH4Cl and h is its degree of hydrolysis,
then
NH4+ + H2O  NH4OH + H+
Equilibrium concentration: c(1- h) hc hc
Therefore, according to law of mass action at equilibrium
 NH 4OH  H  
K
 NH    H O 
 4 2
 NH 4OH  H  
or, K   H 2O  
 NH  
 4
 NH 4OH   H  
or, Kh  (24)
 NH  
 4
where Kh is the hydrolysis constant of salt NH4Cl or NH4+ ion. Also we have for weak
base NH4OH which will get dissociate in water as
NH4OH NH4+ + OH–
 NH    OH  
4
Kb   
(25)
 NH 4OH 
From equation 24 and 25 we can write
Kh × Kb = [H+] [OH–] = Kw
Kw
So, Kh  (26)
Kb
From this equation we can calculate the hydrolysis constant.

Now from equation 24 we can get
 NH 4OH   H   ch  ch h 2c
Kh     h 2c
 NH   (1  h)c 1  h
 4
As h is very small so, (1-h) = 1
Kh Kw
Hence, h   (27)
c K b .c
From this equation we can calculate the degree of hydrolysis of the salt.
Kw K w .c
Now, [H  ]  hc  c 
K b .c Kb
1 1 1
or,  log  H     log K w  log c  log K b
  2 2 2
1 1 1
or, pH   log1014  log c  pK b
2 2 2
1 1
or pH  7  pK b  log c (28)
2 2
This is the equation for the pH of a solution of salt of strong acid and weak base.
(iii) Salt of weak acid and strong base: the salts of this type dissociate in aqueous
solutions to give a anion of a weak acid and the cation belonging to strong base. For
example, CH3COONa dissociates as:
CH3COONa (aq) → Na+ (aq) + CH3COO– (aq)
in this case the cation does not get hydrolysed but the anion get hydrolysed as per the
following equation.
CH3COO– (aq) + H2O (l)  CH3COOH (aq) + OH– (aq)
So in the solution there will be excess OH- ion. Hence the salts of a weak acid and
a strong base, when dissolved in water, will produce a basic solution.
By considering the similar method as above we can show that if c mol/litre is the
concentration of the CH3COONa and h is its degree of hydrolysis then
We can get
Kw
Kh  (29)
Ka
Kw
h (30)
K a.c
1 1
pH  7  pK a  log c (31)
2 2
(iv) Salt of weak acid and weak base: the salts of this type dissociate in aqueous
solutions to give a anion of a weak acid and the cation belonging to a weak base. For
example, ammonium acetate, CH3COONH4 dissociates as:
CH3COONH4 (aq) → NH4+ (aq) + CH3COO– (aq)
In this case both the cation as well as the anion would undergo hydrolysis according
to the following equations
NH4+ (aq) + H2O (l)  NH4OH + H+ (aq)
CH3COO– (aq) + H2O (l)  CH3COOH (aq) + OH– (aq)
Hydrolysis of one ion gives hydrogen ions, whereas that of the other ion gives hydroxyl
ions in solution. Therefore, the pH of the solution will depend on the extent of the hydrolysis
of the two ions. If NH4+ hydrolyses to a greater extent than CH3COO– ion, the solution
will be acidic and, if the reverse is true, then the solution will be basic. If the extent of
hydrolysis is exactly equal, then the solution should be neutral as if no hydrolysis is taking
place.
By considering the similar method we can establish that if c mol/litre is the concentration
of the CH3COONH4 and h is its degree of hydrolysis then
We can get
Kw
Kh  (32)
Ka Kb
Kw
h (33)
Ka  Kb
1 1
pH  7  pK a  pK b (34)
2 2
From the equation 34, we can see that the pH of the solution is independent of the
concentration of the salt.
If pKa = pKb then the pH of the solution is 7.
When pKa >> pKb then the pH > 7, so the solution will be basic.
When pKa << pKb then the pH < 7, so the solution will be acidic.
3.9. Buffer solutions

In section 3.7 we have seen that that the extent of dissociation of a weak acid can
be decreased by adding a salt containing a common ion. Further, it can be shown that
the change in the extent of dissociation can also be varied by changing the concentration
of the common ion. The mixture of a weak base and a salt of common ion also behave
in the same way. These aqueous solutions containing weak acids / bases and a salt of
common ion are important in a yet another way. These act as buffer solutions.
Buffer solutions are the ones that resist a change in its pH on adding a small
amount of an acid or a base.
In laboratory reactions, in industrial processes and in the bodies of plants and animals,
it is often necessary to keep the pH nearly constant despite the addition of acids and
bases. The oxygen carrying capacity of haemoglobin in our blood and activity of the
enzymes in our cells depends very strongly on the pH of our body fluids. pH of the
blood is very close to 7.4 and pH of saliva is close to 6.8. Fortunately, animals and
plants are protected against sharp changes in pH by the presence of buffers.
There are two kinds of commonly used buffer-solutions
i) A weak acid and a soluble ionic salt of the weak acid forms a buffer with pH
less than 7 are called acidic buffers e.g. acetic acid and sodium acetate.
ii) A weak base and a soluble ionic salt of the weak base forms a buffer with pH
above 7 are called basic buffers. e.g. ammonium hydroxide and ammonium
chloride.
Let us consider a buffer solution containing acetic acid, CH3COOH and sodium
acetate CH3COONa to understand about how buffer resist the change of pH in the
solution. In acetic acid - sodium acetate buffer CH3COOH acts as acid reserve while
CH3COONa (or CH3COO- ions) works as the base reserve. In the solution mixture the
added components dissociate as follows. The weak acid dissociates partially while the
salt undergoes complete dissociation.
CH3COOH (aq) + H2O (l)  CH3COO– (aq) + H3O+ (aq)
CH3COONa (aq) → Na+ (aq) + CH3COO– (aq)
If we add a strong acid such as HCl to this solution, it produces H3O+. These added
H3O+ (acid) react with an equivalent amount of the base reserve [CH3COO–] to generate
undissociated acetic acid. The reaction being
CH3COO– (aq) + H3O+ (aq) → CH3COOH (aq) + H2O (l)
The net effect of this reaction is that there is a slight increase in the concentration
of the acid reserve and an equivalent decrease in the concentration of the base reserve.
The effective reaction being
CH3COOH (aq) + HCl (aq) CH3COOH (aq) + NaCl (aq)
Similarly, when small amount of a strong base like NaOH is added, it generates OH-
ions. These additional OH– neutralize some of the H3O+ ions present in the solution.
Since one of the products of the acid dissociation equilibrium (eq) is used up, there is
some more ionisation of CH3COOH to re-establish the equilibrium. The net result is the
neutralization of OH- by CH3COOH. In other words we can say that the added OH-
ions (base) react with the acid reserve to produce CH3COO– ions.
OH– (aq) + CH3COOH (aq) → CH3COO– (aq) + H2O (l)
The effective reaction is the reaction of the added base with acid reserve.
NaOH (aq) + CH3COOH (aq) → CH3COONa (aq) + H2O (l)
The net effect of this reaction is that there is a slight increase in the concentration
of the base reserve and an equivalent decrease in the concentration of the acid reserve.
So we can observe that the added acid or the base only cause minor changes in
the concentrations of the weak acid and the salt. The concentration of the hydronium ions
and thereby the pH does not change significantly.
Now the pH of a buffer solution can be calculated from the Henderson’s equation.
Let us derive the expression for an acidic buffer system that we have discussed above.
In acetic acid – sodium acetate buffer the central equilibrium is
CH3COOH (aq) + H2O (l) CH3COO– (aq) + H3O+ (aq)
which is characterized by the acid dissociation constant,
 H O  CH COO 
3
Ka    
3
 3
CH COOH 
Rearranging, we get
 H O   K  CH3COOH 
 3  a
CH COO 
 3 
The concentration of undissociated acetic acid can be taken as total acid concentration
[Acid] and that of sodium acetate as the total salt concentration [Salt]. Thus the above
equation may be re written as
 H O   K [Acid]
 3  a
[Salt]
Taking logarithm and multiplying by (-1) in both side we get
[Acid]
 log  H3O    log K a  log
  [Salt]
[Acid]
or pH  pK a  log
[Salt]
[Salt]
or, pH  pK a  log (35)
[Acid]
This equation is known as Henderson’s equation. A similar expression can be derived

for a basic buffer (e.g., ammonium hydroxide and ammonium chloride). The expression
is
[Salt]
pOH  pK b  log (36)
[Base]
3.10. Solubility and Solubility Product of Sparingly

Soluble Salts
When a solute is added gradually to an amount of solvent, at a particular temperature,
there comes a point when no more solute can be dissolved. This point gives a saturated
solution. A solution which remains in contact with undissolved solute is said to be saturated.
At the saturated stage, the quantity of the solute dissolved is always constant for the
given amount of a particular solvent at a definite temperature.
Consider in general, the electrolyte of the type AxBy which is dissociated as:
AxBy  xAy+ + yBx–
Applying law of mass action we can write
x y
 A y    Bx  
K   
(37)
 A x By 
 
When the solution is saturated,

[AxBy] = K´ (constant)
So we can write the equation 37 as
[Ay+]x [Bx–]y = K[AxBy] = K.K´ = Ksp (constant) (38)
Ksp is the solubility product constant or simply solubility product. Thus, solubility
product is defined as the product of concentrations of the ions raised to a power equal
to the number of times, the ions occur in the equation representing the dissociation of the
electrolyte at a given temperature when the solution is saturated.
Relationship between solubility and solubility product:
Salts like AgI, BaSO4, PbSO4, PbI2, etc. are ordinarily considered insoluble but they
do possess some solubility. These are sparingly soluble electrolytes. A saturated solution
of sparingly soluble electrolytes contains a very small amount of the dissolved electrolyte.
It is assumed that whole of the dissolved electrolyte is present in the form of ions, i.e.,
it is completely dissociated.
The equilibrium for a saturated solution of a sparingly soluble salt AxBy of solubility
S mol/L may be expressed as:
AxBy (s)  xAy+ (aq) + yBx– (aq)

At equilibrium, [Ay+] = xS mol/L and [Bx–]= yS mol/L
So, Ksp = [Ay+]x [Bx–]y = [xS]x [yS]y = xx. yy. (S)x+y
(39)
Special Cases:
(i) 1: 1 type salts: Examples: AgCl, AgI, BaSO4, PbSO4, etc.
Ksp = S.S = S2
(ii) 1: 2 or 2: 1 type salts: Examples: Ag2CO3, Ag2CrO4, PbCl2, CaF2, etc.
Ksp = S.(2S)2 = 4S3
(iii) 1: 3 type salts: Examples: AlI3, Fe(OH)3, Cr(OH)3, Al(OH)3,etc.
Ksp = S.(3S)3 = 27S4
Example 1. At 298 K, the solubility of silver chloride is 1.37 x 10-5 M. Calculate
its solubility product.
Solution: The equilibrium of silver chloride is AgCl  Ag+ = Cl–
Here x= 1 and y = 1, So, Ksp = S2 = (1.37 × 10–5)2 = 1.88 × 10–10
Effect of common ion on solubility of sparingly soluble salt:
What will happen if we add a soluble salt containing a common-ion to a solution of
a sparingly soluble salt? We may reason out that according to Le Chatelier’s principle,
the common-ion will shift the equilibrium in backward direction which would reduce its
solubility still further. This actually is the case.
Let us extend the problem in example 1 as, what will be the solubility of AgCl in
0.01 M AgNO-3 solution?
Addition of 0.01 M concentration of AgNO3 will provide 0.01 M of Ag+ ions in the
solution as AgNO3 is a strong electrolyte. Assuming this contribution to be much larger
in comparison with Ag+ ion concentration due to dissolved AgCl (solubility S mol/L), we
can write.
[Ag+] = 0.01 and [Cl–] = S
So, Ksp = 1.88 × 10–10 = [Ag+][Cl–] = 0.01 × S
or, S = 1.88 × 10–8
We can see that, as compared to the solubility of AgCl in water (1.37 × 10–5 M),
its solubility in presence of 0.01 M AgNO3 is almost 103 times less.
Application of solubility product in qualitative analysis:

The qualitative analysis of cations is carried out by dividing them into several groups.
This group separation of cations is based upon selective precipitation of some cations out
of many that are present in a solution. This is achieved by adjusting the solution conditions
in such a way that the Ksp of specific salts of some cations is exceeded and they precipitate
out. The remaining cations remain in the solution. A typical example is the use of H2S.
The dissociation of H2S can be written as
H2S (aq)  2H+ (aq) + S2– (aq)
Since the equilibrium involves hydrogen ions, the acidity of the solution would play
an important role in controlling the concentration of sulphide ions. We know that in the
separation of group II sulphides, the medium of the solution is kept acidic. In this medium
the concentration of the S2- ions is very small and only the sulphides of group II are
precipitated. On the other hand in the alkaline medium the concentration of sulphide ions
is fairly high and the sulphides of group IV cations precipitate out.
3.11. Summary
In summary we have started the discussion explaining electrolytes and non electrolytes.
Then we focused our discussion on strong and weak electrolytes followed by degree of
dissociation for weak electrolytes and the factors affecting the degree of dissociation.
Ionization of weak acid and weak bases are discussed. After that, ionic product of water
was explained and the concept was extended for establishing the concept of pH scale.
We have found the effect of common ion in dissociation of weak acid and bases. We
have learned about the salt hydrolysis and calculated the hydrolysis constant, degree of
hydrolysis and pH for different types of salts. We have seen that the presence of common
ions in a solution of a weak acid or a weak base suppress its dissociation. Such solutions
act as buffer solutions which resist a change in their pH on addition of small amount of
an acid or a base. The pH of buffer solutions depend on their composition and can be
found by using a simple equation called Henderson’s equation. After that we have discussed
that the product of the concentration of the ions in the solubility equilibrium is a constant
called solubility product (Ksp) and is proportional to the solubility of the sparingly soluble
salt. We have found that the presence common ion decreases the solubility of a sparingly
soluble salt. This is called common ion effect and has widespread applications in qualitative
analysis.
3.12. Questions
1. Write a short note on pH scale.
2. What is degree of ionization?
3. What are sparingly soluble salts?
4. What will happen if we pass HCl gas in a saturated solution of NaCl?
5. What is buffer? Give example of one acidic and one basic buffer.
6. Why the pH of a buffer remains constant upon addition of small amount of acid
or base?
7. Why the solution of FeCl3 is acidic?
8. If the solubility of Zinc phosphate in water is S mol/L, then find the expression
for the solubility product of the salt. (Ans. 108 S5)
9. Calculate the pH of 0.1 M NaOH solution. (Ans. 13)
10. If in 1 L of buffer solution 0.2 mol of NH4Cl and 0.1 mol of NH4OH is
dissolved then what will be the pH of the solution? Given that Kb of NH4OH is
1.8 x 10–5. (Ans. 8.96)
Unit 4  Kinetic Theory of Gases
Contents
4.0. Objectives
4.1. Introduction
4.2. Postulates of kinetic theory of gases
4.3. Kinetic gas equation
4.4. Maxwell Boltzmann distribution laws of molecular velocities and molecular
energies
4.5. Average, root mean square and most probable velocities
4.6. Collision Parameters
4.7. Viscosity of gases
4.8. Deviation of real gases from ideal behavior
4.9. Critical phenomena
4.10. Summary
4.11. Questions
4.0. Objectives
After studying this unit, we will be able to:
 state the postulates of kinetic theory of gases
1
 derive the kinetic gas equation PV = mnc2
3
 explain the distribution of molecular speeds and energies
 calculate the most probable speed, the average speed and the root mean square
speed
 derive an expression to calculate the collision number between gas molecules
 calculate the mean free path of molecules
 explain the origin and factors responsible for viscosity of gases
 differentiate between ideal gas and real gas and reasons for deviation from ideal
behaviour
 explain the critical phenomenon and critical constants.
4.1. Introduction
The kinetic theory describes a gas as a large number of sub microscopic particles
(atoms or molecules), all of which are in constant, and random motion. The rapidly moving
particles constantly collide with each other and with the walls of the container. Kinetic
theory explains macroscopic properties of gases, such as pressure, temperature, viscosity,
thermal conductivity, and volume, by considering their molecular composition and motion.
The theory depicts that gas pressure is due to the impacts, on the walls of a container,
of molecules or atoms moving at different velocities.
4.2. Postulates of kinetic theory of gases

The kinetic molecular theory of gases explains the laws that describe the behaviour
of gases. This theory developed during the mid-19th century by several physicists, including
the Boltzmann, Clausius and Maxwell. The kinetic molecular theory of gases provides a
molecular explanation for observations that led to the development of the ideal gas law.
The kinetic molecular theory of gases is based on the following postulates:
i. Every gas consists of large number of tiny particles called point masses i.e. the
actual volume of molecules is negligible when compared to the total volume of
the gas.
ii. The gas molecules are always in a state of rapid zig-zag motion in all directions.
These molecules collide with each other and with the walls of the containing
vessel.
iii. A molecule moves in a straight line with uniform velocity between two collisions.
iv. The molecular collisions are perfectly elastic so that there is no net loss of energy
when the gas molecules collide with one another or against the walls of the
vessel.
v. There are no attractive forces operating between molecules or between molecules
and the walls of the vessel in which the gas has been contained. The molecule
move independently of one another.
vi. The pressure of the gas is the hits recorded by the molecules on the walls of the
container in which the gas is contained.
vii. The average kinetic energy of gas molecules is directly proportional to absolute
temperature.
viii. This means that the average kinetic energy of molecules is the same at a given
temperature.
4.3. Kinetic gas equation

Suppose a definite amount gas is placed in a cubic closed vessel of length l. Let the
mass of the each gas molecule is m. The gas consists of total n molecules and each
molecule is moving randomly with a velocity c (root mean square velocity). This velocity
c can be divided into three components of u, v and w along X, Y and Z direction
respectively.
c2 = u2 + v2 + w2
Now, we consider the movement of a molecule along X axis (figure 4.1). If the
velocity of the molecule along X axis is u then the momentum is momentum is mu. Now
when the molecule collides perpendicular to the wall of the container with velocity u, it
will revert back to the opposite direction with same velocity as the collision is an elastic
collision. The velocity after the collision will be –u. As the collision between the molecules
and walls are elastic, so the momentum will be same before and after the collision. So
the change in momentum after a collision with the wall = mu- (-mu) = 2mu
Figure 4.1. Velocity of a gas molecule along X-axis placed in a cubic container.
Now after collision with the A side of the wall it will reflect and will collide with the
opposite wall at a distant of  .
Hence, the number of collision per second for a gas molecule moving along X-axis
u
with a velocity u 
l
So for u component of velocity of a molecule change in momentum per second
u 2mu 2
  2mu 
l l
For the same molecule the change of momentum per second for the v and w
2mv 2 2mw 2
component of the velocity will be and respectively.
l l
Total change of momentum for a molecule per second
2mu 2 2mv2 2mw 2

  
l l l
2mc2

2m 2
l
 2 2
u v w 
l

2mnc2
For n number of molecules rate of change of momentum 
l
From the Newton’s second law we know that rate of change of momentum is equal
to the force. As the pressure (P) is equal to the force acting per unit area and the total
surface area of the container = 6l2.
2mnc2 1 2mnc2 2mnc2 1 mnc2

So we can write, P      
l 6l2 6 l3 6V 3 6V
1
or, PV  mnc 2 (1)
3
This is known as kinetic gas equation.
4.4. Maxwell Boltzmann distribution laws of molecular

velocities and molecular energies
In a given mass of gas, the velocities of all molecules are not the same, even when
bulk parameters like pressure, volume and temperature are fixed. Collisions change the
direction and the speed of molecules. However in a state of equilibrium, the distribution
of speeds is constant or fixed. If at a particular temperature T, dNc number of molecules
are present in between the velocity c and (c + dc) among total N number of molecules
then the Maxwell’s equation of distribution of molecular velocity is given by the following
equation-
3 mc2
dNc  m 
 2 2kT 2
 4   e c dc (2)
N  2kT 
Where, dNc is the number of molecules having velocity between c to c + dc, m

is the mass of the each gas molecule, N is the total number of gas molecules present,
k is Boltzmann constant and T is absolute temperature of the gas. Also the equation can
be written as
3 mc 2
dNc  M 
 2 2RT 2
 4   e c dc (3)
N  2RT 
Where R = universal gas constant, M = Molecular weight of the gas.
Figure 4.2. Plot of Maxwell’s distribution of molecular velocities.

1 dN c
The Maxwell distribution is customarily plotted with the function in the y-
N dc
axis and c as the x-axis. The fraction of the molecules in the speed range c to c + dc
dN c
is ; dividing this by dc gives the fraction of the molecules in this speed range per
dc
unit width of the interval. The Maxwell’s distribution of molecular velocities is plotted in
figure 4.2.
We can see from the plot that the fraction of molecules having velocities greater than
zero increases with an increase in velocity, reaches a maximum and then falls off towards
zero at higher velocities. The important features of the curves are as follows:
i) The fraction of molecules with too low or too high velocities is very small.
ii) There is a certain velocity for which the fraction of molecules is maximum. This
is called the most probable velocity.
Effect of temperature on distribution of molecular velocities for a particular gas:
Effect of temperature on distribution of molecular velocities for a N2 gas is plotted
in figure 4.3. The important features are:
i) The entire distribution curve shifts to the right and becomes broader with increase
in temperature
Figure 4.3. Maxwell distribution for nitrogen at two temperatures.

ii) With increase of temperature fraction of the molecules having high velocities
increases considerably.
iii) The most probable velocity increases with increase in temperature but the number
of molecules present at that velocity decreases.
Distribution of molecular energies:
The Maxwell’s speed distribution, eq. 2, can be converted to an energy distribution.
1 1
1
The kinetic energy of a molecule is   mc 2 . Then, c    2  2 . Thus equation 2
2
2 m
can be converted to energy distribution equation as
3 1 
dN  1  2 2  kT
 2N    e d (4)
N  kT 
where dN  , is the number of molecules having kinetic energies between ε and ε +dε.
Figure 4.4. Energy distribution at 300 K.
Energy distribution curve is distinctly different shape compared to that of the speed
distribution (figure 4.4). In particular, the energy distribution curve rises sharply at the
beginning and thus it rises much more quickly than the velocity distribution. After passing
the maximum, the energy distribution falls off more slowly than does the velocity distribution.
As usual, the distribution is broadened at higher temperatures, a greater proportion of the
molecules having higher energies. As before, the areas under the curves for different
temperatures must be the same.
4.5. Average, root mean square and most probable

velocities
Mean or Average velocity (Cav)
The average speed is the sum of all the velocities ranging from 0 to “ divided by total
number of molecules present (n). If for a gas n1, n2, n3..... number of molecules has the
velocity of c1, c2 c3... respectively then the average velocity will be
n c  n c  n 3c3  ....  n i ci
cav  1 1 2 2 
n1  n 2  n 3  .... n
From Maxwell’s equation of distribution of velocity, it can be shown that the average
velocity for a gas with molecular mass M is
8RT
Cav  (5)
M
where, R is universal gas constant and T is temperature of the gas.

Root Mean Square Velocity (Crms)
The root mean square velocity or rms velocity is the square root of the sum of all
the squared velocities ranging from 0 to  divided by total number of molecules N.
If for a gas n1, n2, n3..... number of molecules has the velocity of c1, c2 c3... respectively
then the root mean square velocity of the gas molecules will be
n1c12  n 2c22  n 3c32  ....  n i ci2

Crms  
n1  n 2  n 3  .... n
From Maxwell’s equation of distribution of velocity, it can be shown that the root
mean square velocity for a gas with molar mass M at temperature T is
3RT
Crms  (6)
M
Most Probable Velocity (Cmp)

The most probable velocity is the velocity possessed by maximum number of molecules
at a particular temperature.
From Maxwell’s equation of distribution of velocity, it can be shown that the most
probable velocity (cmp) for a gas with molar mass M at temperature T is
3RT
Cmp  (7)
M
4.6. Collision parameters

Collision diameter:
The kinetic theory of gases treats molecules as point masses. When two such molecules
approach each other, a point is reached at which the repulsion between the molecules
(resulting from electronic and nuclear repulsion) becomes so strong that it causes reversal
of the direction of their motion. The distance between the centres of the two molecules
at the point of their closest approach is known as collision diameter (σ). Evidently, a
gaseous molecule can be regarded as a hard sphere of radius ‘σ/2’. It can be imagined
that if the distance between the centres of two molecules is less than σ, there would be
a collision between them. Thus, collision is an event in which the centres of two identical
molecules come within a distance between d from each other.
Figure 4.5. The zigzag motion of a gas molecule.
Collision cross section:

The model of gaseous molecules as hard non-interacting spheres of diameter σ can
satisfactorily account for various gaseous properties such as viscosity, diffusion, thermal
conductivity, mean free path, number of collision the molecules undergo. It can be imagined
that when two molecules collide, the effective area of the target is πσ2. The quantity πσ2
is called the collision cross-section of the molecule because it is the cross-sectional area
of an imaginary sphere surrounding the molecule into which the centre of another molecule
cannot penetrate.
Collision number:
Collision number is the number of collisions suffered by a single molecule per unit
time per unit volume of the gas. It can be imagined that a gas molecule having diameter
σ will collide with the molecules present in the area of πσ2. Now if the molecule is
moving with an average velocity of c and n´ number of molecules are present in unit
volume then in one second total number of collisions suffered by the molecule will be
 2  c  n  . Now as all the gas molecules are moving this velocity should be considered
as relative velocity  
2 c . So, the number of molecules with which a single molecule
will collide per unit time is given by Z1  2 2 c n  . This is the expression of collision
number.
Now as n´ number of molecules are present per unit volume of the gas, total number
of collisions per unit time per unit volume is = 2 2 c n 2 . Since each collision
involves two molecules, the number of collisions of like molecules occurring per unit time
per unit volume of the gas is given by
Z11 
1
2
 2 2 c n2  1
2
2 c n2 
1
2
2 n2 
8RT
M
 8RT 
 as c  
 M 
8RT
Z11  22 n 2 
M
This number Z11 represent the number of molecular collisions occurring per unit time
per unit volume of the gas, which is known as collision frequency.
Mean free path of molecules:

Mean free path of a gas molecule (l or λ) is defined as the mean distance travelled
by a gas molecule between two successive collisions.
Now we already know that if a molecule has the average velocity c then the
molecule will face Z1  2 2 c n  number of collisions while travelling c distance.
So, Mean free path,
average velocity of the molecule c 1

l  2

number of collisions per sec ond 2 c n 22 n
where, σ = collision diameter and n´ = number of molecules present per unit volume.
4.7. Viscosity of gases

The viscosity of a fluid is a measure of its resistance to deformation at a given
rate. Viscosity can be conceptualized as quantifying the internal frictional force that arises
between adjacent layers of fluid that are in relative motion. Viscosity in gases arises
principally from the molecular diffusion that transports momentum between layers of
flow. The viscosity coefficient (η) is the force that must be applied to hold the lower
layer stationary if the velocity gradient between the two layers is unity and the plate has
unit area. It can be shown from the kinetic theory that the relation between viscosity
coefficient (η) and mean free path (l) of a gas molecule can be given by the following
equation-
1
  mn  c l where, c is average velocity, n’ is the number of gas molecules
3
present in unit volume and m is the mass of the gas molecules.
Effect of temperature and pressure on coefficient of viscosity:
Effect of pressure: The viscosity of gas is independent of pressure. With increase
of pressure though more number of molecules changes between the layers, but they travel
shorter distance due to higher number of collisions. So the change of pressure does not
affect the viscosity for gases.
Effect of temperature: Viscosity in gases arises from molecules traversing layers of
flow and transferring momentum between layers. The momentum transfer is caused by
free motion of gas molecules between collisions. So, increase of thermal agitation of the
molecules results in a larger viscosity. Hence, gaseous viscosity increases with increase
of temperature.
1 1
We know, l =
2
and   mn c l
2 n  3
1 1 1 m c 1 m 8kT 2 mkT
So,   mn c l        2 (9)
3 2
2 n 3 2 2 3 2 2 m 3 3
From the above equation we can see that,   T
4.8. Deviation of real gases from ideal behaviour

We know that ideal gases obey ideal gas equation (PV = RT, for one mole gas) at
any pressure and temperature. But real gases do not obey ideal gas equation under all
conditions. They nearly obey ideal gas equation at higher temperatures and very low
pressures. However they show deviations from ideality at low temperatures and high
pressures.
Compressibility factor and Boyle temperature:

The deviations of real gases from ideal behaviour are best represented in terms of
the compressibility factor (Z). Compressibility factor is the ratio of the molar volume of a
gas to the molar volume of an ideal gas at the same temperature and pressure. It correlates
the deviation of a real gas from ideal gas behaviour. To display the deviations clearly, the
ratio of the observed molar volume V to the ideal molar volume Vid (= RT/P) is plotted
as a function of pressure at constant temperature. This ratio is called the compressibility
factor (Z = PV/RT).
For the ideal gas, Z = 1 and is independent of pressure and temperature. For real
gases Z is a function of both temperature and pressure. The graphs plotted for the
compressibility factors determined for a number of gases over a range of pressure at a
constant temperature are shown in Figure 4.6. At extremely low pressure all the gases
are known to have Z close to unity which means that the gases behave almost ideally.
At very high pressure, all the gases have Z is greater than unity indicating that the gases
are less compressible than an ideal gas. This is due to the fact that at high pressure, the
molecular repulsive force is dominant. At moderately low pressure carbon monoxide,

methane and ammonia are more compressible than ideal gas (Z<1). The compressibility
factor Z goes on decreasing with increase of pressure passes through a minimum at a
certain stage and then begins to increase with increase in pressure for these gases. For
hydrogen and helium, Z is greater than unity (the ideal value) at all pressures.
Figure 4.6. Compressibility factor Z, plotted against pressure for H2, N2 and CO2 at constant temperature.
From the plot of plot of Z versus p (figure 4.7) for nitrogen at different temperatures
varying between -70°C and 50°C it is seen that as the temperature is raised the dip in
Figure 4.7. Plot of Z against P at different temperature for N2.

the curve becomes smaller and smaller. At 50°C, the curve seems to remain almost
horizontal (Z=1) at the low pressure region. So it can be said that at this region PV
remain constant and thus it obeys the Boyle’s law within this range of pressure at 50°C.
This temperature is called Boyle temperature. The Boyle temperature is different for
different gases.
Causes of deviation and Van der Waals equation of state for real gases:
In order to explain deviations from ideal behaviour, it is necessary to modify the
kinetic theory of gases. Van der Waals realized that two of the assumptions of the kinetic
molecular theory were questionable. The kinetic theory assumes that gas particles occupy
a negligible fraction of the total volume of the gas. It also assumes that the force of
attraction between gas molecules is zero.
The first assumption works at pressures close to 1 atm. But something happens to
the validity of this assumption as the gas is compressed. Imagine for the moment that the
atoms or molecules in a gas were all clustered in one corner of a cylinder. At normal
pressures, the volume occupied by these particles is a negligibly small fraction of the total
volume of the gas. But at high pressures, this is no longer true. As a result, real gases
are not as compressible at high pressures as an ideal gas. The volume of a real gas is
therefore larger than expected from the ideal gas equation at high pressures.
Figure 4.8. Excluded volume in case of real gas.
Van der Waals proposed that we correct for the fact that the volume of a real gas
is too large at high pressures by subtracting a term from the volume of the real gas before
we substitute it into the ideal gas equation. He therefore introduced a constant (b) into
the ideal gas equation that was equal to the volume actually occupied by a mole of gas
particles. Because the volume of the gas particles depends on the number of moles of
gas in the container, the term that is subtracted from the real volume of the gas is equal
to the product of number of moles of gas and b.
P(V - nb) = nRT
When the pressure is relatively small, and the volume is reasonably large, the nb term
is too small to make any difference in the calculation. But at high pressures, when the
volume of the gas is small, the nb term corrects for the fact that the volume of a real gas
is larger than expected from the ideal gas equation.
The assumption that there is no force of attraction between gas particles cannot be
true. If it was, gases would never condense to form liquids. In reality, there is a small
force of attraction between gas molecules that tends to hold the molecules together. This
force of attraction has two consequences: (i) gases condense to form liquids at low
temperatures and (ii) the pressure of a real gas is sometimes smaller than expected for
an ideal gas.
To correct for the fact that the pressure of a real gas is smaller than expected from
the ideal gas equation, van der Waals added a term to the pressure in this equation. This
term contained a second constant (a) and has the form: n2a/V2. The complete van der
Waals equation is therefore written as follows.
 n 2a 
 P  2  (V  nb)  nRT (10)
 V 
This is the van der Waals equation for n moles of gas which contains a pair of
constants ‘a’ and ‘b’. The’ quantities ‘a’ and ‘b’ are called the van’der Waals constants
or parameters. It may be pointed that ‘b’ is a measure of the molecular size and ‘a’ is
related to the intermolecular interaction. The SI unit of a is N m4 mol-2 and the unit of
b is m3 mol-1.
4.9. Critical phenomena

When the molecules of a gas are brought closer to each other due to increase in
the attractive forces a stage may be reached when the gas changes its phase to liquid.
Obviously, an ideal gas cannot be liquefied as there are no interactions in that case. For
the liquefaction of real gases, we can do either of the following: i) increase the pressure
on the gas or ii) decrease the temperature of the gas. Both these processes will tend to
bring the molecules closer and liquefaction may take place. But it is observed practically
that temperature is the dominant factor for liquefaction and pressure assumes a secondary
role. For every real gas a temperature is observed above which it cannot be liquefied
even on the application of very high pressures. This characteristic temperature of a real
gas above which it cannot be liquefied is called “Critical Temperature” represented by
TC.
The importance of critical temperature of a gas was first discovered by Andrew in
his experiments on pressure-volume relationships (isotherms) of carbon dioxide gas at a
series of temperatures. The isotherm of carbon dioxide determined by him at different
temperatures is shown in figure 4.9.
Figure 4.9. P-V isotherms of carbon dioxide.

We observe from the plot that:

i. At high Temperatures (>31.1°C), the isotherms look just like those of ideal gas.
ii. At low temperatures the curve is entirely different. For example, curve ABCD
at temperature 13.1°C, as the pressure increases the volume of the gas decreases
from point A to B. Then there is a sudden reduction in volume without much
increase in pressure of the gas from B to C. In this portion liquefaction is taking
place at constant pressure and due to the difference in the properties of gas and
liquid the volume is reducing so much. And after C even on increasing pressure
there is no appreciable decrease in volume as now only liquid is present. So, AB
represents gaseous phase, BC represents liquid-gas coexistence and CD
represents liquid phase.
iii. On carrying out the same process at a higher temperature we observe that the
width of the horizontal portion decreases and the pressure at which liquefaction
takes place also becomes higher. The horizontal portion decreases because at
higher temperatures the properties of liquid approach that of a gas.
iv. At temperature 31.1°C (TC) the horizontal portion reduces to a mere point at
which liquefaction takes place. Point X is called critical point; at this point the
boundary between liquid and gas phase (meniscus) disappears indicating that
both the phases have identical characteristics.
v. Above this temperature there is no liquefaction of gases and gas behaves almost
ideally.
At critical point X the tangent is horizontal, so that, dP/dV at critical point will be
zero. Thus, the point X is also called the point of deflection.
Critical constants:
Critical temperature, TC is the maximum temperature at which a gas can be liquefied
that is a temperature above which liquid cannot exist.
Critical Pressure, PC is the minimum pressure required for liquefaction to take place
at the critical condition.
Critical volume, VC is the volume occupied by one mole of the gas at critical
temperature and critical pressure.
It can be shown that the values of these parameters are given by the following
expressions:
8a
TC 
27Rb
a
PC 
27b2
VC = 3b
where R is the universal gas constant.
These critical constants are related by the following relation
RTc 8
 (11)
Pc Vc 3
4.10. Summary
In this unit, we have discussed some characteristic microscopic features of gases. It
has been shown how a simple kinetic molecular model of the gas can be used to derive
an equation to calculate the pressure exerted by a gas. This equation can be used further
to derive the ideal gas equation. This model is useful in showing how the constant collisions
between molecules are responsible for a distribution of the speed of molecules. Further,
this model helps us in deriving expressions for various kinds of speeds. We have also
evolved a method of calculating the total collision frequency and the mean free path
assuming hard sphere model for the molecules. We have discussed the viscosity of gases
and effect of temperature on the viscosity. The deviation of real gas from ideal behaviour
was explained and van der Waals equation was derived. Finally the critical phenomenon
and critical constants were explained for real gases.
4.11. Questions
1. Write down the postulates of kinetic theory of gases.
2. Derive the expression of pressure for an ideal gas using kinetic molecular theory
of gases.
3. Write down the expression for Maxwell distribution of molecular velocities.
4. What is mean free path of a gas? What is the relation between mean free path
and collision diameter?
5. How does the viscosity of gas vary with temperature?
6. What is compressibility factor of a gas?
7. What are the reasons for deviation of real gases from ideal behaviour?
8. Write down the definitions of critical constants.
9. Calculate the average velocity of CO2 molecule present in 1 gm of CO2 gas at
27 0C. (Ans. 3.8 x 104 cm/s)
10. If TC = 304.2 K and PC = 72.8 atm for a gas, then calculate the value of va
der Walls constants. (Ans. a = 3.63 atm L2 mol-2, b = 0.0428 L mol-1)
Unit 5  Liquids
Contents
5.0. Objectives
5.1. Introduction
5.2. Surface tension
5.3. Determination of surface tension using stalagmometer
5.4. Viscosity of a liquid
5.5. Determination of coefficient of viscosity using Ostwald viscometer
5.6. Summary
5.7. Questions
5.0. Objectives
After studying this unit, we will be able to
 the surface tension and origin of surface tension of a liquid
 effect of temperature in the surface tension
 determine the surface tension of a liquid
 explain the viscosity of a liquid and effect of temperature on viscosity
 determine the viscosity by using Ostwald viscometer.
5.1. Introduction
Intermolecular forces are stronger in liquid state than in gaseous state. Molecules in
liquids are so close that there is very little empty space between them and under normal
conditions liquids are denser than gases. Molecules of liquids are held together by attractive
intermolecular forces. Liquids have definite volume because molecules do not separate
from each other. However, molecules of liquids can move past one another freely, therefore,
liquids can flow, can be poured and can assume the shape of the container in which these
are stored. In the following sections we will look into some of the physical properties
of the liquids such as surface tension and viscosity.
5.2. Surface Tension

It is well known fact that liquids assume the shape of the container. Why is it then
small drops of mercury form spherical bead instead of spreading on the surface? Why
does a liquid rise (or fall) in a thin capillary as soon as the capillary touches the surface
of the liquid? Why does an iron needle float in the water? All these phenomena are
caused due to the characteristic property of liquids, called surface tension.
If we consider the forces between the molecules of a liquid then we can understand
these phenomena easily. A molecule in the bulk of liquid experiences equal intermolecular
forces from all sides. The molecules therefore do not experience any net force. But for
the molecule on the surface of liquid, net attractive force is towards the interior of the
liquid (Figure 5.1), due to the molecules below it, since there are no molecules or very
less number of molecules as vapour above it. These unbalanced attractive forces acting
downward tend to draw the surface molecules into the body of the liquid and, therefore,
liquids tend to have minimum number of molecules at their surface. A sphere has a minimum
surface for a given volume. As a result of the tendency to contract, surface of a liquid
behaves as if it were in a state of tension. The force that tends to contract the surface
of a liquid is known as surface tension.
Figure 5.1. Forces acting on a molecule on liquid surface and on a molecule inside the liquid.
Surface tension is defined as the force acting per unit length perpendicular to the line
drawn on the surface of liquid. It is represented by Greek letter γ (Gamma). It has
dimensions of kg s–2 and in SI unit it is expressed as Nm–1.
Surface Energy: The effect of surface tension is to reduce the area of the surface
to a minimum. If we wish to increase the area of the surface of a liquid, we have to work
against the force of surface tension. The energy required to increase the surface area of
the liquid by one unit is defined as surface energy of the liquid. Its SI unit is Jm–2.
Effect of Temperature on Surface Tension: The magnitude of surface tension of
a liquid depends on the attractive forces between the molecules. When the attractive
forces are large, the surface tension is large. Increase in temperature increases the kinetic
energy of the molecules and effectiveness of intermolecular attraction decreases, so surface
tension decreases as the temperature is raised.
Some Effects of Surface Tension: Some important effects can be explained by surface
tension.
1. Due to presence of surface tension in liquids every liquid try to reduce the area
of the surface to a minimum. Hence drops of a liquid or the drops of rain are spherical
in shape as sphere has minimum surface area for a given volume.
2. As the surface of a liquid tries to contract due to tension, so it behaves like a
membrane. Also the distances between the surfaces of molecules are less. So an iron
needle can float in the water.
3. Capillary action of a liquid is a well known phenomenon which can be explained
in terms of surface tension. If the liquid in the glass tube is water, the water is drawn
slightly up the walls of the tube by adhesive forces between water and glass. The interface
between the water and the air above it, called a meniscus, is concave, or curved in.
With liquid mercury, the meniscus is convex, or curved out. Cohesive forces in mercury,
consisting of metallic bonds between Hg atoms, are strong; mercury does not wet glass.
The effect of meniscus formation is greatly magnified in tubes of small diameter, called
capillary tubes. In the capillary action, the water level inside the capillary tube is
noticeably higher than outside. The soaking action of a sponge depends on the rise of
water into capillaries of a fibrous material, such as cellulose. The penetration of water
into soils also depends in part on capillary action. Conversely, mercury- with its strong
cohesive forces and weaker adhesive forces- does not show a capillary rise. Rather,
mercury in a glass capillary tube will have a lower level than the mercury outside the
capillary.
Figure 5.2. Capillary action of liquid.
4. When a drop of liquid spreads into a film across a surface, we say that the liquid
wets the surface. Whether a drop of liquid wets a surface or retains its spherical shape
and stands on the surface depends on the strengths of two types of intermolecular forces.
The forces exerted between molecules holding them together in the drop are cohesive
forces, and the forces between liquid molecules and the surface are adhesive forces.
If cohesive forces are strong compared with adhesive forces, a drop maintains its shape.
If adhesive forces are strong enough, the energy requirement for spreading the drop into
a film is met through the work done by the collapsing drop. Water wets many surfaces,
such as glass and certain fabrics. This characteristic is essential to its use as a cleaning
agent. If glass is coated with a film of oil or grease, water no longer wets the surface
and water droplets stand on the glass. Adding a detergent to water has two effects: The
detergent solution dissolves grease to expose a clean surface, and the detergent lowers
the surface tension of water. Lowering the surface tension means lowering the energy
required to spread drops into a film. Substances that reduce the surface tension of water
and allow it to spread more easily are known as wetting agents. They are used in
applications ranging from dish washing to industrial processes.
5.3. Determination of surface tension using

Stalagmometer
Stalagmometer is a simple apparatus and is frequently employed when the values of
surface tension of two or more different liquids are to be compared. It consists of a
bulbed capillary tube, the end of which is flattened and grounded carefully so that there
is a large dropping surface. There are two marks, A and B, on the wall of it which are
arbitrarily etched; one of them is above the bulb and the other is below the bulb. A liquid
is sucked up to the level A and then allowed to flow at a slower rate drop by drop until
it reaches the level B. The speed of the drop formation can be adjusted by attaching a
piece of rubber tube with a screw pinch cock at the upper end of the tube.
When a liquid is allowed to flow through a capillary tube, a drop begins to form at
its lower end, and increases in size to a certain extent, and then falls off. The size of the
drop will depend on the radius of the capillary and the surface tension of the liquid. The
total surface tension supporting the drop is 2πrγ, where r is the outer radius of the
capillary tube, see Fig. 5.3 The drop will fall when its weight ‘w’, just exceeds the force
of surface tension acting along the circumference. Therefore,
w = 2πrγ (1)
Figure 5.3. Drawing of a stalagmometer and the formation of liquid drop from a capillary tube in a
stalagmometer.
where w, is the weight of the drop and 2πr is the outer circumference of the capillary
tube.
From the above expression, it is clear that the surface tension of a liquid can be
determined if the weight of a single drop ‘w’ and the outer radius of the dropping tube,
‘r’ are known.
If, we have two liquids, such that
w1  2 r 1 and w 2  2 r  2
w1 1
then, we can say that  (2)
w2 2
If γ1 for one of the liquids is known, γ2 for other liquid can be determined without
needing a measurement of r, the outer radius of the dropping end of the capillary, provided
the weights of the individual drops of two liquids are known. This method of determination
is also known as Drop Weight Method. Alternatively, the surface tension can also be
determined using the Drop Number Method as given below.
Instead of finding the weights of individual drops, it is easier to count the number
of drops formed by equal volumes of two liquids. With two different liquids, the weights
of equal volumes are proportional to their densities. If nl and n2 are the number of drops
formed by the same volume V of the two liquids, then; vl, the volume of a single drop
of first liquid (i.e., liquid one) = V/nl.
Thus, weight of the single drop of the first liquid = w1 = V/n1.d1.g, where dl is the
density of the first liquid.
And the weight of the single drop of the second liquid = w2 = V/n2.d2.g, where d2
is the density of the second liquid.
Substituting the above values of wl and w2 in equation 2, we get
V d1
d1g
1 n n n d
 1  1  2 1 (3)
2 V d 2 n1d 2
d 2g
n2 n2
where, γ1 and γ2 are the surface tensions of two individual liquids, and d1 and d2 are
their densities, respectively. Thus, for the determination of surface tension of any liquid,
the number of drops produced from equal volume of two liquids and their densities must
be known, in addition to the surface tension of the reference liquid (e.g. water).
5.4. Viscosity of a liquid

Viscosity is one of the characteristic properties of liquids. Viscosity is a measure of
resistance to flow which arises due to the internal friction between layers of fluid as they
slip past one another while liquid flows. Strong intermolecular forces between molecules
hold them together and resist movement of layers past one another. Viscosity can be
defined as the force of friction between two layers of a liquid moving past one another
with different velocities.
Figure 5.4. Gradation of velocity in the laminar flow.
When a liquid flows over a fixed surface, the layer of molecules in the immediate
contact of surface is stationary. The velocity of upper layers increases as the distance of
layers from the fixed layer increases. This type of flow in which there is a regular gradation
of velocity in passing from one layer to the next is called laminar flow. If we choose any
layer in the flowing liquid (Fig.5.4), the layer above it accelerates its flow and the layer
below this retards its flow. If the velocity of the layer at a distance dz is changed by a
du
value: ‘du’ then velocity gradient is given by the amount . A force is required to
dz
maintain the flow of layers. This force is proportional to the area of contact of layers and
velocity gradient i.e.
F  A (A is the area of contact)
du du
F (where, is velocity gradient; the change in velocity with distance)
dz dz
du
F A
dz
du
F  A (4)
dz
‘η’ is proportionality constant and is called coefficient of viscosity. Viscosity coefficient
is the force when velocity gradient is unity and the area of contact is unit area. Thus ‘η’
is measure of viscosity. SI unit of viscosity coefficient is 1 Newton second per square
metre (N s m–2) = pascal second (Pa s = 1kg m–1s–1). In CGS system the unit of
coefficient of viscosity is poise (named after great scientist Jean Louise Poiseuille).
1 poise = 1 g cm–1s–1 = 10–1 kg m–1s–1
Greater the viscosity, the more slowly the liquid flows. The viscosity is very much
influenced by the shape, size and the chemical nature of the liquid molecules. The greater
the size of the molecules and the higher the molar mass, the higher will be the viscosity
because the greater will be the intermolecular interactions. The hydrogen bonds also
enhance the coefficient of viscosity to a large extent. It is, indeed, the presence of a
network of hydrogen bonds which accounts for the very high viscosity of glycerol.
Incidentally, the larger the number of hydroxyl groups in a molecule, the more complex
will be the network of hydrogen bonds and the greater will be the resistance of a liquid
to flow. In long chain hydrocarbons or polymeric compounds the viscosity increases with
the increase in the length of the molecular chain. Due to this reason, heavy hydrocarbon
oil and grease (which are used as lubricants) have fairly high viscosity values.
Effect of Temperature on viscosity of Liquids:
In liquids, as the temperature raises, the kinetic energy of the molecules increases
and the intermolecular forces of attraction become weak, resulting in the subsequent
decrease in the viscosity. The value of the coefficient of viscosity appreciably drops as
the temperature of liquid increases such that for each degree rise in temperature there is
about two percent decrease in the viscosity. The viscosity and temperature are related
to each other by the following expression:
A
log   B
T
where A and B are constants for a given liquid and T is the absolute temperature.
5.5. Determination of Coefficient of Viscosity using

Ostwald Viscometer
For the measurement of coefficient of viscosity of liquids having a laminar or
streamlined flow through a tube or pipe, Poiseuille derived an expression, known as
Poiseuille’s equation. This expression is given below.
pr 4 t
 (5)
8Vl
where = coefficient of viscosity of the liquid
V = volume of the liquid flowing out of the tube
t = time in which the volume V flows
r = radius of the tube
1 = length of the tube
p = driving pressure necessary to maintain uniform rate of flow of volume V, of the
liquid.
Figure 5.5. Diagram of a Ostwald viscometer.

This involves the use of Ostwald Viscometer (Figure 5.5) in which a fixed volume
of a liquid is allowed to fall under its own weight or the force of gravity, and the time
required for a given volume of the liquid to flow is noted. Obviously the driving pressure
p is replaced by h.d.g, where h is the height of the liquid and d is its density and g is
the acceleration due to gravity. Therefore,
p = h.d.g
Substituting h.d.g. for p in Poiseuille’s Equation 5, we get,
 r 4 .h.d.g. t
 (6)
8Vl
If equal volumes of the two liquids (1 and 2) are allowed to fall through the same
capillary tube under identical conditions of temperature and pressure then, from Eq. 5.6
by comparison, we have
1 d1.t1
 (7)
2 d 2 .t 2
where η1, d1and t1 are, respectively, the coefficient of viscosity, density and time of flow
for the liquid 1under examination and η2, d2 and t2 the corresponding values for the
reference liquid (liquid 2). Thus, by knowing η2, d2 , t2 and dl and tl the coefficient of
viscosity of first liquid, could be determined.
5.6. Summary
In this unit we have discussed about the characteristics of liquids. Surface tension
and viscosity of liquids were explained and the dependence of these characteristics on
intermolecular forces was highlighted. Also the theory behind experimental determination
of surface tension and viscosity were discussed.
5.7. Questions
1. What is surface tension? How the surface tension of a liquid varies with
Temperature?
2. What is surface energy? What is its unit?
3. Why the drop of a liquid is spherical?
4. Write down the theory for determination of surface tension using stalagmometer
by drop count method.
5. Why the viscosity of water is higher than alcohol?
6. How viscosity coefficient of a liquid does vary with temperature?
7. Write down the theory for determination of viscosity of a liquid using Ostwald
viscometer.
8. If 10 ml of water and ether forms 29 and 86 drops respectively in a viscometer
at 293 K, then calculate the surface tension of ether. Given that surface tension
of water is 7.2 x 10-2 N/m and density of ether is 0.7 gm/cc at 293 K.
(Ans. 1.6995 × 10-2 N/m)
9. In an Ostwald viscometer the flow time for water and toluene of equal volume
is 102.2 second and 68.9 second respectively. Find out the viscosity coefficient
of toluene if the viscosity coefficient of water is 0.01009 dyne s cm-2.
(Ans. 5.9 × 10-3 dyne s cm-2)
Unit 6  Solids
CONTENTS
6.0. Objectives
6.1. Introduction
6.2. Forms of solids
6.3. Symmetry elements
6.4. Unit cell
6.5. Crystal systems
6.6. Bravais lattice types
6.7. Law of Crystallography
6.7.1. Law of constancy of interfacial angles
6.7.2. Law of symmetry
6.7.3. Law of rational indices
6.8. Miller indices
6.9. X-Ray diffraction by crystals and Bragg's law
6.10. Structure of NaCl, KCl and CsCl
6.11. Defects in crystals
6.12. Summary
6.13. Questions
6.0. Objectives
After studying this Unit, we will be able to
 describe general characteristics of solid state
 distinguish between amorphous and crystalline solids
 identify the symmetry elements in a solid
 define lattice, basis, unit cell, primitive and nonprimitve cells
 describe the seven crystal systems and the fourteen Bravais lattices
 state the laws of crystallography

 state the crystal planes in terms of Miller indices,
 state Bragg’s law
 describe the structure of NaCl, KCl and CsCl
 describe the imperfections in solids and types of defects in a crystal
6.1. Introduction
We are mostly surrounded by solids and we use them more often than liquids and
gases. For different applications we need solids with widely different properties. These
properties depend upon the nature of constituent particles and the binding forces operating
between them. In gaseous state we have studied that if thermal energy is much greater
than the forces of attraction then we have matter in gaseous state. Molecules in gaseous
state move with very large speeds and because of very small attraction forces, the gas
molecules move practically independent of one another.
In the liquid state the forces of attraction are greater than the thermal energy. We
have also studied that molecules in liquid state too have kinetic energy, they cannot move
very far away because of the larger forces of attraction amongst them. Because of this
property, liquids have definite volume, but they do not have definite shape. Liquids also
resemble gases in their ability to flow. Gaseous and liquid states are, therefore, both
classified as fluids.
The solids are distinguished from a liquid or gas in terms of their rigidity which makes
them occupy definite volume and have a well defined shape. In solid state, the constituent
particles are in close contact and have strong forces of attraction between them.
A true solid possesses the following characteristics
(a) A sharp melting point
(b) A characteristic heat of fusion
(c) General incompressibility
(d) A definite three-dimensional arrangement
Hence solids are characterised by high density and low compressibility compared to
those of the gas phase. In solids, atoms, ions and molecules are held together by relatively
strong chemical forces- ionic bond, covalent bond, or by intermolecular Van der Waal’s
forces. They do not translate although they vibrate to some extent on their fixed positions.
This explains why solids are rigid and have definite shape.
6.2. Forms of solids

Solids can generally be classified into two broad categories:
(i) Crystalline solids
(ii) Amorphous solids
Figure 6.1. Two dimensional structure of (a) quartz and (b) quartz glass.
A crystalline solid exists as small crystals, each crystal having a characteristic

geometrical shape. In a crystal, the atoms, molecules or ions are arranged in a regular,
repeating three-dimensional pattern called the crystal lattice. Examples of crystalline solids
are sugar, salt, quartz etc. An amorphous solid (Greek amorphos = no form) consists
of particles of irregular shape. The arrangement of constituent particles (atoms, molecules
or ions) in such a solid has only short range order. In such an arrangement, a regular
and periodically repeating pattern is observed over short distances only. Such portions
are scattered and in between the arrangement is disordered. Examples of amorphous
solids are rubber, plastics and quartz glass. In their disordered structure, amorphous solids
are regarded as super-cooled liquids with high viscosity. The structures of quartz
(crystalline) and quartz glass (amorphous) are shown in Fig. 6.1 (a) and (b) respectively.
While the two structures are almost identical, yet in the case of amorphous quartz glass
there is no long range order.
Anisotropy and isotropy:

Amorphous substances differ from crystalline solids and resemble liquids in another
important aspect. Their properties such as electrical conductivity, thermal conductivity
mechanical strength and refractive index are same in all directions. Amorphous substances
are said to isotropic. Liquids and gases are also isotropic.
Figure 6.2. Anisotropy in crystals is due to different arrangement of particles along different directions.
Crystalline solids on the other hand are anisotropic, because their physical properties
are different in different directions. For example the velocity of light through a crystal
varies with the direction in which it is measured. Thus, a ray of light enter such a crystal
may split up into two components each following different velocity. This phenomenon is
known as double refraction. This can be shown in fig 6.2 in which simple two-dimensional
arrangement of only two different kinds of atoms is depicted if the properties are measured
along the direction indicated by the slanting line CD, they will be different from those
measured in the direction indicated by the vertical line AB. The reason is that while in
the first case, each row is made up of alternate types of atoms, in the second case; each
row is made up of one type of atoms only. In amorphous solids, atoms or molecules are
arranged at random and in a disorderly manner and, therefore all directions are identical
and all properties are alike in all directions.
6.3. Symmetry elements

In crystallography, symmetry is used to characterize crystals, identify repeating parts
of molecules. An object is described as symmetric with respect to a transformation if the
object appears to be in a state that is identical to its initial state, after the transformation.
In crystallography, most types of symmetry can be described in terms of an
apparent movement of the object such as some type of rotation or translation. The apparent
movement is called the symmetry operation. The locations where the symmetry operations
occur such as a rotation axis, a mirror plane or an inversion center are described
as symmetry elements.
Figure 6.3. Symmetry elements.
Plane of symmetry
When an imaginary plane can divide by a crystal into two parts such that one is the
exact mirror image of the other, the crystal is said to have a plane of symmetry.
Axis of symmetry
An axis of symmetry is a line about which the crystal is rotated such that it presents
the similar appearance more than once during complete rotation i.e. rotation through an
angle of 3600. Depending upon its nature, a crystal may have 2-fold, 3-fold, 4-fold or
6-fold axes of rotation.
Centre of Symmetry
It is a found at the centre of the crystal so that any line drawn through it will meet
the surface of the crystal at equal distance on either side. It may be pointed out that a
crystal may have number of planes or axis of symmetry but it has only one centre of
symmetry.
6.4. Unit cell

The main characteristic of crystalline solids is a regular and repeating pattern of
constituent particles. If the three dimensional arrangement of constituent particles in a
crystal is represented diagrammatically, in which each particle is depicted as a point, the
arrangement is called crystal lattice. Thus, a regular three dimensional arrangement of
points in space is called a crystal lattice. A portion of a crystal lattice is shown in Fig.
6.4.
Figure 6.4. Crystal lattice and unit cell of a solid.
Unit cell is the smallest portion of a crystal lattice which, when repeated in different
directions, generates the entire lattice. A unit cell is characterised by:
(i) its dimensions along the three edges, a, b and c. These edges may or may not
be mutually perpendicular.
(ii) angles between the edges, α (between b and c) β (between a and c) and ã
(between a and b). Thus, a unit cell is characterised by six parameters, a, b, c,
α, β and γ.
Unit cells can be of following types;
(a) Simple or primitive unit cell (P): The simplest unit cell which has the lattice
points at the corners is called a simple or primitive unit cell. It is denoted by P.
(b) Non primitive or multiple unit cell: When unit cell contains more than one
lattice points, it is called non primitive or multiple unit cell. It is further divided into the
following three categories:
(i) Face centred unit cell (F): When a unit cell, besides the points present at the
corners of the unit cell, there is one point at the centre of each face, it is called
face centred arrangement or face centred unit cell. It is denoted by F.
(ii) Body centred unit cell (I): When in a unit cell, besides the points at the
corners of the cell, there is one point at the centre with in its body, it is called
body-centred arrangement or body-centred with cell. It is denoted by I.
(iii) Side centre or end face unit cell: When in a unit cell, besides the points at
the corners of the cell, the points are located at the centre of any two parallel
faces of the unit cell, it is called side-centred or end face unit cell. It is denoted
by c.
6.5. Crystal systems

It can be shown from geometrical considerations that, theoretically, there can be 32
different combinations of elements of symmetry of crystal. These are called 32 point
Figure 6.5. Seven crystal system.

group or 32 crystal systems. Some of the systems, however, have been grouped together
so that we have only seven different categories, known as the seven basic crystal systems.
These are cubic, orthorhombic, tetragonal, monoclinic, triclinic, hexagonal and rhombohedral
or trigonal (figure 6.5). Crystal systems differ in length of the unit cell edges and the
angles between the unit cell edges.
6.6. Bravais lattice types

These seven different kinds of crystal systems in combination with four different kinds
of centerings (primitive, base-centered, body-centered, face-centered) can yield 14 distinct
lattice types which are called Bravais lattices. However, not all of the combinations of
crystal systems and centerings are unique; some of the combinations are equivalent while
other combinations are not possible due to symmetry reasons. This reduces the number
of unique lattices to the 14 Bravais lattices. The distribution of the 14 Bravais lattices into
lattice systems and crystal families is given in the figure 6.6.
Figure 6.6. The Fourteen Bravais lattices.

6.7. Law of Crystallography

There are three laws of crystallography which deal with the interfacial angles and the
rational indices.
6.7.1. Law of constancy of interfacial angles

Crystals are bound by surface which is usually planner. These surfaces are called
faces and where two faces intersect an edge is formed. The angle between the normals
to the two intersecting faces is the interfacial angle or the angle between any two faces
is called interfacial angle. Although the size of the faces or even shapes of crystals of one
and the same substances may vary widely with the condition of formation or other factors,
yet the interfacial angles between any two corresponding faces of the crystal remain
invariably the same throughout. This is shown in fig 6.7. Now it is clear that although the
external shape is different yet the interfacial angles are the same.
Figure 6.7. Constancy of interfacial angles.
6.7.2. Law of symmetry

The law of symmetry states that, all crystals of the same substance possess the same
elements of symmetry. Symmetry in crystals may be with respect to a plane, a line or
a point, accordingly there are three types of symmetry associated with a crystal which
was described earlier.
6.7.3. Law of rational indices

This law states that the intercepts of any face of a crystal along the crystallographic
axes are either equal to the unit intercepts (a, b, c) or some simple whole number multiples
of them, e.g., na, n’b, n”c, etc., where n, n’, n”, etc., are simple whole numbers.
Figure 6.8. Crystallographic axes and the law of rational indices.
Let OX, OY and OZ represent the three crystallographic axes and let ABC be a
unit plane (figure 6.8). The unit intercepts will then be a, b and c. According to the above
law, the intercepts of any face such as KLM, on the same three axes will be simple
whole number multiples of a, b and c, respectively. As can be seen from the figure, the
simple multiples in this case are 2, 2 and 3.
6.8. Miller indices

Miller indices are a set of integers (h, k, l) which are used to describe a given plane
in a crystal. The miller indices of a face of a crystal are inversely proportional to the
intercepts of that face on the various axes. The procedure for determination of Miller
indices for a plane is as follows:
(i) Write the intercepts as multiples of a, b, c say la, mb, nc
(ii) Take the reciprocals of l, m and n
(iii) Clear fraction to get whole numbers h,k,l.
(iv) Miller indices to the plane are (h,k,l).
Example: calculate the Miller indices of crystal planes which cut through the crystal
axes at (i) 2a, 3b, c and (ii) 6a, 3b, 3c
Solutions:
(i) a b c (ii) a b c
2 3 1 intercepts 6 3 3 intercepts
½ 1/3 1 reciprocals 1/6 1/3 1/3 reciprocals
3 2 6 clear fraction 1 2 2 clear fraction
Hence Miller indices are (326) Hence Miller indices are (122)
In a crystal, several planes can be imagined through the lattice points and they are
designated by Miller indices. If the Miller indices of a plane is (h, k, l), then all the planes
parallel to this plane will have the same Miller indices. The interplanar distance between
these parallel planes (dhkl) is given by the following equation:
2 2 2
1 h k l 
      
 d hkl 2 a  b c
Where h, k, l are the Miller indices of the planes and a, b, c are the dimensions
of the cell.
For a cubic system, a = b = c so the distance between two planes (dhkl) in a cubic
system
a
d hkl 
h  k2  l2
2
6.9. X-Ray diffraction by crystals and Bragg’s law

M. von Laue, a German physicist in 1913, suggested the possibility of diffraction of
X-rays by crystals as the wavelength of the X-rays was of about the same order as the
interatomic distances in a crystal. He has been awarded the 1914 Physics Nobel Prize
for his discovery of diffraction of X-rays by crystals. In fact W. H. Bragg succeeded in
diffracting X-rays from NaCl crystal. This observation has proved to be highly useful in
determining structures and dimensions of crystals.
Bragg’s pointed that the scattering of x-rays by crystal could be taken to be equivalent
to reflection from successive planes of atoms in the crystal. However the reflection of x-
rays can take place only at certain angles which are dependent on wavelength of the x-
rays and the distance between the planes of the crystal. The fundamental equation which
gives a simple relation between the wavelength of x-rays, the interplaner distance in the
crystal and the angle of reflection is known as Bragg’s equation.
Figure 6.9. X-Ray reflections from a crystal.
The horizontal lines represent parallel planes in the crystal structure separated from
one another by a distance d. Suppose, a beam of x-ray (MA) incident at an angle è falls
on the crystal and reflected from the crystal (AO). Some of them will be reflected from
uppermost plane at the same angle, while the other will be absorbed and get reflected
from successive planes, as shown in figure 6.9. Similarly, ray NB is reflected from the
second plane to yield BP. If the rays AO and BP are to reinforce one another for
constructive interference, they must have the same phase; this condition is met if the extra
distance traversed by NBP ray (i.e. QBR) is equal to an integral number of wavelengths
of the x-ray. The extra distance is (QB+ BR), so that (QB + BR) = nλ, where n is an
integer. But from the geometry of the situation, QB = BR = d sin θ. Consequently, in
terms of the interplanar spacing d, the condition for constructive interference becomes
2d sin θ = nλ, n = 1, 2, 3, . . . ,
which is the fundamental law of x-ray crystallography, the Bragg condition, or Bragg’s
law. For a given wavelength of x-rays, the reflected beam will emerge only at those
angles for which the Bragg condition is satisfied.
6.10. Structure of NaCl, KCl and CsCl

The ionic crystal of NaCl is shown in Fig 6.10. Each sodium ion is surrounding by
six chloride ions and each chloride ions is surrounded by six sodium ions. The maximum
intensity of reflection occurs at the glancing angle of 5.90, 8.40 and 5.20 for 100, 110
and 111 planes, respectively for first order reflection. From this x-ray diffraction data it
can be shown that the NaCl crystal has a face centred cubic (FCC) lattice structure.
Figure 6.10. Structure of NaCl crystal.
The structure of KCl crystal is similar (isomorphous) to that of NaCl. But investigating
the KCl crystal, the maximum reflection of x-rays, corresponding to first order reflections
are observed to occur at the glancing angles of 5.380, 7.610 and 9.380 for (100), (110)
and (111) faces, respectively which corresponds to a simple cubic lattice structure. The
explanation for this apparent anomaly is very simple and can be explained on the basis
that the x-rays scattering power for an atom or ion is governed by the number of electrons
or atomic number.
The atomic numbers of potassium (K=19) and chlorine (Cl=17) are not very different
and the x-rays are unable to detect any difference between the two kinds of atoms. If
we imagine all the atoms to be identical, it is evident that face-centred arrangement has
become a simple cubic arrangement. This is the reason for the KCl spectrum corresponding
apparently to the simple cubic lattice. With KCl, the structure is face-centred, but the
face-centred characteristics are marked by the fact that the two types of atoms composing
the substance have nearly the same atomic numbers and atomic weights (K=39, Cl=35.5).
But in the case of sodium chloride the atomic numbers differ considerably (Na=11, Cl=17),
and so their scattering powers are different and hence the true structure as two
interpenetrating face-centred lattices become apparent.
Cesium chloride, CsCl, has a body centred cubic (BCC) structure. In its crystal
lattice, each Cs+ ion is surrounded by 8 Cl- ions and its coordination number is 8. The
value of distance between Cs+ ion and Cl- ion as determined by Bragg’s spectrometer is
3.510Å (figure 6.11).
Figure 6.11. Structure of cesium chloride crystal lattice.

6.11. Defects in crystals

Although crystalline solids have short range as well as long range order in the
arrangement of their constituent particles, yet crystals are not perfect. The defects are
basically irregularities in the arrangement of constituent particles. Broadly speaking, the
defects are of two types, namely, point defects and line defects. Point defects are the
irregularities or deviations from ideal arrangement around a point or an atom in a crystalline
substance, whereas the line defects are the irregularities or deviations from ideal
arrangement in entire rows of lattice points. These irregularities are called crystal defects.
Point defects can be classified into three types: (a) stoichiometric defects, (b) impurity
defects and (c) non-stoichiometric defects.
(a) Stoichiometric Defects: These are the point defects that do not disturb the
stoichiometry of the solid. They are also called intrinsic or thermodynamic defects. Basically
these are of two types, vacancy defects and interstitial defects.
(i) Vacancy Defect: When some of the lattice sites are vacant, the crystal is said
to have vacancy defect (Fig. 6.12 i). This results in decrease in density of the
substance. This defect can also develop when a substance is heated.
(ii) Interstitial Defect: When some constituent particles (atoms or molecules)
occupy an interstitial site, the crystal is said to have interstitial defect (Fig. 6.12
ii). This defect increases the density of the substance.
Figure 6.12. Stoichiometric defects: (i) vacancy defect and (ii) interstitial defect.
Vacancy and interstitial defects as explained above can be shown by non-ionic solids.
Ionic solids must always maintain electrical neutrality. Rather than simple vacancy or
interstitial defects, they show these defects as Schottky and Frenkel defects.
100  NSOU  GE-CH-11
(iii) Schottky Defect: It is basically a vacancy defect in ionic solids. In order to

maintain electrical neutrality, the number of missing cations and anions are equal
(Fig 6.13a) in the crystal. Like simple vacancy defect, Schottky defect also
decreases the density of the substance. Number of such defects in ionic solids
is quite significant. For example, in NaCl there are approximately 106 Schottky
pairs per cm3 at room temperature. In 1 cm3 there are about 1022 ions. Thus,
there is one Schottky defect per 1016 ions. Schottky defect is shown by ionic
substances in which the cation and anion are of almost similar sizes. For examples,
NaCl, KCl, CsCl and AgBr. It may be noted that AgBr shows both, Frenkel
as well as Schottky defects.
Figure 6.13. Schottky defect and Frenkel defect in a crystal lattice.
(iv) Frenkel Defect: This defect is shown by ionic solids. The smaller ion (usually
cation) is dislocated from its normal site to an interstitial site (Fig. 6.13b) of the
crystal. So it creates a vacancy defect at its original site and an interstitial defect
at its new location. Frenkel defect is also called dislocation defect. It does not
change the density of the solid. Frenkel defect is shown by ionic substance in
which there is a large difference in the size of ions, for example, ZnS, AgCl,
AgBr and AgI due to small size of Zn2+ and Ag+ ions.
(b) Impurity Defects: If molten NaCl containing a little amount of SrCl2 is
crystallised, some of the sites of Na+ ions are occupied by Sr2+ (Fig 6.14). Each Sr2+
replaces two Na+ ions. It occupies the site of one ion and the other site remains vacant.
The cationic vacancies thus produced are equal in number to that of Sr2+ ions. Another
similar example is the solid solution of CdCl2 and AgCl.
NSOU  GE-CH-11  101
Figure 6.14. Impurity defect in NaCl crystal by presence of Sr2+ ion as impurity.
(c) Non-Stoichiometric Defects: The defects discussed so far do not disturb the
stoichiometry of the crystalline substance. However, a large number of nonstoichiometric
inorganic solids are known which contain the constituent elements in non-stoichiometric
ratio due to defects in their crystal structures. These defects are of two types: (i) metal
excess defect and (ii) metal deficiency defect.
(i) Metal Excess Defect: This type of defects in crystals can be formed by
absence of anion in the lattice site or by the presence of extra cation in the
interstitial position.
Metal excess defect due to anionic vacancies: Alkali halides like NaCl and KCl
show this type of defect. When crystals of NaCl are heated in an atmosphere of sodium
vapour, the sodium atoms are deposited on the surface of the crystal. The Cl– ions diffuse
to the surface of the crystal and combine with Na atoms to give NaCl. This happens by
loss of electron by sodium atoms to form Na+ ions. The released electrons diffuse into
the crystal and occupy anionic sites (Fig 6.15). As a result the crystal now has an excess
of sodium. The anionic sites occupied by unpaired electrons are called F-centres. They
impart yellow colour to the crystals of NaCl. The colour results by excitation of these
electrons when they absorb energy from the visible light falling on the crystals. Similarly,
excess of lithium makes LiCl crystals pink and excess of potassium makes KCl crystals
violet (or lilac).
102  NSOU  GE-CH-11
Figure 6.15. Metal excess defect and F-centres.
Metal excess defect due to the presence of extra cations at interstitial sites:
Zinc oxide is white in colour at room temperature. On heating it loses oxygen and turns
yellow.
1
 Zn 2  O 2  2e
heating
ZnO 
2
Now there is excess of zinc in the crystal and its formula becomes Zn1+xO. The
excess Zn2+ ions move to interstitial sites and the electrons to neighbouring interstitial sites
(Fig 6.16).
(ii) Metal Deficiency Defect: There are many solids which are difficult to prepare
in the stoichiometric composition and contain less amount of the metal as
compared to the stoichiometric proportion. In this case some of the metal ions
posses’ higher valences to maintain the electronutrality of the crystal. A typical
example of this type is FeO which is mostly found with a composition of Fe0.95O.
NSOU  GE-CH-11  103
Figure 6.16. Metal excess defect due to the presence of extra cations at interstitial sites.
It may actually range from Fe0.93O to Fe0.96O. In crystals of FeO some Fe2+
cations are missing and the loss of positive charge is made up by the presence
of required number of Fe3+ ions.
Figure 6.17. Metal deficiency defect in crystals.

104  NSOU  GE-CH-11
6.12. Summary
In this unit, we have briefly described different forms of solid substances and found
that they can be distinguished as crystalline and amorphous. We have studied the terms-
lattice, basis and unit cell of crystalline solids. Symmetry elements present in the different
crystal lattice were discussed. Seven crystal systems and fourteen Bravais lattices were
explained. Different laws of crystallography were discussed and indexing of crystal planes
was explained. Diffraction method and its utility in crystal structure determination were
emphasised on the basis of Bragg’s law. Finally different types of crystal defects were
highlighted.
6.13. Questions
1. Define the term amorphous. Give a few examples of amorphous solids.
2. What is lattice?
3. Give definition of unit cell.
4. What are the symmetry elements present in a crystal?
5. What is the Miller indices of a crystal plane which makes intercepts 3a/2, 2b,
c.? [Ans. (4, 3, 6)]
6. What are the separations of the planes with Miller indices (2, 2, 1) for a cubic
lattice of side length 3Å? [Ans. 1 Å]
7. If an X-ray (wavelength = 1.539 Å) gets reflected at an angle of 22.50 from a
set of crystal planes, then find out the distance between the crystal planes.
[Ans. 2.01 Å]
8. Write down the differences in structure between the crystals of NaCl and KCl.
9. What are Frenkel and Schottky defects? Explain with examples.
NSOU  GE-CH-11  105
Unit 7  Solutions
Contents
7.0. Objectives
7.1. Introduction
7.2. Units for the expression of concentration of solution
7.3. Ideal Solution
7.4. Raoult's law
7.5. Non-ideal solution and deviation from Roult's law
7.6. Vapour pressure-composition curves of ideal and non-ideal solutions
7.7. Temperature-composition curves of ideal and non-ideal solutions
7.8. Partial miscibility of liquids
7.9. Critical solution temperature
7.10. Principle of steam distillation
7.11. Nernst distribution law and its applications
7.12. Solvent extraction
7.13. Summary
7.14. Questions
7.0. Objectives
After studying this unit, we will be able to
 describe the formation of different types of solutions;
 express concentration of solution in different units;
 state and explain Raoult’s law;
 distinguish between ideal and non-ideal solutions;
 explain deviations of real solutions from Raoult’s law;
106  NSOU  GE-CH-11
 describe partial miscibility of liquids and critical solution temperature;

 explain steam distillation and solvent extraction process.
7.1. Introduction
Solutions are homogeneous mixtures of two or more than two components. By
homogenous mixture we mean that its composition and properties are uniform throughout
the mixture. Generally, the component that is present in the largest quantity is known as
solvent.
Solvent determines the physical state in which solution exists. One or more components
present in the solution other than solvent are called solutes. Depending upon the nature
of solvent and solute, solutions can be of different types. On the basis of physical state
of solute and solvent it can be categorize in the following ways:
Type of Solution Solute Solvent Common Examples
Gaseous Solutions Gas Gas Mixture of oxygen and nitrogen gas (Air)
Liquid Gas Chloroform mixed with nitrogen gas
Solid Gas Camphor in nitrogen gas
Liquid Solutions Gas Liquid Oxygen dissolved in water
Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water
Solid Solutions Gas Solid Solution of hydrogen in palladium
Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold
7.2. Units for the Expression of Concentration of Solution

There are several ways by which we can describe the concentration of the solution
quantitatively.
Normality: Normality (N) is defined as number of gram equivalent of solute dissolved
in one litre (or one cubic decimetre) of solution.
Gram equivalent of solute
Normality 
Volume of solution in litre
NSOU  GE-CH-11  107
For example, 1.00 g.equiv L–1 (or 1.00 N) solution of H2SO4 means that 1 gram
equivalent (49 g) of H2SO4 is dissolved in 1 litre of solution.
Molarity: Molarity (M) is defined as number of moles of solute dissolved in one
litre (or one cubic decimetre) of solution.
Moles of solute
Molarity 
Volume of solution in litre
For example, 0.25 mol L–1 (or 0.25 M) solution of NaOH means that 0.25 mol of
NaOH has been dissolved in one litre (or one cubic decimetre).
Molality: Molality (m) is defined as the number of moles of the solute per kilogram
(kg) of the solvent and is expressed as:
Moles of solute
Molality 
Volume of solvent in kg
For example, 1.00 mol kg–1 (or 1.00 m) solution of KCl means that 1 mol (74.5
g) of KCl is dissolved in 1 kg of water.
Mole fraction: Commonly used symbol for mole fraction is x and subscript used
on the right hand side of x denotes the component. It is defined as:
Number of moles of the component

Mole fraction of a component 
Total number of moles of all the components
For example, in a binary mixture, if the number of moles of A and B are nA and nB
respectively, the mole fraction of A will be
nA
xA 
nA  nB
For a solution containing i number of components, we have:
ni n
xi   i
n1  n 2  n 3  ... ... ...  n i  n i
It can be shown that in a given solution sum of all the mole fractions is unity, i.e.
x1 + x2 + x3 + .................. + xi = 1
108  NSOU  GE-CH-11
Mole fraction unit is very useful in relating some physical properties of solutions, say
vapour pressure with the concentration of the solution and quite useful in describing the
calculations involving gas mixtures.
Parts per million (ppm): When a solute is present in trace quantities, it is convenient
to express concentration in parts per million (ppm) and it is defined as:
Number of parts of the component

Parts per million  106
Total number of parts of all components of the solution
As in the case of percentage, concentration in parts per million can also be expressed
as mass to mass, volume to volume and mass to volume. A litre of sea water (which
weighs 1030 g) contains about 6 × 10–3 g of dissolved oxygen (O2). Such a small
concentration is also expressed as 5.8 g per 106 g of sea water or 5.8 ppm. The
concentration of pollutants in water or atmosphere is often expressed in terms of μg
mL–1 or ppm.
7.3. Ideal Solution

The solutions which obey Raoult’s law over the entire range of concentration are
known as ideal solutions. The ideal solutions have two other important properties. For
an ideal solution, enthalpy of mixing is zero (ΔHmix = 0) and volume of mixing is also zero
(ΔVmix = 0). It means that no heat is absorbed or evolved when the components are
mixed and also final volume of the solution is equal to the sum of volume of two
components being mixed. In ideal solution, the interaction between A-B is same as the
interaction between A-A and B-B which are the constituent. The partial molar volume of
a constituent in an ideal solution is equal to the molar volume of the constituent when
present in the pure form. A perfectly ideal solution is rare but some solutions are nearly
ideal in behaviour. Solutions of n-hexane and n-heptane, bromoethane and chloroethane,
benzene and toluene, etc. fall into this category.
7.4. Raoult’s law

Let us consider a binary solution of two volatile liquids and denote the two components
as A and B. When taken in a closed vessel, both the components would evaporate and
eventually an equilibrium would be established between vapour phase and the liquid phase.
Let the total vapour pressure at this stage be ptotal and pA and pB be the partial vapour
NSOU  GE-CH-11  109
pressures of the two components A and B respectively. These partial pressures are related
to the mole fractions xA and xB of the two components A and B respectively.
The French chemist, Francois Marte Raoult (1886) gave the quantitative relationship
between them. The relationship is known as the Raoult’s law which states that for a
solution of volatile liquids, the partial vapour pressure of each component of the solution
is directly proportional to its mole fraction present in solution.
Thus, for component A
pA  xA
so, pA = pA0.xA
where pA0 is the vapour pressure of pure component A at the same temperature.
Similarly, for component B
pB = pB0.xB
where pB0 represents the vapour pressure of the pure component B.
According to Dalton’s law of partial pressures, the total pressure (ptotal) over the
solution phase in the container will be the sum of the partial pressures of the components
of the solution and is given as:
ptotal = pA + pB
Figure 7.1. The plot of vapour pressure and mole fraction of an ideal solution at constant temperature.
110  NSOU  GE-CH-11
Substituting the values of pA and pB, we get
ptotal = xA.pA0 + xB.pB0 = (1 – xB).pA0 + xB.pB0 = pA0- xB (pB0 - pA0)
A plot of pA or pB versus the mole fractions xA and xB for a solution gives a linear
plot as shown in Fig. 7.1. These lines (I and II) pass through the points for which xA
and xB are equal to unity. Similarly the plot (line III) of ptotal versus xB is also linear (Fig.
7.1). The minimum value of ptotal is pA0 and the maximum value is pB0, assuming that
component B is less volatile than component A, i.e., pA0 > pB0.
7.5. Non-ideal Solution and Deviation from Roult’s Law

Non- ideal solutions are also known as non- ideal liquid mixtures or real solutions.
If a solution does not obey Raoult’s law over the entire range of concentration and
temperature, the solution is said to be non-ideal solution. The vapour pressures of these
solutions are higher or lower than the pressure obtained by using Raoult’s law. Here the
enthalpy of mixing (ΔHmix) and volume of mixing (ΔVmix) is not equal to zero. In these
solutions, the force between A-B is different from A-A and B-B (individual components).
Non- ideal solutions are classified into two types: Non- ideal solution showing positive
deviation (vapour pressure obtained is higher than calculated using Raoult’s law) and
non- ideal solution showing negative deviation (vapour pressure obtained is lower than
calculated using Raoult’s law).
Non-ideal solution showing positive deviation: In the solution of component A
and B, the interaction between A-B is weaker than A-A and B-B interaction. In this case
the intermolecular attractive forces between the solute-solvent molecules are weaker than
those between the solute-solute and solvent-solvent molecules. This means that in such
solutions, molecules of A (or B) will find it easier to escape than in pure state. Hence
the vapour pressure of the solution is higher than the pressure predicted by Raoult. The
enthalpy of mixing is positive. For example, the mixture of ethanol and hexane, acetone
and carbon disulphide, carbon tetrachloride and benzene, carbon tetrachloride and toluene
shows positive deviation. In pure ethanol, molecules are hydrogen bonded. On adding
acetone, its molecules get in between the host molecules and break some of the hydrogen
bonds between them. Due to weakening of interactions, the solution of ethanol and acetone
shows positive deviation from Raoult’s law. Figure 7.2 represents the curve showing positive
deviation.
NSOU  GE-CH-11  111
Figure 7.2. The vapour pressures of two component system as a function of composition for a
solution that shows positive deviation from Raoult’s law.
Non-ideal solution showing negative deviation: In the solution of component A

and B, the interaction between A-B is stronger than A-A and B-B interaction. Here the
vapour pressure of a solution is lower than the pressure predicted by Raoult. The enthalpy
of mixing is negative. For example, the mixtures of acetone and water, phenol and aniline,
Figure 7.3. The vapour pressures of two component system as a function of composition for a
solution that shows negative deviation from Raoult’s law.
112  NSOU  GE-CH-11
chloroform and benzene, acetic acid and pyridine shows negative deviation. A mixture of
chloroform and acetone shows negative deviation from Raoult’s law, because chloroform
molecule forms hydrogen bond with acetone molecule which decreases the escaping
tendency of molecules for each component. Thus vapour pressure decreases resulting in
negative deviation from Raoult’s law. Figure 7.3 represents the curve showing negative
deviation.
7.6. Vapour Pressure-composition Curves of Ideal and

Non-ideal Solutions
So far we have seen the variation of total vapour pressure with the mole fraction of
the either constituent in the liquid. Now, in order to find the variation of total vapour
pressure with the mole fraction of either A or B in the vapour we can plot the vapour
pressure composition curve shown in figure 7.4. Curve I shows the variation of total
vapour pressure with respect to the mole fraction in the liquid phase. Similarly, curve II
shows the variation of the total vapour pressure with respect to the mole fraction in the
vapour phase. It is expected that the mole fraction of a more volatile component in an
ideal solution will be more in the vapour phase than in the liquid phase. So the vapour
Figure 7.4. Liquid and vapour composition curves for an ideal solution.
NSOU  GE-CH-II  113
phase curve (curve II) lies below the liquid phase curve (curve I). The line ab is called
a tie line and it gives us the composition of the solution in the liquid and vapour phases
in equilibrium at a particular total vapour pressure.
The curves I and I1 of Fig. 7.4 are obtained in the case of solutions obeying Raoult’s
law. In the case of solutions showing positive deviation from Raoult’s law, the liquid and
vapour composition curves are of the type shown in Fig. 7.5. Note that there is a maximum
point, M, where both the liquid and vapour phases have the same composition.
Figure 7.5. Liquid and vapour composition curves for a liquid mixture showing positive deviation.
In the case of a solution showing negative deviation from Raoult’s law, the liquid and
vapour composition curves are of the type shown in Fig. 7.6. Note that the curves meet
at the minimum point M where both the liquid and vapour phases have the same
composition.
7.7. Temperature-composition Curves of Ideal and Non-

ideal Solutions
Let us consider a binary mixture consisting of two liquids A and B which are completely
miscible with each other. On heating under constant pressure, say, under atmospheric
114  NSOU  GE-CH-11
Figure 7.6. Liquid and vapour composition curves for a liquid mixture showing negative deviation.
pressure, it will start boiling when the total vapour pressure becomes equal to the
atmospheric pressure. If p represents the atmospheric pressure, then the condition for
boiling is
p = pA + pB
where pA and pB are the partial pressures of the two components A and B. Since different
compositions of a solution have different vapour pressures, the various solutions will not
reach a total vapour pressure equal to the atmospheric pressure at the same temperature.
Hence, the solutions of different compositions will boil at different temperatures. In general,
solutions of low vapour pressure will boil at temperatures higher than those of solutions
for which the vapour pressures are high. It is because solutions of high vapour pressure
can have the total pressure equal to the atmospheric pressure at relatively lower
temperatures as compared to solutions for which vapour pressures are low. Hence it is
possible to draw temperature-composition diagrams which will correspond to the three
general types of vapour pressure composition diagrams.
For an ideal solution of two miscible liquid A and B the boiling point-composition
curve is shown in figure 7.7. Let the vapour pressure of pure A be higher than that of
pure B. Consequently at constant pressure, the boiling point of A (TA) will be lower than
NSOU  GE-CH-11  115
that of B (TB). Now as compared to the liquid mixture, the vapour is richer in the more
volatile component. So as in the present case A is more volatile than B, hence, the
vapour composition at any temperature must lie closer to A than the corresponding liquid
composition. In other words, in the composition against temperature plot, the vapour
composition curve must lie above the liquid composition curve. From this plot it can be
understood that by boiling the solution from a mixture of two miscible liquids pure liquids
can be separated. This process is known as fractional distillation.
Figure 7.7. Boiling point-composition diagram of an ideal liquid.
Boiling point-composition diagram of a liquid mixture showing positive deviation from

Raoult’s law is shown in Fig. 7.8(I). Note that this system has a minimum point (C)
where the liquid and vapour phases have the same composition. Similarly the boiling
point-composition diagram of a liquid mixture showing negative deviation from Raoult’s
law and it is shown in Fig. 7.8(II). For this type of solutions a maximum point D is
observed where the liquid and vapour phases have the same composition.
The constant boiling mixtures having composition C in type I solutions (Fig. 7.8.(I))
and composition D in type II solutions (Fig. 7.8.(II)) are called azeotropes (i.e., liquids
116  NSOU  GE-CH-11
boiling unchanged). They resemble pure compounds in their boiling behaviour. However,
changes in pressure produce changes in the composition as well as the boiling point of
the azeotropes. The azeotropes are not chemical compounds but are rather mixtures
resulting from the interplay of intermolecular forces in solution.
Figure 7.8. (I) Boiling point-composition diagram of a liquid mixture showing positive deviation; (II)
Boiling point-composition diagram of a liquid mixture showing negative deviation.
7.8. Partial miscibility of liquids

Some liquid pairs do not form solutions in all compositions. Such liquid pairs are said
to be partially miscible liquids. However, due to increased solubility with increase or
decrease of temperature, these may become completely miscible.
We can understand such a system by using the example of a system containing phenol
and water. When a very small amount of phenol is added to water at room temperature,
it dissolves completely to give a single liquid phase. However, when the addition of phenol
is continued, a point is reached when phenol does not dissolve anymore. At this point,
two phases, i.e., two liquid layers are formed–one consisting of water saturated with
phenol and the other containing phenol saturated with water. Further addition of phenol
causes water to shift from water–rich layer to phenol–rich layer. If the addition of phenol
is continued, a point is reached when phenol acts as a solvent for all the water present
and the two phases merge with each other to form a single phase, i.e., solution of water
in phenol. Thus, on shaking equal volumes of phenol and water, two layers are formed–
one of saturated solution phenol in water and the other of saturated solution water in
phenol.
NSOU  GE-CH-11  117
7.9. Critical solution temperature

The temperature above (or below) which a pair of partially miscible liquids becomes
miscible in all proportions, is called critical solution temperature (CST) or consolute
temperature for the pair.
As discussed earlier, phenol and water are only partially miscible at ordinary
temperature. On shaking these two liquids with each other, two saturated solutions of
different compositions, one of phenol in water and the other of water in phenol, are
obtained. Such solutions of different compositions co-existing with one another are termed
conjugate solutions. Since the mutual solubility of phenol and water increases with rise
in temperature, the critical solution temperature (CST) lies on top of the dome. Hence,
such liquid systems are said to possess an upper critical solution temperature or upper
consolute temperature. Thus, the critical solution temperature, for phenol-water system is
338.8 K. At and above 338.8 K, phenol and water are completely miscible with each
other in all proportions. At this temperature, the composition of the solution is 36.1%
phenol and 63.9% water. Outside the curve we have a homogeneous solution of phenol
and water and inside the curve we have two conjugate solutions L1 (phenol in water)
and L2 (water in phenol) in equilibrium with each other (Figure 7.9 ).
Figure 7.9. Temperature versus solubility plot for phenol-water system.
There are some liquid pairs (e.g., triethylamine-water) for which mutual solubilities
decrease with rise in temperature. As the temperature is decreased, the mutual solubilities
118  NSOU  GE-CH-11
increase and below the consolute temperature, the two liquids become miscible in all
proportions. Such systems possess lower consolute temperature. The variation of mutual
solubility of triethylamine and water with temperature is shown in Fig. 7.10.
Figure 7.10. Temperature composition diagram for triethylamine-water system.
There are a few liquids pairs, e.g., nicotine and water which show both the upper
and lower consolute temperatures. These liquid pairs are completely miscible above a
Figure 7.11. Temperature composition diagram for nicotine-water system.

NSOU  GE-CH-11  119
certain temperature (upper consolute temperature) and also below a certain temperature
(lower consolute temperature). The variation of mutual solubilities of nicotine and water
with temperature is shown in Fig. 7.11.
The presence of an impurity, dissolved in one or both of the phases, changes the
CST values as well as the liquid composition at CST. Substance soluble in only one of
the liquids raises the upper CST and lowers the lower CST.
7.10. Principle of steam distillation

The fact, that a system of immiscible liquids starts boiling at temperatures less than
the normal boiling points of both the liquids, is made use of in steam distillation. The
steam distillation is a process of purifying organic liquids which have high boiling points
and are immiscible with water. For purification by steam distillation, an impure compound
i) must be immiscible in water,
ii) should not decompose at the temperature of steam,
iii) should have a fairly high vapour pressure at 373 K,
iv) should have non-volatile impurities.
Figure 7.12. Experimental setup for steam distillation.

120  NSOU  GE-CH-11
For example, chlorobenzene has a boiling point of 405 K. A mixture of water and
chlorobenzene distils at a constant temperature of 363.3 K, when the external pressure
in 9.8 × 104 Pa, by passing steam through it. Let us explain the procedure for purifying
an organic liquid using steam distillation. The apparatus used for steam distillation is as
shown in Figure 7.12.
The impure organic compound is taken in a round-bottomed flask (A) and a small
quantity of water is added. The flask must be kept in a slanting position to prevent the
impure liquid from splashing up into the condenser. The flask A is then heated gently.
Now, steam from container B is bubbled through the contents of the flask A. Vapours
of the organic compound mix with steam and escape into the water condenser C. The
condensate thus obtained in the flask F is a mixture of water and the organic compound.
This mixture can then be separated by means of a separating funnel.
7.11. Nernst distribution law and its applications

When two immiscible solvents A and B taken in a beaker, they form separate layers.
Now a solute X which is soluble in both solvents is added, it gets distributed or partitioned
between them. Molecules of X pass from solvent A to B and from B to A. finally a
dynamic equilibrium is set up. At equilibrium, the rate, at which molecules of X pass from
one solvent to the other is balanced.
Concentration of X in A
 a constant
Concentration of X in B
Nernst (1891) studied the distribution of several solutes between different appropriate
pairs of solvents and gave a generalization which governs the distribution of a solute
between two non-miscible solvents. This is called Nernst’s Distribution law or Nernst’s
Partition law or simply Distribution law or Partition law.
It states that,
“if a solute X distributes itself between two immiscible solvents A and B at constant
temperature and X is in the same molecular condition in both solvents.”
Concentration of X in A
 KD
Concentration of X in B
NSOU  GE-CH-11  121
If C1 denotes the concentration of the solute in solvent A and C2 the concentration

in solvent B, Nernst’s Distribution law can be expressed
C1
 KD
C2
The constant KD (or simply K) is called the distribution coefficient or Partition

coefficient or Distribution ratio.
When a solute is shaken with two non-miscible solvents, at equilibrium both the
solvents are saturated with the solute. Since the solubility also represents concentration,
the Distribution Law is also written as,
C1 S1
  KD
C 2 S2
where S1 and S2 are the solubilities of the solute in the two solvents.
Limitations of Distribution law:

Nernst distribution law is applicable for the following conditions only
1. Temperature should remain constant
2. Similar molecular species of the solute should remain in the two phases in
contact with each other.
3. The solutions should be dilute.
4. The two liquids should be mutually insoluble or only very sparingly soluble (e.g.,
benzene and water) and their mutual solubility should not be altered by the
presence of the solute.
Applications of the Distribution Law:

The study of the distribution of a solute between two immiscible solvents is quite
useful in a number of ways. A few of these applications are:
1. Association of the solute molecule in one solvent can be studied from the study
of distribution. As for example, by studying the distribution of acetic acid and
benzoic acid between water and benzene, it is possible to show that acetic acid
and benzoic acid exist as dimers in benzene.
122  NSOU  GE-CH-11
2. If a solute dissociates in one of the solvents, then knowing the distribution

coefficient, the degree of dissociation of the solute can be calculated at a particular
temperature.
3. The distribution law has also been used in the study of many problems e.g.,
solvent extraction, analysis and determination of equilibrium constants.
7.12. Solvent extraction

Solvent extraction is used both at laboratory and industrial scale in various processes.
An organic compound can often be extracted economically from an aqueous solution or
a suspension by,
 adding an organic solvent,
 shaking and separating the two layers, and
 finally, distilling off the organic solvent to recover the separated compound.
In the process of extraction, we make use of the fact that the distribution coefficient
of most of the organic compounds is very large in favour of organic solvents. It can be
shown that with a given volume of an extracting liquid, the organic compound extracted
is more if the given volume of the extracting liquid is used in a number of smaller portions
than if the whole of it is used in one portion.
Let us consider an aqueous solution of volume V. Let the mass of an organic compound
dissolved in it be w. Let us use volume v of the organic liquid for each extraction and
let the mass of the organic compound that remained unextracted in water one extraction
be w1. Then after, the first extraction
w1
Concentration of the organic compound in the aqueous layer =
V
Mass of the organic compound in the organic layer = w – w1
w  w1
Concentration of the organic compound in the organic layer =
v
Distribution coefficient, K, is given by the following expression:
w1
w1v
K V 
w  w1  w  w1  V
v
NSOU  GE-CH-11  123
From this expression we get the amount of the organic compound that remained
KV
unextracted after first extraction (w 1 )  w
v  kV
Similarly, after the second extraction, the mass of the organic compound that remains
2
 KV 
unextracted is, w 2  w  
 v  kV 
In general, the mass of the organic compound that remains unextracted after n
n
 KV 
extractions is given by, w n  w  
 v  kV 
7.13. Summary
In this unit we have learnt about the solutions and different type of solutions. Then
we have learnt that completely miscible liquid pairs may be ideal or non-ideal. Ideal
solutions obey Raoult’s law. Non-ideal solutions either show positive or negative deviation
from
Raoult’s law. We have learnt to draw the vapour pressure-composition and
temperature-composition curves for ideal and non-ideal solutions. We have discussed
about the partially miscibility of liquids and critical solution temperature. Then we have
seen that a pair of immiscible liquids boil at a temperature lower than the boiling points
of any of the liquids. This fact is made use of in steam distillation. We have learned about
the principle of steam distillation. Finally we have learned about the Nernst distribution
law for a system when a solute is added to a pair of immiscible liquids and its applications
in solvent extraction.
7.14. Questions
1. Give an example of a solid solution in which the solute is a gas.
2. Define the following terms: (i) Mole fraction (ii) Molality (iii) Molarity.
3. Write down the differences between ideal and non-ideal solution.
4. What is meant by positive and negative deviations from Raoult’s law?
124  NSOU  GE-CH-11
5. Draw the phase diagram of phenol-water system and explain the plot.
6. Write down the principle of steam distillation.
7. Describe Nernst distribution law and state its limitations.
8. If the solubility of I2 in water is 0.345 g/L at 30 0C then what is the solubility
of I2 in CCl4 at 30 0C? Given that the distribution coefficient for I2 in CCl4 and
water is 86. (Ans. 29.67 g/L)
Unit 8  Chemical Kinetics
Contents
8.0. Objectives
8.1. Introduction
8.2. The concept of reaction rates
8.3. Factors affecting reaction rates
8.4. Order and molecularity of a reaction
8.5. Derivation of integrated rate equations
8.5.1. Zero order reaction
8.5.2. First order reaction
8.5.3. Second order reaction
8.6. Half-life of a reaction
8.7. General methods for determination of order of a reaction
8.8. Concept of activation energy and its calculation from Arrhenius equation
8.9. Theories of Reaction Rates
8.9.1. Collision theory
8.9.2. Activated complex theory of bimolecular reactions
8.10. Summary
8.11. Questions
8.0. Objectives
After studying this unit, we should be able to:
 define rate law, rate constant of reaction,
 discuss the dependence of rate of reactions on pressure, temperature and
catalyst
126  NSOU  GE-CH-11
 differentiate between order and molecularity of a reaction,

 state the experimental methods for studying the reaction rates,
 derive integrated rate laws for zero order, first order and second order reactions
and use them for calculating rate constants,
 state the methods for determining the order of reaction,
 explain Arrhenius equation and activation energy,
 describe collision theory and activated complex theory.
8.1. Introduction
The branch of physical chemistry which deals with the speed or rate at which a
reaction occurs is called chemical kinetics. Chemical Kinetics is the study of rate of a
reaction under different conditions like different concentrations, pressures, temperatures,
catalyst, pH, dielectric constant of the medium, free radical scavengers, neutral salts etc
and suggesting a suitable mechanism for the reaction.
Chemical kinetics constitutes an important topic in physical chemistry. It concerns
itself with measurement of rates of reactions proceedings under given condition of
temperature, pressure and concentration.
The study of chemical kinetics has been highly useful in determining the factors which
influence rate of reaction as well as in understanding mechanism of a number of chemical
reactions. The experimental data have led to the development of the modern theories of
chemical reactivity of molecules.
In this Unit, we shall be dealing with rate of reaction and the factors affecting these.
Some elementary ideas about the collision theory and activated complex theory of reaction
rates are also given. However, in order to understand all these, let us first learn about
the reaction rate.
8.2. The concept of reaction rates

The rate of a reaction tells us to what speed the reaction occurs. Let us consider
a simple reaction
A→B
The concentration of A decreases and that of B increases with time. The rate of a
reaction is defined as the change in concentration of any of reactant or product with time.
NSOU  GE-CH-11  127
As you know during the progress of a reaction the concentration of A keeps on

falling with time. The rate of reaction at any given instant is given by the
expression
dCA
r (1)
dt
where –dcA is very small decrease in concentration of A in a very small time interval dt.
Now the concentration of product B increases with time. Hence rate of reaction can also
be expressed in terms of increase in concentration of the product B as well.
Thus
dCB
r (2)
dt
where dcB is very small increase in the concentration of product B in a very small time
interval of time dt.
Now it is from (1) and (2)
dCA dCB
r  (3)
dt dt
So for a reaction
A + B → M + N
the rate can be expressed
dCA dC dCM dC N
r  B   (4)
dt dt dt dt
Now let us consider a reaction

aA + bB → cC + dD
In this reaction a moles of A reacts with b moles of B to form c moles of C and
d moles of D. The rates of such a reaction can be expressed either in terms of decrease
in concentration of a reactant per mole or increase in concentration of a product per
mole.
128  NSOU  GE-CH-11
Thus we can write as follows:
1 dC A 1 dC B 1 dCC 1 dCD
r     kCaA CB
b
(5)
a dt b dt c dt d dt
Rate Law and the Rate Constant:

The rate of a chemical reaction at a given temperature may depend on the concentration
of one or more reactants and products. The representation of rate of reaction in terms
of concentration of the reactants is known as rate law. It is also called as rate equation
or rate expression. The rate of a reaction decreases with the passage of time as the
concentration of reactants decrease. Conversely, rates generally increase when reactant
concentrations increase. So, rate of a reaction depends upon the concentration of reactants.
The rate of the reaction
A → Products,
is experimentally found to be given by
dCA
r  kC A (6)
dt
where k is the rate constant or the velocity constant of the reaction at the given temperature.
This form of rate equation is known as the differential rate equation. If concentration of
A is unity, i.e., CA = 1, then, evidently, r = k. For a general reaction of the type:
aA + bB + cC → Products
The rate of the reaction is given by the rate law expression
r  kCaA CB
b c
CC (7)
If cA = cB = cC = 1, then k = r. Thus, the rate constant of a reaction, in general

is defined as the rate of the reaction when the concentration of each reactant is unity.
8.3. Factors affecting reaction rates

There are a number of factors which affect the rate of a reaction, the most important
of them are:
(a) Effect of concentration: The rate of a chemical reaction is influenced by the
no. of collisions per second between the reacting molecules. On increasing the concentration
NSOU  GE-CH-11  129
of the reactant, the number of collisions will increase and the rate of reaction will increase
and on decreasing the concentration the rate will decrease.
(b) Effect of nature of reactants: Reactions between polar or ionic molecules
occur almost instantaneously. Those reactions in which the bonds are arranged or electrons
are transferred takes a comparatively longer time than the reaction between ionic molecules.
We can cite the examples of neutralisation reactions or double displacement reactions
which are very fast while the oxidation reduction reactions are slower.
(c) Effect of catalyst: A catalyst can increase or decrease the rate of a chemical
reaction. For example the combination of hydrogen and oxygen to form water is slow
at ordinary temperature, while it proceeds rapidly in presence of platinum.
(d) Effect of surface area of reactant: Surface area of reactants is of importance
only for heterogeneous reactions. With the decrease in the particle size, surface area of
the reactant for the same mass increases. The smaller particle thus reacts more rapidly
than the larger particles. For example, burning of coal dust in air takes place more rapidly
than large lump of coal.
(e) Effect of temperature: With the exception of few reactions, it has been found
that generally an increase of temperature increases the rate of reaction. The ratio of rate
constants of a reaction at two temperatures differing by 100C is known as temperature
coefficient of the reaction. The temperatures usually selected for this purpose are 250C
and 350C. Thus
Rate at 350 C k 35
Temperature coefficient  0

Rate at 25 C k 25
The value of temperature coefficient for most of the reactants is close to 2 and in
some cases it approaches to 3.
8.4. Order and molecularity of a reaction

In the rate equation (7)
r  kCaA CBb CCc
a, b and c indicate how sensitive the rate is to the change in concentration of A and B.
Sum of these exponents, i.e., a + b + c gives the overall order of a reaction
130  NSOU  GE-CH-11
whereas a, b and c represent the order with respect to the reactants A, B and C
respectively.
Hence, the sum of powers of the concentration of the reactants in the rate law
expression is called the order of that chemical reaction.
Order of a reaction can be 0, 1, 2, 3 and even a fraction. A zero order reaction
means that the rate of reaction is independent of the concentration of reactants.
A balanced chemical equation never gives us a true picture of how a reaction
takes place since rarely a reaction gets completed in one step. The reactions taking
place in one step are called elementary reactions. When a sequence of elementary
reactions (called mechanism) gives us the products, the reactions are called complex
reactions.
The number of reacting species (atoms, ions or molecules) taking part in an elementary
reaction, which must collide simultaneously in order to bring about a chemical reaction
is called molecularity of a reaction. The reaction can be unimolecular when one reacting
species is involved as for example, decomposition of ammonium nitrite.
NH4NO2 → N2 + 2H2O
Bimolecular reactions involve simultaneous collision between two species, for example,
dissociation of hydrogen iodide.
2HI → H2 + I2
Trimolecular or termolecular reactions involve simultaneous collision between three
reacting species, for example,
2NO + O2 → 2NO2
The probability that more than three molecules can collide and react simultaneously
is very small. Hence, reactions with the molecularity three are very rare and slow to
proceed.
It is, therefore, evident that complex reactions involving more than three molecules
in the stoichiometric equation must take place in more than one step.
The molecularity of any process can only be small position integers, while order of
reaction can have zero as well as fractional values.
NSOU  GE-CH-11  131
8.5. Derivation of integrated rate equations

We have already noted that the concentration dependence of rate is called differential
rate equation. It is not always convenient to determine the instantaneous rate. This makes
it difficult to determine the rate law and hence the order of the reaction. In order to avoid
this difficulty, we can integrate the differential rate equation to give a relation between
directly measured experimental data, i.e., concentrations at different times and rate constant.
The integrated rate equations are different for the reactions of different reaction
orders. We shall determine these equations for zero, first and second order chemical
reactions.
8.5.1. Zero order reaction

Zero order reaction means that the rate of the reaction is proportional to zero power
of the concentration of reactants. Consider the reaction,
A→P
dCA
Rate  r    kC0A (8)
dt
As any quantity raised to power zero is unity
dC A
  kC0A  k  1  k
dt
dcA = – k dt
Let the initial concentration at initial time of the reaction, t= 0 be c0. Subsequently
at any other time t, the concentration will be ‘c’. On integration we obtain
c t
c 0
dc A    kdt
0
c – c0 = – kt
c = – kt + c0 (9)
This is the integrated rate equation for zero order reaction. If we plot concentration
(c) against t, we get a straight line (Fig. 8.1) with slope = –k and intercept equal
to c0.
132  NSOU  GE-CH-11
Further simplifying equation (9), we get the rate constant, k as
c0  c
k (10)
t
Photochemical reaction between H2 and Cl2 over water (saturated with HCl) surface
is an example of zero order reaction.
Figure 8.1. Variation in the concentration vs time plot for a zero order reaction.
8.5.2. First order reaction

The differential rate expression for the first-order reaction A → P is given by
dc A dcP
Rate  r     kCA
dt dt
Bringing concentration terms in one side and the time on the other side, we can write
the above equation as
dc A
  k1dt
cA
Now if the initial concentration at initial time t=0 be c-0, and at any other time t, the
concentration is c then, by integration we get
NSOU  GE-CH-11  133
c dcA t
c 0

cA
  k1dt
0
c
 ln  k1t
c0
c  c0 e k1t (11)
From equation 11 we can write
1 c
k1  ln c0 (12)
t
2.303 c
or, k1  log 0 (13)
t c
This is the expression for the first order rate constant k1.
Sometimes equation 12 is expressed in another format. If initial concentration of the
reactant is a and x moles of it react in time t; then the concentration of the reactant left
behind at time t will be a-x. In such a case the equation 12 can be written as
1
k1  ln a a x (14)
t
Figure 8.2. The plot of concentration versus time (a) and ln(concentration) versus time (b) for a first-
order reaction.
134  NSOU  GE-CH-11
From equation 14 it can be seen that the concentration of reactant in a first order
reaction decreases exponentially with time. A plot of ln(concentration) versus time will
give a straight line with slope = -k1. This is shown in figure 8.2.
8.5.3. Second order reaction

There are two types of second order reactions
Case I: When both the reactants are same. This, in effect, means that two molecules
of the same reactant are involved in the chemical reaction. The second-order reaction in
this case would be represented as
2A → P
The rate of the reaction can be expressed as
dc A dcP
Rate  r     k 2C 2A
dt dt
Where k2 is the second order rate constant. Now if a is the initial concentration of
A, x is the concentration of the product formed after time t and (a-x) is the concentration
of A remaining at time t, then,
dx
Rate  r   k 2 (a  x) 2 (15)
dt
By separating the variables and integrating, we get
x dx t
0  a  x 2 0 k 2dt
1 1
  k2t
(a  x) a
1 1 1 1  x 
k2     
t  (a  x) a  t  a(a  x) 
(16)
This is the integrated expression for the rate constant of a second order reaction in
which two molecules of the same reactant are involved in the reaction. The most common
NSOU  GE-CH-11  135
example of the above type of the second order reaction is the gaseous decomposition
of hydrogen iodide.
2HI (g) → H2 (g) + I2 (g)
The rate expression for this reaction is
d[HI]
Rate  r   k 2 [HI]2
dt
Case II: When the reactants are different
Consider a second order reaction
A + B → P
where the initial concentration of A is a mol dm–3 and that of B is b mol dm–3. After time
t, x mol dm–3 of A and x mol dm–3 of B react to form x mol dm–3 of the product. Thus
the reactant concentration at time t are (a–x) and (b–x), respectively. The differential rate
expression for the second order reaction is,
dc A dc dc
Rate  r     B  P  k 2CA CB
dt dt dt
This can be written as
dx
r  k 2 (a  x) (b  x) (17)
dt
where k2 is the second order rate constant. Separating the variables, we get
dx
 k 2dt (18)
(a  x)(b  x)
Resolving into partial fractions (assuming that a>b), we can write
1 1  1 1 
  (19)
(a  x)(b  x) (a  b)  b  x a  x 

Using equation 19 in equation 18 and integrating we can write
x dx 1  x 1 x 1  t
0 (a  x)(b  x)  (a  b)  0 b  x  0 a  x   k 2 0 dt (20)
136  NSOU  GE-CH-11
By solving this integration we get
1 ax  1 a
ln   ln    k 2 t (21)
(a  b)  b  x  (a  b)  b 
Rearranging and solving this equation 21, we get
1  ax  a 1  b(b  x) 
k2  ln    ln   ln
 b  (a  b)t  a(b  x) 
(22)
(a  b)t   b  x 
This is the integrated expression for the rate constant of a second order reaction.
Here we have assumed that a > b. If we had assumed b > a then the expression becomes
as follows
1  a(b  x) 
k2  ln
(a  b)t  b(a  x) 
8.6. Half-life of a Reaction

The time required for a reaction to reduce the concentration of the reactant to the
half of its initial concentration is called half life period (t1/2).
Half life for a zero order reaction:
For a zero order reaction, from the integrated rate law we get
c0  c
k
t
c0
At t  t1 2 , c 
2
c0
c0 
Then, t1  2  c0 (23)
k 2k
2
So for a zero-order reaction, the half-life period depends on the initial concentration
of the reactant and the rate constant.
NSOU  GE-CH-11  137
Half life for a first order reaction:

For the first order reaction
2.303 c
k1  log 0
t c
c0
At t  t1 2 , c 
2
2.303 c
t1  log 0
k1 c0
2
2
2.303
t1  log 2
k1
2
0.693
t1  (24)
k1
2
It can be seen from equation 24, that for a first order reaction, half-life period is
constant, i.e., it is independent of initial concentration of the reacting species. The half-
life of a first order reaction can be readily calculated from the rate constant and vice
versa.
Half life for a second order reaction:
For the second order reaction, we can write from equation 16
1 x 
k2  
t  a(a  x) 
At x = a/2, t = t1/2
1  a 2  1 a 2 1
k2    
t1 2  a(a  a 2)  t1 2  a  a t1 2
a 
2
138  NSOU  GE-CH-11
1
t1  (25)
k 2a
2
So from equation 25, we can find that t1/2 of a second order reaction is inversely
proportional to the initial concentration of the reactant and thus it does not remain constant
as the reaction proceeds.
Half life for nth order reaction:

It can be shown that for a nth order reaction of
nA → Products
The half life time can be expressed by the following equation
2n 1  1
t1  (26)
2
k n (n  1) a 0n 1
Where a0 is the initial concentration of the reactant A and kn is the nth-order rate
constant. From the equation 26 we can see that
1
t1 2  (27)
a 0n 1
8.7. General methods for determination of order of a

reaction
The order of a reaction is never known before hand, though most of the reactions
are of the first or second order. In order to write the rate law, we must know the order
of reaction with respect to each reactant. The following methods are commonly used for
determining the order of a reaction
i) Method of Initial Rate:

The instantaneous rate of reaction extrapolated to the instant when the reagents were
just mixed is called the initial rate of the reaction. Let us consider the reaction,
A + B → Products
NSOU  GE-CH-11  139
Let the rate of reaction be represented as,

r = k [A]m [B]n
where the reaction is mth order in A and nth order in B. The rate constant for the reaction
is k. We have to obtain the initial rates from at least two experiments in which the initial
concentrations of A (a1 and a2) are different while the initial concentration of B (bl) is
constant.
Rate in Experiment I = r1 = ka1m b1n
Rate in Experiment I1 = r2 = ka m n
2 b1
r1
From the ratio , we can calculate order m, since a1 and a2 are known
r2
m
Rate in exp eriment I r1 ka1m b1n  a1 
   
Rate in exp eriment II r2 ka m n
2 b1  a2 
Taking logarithms we can write
r1 a
log  m log 1 (28)
r2 a2
Similarly, the rate for one more experiment in which the initial concentration of A is a2
and the initial concentration of B is b2.
m n
So, rate in Experiment III = r3 = ka 2 b 2
n
Rate in exp eriment II r2 ka m2 b1
n
b 
  m n  1 
Rate in exp eriment III r3 ka 2 b 2  b2 
r2 b
log  n log 1 (29)
r3 b2
Since r2, r3, b1 and b2 are known, n can be calculated. The overall reaction order =
m + n.
140  NSOU  GE-CH-11
ii) Using Integrated Rate Expression:

We can determine the order of reaction
a) by substitution of experimental data into integrated rate law equations; i.e.; in
equation 10, 13 and 16.
b) by graphical method using plots such as [A] against t, log[A] against t and 1/
[A] against t. The order of the reaction is one, two or zero depending on which
of the equations gives rise to a constant value for k or which of the plots gives
a straight line.
iii) Half-Life Method:
The half-lives are determined using different initial concentrations of the reactant. If the
half-life is independent of initial concentration, the reaction is first order. If the half-life is
inversely proportional to the first power of initial concentration, the reaction is second
order. If the half-life is directly proportional to the first power of initial concentration, the
reaction is zeroth order.
In general, half-life period (t1/2) is proportional to (1/a0)n-1 where ao is the initial
concentration of the reactant and n is the order of the reaction.
If the half-life periods are (tl/2)1 and (t1/2)2 corresponding to the initial concentrations
a1 and a2 of a reactant, then
 t1 2 1   a 2 n1
 
 t1 2 2  a1 
ln
 t1 2 1  (n  1) ln  a 2 
 
or,
 t1 2 2  a1 
ln
 t1 2 1
n  1
 t1 2 2
or, (30)
a 
ln  2 
 a1 
NSOU  GE-CH-11  141
iv) Isolation Method:

In the case of reactions having more than one reactant, the rate law can be simplified
if the concentrations of all reactants except one are taken in excess. The reaction rate then
depends on the reactant present in lesser quantity. The order of the reaction is determined
by one of the methods given above. It is equal to the order in the reactant present in lesser
quantity. This procedure is repeated in turn with each of the reactants being in
lesser amount while others are in excess. This procedure is called van’t Hoff s isolation
method.
8.8. Concept of activation energy and its calculation

from Arrhenius Equation
We have seen about the temperature dependence of rate of a reaction in section 8.3.
The temperature dependence of the rate of a chemical reaction can be accurately explained
by Arrhenius equation. Arrhenius proposed the following empirical relationship between the
rate constant, k, and temperature, T.
k=Ae –Ea /RT
(31)
where A is the Arrhenius factor or the frequency factor. It is also called pre-exponential
factor. It is a constant specific to a particular reaction. R is gas constant and Ea is activation
energy measured in joules/mole (J mol–1).
It can be understood clearly using the following simple reaction
H2 (g) + I2 (g) → 2HI (g)
According to Arrhenius, this reaction can take place only when a molecule of hydrogen
and a molecule of iodine collide to form an unstable intermediate. It exists for a very short
time and then breaks up to form two molecules of hydrogen iodide.
The energy required to form this intermediate, called activated complex (C), is known
as activation energy (Ea). Fig. 8.3 is obtained by plotting potential energy vs reaction
coordinate. Reaction coordinate represents the profile of energy change when reactants
change into products. Some energy is released when the complex decomposes to form
products. So, the final enthalpy of the reaction depends upon the nature of reactants and
products.
142  NSOU  GE-CH-11
Figure 8.3. Diagram showing plot of potential energy vs. reaction coordinate.
All the molecules in the reacting species do not have the same kinetic energy. For
the formation of product the reactant molecules must possess sufficient energy. Increasing
the temperature of the substance increases the fraction of molecules, which collide with
energies greater than Ea. Thus, with increase of the reaction temperature the rate of the
reaction increases. In the Arrhenius equation (31) the factor e-Ea /RT corresponds to the
fraction of molecules that have kinetic energy greater than Ea.
Taking natural logarithm of both sides of equation 31, we get
Ea
ln k    ln A (32)
RT
From equation 32, it is evident that a plot of lnk versus 1/T (figure 8.4) gives a straight
line with slope = – Ea/R and intercept = lnA.
By differentiating equation 32 with respect to temperature, we can write
dlnk E
 a2 (33)
dT RT
Integrating equation 33 between temperature T1 and T2 when the corresponding rate
constants are k1 and k2, respectively and assuming that Ea is constant over this temperature
range, we obtain
k1 Ea  T2  T1 
ln    (34)
k 2 R  T1T2 
NSOU  GE-CH-11  143
Figure 8.4. Plot of ln k vs 1/T.
This is the integrated Arrhenius equation. From this equation 34 by knowing the rate
constants at two different temperatures, the energy of activation Ea can be readily determined.
8.9. Theories of reaction rates

There are two important theories of reaction rates. These are the collision theory
developed by Arrhenius and van’t Hoff and the modern activated complex theory, or also
called the transition state theory developed by Eyring, Polanyi and Evans.
8.9.1. Collision theory

This is the earliest theory of reaction rates. Since reaction between two species takes
place only when they are in contact, it is reasonable to suppose that the reactant species
must collide before they react. Since our knowledge of molecular collisions is more complete
for the gaseous phase than for the liquid phase, we will restrict our discussion to bimolecular
reactions in the gaseous phase.
From the kinetic theory of gases (discussed in unit 4), the number of bimolecular
collisions per second per cm3 among molecules of one species is given by
12
 8kT 
Z  2n 22   (35)
 M 
144  NSOU  GE-CH-11
For a reaction involving two different gases A and B, the rate of bimolecular collisions
between unlike molecules is given by
1/2
2  8kT 
ZAB  2n A n Bav   (36)
  
where nA and nB are numbers of A and B molecules, respectively, σav is the average
collision diameter defined as (σA+ σB)/2 and μ is the reduced mass defined as μ =
(mAmB)/(mA + mB). The collision number ZAB is given, in terms of molar masses MA and
MB of the two gases, by the expression
12
2   M A  M B  8kT 
ZAB  n A n Bav   (37)
 MAMB 
Let us calculate ZAB for the reaction between H2 and I2 at 700 K and 1 atm pressure,
the quantities of the two gases being 1 mole each. Accordingly, n H2  n I2  1019
molecules cm–3, H2 = 2.2 Å, I2 = 4.6 Å so that σav = 3.4 Å. Hence, according to
Eq. 37,
12
  2  254  8  3.14  8.314  107  700 
ZAB  10  3.4 10 
19 2 8

2  254

 
= 1038 × 1.16 × 10–15 × 8.58 × 105  1029 collisions s–1 cm–3

Since there are approximately 1029 collisions per second for 1019 molecules of each
species, each molecule makes about 1010 collisions s-1 with the molecules of other species.
If each collision were lead to a chemical reaction, then the whole reaction would have
been completed in about 10-10s. However this is not in agreement with the experimental
value. So each collision does not result in chemical reaction.
In order for a reaction to occur, the energy of collision must equal or exceed the
threshold energy. The effective energy is, of course, not the total kinetic energy of the
colliding molecules but is, instead, the kinetic energy corresponding to the component at
the moment of the relative velocity of the two molecules along the line of their centres
at the moment of collision. It is this energy with which the two molecules are pressed
together.
NSOU  GE-CH-11  145
The detailed analysis of the dynamics of bimolecular collisions leads to the result that
the number of collisions S-1cm-3 between molecules A and B, when the relative kinetic
energy E along the line of centres is greater than the threshold energy is given by
ZAB  ZABe E RT (38)
Assuming that ZAB gives the rate of relative collisions between A and B, we can
write
 dn A dt  ZAB
12
  M A  M B  8kT 
So,  dn A dt  2
n A n Bav   e E RT
molecules cm 1s1 (39)
 MAMB 
Now if the concentrations of the reactants are expressed in mol dm-3, then
103 n A 103 n B
[A]  and [A]  (40)
nA NA
Here NA is Avogadro’s number. Hence, the rate law expression

–dnA/dt = k2[A][B]
Can be written as
103 dn A 106
  k2 nAnB (41)
N A dt  N A 2
NA dn A
Hence, k 2    (42)
103 n A n B dt
Using equation 39 for , we have
1/2
N 2   M  M B  8RT 
k 2  A 3av  A  eE RT (43)
10  MAMB 
146  NSOU  GE-CH-11
Comparing equation 43 with the Arrhenius equation (Eq 31) k = A e –Ea /RT, we find
that the Arrhenius pre-exponential factor is given by
1/2
N 2   M  M B  8RT 
A  A 3av  A  (44)
10  MAMB 
The activation energy Ea, in the Arrhenius equation is thus identified with the relative
kinetic energy E along the line of centres of the two colliding molecules which is required
to cause a reaction between them.
Now let us calculate A and k2 for the H2-I2 reaction at 700 K, considered in the
beginning of this section. Ea has been found to be 167.4 kJ mol-1. Substituting the various
values in equation 44, A comes out to be = 6.0 x 1011 dm3 mol-1 s-1. Hence, from
Arrhenius equation (Eq 31),
k2 = 6.0 × 1011dm3 mol–1 s–1. exp(-167400 J mol–1/ 8.314 J K–1 mol–1 . 700K)
= 0.22 dm3 mol–1 s-1
which is comparable with the experimental value of 0.064 dm3 mol–1 s–1, considering the
uncertainty in the values of the activation energy and average collision diameter.
The collision theory is applicable to simple gaseous reactions. For reactions between
complicated molecules, the observed rate is found to be much smaller than the theoretically
predicted rate. The discrepancy arises due to the facts that the colliding reactant molecules
are treated as hard spheres without any internal energy. Again the spherical model ignores
the dependence of the effectiveness of the collision on the relative orientation of the
colliding molecules. Also the activation energy was treated as though it were related entirely
on translational motion. For this reasons the collision theory is applicable to reactions
between very simple gaseous molecules.
The collision theory can be generalized by introducing the so-called steric factor, p,
into the equation for the bimolecular rate constant in order to take account of the
orientational requirement. Accordingly the equation becomes
k2 = p A e –Ea /RT
(45)
8.9.2. Activated complex theory of bimolecular reactions

As a result of the development of the quantum mechanics, another theoretical approach
to chemical reaction rates has been developed which gives a deeper understanding of the
NSOU  GE-CH-11  147
reaction process. It is known as the absolute reaction rate theory or the transition state
theory or more commonly as activated complex theory. According to the activated complex
theory, the bimolecular reaction between two molecules A2 and B2 progresses through
the formation of the so-called activated complex which then decomposes to yield the
product AB. It must be remembered that the activated complex is not merely an
intermediate in the process of breaking or forming of chemical bonds. It is unstable because
it is situated at the maximum of the potential energy barrier separating the products from
the reactants (Figure 8.5). The difference between the energy of the activated complex
and the energy of the reactants is the activation energy, Ea.
Figure 8.5. Energy versus reaction coordinate in activated complex theory in the case of an exothermic
and endothermic reaction.
Let us consider a simple bimolecular reaction
K# k
(AB) # 
A  B  2
 Products (46)
where (AB)# is the activated complex and K# is the equilibrium constant between the
reactants and activated complex. From classical mechanics, the energy of vibration of the
activated complex (AB)# is given by RT/NA (or kBT where kB is the Boltzmann constant)
whereas from quantum mechanics, it is given by hv so that hv = RT/NA or v = RT/NAh
= kBT/h. The vibrational frequency v is the rate at which the activated complex
molecules move across the energy barrier. Thus, the rate constant k2 can be identified
with v.
148  NSOU  GE-CH-11
The reaction rate is given by
dA k T
  k 2 (AB) #    B (AB) #  (47)
dt   h  
where the factor κ, called the transmission coefficient, is a measure of the probability that
a molecule, once it passes over the barrier, will keep on going ahead and not return.
The value of κ is taken to be unity; it is thus omitted from the rate expression. The
concentration of the activated complex , can be obtained by writing the equilibrium
expression
(AB)# 
K # 
[A] [B]
Hence (AB)   K [A] [B]

# #
(48)
Substituting the value in equation 47, we get
dA k BT #
  K [A] [B] (49)
dt h
Thus the rate constant k2 may be expressed as
k BT #
k2  K (50)
h
The equilibrium constant K# can be expressed in terms of (ΔGo)#, called the standard
Gibbs free energy of activation.
Since for the activated complex, we can write
 G      H   
# # # #
0
 RT ln K # and G 0 0
 T S0 (51)
Here, (ΔHo)# is the standard enthalpy of activation and (ΔSo)# is the standard entropy
of activation
So we can write, K #  e( G 0 )# RT

 e( S
0 #
) R
.e( H
0 #
) RT (52)
NSOU  GE-CH-11  149
Now substituting in equation 50, we get
k BT ( S0 )# 0 #
k2  e R
.e  ( H ) RT
h
This is the well known Eyring equation. The application of the activated complex
theory is to reactions in solution is quite complicated because of the participation of the
solvent molecules in the activated complex. Fortunately, the Eyring equation is applicable
for reactions in the solutions phase also.
Taking logs of both sides of equation 53 and differentiating with respect to T we
get
2
d ln k 2 dT  ( H 0 ) # RT  1 T   ( H 0 ) #  RT  RT 2 (54)
 
Also, from the Arrhenius equation we get,
d ln k 2 dT  E a RT 2 (55)
By comparing equation 54 and 55, we obtain
E a  (H 0 ) #  RT
or, (H 0 )#  E a  RT (56)
Again, by comparing equation 53 and 45, we have
k BT ( S0 )# 0 #
pAe  Ea RT
 e R
.e  ( H ) RT (57)
h
If E a  (H 0 ) # , wecan equate the exponential factors in equation 57
k BT ( S0 ) # R
pA e (58)
h
For a first order gaseous reaction, p = 1 and A = 1010 s–1.
k BT
At room temperature the value of  1013 s 1 .
h
150  NSOU  GE-CH-11
Hence,
0 # 1010 s1
e( S ) R
 13 1
 103
10 s
(S0 )#  57.4 J K 1 mol1

So if p < 1 (as in the case of complex molecules) (ΔSo)# is lower than this value.
Qualitatively, a negative value of entropy of activation corresponds to an increase in
molecular order in the activated complex relative to the reactant molecules. A large negative
value of (ΔSo)# corresponds to a highly ordered activated complex and this implies a
small value of the steric factor. Finally it may be remarked that for reactions involving
simple molecules, the collision theory and the activated complex theory give identical
results.
8.10. Summary
In this unit, we started with the definitions of the terms such as, rate of reaction, rate
law, order and molecularity of reaction. We derived the integrated forms of rate expressions
for first order, second order and zeroth order reactions. We have discussed about the
half life of the different order reactions. We explained the methods of determination of
order of reaction. Finally the concepts of activation energy, Arrhenius equation, collision
theory and the activated complex theory were discussed.
8.11. Questions
1. Rate of reaction depends upon which factors?
2. What are the differences between order and molecularity of a reaction?
3. What do you mean by a zero order reaction? Give example.
4. Show that half life of a first order reaction does not depend on the initial
concentration of the reactants.
5. Describe any method for determination of order of reaction.
6. How the rate of a reaction depends upon temperature?
7. What is activation energy of a reaction?
NSOU  GE-CH-11  151
8. Why the rate of a reaction increases in the presence of a catalyst?

9. The half life of a first order reaction is 15 min. What is the rate of the reaction?
How much time it will take to complete the 80 % of the reaction?
(Ans. 0.0462 min-1, 34.84 min)
10. The rate of a reaction is 3.46 x 10-5 min-1 and 4.87 x 10-5 min-1 at 298 K and
338 K respectively. Calculate the activation energy of the reaction. Given the
value of R = 1.987 cal deg-1 mol-1. (Ans. 24.756 kcal/mol)
8.12 Further Readings

1. Physical Chemistry, Gilbert W. Castellan, Narosa Publishing House, 3rd ed.,
1983.
2. Physica1 Chemistry, P.C. Rakshit. Sarat Book House, 5th ed., 1988.
3. Principles of Physical Chemistry, Puri, Sharma and Pathania, Vishal Publishing
Co., 46th ed., 2012.
4. General Chemistry- Principles and Modern Applications, Petrucci, Herring,
Madura and Bissonnette, Pearson Canada Inc., 11th ed, 2017.
5. Physica1 Chimistry through Problems, S. K. Dogra and S. Dogra, Wiley
Eastern Ltd., 1984.
6. Principles of Physical Chemistry, Samuel H. Maron and Carl F. Prutton,
Oxford and IBH Publishing Co., 4th ed., 1985.
152  NSOU  GE-CH-11
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PREFACE

In a bid to standardize higher education in the country, the University Grants

Professor (Dr.) Subha Sankar Sarkar

First Print — June, 2021

Printed in accordance with the regulations of the Distance Education

Course : Basic Physical Chemistry

Unit – 1 Chemical Energetic 7-21

Unit – 2 Chemical Equilibrium 22-33

Unit – 3 Ionic Equilibrium 34-54

Unit – 4 Kinetic Theory of Gases 55-73

Unit – 5 Liquids 74-84

Unit – 6 Solids 85-104

Unit – 7 Solutions 105-124

Unit – 8 Chemical Kinetics 125-151

1.2. Brief review of thermodynamics and the Laws of

1.2.1 System and surrounding

1.2.2 State of a system

1.2.3 Properties of a system

1.2.4 Types of processes

b) Adiabatic Process: In an adiabatic process there is no exchange of heat between

1.2.5 Work, heat and heat capacity

1.2.6 The Zeroth law of thermodynamics

1.2.7 The First law of thermodynamics

1.2.8 Internal energy (U)

1.2.9 Enthalpy (H)

1.3. Important Principles and Definitions of

1.3.2 Thermochemical equations

(iii) Thermochemical equations may be balanced even by using fractional coefficients,

1.3.3 Standard enthalpy of reactions

1.3.4 Hess’s law of constant heat summation

1.4. Standard enthalpies of formations

1.5. Enthalpies of solution and dilution

The values of ΔH show general dependence of the enthalpy of solution on amount of

1.6. Bond energy, bond dissociation energy and resonance

Hence, Resonance energy = observed ΔfHo – calculated ΔfHo

1.7. Variation of enthalpy of a reaction with temperature

Integrating the equation between temperature T1 and T2,

r H0 (T2 )  r H 0 (T1 )   C0p  T2  T1 

r H0 (T2 )  r H0 (T1 )   C0p  T2  T1 

1.8. Third Law of thermodynamics and calculation

of thermodynamics. Then we have focused our discussion on thermochemistry – the study

2.2. Free energy change in a chemical reaction

2.3. Law of mass action

k f [A]a [B]b  k r [M]m [N]n

where, Δn = (sum of stoichiometric coefficients of products – sum of stoichiometric

[H2] = (2–x)/2 =1.25/2

2.4. Thermodynamic Derivation of the Law of Chemical

This is the law of chemical equilibrium.

So we obtain similar equation like equation 12

From which we obtain the following expression

2.5. Distinction between ΔG and ΔG0

2.6. Relationships between Kp, Kc and Kx for reactions

So from equation 19 and 20 we can write

This is the relation between different equilibrium constants.

2.7. Le Chatelier’s principal

2.7.1 Effect of change of concentration

2.7.2 Effect of change of pressure

2.7.3 Effect of change of temperature

N2 (g) + 3H2 (g)  2NH3 (g) ΔH = – 92.38 kJ