CLASS

CBSE-i
XI
UNIT-9

Students’
Manual

Shiksha Kendra, 2, Community Centre, Preet Vihar, Delhi-110 092 India

 CBSE-i

Students’
Manual

CLASS

XI
UNIT-9

Shiksha Kendra, 2, Community Centre, Preet Vihar, Delhi-110 092 India

The CBSE-International is grateful for permission to reproduce
and/or translate copyright material used in this publication. The
acknowledgements have been included wherever appropriate and
sources from where the material may be taken are duly mentioned. In
case any thing has been missed out, the Board will be pleased to rectify
the error at the earliest possible opportunity.
All Rights of these documents are reserved. No part of this publication
may be reproduced, printed or transmitted in any form without the
prior permission of the CBSE-i. This material is meant for the use of
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 Preface
Education plays the most important role in acquiring professional and social skills and a positive attitude to face
the challenges of life. Curriculum is a comprehensive plan of any educational programme. It is also one of the
means of bringing about qualitative improvement in an educational system. The Curriculum initiated by Central
Board of Secondary Education -International (CBSE-i) is a progressive step in making the educational content
responsive to global needs. It signifies the emergence of a fresh thought process in imparting a curriculum which
would restore the independence of the learner to pursue the learning process in harmony with the existing
personal, social and cultural ethos.
The CBSE introduced the CBSE-i curriculum as a pilot project in few schools situated outside India in 2010 in
classes I and IX and extended the programme to classes II, VI and X in the session 2011-12. It is going to be
introduced in classes III, VII and for Senior Secondary classes with class XI in the session 2012-13.
The Senior Secondary stage of education decides the course of life of any student. At this stage it becomes
extremely important for students to develop the right attitude, a willingness to learn and an understanding of the
world around them to be able to take right decisions for their future. The senior secondary curriculum is expected
to provide necessary base for the growth of knowledge and skills and thereby enhance a student's potential to
face the challenges of global competitiveness. The CBSE-i Senior Secondary Curriculum aims at developing
desired professional, managerial and communication skills as per the requirement of the world of work. CBSE-i
is for the current session offering curriculum in ten subjects i.e. Physics Chemistry, Biology, Accountancy,
Business-Studies, Economics, Geography, ICT, English, Mathematics I and Mathematics II. Mathematics at two
levels caters to the differing needs of students of pure sciences or commerce.
The Curriculum has been designed to nurture multiple intelligences like linguistic or verbal intelligence, logical-
mathematical intelligence, spatial intelligence, sports intelligence, musical intelligence, inter-personal
intelligence and intra-personal intelligence.
The Core skills are the most significant aspects of a learner's holistic growth and learning curve. The objective of
this part of the core of curriculum is to scaffold the learning experiences and to relate tacit knowledge with formal
knowledge. This involves trans-disciplinary linkages that would form the core of the learning process.
Perspectives, SEWA (Social Empowerment through Work and Action), Life Skills and Research would be the
constituents of this 'Core'.
The CBSE-i Curriculum evolves by building on learning experiences inside the classroom over a period of time.
The Board while addressing the issues of empowerment with the help of the schools' administering this system
strongly recommends that practicing teachers become skilful and lifelong learners and also transfer their
learning experiences to their peers through the interactive platforms provided by the Board.
The success of this curriculum depends upon its effective implementation and it is expected that the teachers will
make efforts to create better facilities, develop linkages with the world of work and foster conducive
environment as per recommendations made in the curriculum document.
I appreciate the effort of Dr.Sadhana Parashar, Director (Training), CBSE, Dr. Srijata Das, Education Officer,
CBSE and Ms. Anjali Chhabra, Assistant Education Officer, CBSE and their teams involved in the development of
this document.
The CBSE-i website enables all stakeholders to participate in this initiative through the discussion forums. Any
further suggestions on improving the portal are always welcome.

Vineet Joshi
Chairman, CBSE
 Acknowledgements
Advisory Conceptual Framework
Shri Vineet Joshi, Chairman, CBSE Shri G. Balasubramanian, Former Director (Acad), CBSE
Dr. Sadhana Parashar, Director (Training), CBSE Ms. Abha Adams, Consultant, Step-by-Step School, Noida
Dr. Sadhana Parashar, Director (Training), CBSE
Ideators Classes XI and XII
Prof. A K Bakshi Ms. P Rajeshwari Dr. Niti Nandini Chatnani Ms. Neeta Rastogi
Dr. N K Sehgal Ms. Gyatri Khanna Dr. Anil K Bali Dr. Anshu
Prof. Kapil Kapor Mrs. Anita Makkar Dr. Preeti Tewai Dr. Rajesh Hassija
Ms. Renu Anand Prof. Biswajit Nag Dr. Deeksha Bajpai Mr. Mukesh Kumar
Dr. Barkatullah Khan Ms. Usha Sharma Mr. S K Agarwala Dr. Om Vikas
Ms. Avnita Bir

Material Production Groups: Classes XI-XII

English : Biology : Geography: Accountancy :
Ms. Gayatri Khanna Dr. Ranjana Saxena Dr. Preeti Tewari Mr. S S Sehrawat
Ms. Renu Anand Dr. Neeraja Sood Ms. Rupa Das Dr. K Mohna
Ms. P Rajeshwary Dr. P Chitralekha Mr. S Fazal Daoud Firdausi Dr. Balbir Singh
Ms. Sandhya Awasthi Ms. Mridula Arora Ms. Neena Phogat Ms. Bhupendra Kriplani
Ms. Manna Barua Ms. Lucy Jad Ms. Sujata Sharma Ms. Shipra Vaidya
Ms. Veena Bhasin Ms. Priyanka Choudhury Ms. Deepa Kapoor Mr. Sandeep Sethi
Ms. Urmil Guliani Ms. Prerna Gosain Ms. Bharti Malhotra
Ms. Sudha Ravi Ms. Malini Sridhar Ms. Isha Kaushik Business Studies :
Mr. Anil Kumar Mr. Riyaz Khan Dr. S K Bhatia
Physics :
Ms. Vijaylaxmi Raman Ms. Meenu Ranjan Arora
Dr. B. Biswal
Ms. Neerada Suresh Economics: Mrs. Shegorika
Ms. Namarata Alwadhi
Ms. Himaal Handoo Mr. S K Agarwala Mr. Sandeep Sethi
Mr. Dhirender Sharma
Ms. Ambika Gulati Ms. Usha Sharma
Chemistry : Ms. Vandana Banga
Ms. Nidhi Singh Ms. Komal Bhatia
Dr. G S Sodhi Mr. Vivek
Ms. Malti Modi Ms. Ravisha Aggarwal
Dr. Vimal Rarh
Mathematics : Ms. Sapna Das
Dr. Shalini Baxi
Dr. Sushil Kumar Ms. Ingur Agarwal ICT :
Dr. Vinita Arora
Mrs. Monica Talwar Ms. Shankar Kulkarni Mr. Mukesh Kumar
Dr. Vandana Soni
Mrs. Charu Dureja Mr. Sandeep Sethi Ms. Nancy Sehgal
Ms. Charu Maini
Mrs. Seema Juneja Ms. Purvi Srivastava
Ms. Rashmi Sharma
Dr. H L Bhatia Ms. Gurpreet Kaur
Ms. Kavita Kapoor
Dr. Sushma Bansal
Mrs. Neeru Aggarwal
Dr. Saroj Khanna

Coordinators:

Ms. Sugandh Sharma, EO Dr Rashmi Sethi, EO Ms. S. Radha Mahalakshmi, EO Mr. Navin Maini, RO (Tech)
Ms. Madhuchhanda, RO (Inn) Shri Al Hilal Ahmed, AEO Ms. Anjali Chhabra, AEO Shr. R. P. Singh, AEO
Shri R. P. Sharma, Ms. Neelima Sharma, Ms. Reema Arora, Mr. Sanjay Sachdeva, SO
Consultant (Science) Consultant (English) Consultant (Chemistry)
 Contents
Preface

Acknowledgments

1. Syllabus Coverage 1

2. Learning Outcomes 3

4. Cross-curricular links 6

5. Mind Map 7

6. Content 8-122

7. Student Worksheets 123-137

8. Summary 138

9. Crossword Puzzle 139

10. Common Misconceptions 143

11. Additional Resource Links 143

 Syllabus Coverage
9.1 Introduction to equilibrium

9.1.1 Dynamic nature of equilibrium

9.2 Equilibrium in Physical processes

9.2.1 Solid - liquid equilibrium

9.2.2 Liquid - vapour equilibrium

9.2.3 Solid Solution equilibrium

9.2.4 Equilibrium involving dissolution of gases in liquids

9.3 Equilibrium in Chemical Processes

9.3.1 Dynamic nature of chemical equilibrium

9.4 Applications of Equilibrium Constant

9.4.1 Law of Chemical Equilibrium

9.4.2 Equilibrium Constant

9.4.3 Predicting the direction of the reaction

9.4.4 Calculating Equilibrium Constant

9.5 Factors affecting Equilibria

9.5.1 Le Chatelier’s principle

9.6 Ionic Equilibrium in solution

9.6.1 Strong and weak electrolytes

9.6.2 Acids, bases and salts

1
9.7 Ionization of acids and bases

9.7.1 Ionic product of Water

9.7.2 pH scale

9.7.3 Ionization constant of weak acids and bases

9.7.4 Ionisation of polybasic acids and polybasic bases

9.7.5 Factors affecting acid strength

9.7.6 Hydrolysis of salts

9.7.7 Acid Base Titrations

9.8 Buffer Solutions

9.8.1 Henderson- Hasselbalch equation

9.9 Solubility equilibria of sparingly soluble salts

9.9.1 Solubility product and Common ion effect

2
Learning Outcomes
At the end of this unit student would be able to:

 Understand the term equilibrium and identify its dynamic nature.

 Know all reactions do not go to completion.

 Know the importance of equilibria in biological and environmental processes.

 Discuss the equilibria during phase transformation processes for Solid- liquid
equilibrium, Liquid- vapour equilibrium, Solid- vapour equilibrium.

 Explain the equilibrium involving dissolution of solid in liquids and gases in

liquids.

 State the Henry’s Law and know its application.

 Comprehend features and general characteristics of Equilibria involving

physical processes.

 Understand the attainment of equilibrium in a chemical reaction.

 Interpret the meaning of equilibrium by plotting a graph of the concentration

of reactants and products versus time.

 List the general characteristics of chemical equilibrium.

 Explain and Derive a mathematical formulation of Law of Mass Action.

 Derive the mathematical expression for the law of chemical equilibrium for a
general reaction.

 Understand the meaning of equilibrium constant and discuss its

characteristics.

 Differentiate between Kp and Kc and Derive a mathematical relation between

Kp and Kc.

 Solve numerical based on the law of chemical equilibrium.

3
 Distinguish between homogenous and heterogeneous equilibria.

 Understand that the magnitude of Kc or Kp does not give any information

about the rate.

 Distinguish between reaction quotient and equilibrium constant.

 Recognize the usefulness of the reaction quotient in predicting the direction of

reaction by comparing the values of reaction quotient and equilibrium
constant.

 Calculate the equilibrium concentrations with the help of equilibrium constant.

 State the Le Chatelier’s principle.

 Comprehend the effect on equilibria due to change in concentration, pressure,

inert gas addition, temperature, addition of catalyst.

 Know examples of equilibria which involves ions.

 Classify substances according to their ability to conduct electricity into

electrolytes and non-electrolytes

 Categorize electrolytes into strong and weak electrolytes

 Recognize that acids, bases and salts fall under the category of electrolytes.

 Recall the characteristics and examples of acids, bases and salts.

 Differentiate between dissociation and ionisation.

 Discuss the theories of acids and bases.

 Write conjugate acid and conjugate bases for Bronsted bases and Bronsted
acids respectively.

 Identify chemical species as Lewis acids and Lewis bases.

 Recognize that water can act as an acid as well as base.

 Write the reaction for self ionisation for water.

 Describe ionic product of water and appreciate its temperature dependence.

4
 Distinguish between acidic, neutral and basic aqueous solutions by relative
values of hydronium ion and hydroxyl ion.

 Define pH of a solution and solve numerical based on pH.

 Derive the mathematical expression for equilibrium constant of weak acid (Ka)
and weak base (Kb).

 Comprehend the usefulness of pKa and pKb.

 Calculate the pH of a weak electrolyte.

 Write multi-step equilibrium reactions for polybasic acids and polyacidic

bases.

 Explain common ion effect and apply the concept to solve numerical.

 Understand the meaning of hydrolysis of salts.

 Classify the salts and determine the pH of their solutions for Salts of weak
acids and strong bases, Salts of strong acids and weak bases, Salts of weak
acids and weak bases.

 Describe a buffer solution.

 Explain buffer action with the help of examples.

 Calculate the pH of a buffer mixture using Henderson- Hasselbalch equation.

 List the factors on which solubility depends.

 Categorize salts on the basis of their solubility into soluble, slightly soluble and
sparingly soluble.

 Comprehend the meaning of solubility product.

 Calculate solubility of a salt by knowing the numerical value of solubility

product constant.

5
Cross Curricular Links
 In biological systems: The pH of the blood ranges between 7.36 - 7.42. It is
controlled by the buffer action of HCO3- and H2CO3 present in the body.

 In agriculture: The yield of the crop depends upon the pH of the soil. A
mixture of salts and organic acids present in the soil control the pH of the soil.

 In food preservation: The control of the pH of the medium is very important in

the preservation of food.

6
Mind Map
Equilibrium

9.1 Introduction to Equilibrium 9.1.1 Dynamic Nature of Equilibrium

9.2.1 Solid – Liquid Equilibrium

9.2.2 Liquid – Vapour Equilibrium
9.2 Equilibrium in Physical Processes
9.2.3 Solid Solution Equilibrium
9.2.4 Equilibrium Involving Dissolution
of Gasses in Liquids

9.3 Equilibrium in Chemical Process 9.3.1 Dynamic Nature of Chemical Equilibrium

9.4.1 Law of Chemical Equilibrium

9.4 Application of Equilibrium Constant 9.4.2 Equilibrium Constant

9.4.3 Predicting the Direction of Reaction

9.4.4 Calculating Equilibrium Constant

9.5 Factors Affecting Equilibria 9.5.1 Le Chatelier’s Principle

9.6.1 Strong and Weak Electrolytes

9.6 Ionic Equilibrium in Solution 9.6.2 Acids, Bases and Salts

9.7.1 Ionic Product of Water

9.7.2 pH Scale
9.7.3 Ionisation Constant of Weak Acids and
Bases
9.7 Ionization of Acids and Bases 9.7.4 Ionisation of Polybasic Acids and
polybasic Bases
9.7.5 Hydrolysis of Salts
9.7.6 Acids Base Titrations

9.8 Buffer Solutions

9.8.1 Henderson – Hasselbalch Equation

9.9.1 Solubility Product and

9.9 Solubility Equilibria of Sparingly Soluble Salts
Common Ion Effect

7
 9.1 Introduction to Equilibrium

The teacher must start by asking the following thought provoking questions:

1. Ice-breaker:

Try to find out the answer to some phenomenon from daily life illustrating the
effect of change of concentration on equilibrium.

(i) Why do clothes dry quicker when the fan is on or if there is a breeze?

(ii) In Chennai or Kolkata why do we sweat more on a humid day, than in

Jaipur?

(iii) How is oxygen carried by haemoglobin in blood?

(iv) How does blood help in the removal of CO2 from the tissues?

(v) How do sweet substances cause tooth decay?

Explanation:

(i) Clothes dry quickly in the breeze or under a fan because the water vapour of
nearby air is removed and the clothes lose water vapour to re-establish the
equilibrium with the surrounding air.

(ii) We sweat more in humid climate because the surrounding air has large
amounts of water vapour and our body cannot lose water as water vapour.

(iii) The haemoglobin (Hb) in the red corpuscles of our blood carries oxygen to
the tissues. This involves the equilibrium

Hb(s) + O2(g) HbO2(s)

(iv) The blood that is in equilibrium with the oxygen in air in the lungs finds a
situation in the tissues where the partial pressure of oxygen is low and hence
the equilibrium readjusts itself by some of the oxyhaemoglobin

8
 releasing oxygen. When blood returns to the lungs the partial pressure of
oxygen is higher and more oxyhaemoglobin is formed.

(v) Blood removes CO2 from the tissues in a similar way as oxygen is carried by
haemoglobin. The equilibrium is

CO2(g) + H2O(ℓ) H2CO3(aq) H+(aq) + (aq)

(vi) CO2 dissolves in the blood in the tissues since its partial pressure is high; in
the lungs where the partial pressure of CO2 is low, it is released from the
blood.

(vii) Tooth enamel consists of an insoluble substances called hydroxyapatite

Ca5(PO4)3OH. The dissolution of this substance is demineralisation and its
formation is called remineralisation. Even with healthy teeth there is an
equilibrium in the mouth as
demineralisation
Ca5(PO4)3OH(s) 5Ca2+(aq) + 3PO43-(aq) + OH-(aq)
mineralisation

Warm Up Activity

Aim: To demonstrate the dynamic nature of equilibrium.

Procedure: Take two 100 ml measuring cylinders and mark them as 1 and 2 to avoid
any confusion. Two glass tubes of length 30 cm each are also needed. Fill the cylinders
with coloured water and keep the second one empty. Put one glass tube in first cylinder
and second in the empty one. Glass tube is immersed in cylinder 1 and closes its upper
tip with finger and water contained in its lower portion should be transferred to
cylinder 2. Using the other glass tube, repeat the above mentioned step from cylinder-2
to cylinder-1. Keep doing this until you notice that the level of coloured water in both
the cylinder becomes constant. If this inter-transference between the cylinders
continues, there will be no further change in levels of coloured water. If we take
concentration analogous to level, we can say that the process continues though

9
constancy level has been reached. This constancy level is indicative of dynamic nature
of equilibrium.

Exploratory Activity: Dynamic Equilibrium

Introduction: The concept of equilibrium is a very important one to scientists in all

fields. Static equilibrium refers to a condition in which the parts of a system have
stopped moving, and is rare in nature. Dynamic equilibrium refers to a condition in
which the parts of a system are in continuous motion, but they move in opposing
directions at equal rates so that the system as a whole does not change. In this exercise,
you will explore the concept of dynamic equilibrium.

Materials: Clear plastic containers (2), paper cups, water, meter stick.

Methods: Pour water into the plastic containers until the water level is the same in each
container. Measure and record the depth of the water. Obtain two paper cups and
submerge each in a separate container of water. When given a signal by one of the lab
team members, simultaneously pour each cup of water into the other container. Repeat
this process four more times, then measure and record the depth of the water. Then

10
repeat the cycle of five transfers two more times, and measure the depth of the water
after each cycle. Record your observations.

Pour all of the water into one of the containers. Measure and record the depth of water
in that container. Proceed as before. At the beginning, one cup will be empty and the
other full. Simulate the pouring with the empty cup at each transfer. As water is put
into the empty container, gather as much water as possible in the cup for each transfer.
Measure and record the depth of the water after each five transfers, and continue until
twenty transfers have been made. If time allows, do the whole procedure again with
different starting depths. Dispose of the water and return the materials to the front
desk.

Laboratory Report

Observations:

Prepare a data table to record the changes in the depth of the water in both containers
under each set of conditions. The table should have five columns: Time, Trial 1
Container 1, Trial 1 Container 2, Trial 2 Empty Container, Trial 2 Full Container. You
may add more columns if you collect more data.

Prepare graphs of your data. Put time on the horizontal axis and depth on the vertical
axis. Be sure to indicate the units of measure. Plot both the data for both containers for
each trail on the same graph (remember to use different line types).

Conclusions:

1. What happened to the water levels in Trials 1 and 2?

2. How would you describe the shape of the graph for each set of data?

3. In Trial 2, one of the cups initially has no water in it. What happens to the
amount of water transferred from the empty side to the full side as the trial
continues?

11
 4. Are the final water levels in each trial the same? Why?

5. What would happen to the water level in each system if you continued to
transfer the water indefinitely? Why?

This should be discussed by the teacher in the class:

Welcome Note

We have already considered several physical processes, including melting,

vapourisation, dissolution, etc. that reach a dynamic equilibrium. The same ideas can be
applied to chemical changes. We shall discuss equilibria quantitatively and discover the
power to control the direction of any given reaction as well as the yield of products. We
shall study how dynamic equilibria are responsive to changes in conditions. Before we
start, let us revise a few concepts we have studied earlier.

I. Statement: The different types of chemical reactions

Explanation:
The process in which a substance(s) undergoes a change to produce new
substances with new properties is known as a chemical reaction or the
rearrangement of the atoms present in the reacting substance occurs to give new
chemical combinations. Chemical Reactions are of different types

(i) Combination reactions or synthesis reactions

(ii) Decomposition reactions

12
(iii) Substitution reactions

(iv) Electrolytic decomposition

(v) Isomerisation reactions

(vi) Polymerisation reactions

Polymerisation

(vii) Photochemical reactions

(viii) Redox reactions

13
II. Statement: Rates of reactions

Explanation:

The rate of a reaction is defined as the speed with which the reactants are
converted into products. There are some reactions which are very slow whereas
there are some which are very fast.

Slow reactions

(i)

(ii)

Fast reactions

(i)
(ii)

Factors affecting rate of reactions

(i) Concentration of reacting reactants

Rate of reaction is directly proportional to the concentration of reactants.

(ii) Nature of reactants

(a) Physical state of the reactants

(b) Chemical nature of reactants

14
(iii) Temperature of the system: The rate of reaction increases with increase in
temperature due to increase in the number of effective collisions.

(iv) Presence of catalyst: A catalyst is the substance which increases the rate of
reaction and can be recovered chemically unchanged in mass and composition
after the reaction. It is highly specific in nature and does not change U of
reaction. It lowers the activation energy by forming activated complex.

(v) Exposure to radiation: Sometimes chemical reactions are also brought about by
light. A mixture of H2 and Cl2 reacts explosively in light; no reaction in dark.

III. Statement: Enthalpy of a physical change

Explanation:

Physical change means the conversion of one bulk phase (such as a liquid) to
another (such as vapour). The vaporisation of liquid, such as conversion of liquid
water to water vapour when water evaporates at 20oC or boils at 100oC is an
endothermic process because heat must be supplied to bring about the change.
The heat that must be supplied at constant pressure per mole of molecules that
are vaporised is called the enthalpy of vaporisation of liquid and is denoted
by vapH.

vapH = +44 kJ

Another common phase transition is fusion or melting example when ice melts to
water. The change in enthalpy per mole of molecules that accompanies fusion is
called enthalpy of fusion.

fusH = +6.01 kJ (at 0oC)

15
 The reverse of vaporisation is condensation and the reverse of fusion is freezing.
The enthalpy changes are, respectively, the negative of the enthalpy of
vaporisation and fusion.

H = -6.01 kJ

The direct conversion of a solid to a vapour is called sublimation.

The vaporisation of solid carbon dioxide (dry ice) is an example of sublimation.
The molar enthalpy change accompanying sublimation is called enthalpy of
sublimation. subH.

subH = fusH + vapH

IV. Statement: The enthalpy of a chemical change

Explanation:

Thermochemistry is that branch of chemistry which deals with heat energy

changes as a result of chemical reactions. During a chemical reaction, energy is
either evolved (exothermic reactions) or absorbed (endothermic reactions) in the
form of heat.

The enthalpy of a reaction is the enthalpy change accompanying a reaction as

specified in the accompanying chemical equation example for the hydrogenation
of ethene

rH = - 137 kJ mol-1 at 25oC

The reaction enthalpy of -137 kJ signifies, enthalpy of reaction decreases by 137

kJ when 1 mol H2 combines with 1 mol ethene at 25oC. The numerical value of
enthalpy of a reaction depends upon the conditions - state of purity of the

16
 reactants and products, the pressure and the temperature under which the
reaction takes place.

The standard enthalpy of reaction rHo is the enthalpy of reaction for the
conversion of reactants in their standard states into products in their standard
states example.

rHo = - 572 kJ mol-1 at 25oC

The standard enthalpy of formation fHo of a substance is the standard enthalpy

of the reaction in which it is formed from its elements in their reference states
expressed as enthalpy change per mole of substance.

V. Statement: Free Energy

Explanation:

Gibbs free energy: Commonly referred to as 'free energy', is also called the
Gibbs function and is defined as

G=H–TS
A change in value of G at constant temperature arises from change in the
enthalpy and entropy.

G= H–T S

It follows that at constant temperature and pressure.

G=–T Stotal

(change in free energy is simply another way of expressing change in overall

entropy when a process occurs at constant temperature and pressure). Only

17
 those chemical processes are feasible or spontaneous in which free energy
decreases i.e. G is negative.

There are three possibilities for G

(i) G=0 In this case, the process does not proceed in any direction and the
system is said to be in the equlibrium state.

(ii) G= +ve In this case, the reaction is non-spontaneous.

(iii) G= –ve In this case, the reaction is spontaneous.

Another important feature of free energy is that its value gives the maximum
amount of non-expansion work that can be extracted from a system that is
undergoing a change at constant temperature and pressure.

G = w'(maximum) at constant T and p.

G = -Wnon-expansion = Wuseful

To illustrate this point, take the example of electrolysis of water. The electrical supplied
to the system decomposes H2O to H2 and O2 resulting into increase in volume of
system. This is because of production of gaseous products. So work done by the system
is work of expansion. Useful work obtained is production of gases.

18
From our experience, we understand that, when we mix together reactants in the exact
proportion, all the reactants get converted into products. But this is not true for all
cases. It is observed in a number of cases that reaction do not proceed to completion.
When a chemical reaction reaches this state, chemical equilibrium has been attained.
Equilibrium in general not only applies to chemical reactions but also to physical
changes as well. Example: ice and water are in equilibrium at 0oC and atmospheric
pressure. So, we can say that equilibrium represents the state of a process in which the
macroscopic properties like temperature, pressure and concentration do not show any
noticeable change.

It must be noted that in all processes attaining equilibrium, two opposing forces are
always present in the reaction or system which are mainly responsible for the
attainment of equilibrium.
When a system is in equilibrium, it has no tendency to change in either
direction (forward or reverse) and will remain in its state until there is an external
disturbance. A steel glass in the kitchen is at the same temperature as its surroundings,
and we say that it is in thermal equilibrium with it. There is no tendency of energy to
flow into or out of the glass as heat. Now consider a gas confined to a cylinder by a
piston, which has the same pressure as the surroundings. This system is in mechanical
equilibrium with its surroundings, and the gas has no tendency to expand or contract.

At the beginning of the twentieth century, an acute need for nitrogen compounds was
felt, essentially due to the looming prospects of World War I. The nitrates, normally
used for fertilisers in the agricultural sector, were increasingly being used for the
19
manufacture of explosives. The limited supply of nitrates that could be quarried (from
deposits in Chile) led scientists from both sides in the conflict to attempt converting
atmospheric nitrogen into compounds. Most of these methods were too expensive to
employ on a large scale. Finally, a German chemist, Fritz Haber, found an economical
way of using nitrogen from the air to provide an abundant source of compounds, not
only for agriculture but also for explosives.

Why was Haber successful? He applied the principle of chemical equilibrium, which is
that stage in a chemical reaction where there is no further tendency for the composition
of the reaction mixture to change.

 What is an equilibrium state in a chemical reaction?

 Is there any method for recognising such a state?

 Why do only certain reactions show this behaviour?

 What are the factors that can change the state of equilibrium?

9.2 Equilibrium in Physical Processes

From the physical equilibrium criteria, we have noticed that, at equilibrium, some
measurable properties of the system become constant e.g.

9.2.1 Solid – Liquid Equilibrium

For solid liquid equilibrium, the two phases can co-exist only at a definite
temperature called melting or freezing point. Thus, for such equilibrium, temperature
is constant. Example: If some ice cubes with some water at 0oC and normal atmospheric
pressure are placed in a closed system, the mass of ice and water is found to be constant
due to two opposing forces (melting and freezing of water) are operating
simultaneously at equilibrium.

Rate of melting of ice = Rate of freezing of water

20
9.2.2 Liquid – Vapor Equilibrium

In case of liquid gas equilibrium, the pressure of the vapours above the liquid
becomes constant at a particular temperature.

Let us take a closed vessel connected to manometer. Suppose the vessel is first
evacuated. The level of both the limbs of manometer is some. However, when some
water is added into the vessel. You will observe that level of mercury in left limb of
manometer begins to fall and there is gradual increase in reading of right limb. After
sometime, the level becomes constant. The increase in level of mercury is due to vapour
pressure exerted by water vapours. The final situation indicates that:

Rate of evaporation = Rate of condensation

9.2.3 Solid – Solution Equilibrium

In solid solution equilibrium (for dissolution of solid in liquid), the solubility is

constant at a given temperature. Solubility generally increases with increase in
temperature.

solid(s) solid(aq): solubility is constant

Suppose we add some salt in a fixed amount of water at a fixed temperature and
pressure. It we keep on dissolving it, a stage will come when no more salt dissolves in

21
it. Although the dissolution process doesn't stop but the opposing force i.e. precipitation
is also taking place at the same rate. So in this case at equilibrium,

Rate of dissolution = Rate of precipitation

9.2.4 Equilibria involving dissolution of gases in liquids

For dissolution of gases in liquids, the concentration of a gas in liquid at a given

temperature is proportional to the pressure of the gas over the liquid. This statement is
called Henry's Law. Example:

is constant at constant temperature.

General characteristics of equilibria involving physical processes are summed up as

follows:

1. At equilibrium, the measurable properties of the system become constant

example in case of evaporation of water, vapour pressure of water becomes
constant.

22
2. Equilibria involving gases can be attained only in the case of closed systems i.e.
the system should neither gain nor lose matter to the surroundings. This is because
if the container is open, the gas will escape and there will be no equilibrium.

Vapour pressure of water becomes constant

A simple experiment will demonstrate that in a closed vessel, the two phases
(liquid and vapour) reach equilibrium.

Take a long glass tube filled with mercury and upturn it in a dish of mercury.
The mercury inside the tube falls to a height proportional to the external
atmospheric pressure, leaving it 76 cm high at sea level. The space above the
mercury is almost a vacuum. Now, if we introduce a trace of water in this
vacuum, then the vapour pressure (water evaporates) pushes the mercury level
down a few centimetres. This pressure exerted by the vapour depends upon the
amount of water added. But if we add so much water that a little liquid remains
on the surface of mercury then we notice that the vapour pressure remains
constant, no matter what the quantity of water added.

At a fixed temperature, the vapour exerts a characteristic pressure, regardless of

the amount of water present.

When a liquid and its vapour is in dynamic equilibrium inside a closed

container, the rate at which the molecules leave the liquid is equal to the rate at
which they return.

23
3. The equilibrium is dynamic in nature i.e. the process does not stop but the
change takes place in the forward and backward directions with the same rate.

Take a general case of reversible reaction A + B C+D

Where A and B are reactants and their concentrations as well as rate of forward
reaction decreases with the passing of time. Concentration of C and D increases
gradually with the passage of time and a time will come when the concentration
of A, B, C and D will become constant. This state of system is known as
equilibrium state.

Attainment of chemical equilibrium

Though equilibrium state has been attained but this doesn't mean that the
reaction has stopped. Forward and backward reaction continues to take place at
equal rates. Only the concentration of products and reactants remains constant. It
should be noted here that the physical conditions like temperature and pressure
should be kept constant.

The dynamic nature of equilibrium can also be illustrated by the synthesis of

ammonia by Haber's process. Haber started with known amounts of N2 and H2
which are kept at high temperature and pressure and determined the ammonia
present at regular intervals of time. He was also successful in determining the

24
concentration of unreacted N2 and H2. After sometime he observed that the
concentration of all the three species becomes constant. This constancy indicates
that the reaction has reached equilibrium. To prove the dynamic nature of
equilibrium, he demonstrated the same experiment with same starting
conditions of concentration, temperature and pressure but using D2(Deuterium)
instead of H2. This reaction mixture also reached equilibrium with same
composition except that D2 and ND3 are present instead of H2 and NH3. When
the above two mixtures (H2, N2, NH3, ND3) are mixed together, it was found that
concentration of ammonia was unaltered. But when the mixture was analysed by
mass spectrometer, it is found that NH3, NH2D, NHD2, ND3, H2, HD, D2 are
present. So one can conclude that forward and backward reactions are still taking
place otherwise there would not have been the formation of new species along
with the existing one.

The dynamic nature can be demonstrated by adding radioactive sugar

(14C12 H22O11) to a saturated solution of sugar [where equilibrium exists between
the sugar (C12H22O11) dissolved in solution and sugar (C12H22O11) which remains
undissolved]. After sometime, it is observed that the solution as well as the
earlier solute (undissolved) acquire radioactive species (Figure 9.1)

25
 Figure 9.1: Demonstration of dynamic nature of solid in liquid equilibrium

4. At equilibrium, there exists an expression of concentrations of the substances

involved in equilibrium which becomes constant at constant temperature.

For

= constant at constant temperature

This constant is called the equilibrium constant.

6. The magnitude of equilibrium constant gives an indication of the extent to which

the process proceeds before acquiring equilibrium e.g. the greater value of the
equilibrium constant for the dissolution of CO2 in water, shows greater
dissolution of CO2 in water.

Student Activity – 1
Exploratory Activity: Dynamic Equilibrium

Introduction: The concept of equilibrium is a very important one to scientists in all

fields. Static equilibrium refers to a condition in which the parts of a system have
stopped moving, and is rare in nature. Dynamic equilibrium refers to a condition in
which the parts of a system are in continuous motion, but they move in opposing

26
directions at equal rates so that the system as a whole does not change. In this exercise,
you will explore the concept of dynamic equilibrium.

Materials: Clear plastic containers (2), paper cups, water, meter stick.

Methods: Pour water into the plastic containers until the water level is the same in each
container. Measure and record the depth of the water. Obtain two paper cups and
submerge each in a separate container of water. When given a signal by one of the lab
team members, simultaneously pour each cup of water into the other container. Repeat
this process four more times, then measure and record the depth of the water. Then
repeat the cycle of five transfers two more times, and measure the depth of the water
after each cycle. Record your observations.

Pour all of the water into one of the containers. Measure and record the depth of water
in that container. Proceed as before. At the beginning, one cup will be empty and the
other full. Simulate the pouring with the empty cup at each transfer. As water is put
into the empty container, gather as much water as possible in the cup for each transfer.
Measure and record the depth of the water after each five transfers, and continue until
twenty transfers have been made. If time allows, do the whole procedure again with
different starting depths. Dispose of the water and return the materials to the front
desk.

Laboratory Report

Observations:

Prepare a data table to record the changes in the depth of the water in both containers
under each set of conditions. The table should have five columns: Time, Trial 1
Container 1, Trial 1 Container 2, Trial 2 Empty Container, Trial 2 Full Container. You
may add more columns if you collect more data.

27
Prepare graphs of your data. Put time on the horizontal axis and depth on the vertical
axis. Be sure to indicate the units of measure. Plot both the data for both containers for
each trail on the same graph (remember to use different line types).

Conclusions:

1. What happened to the water levels in Trials 1 and 2?

2. How would you describe the shape of the graph for each set of data?

3. In Trial 2, one of the cups initially has no water in it. What happens to the
amount of water transferred from the empty side to the full side as the trial
continues?

4. Are the final water levels in each trial the same? Why?

5. What would happen to the water level in each system if you continued to
transfer the water indefinitely? Why?

9.3 Equlibrium in Chemical Processes

9.3.1 Dynamic nature of Chemical Equilibria

Chemical equilibrium involves different chemical species in equilibrium with

each other. The chemical equilibrium may be classified as homogeneous or
heterogeneous depending on whether the reaction involves only one phase or
more than one phase, respectively.

A few examples are given below

Homogeneous chemical equilibria

28
 Heterogeneous chemical equilibiria

At equilibrium, the process of conversion of reactant(s) into products and vice

versa does not stop, but both of them occur simultaneously with equal rate;
consequently, their composition remains constant. Thus, at equilibrium, the rate
of forward reaction becomes equal to the rate of backward reaction.

The reaction is then said to be in dynamic equilibrium, the reactant(s) and

product(s) are formed as quickly as they are destroyed.

The variation of reaction rates with time and ultimately the attainment of
equilibrium may be illustrated with the following examples:

(i) Decomposition reaction

The decomposition of N2O4 in a closed vessel is a reversible reaction.

N2O4 is almost stable at 273 K and is colourless.

The equilibrium state can be attained starting from either the reactant (any
amount of N2O4) or product (any amount of NO2) or both (any arbitrary amounts
of N2O4 and NO2) can be taken. Irrespective of how the equilibrium is attained, at
equilibrium the rate of formation of NO2 from N2O4 and the rate of formation
of N2O4 from NO2 are equal.

Initially, if we start from N2O4 the rate of formation of NO2 is fast and it
steadily decreases with time till it reaches a constant value (at the equilibrium
stage). Similarly, if we start from NO2, then the rate of consumption of NO2 to
29
 form N2O4 is rapid to start with and steadily decreases with time till it becomes
constant at the equilibrium state.

Figure 9.2 (a) and (b): (a) Formation of NO2 starting from N2O4 and (b) formation of
N2O4 starting from NO2.

Since the equilibrium position can be reached in either direction,

(reactants equilibrium products) such reactions are called reversible reactions.

Decomposition reaction

Decomposition reaction is a reaction in which a single compound reacts to give

two or more substances.

Chemical equilibrium

30
 Chemical equilibrium is the state reached by a reaction mixture when the rates
of forward and reverse reactions become equal.

(ii) Decomposition of CaCO3 in a closed vessel

When solid calcium carbonate is heated in a closed vessel, calcium oxide and
carbon dioxide are formed. Due to evolution of CO2 gas, pressure will be
developed in the vessel which can be noted down with the help of a manometer.

Figure 9.3

As the decomposition of calcium carbonate continues, the pressure goes on

increasing. After some time, it is observed that pressure becomes constant, at
constant temperature, even though some calcium carbonate is still left. This
shows that the amount of carbon dioxide produced has become constant.

Characteristics of Chemical Equilibrium

(i) Chemical equilibrium is dynamic in nature.

(ii) The properties of a system become constant at equilibrium and remain

unchanged thereafter.

(iii) At equilibrium the rate of forward reaction becomes equal to the rate of
backward reaction.

(iv) A chemical equilibrium can be attained only if none of the products is allowed to
escape out.

31
(v) Chemical equilibrium can be attained from either direction i.e. from the direction
of the reactants as well as from the direction of the products.
N2O4 2NO2

(vi) At equilibrium, the free energy change of the system i.e. G = 0

(vii) A catalyst does not alter the state of equilibrium.

Free energy change

Free energy is a thermodynamic quantity defined by the equation

G = H – TS

Student Activity – 2

Reversible Reactions

2 NO2 (g) N2O4 (g)

Red Colourless

USE CAUTION - concentrated acid

PROCEDURE

1. Place about 10 mL of concentrated nitric acid in a flask.

2. Carefully add a penny. A deep red gas, NO2, will form.

3. Carefully "pour" the gas into two test tubes and stopper them.

4. Place one tube in a beaker of boiling water. The colour gets a deeper
brown.

5. Place the other tube in an ice bath. The gas will become almost colourless.

6. Return both tubes to room temperature. The gases will return to their
original colour.

32
 9.4 Application of Equilibrium Constant

9.4.1 Law of Chemical Equilibrium

 Most reactions do not go to completion i.e. when reactants are mixed in

stoichiometric proportions, they are not converted to products completely.

 Reversible reactions are those reactions which do not go to completion and can
occur in either direction.

aA + bB cC + dD

where a, b, c, d represent stoichiometric coefficients in a balanced equation. A, B, C,

D represent chemical formulae.

indicates that both forward and backward reactions occur simultaneously or

that the reaction is reversible.

 When A and B react to form C and D at the same rate at which C and D react to
form A and B, then the system is at equilibrium.

 Chemical equilibrium exists when two opposing reactions occur simultaneously

at the same rate.

Chemical equilibria are dynamic equilibria in which individual molecules are

continually reacting. The overall composition of the reaction mixture does not
change.

 In a system at equilibrium:

The equilibrium lies to the right if more C and D are present, than A and B.
The equilibrium lies to the left if more A and B are present.

 Consider a reaction where the coefficients in the equation are all unity.
The figure below represents variation in the concentration of species present in the

33
 A + B C + D system as equilibrium is approached, beginning with equal
concentrations of A and B only.

A+B C+D

Figure 9.4: Equilibrium is established

 The square brackets, [ ], represent concentrations of the species in moles per litre.

The SO2 / O2 / SO3 system

 This reversible reaction can be represented as

 Suppose 0.400 mol of SO2 and 0.200 mol of O2 are injected in a closed one litre
container. When equilibrium is established, at time te then we observe that 0.056 mol
of SO3 has been formed and 0.344 mol of SO2 and 0.172 mol of O2 remains unreacted.

Figure: 9.5

34
 This reaction does not go to completion

Note: Greater changes in concentrations occur in order to establish equilibrium

when starting with SO3 than when starting with SO2 and O2.

The equilibrium favours SO2 and O2.

Figure 9.6: Establishment of equilibrium in system

In (a) we begin with stoichiometric amounts of SO2 and O2 and no SO3.

In (b) we begin with only SO3 and no SO2 or O2.

Consider a reversible reaction that takes place in one single step

Rate of forward reaction is

Rate of reverse reaction is

Here, kf and kr are the rate constants of the forward and reverse reactions, respectively.

At equilibrium

35
Dividing both sides by kr[A]2[B]

At any specific temperature, both kf and kr are constants. Therefore,

We call this ratio by a special name and symbol: the equilibrium constant, Kc or simply
K.

Note: The subscript 'c' refers to concentration. Here the [ ] indicates equilibrium
concentrations in mol L-1.

Now let us study a reaction that takes place in two steps.

Overall reaction:

2A + B A2 B

The equilibrium constant expression for steps (i) and (ii) are

36
If we multiply k1 by k2, then [A2] term may be eliminated. Now k1 and k2 are both
constants, hence their product is a constant.

Important: Regardless of the mechanism by which this reaction takes place, the
equilibrium constant expression has the same form.

9.4.2 Equilibrium Constant

The equilibrium constant Kc defined as the product of the equilibrium concentrations

(moles per litre) of the products, each raised to a power that corresponds to its
coefficients in the balanced equation, divided by the product of the equilibrium
concentrations of the reactants, each raised to the power that corresponds to its
coefficient in the balanced equation.

Note: The numerical values of Kc can generally come only from experiments.
Given below are equilibrium constant expressions and their numerical values at
25oC.

Relation between equilibrium constant for a general reaction and its multiples

37
 Chemical Equation Equilibrium constant

aA + bB cC + dD K

cC + dD aA + bB 1/K

naA + nbB nCC + ndD Kn

The equilibrium constant

Value of Kc

We have already considered the equation for the reaction of SO2 with O2 to form SO3
and its equilibrium constant expression as:

Now if we write the equation for the same reaction in reverse, then the equlibrium
constant K'c for reaction is written as

Here K'c the equilibrium constant for the reverse reaction is reciprocal of Kc. If the
equation for the reaction was written as

If the equation for a reaction is multiplied by a positive or negative number n, then the
original value of Kc is raised to the nth power.

Thermodynamic Equilibrium Constant

The thermodynamic definition of equilibrium constant involves activities rather than

concentrations.

38
What is the activity of a component of an ideal mixture? It is the ratio of its
concentrations or partial pressure to a standard concentration (1 M) or pressure
(1 atm).

We shall consider the activity of each species to be a dimensionless quantity. The

numerical value of this may be determined as

For pure liquids and solids: Activity is taken as 1

For components of ideal solutions: Activity of each solution is taken to be equal to

its molar concentration

For gases in an ideal mixture: Activity of each component is taken to be equal

to its partial pressure in atm

Because of the use of activities, the equilibrium constant has no units. The values we
put into Kc are numerically equal to molar concentration but the values are
dimensionless i.e. have no units.

Important: For any reaction,

(i) value of Kc varies only with temperature.

(ii) is constant at a given temperature.

(iii) is independent of the initial concentrations.

(iv) the magnitude of Kc is a measure of the extent to which the reaction occurs.

i.e. if value > 1; at equilibrium almost the entire quantity of reactants change to
products

if value < 1; equilibrium is established when most of the reactants remain unreacted
and very less amount of products is formed.

Consider the SO2/O2/SO3 equilibrium described earlier.

39
0.344 M 0.172 M 0.056 M (equilibrium concentrations)

Now, let us substitute these numerical values without units in the equilibrium
expression.

For this reaction, Kc is 0.15 at 1500 K

Illustrative example

If we place some nitrogen and hydrogen in an empty 5 L vessel at 500oC then when
equilibrium is established, we find 3.01 mol of N2, 2.10 mol of H2 and 0.565 mol of NH3
are present. Let us evaluate Kc for the following reaction:

N2 (g) + 3H2(g) 2NH3(g)

Solution
The equilibrium concentrations are obtained by dividing the number of moles of each
reactant and product by the volume i.e. 5 litres.

Substituting these numerical values into the expression for Kc

40
The small value of Kc indicates that the equilibrium lies to the left.
Important: The value of Kc depends upon the form of the balanced equation for the
reaction.

It is important that we always write the balanced chemical equation as well as the
value of Kc for a chemical reaction.

9.4.3 Predicting the direction of reaction

Reaction Quotient

The reaction quotient for aA+bB cC+dD is

where the concentrations are not necessarily the equilibrium concentrations.

Q, or reaction quotient has the same form as the equilibrium constant but it involves
specific values that are not necessarily equilibrium concentrations.

When they are equilibrium concentrations then,

What is the use of the concept of reaction quotient?

Well, we can compare the magnitude of Q with that of K for a reaction under given
condition to decide whether net forward or reverse reaction must occur to establish
equilibrium.

A net forward reaction occurs when the forward reaction occurs to a greater extent than
the reverse reaction.

Q<K : Forward reaction predominates until equilibrium is reached

Q=K : System at equilibrium
Q>K : Reverse reaction predominates until equilibrium is established

41
Important:
The value of equilibrium constant changes only with temperature.

9.4.4 Calculating Equilibrium Constant

Importance of Equilibrium constant, Kc

(i) We can calculate value of Kc from one set of equilibrium concentrations

(ii) Once we have the values, we can calculate the equilibrium concentrations from
the equilibrium constant.

Illustrative example

At a very high temperature Kc = 1.0 10-13 for the following reaction

2HF(g) H2(g) + F2(g)

At a given time, the following concentrations were detected.

[HF] = 0.500 M, [H2] = 1.00 10-3 M, [F2] = 4.00 10-3 M

Is the system at equilibrium? If not, what must happen for equilibrium to be

established?

Solution

Let us substitute the values in the following expression

But Kc = 1.0 10-13 so Q > Kc

Hence, the system is not at equilibrium.

42
For equilibrium to be established, Q value must become smaller till it equals Kc. For this
to happen, the right to left reaction must occur to a greater extent i.e. H2 and F2 must
react to form more HF.

Equilibrium constant and partial pressures

It is more convenient to measure the pressures of gases rather than their concentrations.
The ideal gas law for pressure gives

The pressure of a gas α concentration

For equilibria involving gases, the equilibrium constant can be expressed in terms of
partial pressures in atmospheres (Kp) rather than in terms of concentrations (Kc)

Important:
Kp has no units, for the same reasons that Kc has no units.

aA(g) + bB(g) cC(g) + dD(g), =

Relationship between Kp and Kc

Rearranging the ideal gas equation

[concentration] =

Substituting P/RT for n/V in the Kc expression for the N2/H2/NH3 equilibrium

43
 =

In general,

[Where ng = n(gas produced) - n(gas reacted)]

Important: n refers to the change in the stoichiometric number of gaseous species in

the balanced equation and not in the reaction vessel.

Now,

Kc refers to mol L-1 and Kp refers to atmospheres.

R must be expressed in

For reactions with equal number of gaseous species on both sides of the equation

n=0

Kp = Kc

Consider the ammonia equilibrium

N2(g) + 3H2(g) 2NH3(g)
ng= 2 - 4 = -2
Kp = 7.10 10-5 at C

= (7.10 10-5) [(0.0821)(773)]-(-2) = 0.286

44
Example:

Calculate value of Kp for the given reaction

2NOCl(g) 2NO(g) + Cl2(g)

if Kc is 3.75 10-5 at 1000 K.

Solution:

For the given reaction, n = (2 + 1) - 2 = 1

Applying Kp = Kc (RT) n

Kp = 3.75 10-5 (0.0821 1000)1

Kp = 3.07 10-4

Heterogenous Equilibria

Equilibria involving species in more than one phase.

So far we have considered only single phase equilibria i.e. homogeneous equilibria.

Now consider the following reversible reaction at C.

2HgO(s) 2Hg(ℓ) +

At equilibrium a solid, a liquid and a gaseous state co-exist.

We know that pressure changes do not significantly affect solids and liquids.

For solids and liquids, the activity is taken as unity, hence terms for solids and liquids
do not appear in the K expressions for heterogeneous equilibria.

For the above reaction

Kc = [O2]

45
Kp =

Let us take an interesting example of heterogenous equilibrium

CaCO3(s) CaO(s) + CO2(g)

We know that =

But [CaCO3(s)] and [CaO(s)] has constant activity.

So modified Kc = [CO2(g)]

Now, we can also write the expression for Kp.

Kp =

Example: What is Kp for the given reaction

2NO2(g) N2O4(g)

if partial pressures of NO2 and N2O4 are equal with a value of 2.5 104 Pa each?

Solution:

Important: This expression indicates that equilibrium exists at a given temperature for
one and only one concentration and one partial pressure of oxygen in contact with
liquid mercury and solid mercury (II) oxide.

46
 The activity of a component of an ideal mixture is a dimensionless quantity whose
magnitude is

equal to molar concentration in an ideal solution

equal to partial pressure in atmosphere in an ideal gas mixture

defined as 1 for pure solids and liquids

Also, thermodynamic standard states are

pure solids or pure liquids at 1 atm

solutions at one molar concentrations

gases at partial pressures of 1 atm.

Relationship between Go and the equilibrium constant

The standard free energy change for a reaction is Go i.e. the free energy change that
would accompany complete conversion of all reactants initially present in their
standard states to all products in their standard states.

The free energy change for any other concentrations or pressure is G

G = Go + RT lnQ

G = Go + 2.303 RT log Q

where

R = universal gas constant

T = absolute temperature

Q = reaction quotient

When the system is at equilibrium

47
 G=0

Q=K

Rearranging, we get the relationship between standard free energy change and the
thermodynamic equilibrium constant.

Go = —RT lnK or

Go = —2.303 RT log K

For reactions involving gases, the thermodynamic equilibrium constant (related to

Go) is Kp

For those involving species in solution, it is Kc.

Important

Forward reaction would be spontaneous at unit

Go is negative K>1
concentrations or partial pressures
System would be at equilibrium at unit concentrations or
Go is zero K=1
partial pressures (very rare).
Reverse reaction would be spontaneous at unit
Go is positive K<1
concentrations or partial pressure.

We can use the measured K values to calculate Go.

Illustrative Example

The equilibrium constant, Kp, for the following reaction is 5.04 1017 at 25oC.

Calculate Go298K for the hydrogenation of ethylene to form ethane.

Solution

We know,

Go298 K = —2.303 RT log Kp

= —2.303 (8.314) (298) log (5.04 1017)

48
= —5706 (17.702)

= —1.010 105 J mol-1

Go298 K = — 101 kJ mol-1

Evaluating K at different temperatures

If we determine the equilibrium constant KT1 for a reaction at one temperature T1, as
well as its Ho, then we can estimate the equilibrium constant at a second temperature
T2 using the van't Hoff equation

ln

or

ln

Pollution and the Equilibrium

Calculations show that in 1cm3 of air at 1100 K, there would be around 2 x 1015
molecules of nitrogen oxide are found at equilibrium- which is a small portion but pose
a pollution threat.

N2 (g) + O2 (g) 2NO (g)

49

Vehicle engines are a significant source of nitrogen oxide molecules. They contribute a
complex series of reactions with other molecules suchas carbon monoxide, sulphur
Vehicle engines are a significant source of nitrogen oxide molecules. They contribute a
complex series of reactions with other molecules suchas carbon monoxide, sulphur
dioxide and hydrocarbons. In view of the problems scientist sggested the use of
catalytic converters in cars. These converters remove NO, CO and unburnt
hydrocarbons. Vehicles that burn hydrocarbons contributre large quantities of CO2 to
the atmosphere, which adds up to global warming. However, even these alternatives
have environmental consequences. Some photochemical smog occurs naturally. For
example, the Smoky Mountains in the USA seems to be caused by the reactions
between oils from the pine forests and citrus groves with naturally occuring ozone.

9.5 Factors Affecting Equilibria

9.5.1 Le Chatelier's Principle

If a change of conditions (stress) is applied to a system at equilibrium,

the system responds in the way that best tends to reduce the stess in
reaching a new state of equilibrium

 There are four types of changes to consider:

A. Concentration changes

B. Pressure changes (volume changes for a gas-phase reaction)

C. Temperature changes

D. Presence of catalysts

The reaction quotient Q, helps to predict the direction of the response of the
system to the above changes

50
A. Concentration Changes

Consider the following system starting at equilibrium

A+B C+D

 If a reactant or product is added to the system, then the stress is relieved by

shifting the equilibrium in the direction that consumes or uses up the added
substance.

Let us compare the values of Q and K for clarity. If more A or B is added, Q < K,
forward reaction occurs to a greater extent to re-establish the equilibrium.

If more C or D is added, Q > K, reverse reaction occurs to a greater extent until

equilibrium is established again.

We can follow the same reasoning if substances are removed from the system at
equilibrium.

In general, the reaction that produces the substance that was removed, occurs to
a greater extent, than its reverse.

Direction of shift
Stress Q
A+B C+D

Increase concentration of A or B Q<K Right

Increase concentration of C or D Q>K Left

Decrease concentration of A or B Q>K Left

Decrease concentration of C or D Q<K Right

51
A solution of CoCl2.6H2O in isopropyl is blue due to [COCl4]2- ion. If we add
water, the reaction to the left is favoured to form a mixture of pink and blue
complexes to give a purple-coloured complex in the middle test tube. If we add
concentrated HCl, the excess of Cl- shifts the equilibrium to the right.

Source: Google Images

Effects of changes in concentration on the equilibrium

[Co(H2O)6]2+(aq) + 4Cl– (aq) [CoCl4]2–(aq) + 6H2O

For illustration, take the reaction

H2 (g) + I2(g) 2HI (g)

On adding I2 at equilibrium, concentration of I2 is increased. So it will no longer

be in equilibrium state and react with more of H2 to give HI in order to
re-establish equilibrium by following Le-Chatelier's principle. The net shift of
equilibrium is towards the right. We can get similar results if we use H2 instead
of I2 i.e. in that case also the shifting will be towards right side.

52
 Figure: 9.7

B. Changes in Volume and Pressure

Changes in pressure affect the concentration of solids and liquids to a very little
extent. Why?

 However, changes in pressure cause significant changes in concentration of

gases, which affects the value of Q for the reaction in which the number
of gaseous reactants differs from the number of gaseous products.

 For an ideal gas

PV=nRT

P=

The term represents the concentration

At constant temperature, n, R, T are constants.

So, if the volume of a gas decreases, its partial pressure increases, its
concentration increases.

53
 Similarly, if the volume occupied by a gas increases, both, its partial pressure
and its concentration decrease.

 A gaseous system at equilibrium

A(g) 2B(g)

K=

Stress Direction of shift

A(g) 2B(g)

Pressure increases Towards smaller number of gaseous molecules

(volume decreases) left

Pressure decreases Towards larger number of gaseous molecules

(volume increases) right

C. Changes in Temperature

 Consider the following system at equilibrium

A+B C + D + heat; H = negative

Heat is produced by the forward exothermic reaction. If we increase the

temperature at constant pressure, then the reaction to the left is favoured in
order to remove the extra heat.

If we decrease or lower the temperature, it favours the forward reaction.

 Consider the following reaction at equilibrium

L + M + heat N + O; H = positive

54
For this endothermic reaction, an increase in temperature, at constant pressure
favours the reaction to the right.

A decrease in temperature favours the reaction to the left.

Important: The values of the equilibrium constant changes with temperature.

Hence,

K of exothermic reactions decrease with increasing temperature.

K of endothermic reactions increase with increasing temperature.

Source: Google Images

The gas phase equilibrium for the exothermic reaction

The two flasks contain the same amount of gas. Which flask has more NO2 gas?
Why does the amount of NO2 gas decrease when temperature is decreased?

Source: Google Images

55
Effect of temperature changes on the equilibrium of the endothermic reaction

[Co(H2O)6]2+(aq) + 4Cl- + Heat [CoCl4]2- + 6H2O

We begin with a purple equilibrium mixture of the pink and blue complexes at
room temperature (not shown). In hot water the forward reaction (endothermic)
is favoured and Kc is higher, so the solution is blue (right). At 0oC, the reverse
reaction (exothermic) is favoured and Kc is lower, so the solution is pink (left).
Each insert shows the structure of the cobalt complex species present in the
highest concentration; other ions and solvent molecules are not shown.

For more understanding this point, take a reaction like

CO(g) + 3H2(g) CH4(g) + H2O (g)

Let this equilibrium mixture is kept on in a cylinder fitted with a piston at

constant temperature. When the piston is compressed to half of its original
volume, pressure inside the cylinder becomes double according to Boyle's law.
Now, partial pressures of each component also change and they are no longer in
equilibrium state. So to re-establish equilibrium and to undo the effect of change
imposed on them, the reaction will shift in forward direction i.e. more number of
moles of CH4 and H2O are formed. It can also be predicted by determining
reaction quotient. When volume of reaction mixture is halved, partial pressures
and concentration are doubled.

So, =

Qc < Kc

So reaction proceeds in forward direction.

56
 Temperature Kc

298 4.9 1027

800 1.8 105

1000 2.54 102

1200 3.92

Table for equilibrium constant for methanation at different temperature.

(Exothermic reaction) we can observe from this table that for methanation
reaction:
CO(g) + 3H2(g) CH4(g) + H2O(g)

H = negative equilibrium constant decreases with the rise in temperature i.e. it

favours backward process and vice versa for endothermic reaction.

57
D. Presence of a Catalyst

 Introduction of a catalyst to a system changes the reaction rate. But it cannot shift
the equilibrium in favour of either products or reactants. Why? Since the catalyst
affects the activation energy of both the reactions, it changes both the rates
equally. What changes, however, is the time required for the equilibrium to be
established. Hence, a catalyst changes neither Q nor Kc.

For example, for the reaction

2SO2(g) + O2(g) 2SO3(g)

the reaction rate is very slow but after adding Vanadium pentoxide (V2O5), we
can achieve the equilibrium point much quicker because catalyst alters the
reaction machanism by forming activated complex giving easy way for the
reactants to give products. Fe, No, Ni, TiCl4 + Al(CH3)2, etc. are some of
examples of catalyst.

Haber's Process

 Industrial production of ammonia

 Exothermic reaction between nitrogen and hydrogen is reversible.

= = at

 This reaction is never allowed to reach a state of equilibrium, but moves towards
it.

 The large value of Kc indicates that at equilibrium, nearly all of N2 and H2

(1:3 mole ratio) would be converted into NH3.

58
 But at , the reaction is very slow, and no significant amount of NH3 is
produced in a reasonable time span.

 4 moles of gases on the left side and two moles only on the right side show that
increasing pressure would favour the product formation (NH3).

 The reaction is exothermic, hence increasing temperature would favour

decomposition of NH3.

 Addition of catalysts (finely divided iron) speeds up both forward and reverse
reactions. NH3 is produced at a lower temperature.

 High yield condition: temperature, high pressure, removal of liquid NH3

(boiling point = ), excess N2.

STUDENT ACTIVITY – 3

Le Châtalier's Principle - Equilibrium involving Copper (II) ions -

Procedure
Place approximately 2 mL of 0.1 M CuSO4 in a test tube. CuSO4 is a light blue solution.

Add several drops of 1 M NH3. The result will be a light blue precipitate. The addition
of more NH3 causes the solution to turn a darker blue.

Next add several drops of 1 M HCl until a change is noted - the solution will become a
lighter blue.

Explanation
An ammonia solution (Reaction 1) produces ammonium and hydroxide ions. When
added to the CuSO4 solution, OH– reacts with the Cu2+ to produce the precipitate,
Cu(OH)2 (Reaction 2).

59
Adding H+ (as HCl) removes OH– from the solution (Reaction 1). This shifts the
equilibrium in Reaction 1 towards the right (the products), resulting in a decrease in
[NH3]. This reduction in [NH3] causes the equilibrium in Reaction 3 to shift to the left
(the reactants)

Reaction 1:

NH3 (aq) + H2O( ) NH4+ + OH–(aq)

Reaction 2:

Cu2+(aq) + OH–(aq) Cu(OH)2 (s)

Reaction 3:

Cu(H2O)42+(aq) + 4NH3 (aq) Cu(NH3)42+(aq) + 4H2O(ℓ)

light blue dark blue

Le Châtalier's Principle - Equilibrium involving Cobalt (II) ions

This easy-to-do demonstration can be used to illustrate both the effect of concentration
and temperature on equilibrium systems. The cobalt chloride solution can be kept and
reused for future classes.

View a demonstration

Materials Required

 0.2 M Cobalt chloride hexahydrate, CoCl2· 6H2O

Prepare a 0.2 M cobalt chloride solution by dissolving 2.6 g CoCl 2· 6H2O in 100 mL
of distilled water.

 concentrated (12M) HCl - caution!

 hot water bath

 ice water bath

60
Safety
Use extreme caution when handling the hydrochloric acid.

Procedure
The cobalt equilibrium system is represented by the following equation:

Co(H2O)62+(aq) + 4 Cl-(aq) CoCl42-(aq) + 6 H20( ) ΔH = +50 kJ

Pink blue

hydrated cobaltous ion chloro complex

Part 1 : The Effect of Concentration

1. Begin with 50 mL or so of the pink hydrated form of the cobalt ion in a larger
(250 mL) beaker or Erlenmeyer flask.

2. Carefully add concentrated HCl to the solution until the blue form of the
equilibrium system appears.

3. Add distilled water to the solution in the beaker or flask. The equilibrium will shift
back to the pink form.

Part 2: The Effect of Temperature

1. Add some pink form of the system to a test tube and place it into the hot water bath,
or carefully warm the solution using a bunsen burner. The solution will turn blue.

2. Place the blue test tube in the ice water bath; it will return to its pink colour.

Explanation

Part 1: The effect of concentration. When HCl is added to the pink hydrated form of
the cobalt ion, the concentration of increases. (H+ remains in solution as a spectator
ion). The increase in causes the equilibrium to shift to the product side, and the
solution turns blue.

61
Adding water will shift the equilibrium to the left, forming more pink hydrated
cobaltous ion.

Part 2: The effect of temperature. As written above, the forward reaction is an

endothermic reaction. According to Le Châtalier's Principle adding heat favours the
endothermic direction. Thus warming the system will favor the blue chloro complex
side of the reaction. When placed in an ice bath, the exothermic direction will now be
favored, shifting the equilibrium to the pink hydrated side.

9.6 Ionic Equilibrium in Solutions

Consider a solution of ZnSO4, saturated with H2S. The dissolved H2S ionises to give S2-
ions and H3O+ ions, where [S2-] is linked with the [H3O+] through equilibrium constant
values.

 If [H3O+] is increased (for example by adding HCl) then [S2-] is decreased ZnS
is not precipitated.

 If [H3O+] is decreased (for example by adding NH3 and NH4Cl), then [S2-] is
increased.
ZnS is precipitated.

If we have a similar solution of CuSO4, saturated with H2S, then CuS will be
precipitated, even if we increase [H3O+] by adding HCl. This is because CuS is much
less soluble than ZnS.

The solubility of CdS is somewhere between that of ZnS and CuS. Hence, in the
presence of HCl and H2S, we get a precipitation of CdS. But if concentrated HCl is used
then the [S2-] becomes so low that CdS does not get precipitated.

The above examples show, how acid-base and other ionic equilibria are useful for
understanding analytical chemistry.

62
The understanding of ionic equilibria is, however, important not only in chemistry, but
also important for professionals engaged in diverse areas of science, technology or
medicine. Engineers dealing with corrosion of materials, doctors studying abnormalities
in body fluids such as blood and urine, geologists trying to understand, for example the
formation of stalagmites and stalactites, biologists trying to regulate metabolic
processes in plants and animals, are only some examples from an endless list.
When we consider even simple aqueous solutions, we find that there are a number of
different equilibrium processes operating simultaneously and many of the ions present,
simultaneously participate in more than one such equilibrium process.

In chemistry we deal with a large number of reaction in aqueous solution involving

chemicals which are ionic in nature. We will now discuss how to apply the concepts of
equilibrium to solutions containing ions.

Solutions
A solution is defined as a homogeneous mixture of two or more substances in which the
intermingling particles are of atomic size or molecular dimensions. The substance
which is to be dissolved is called solute and in which the solute is dispersed is called
solvent. We know that aqueous solutions of some substance conduct electricity and
some don't. On this basis, Michael Faraday classified substances into electrolytes and
non-electrolytes.

9.6.1 Strong and Weak Electrolytes

Electrolytes

Substances whose solution contain ions and conduct electric current by migration of
ions. Faraday further classified them into strong and weak electrolytes.

a) Strong Electrolytes: An electrolyte that is completely dissociated into its ions

when dissolved in water like NaCl.

b) Weak Electrolytes: An electrolyte that is dissociated only to a small extent is

called a weak electrolyte.

63
Ionisation of electrolytes

Ions in solution arise in two ways:

a) The solute is truly ionic compound or salt, so that the ions which already exist in
the solid, separate more freely in solution.

Examples - NaCl, KBr, NH4Cl, NaOH, KCl.

b) The solute is a polar covalent compound that reacts with the solvent to form ions.
In case of a polar covalent compound, a solute may be a strong or a weak
electrolyte depending on the extent to which it is dissociated.
Examples - HCl, HNO3, H2SO4 are strong electrolytes and CH3COOH, NH3 are
weak electrolytes.

9.6.2 Acids, Bases and Salts

Acids and Bases

Acids and bases are quite common in our daily life. We come across these substances
quite frequently. For example, acetic acid is major constituent in vinegar, citric acid is
present in lemons, amla, oranges etc. Tartaric acid is found in tamarind paste.

Some of the commonly used bases are washing soda and ammonia solution used for
cleaning window panes. NaHCO3 is used as a mild antiseptic for skin disease and to
neturalise acidity of stomach in the form of ENO. It is also used in fire extinguishers.
Likewise there is an endless list of uses of such substances. Now you have studied in
previous classes that acids are substances that taste sour, turn blue litmus red, react
with metal to give H2 gas and are able to neturalise bases. On the contrary, bases are
known to be of bitter in taste, turns red litmus blue and neutralise acids. However, it is
noticeable that many substances usually conduct electricity in their molten state. This is
due to high dielectric constant of water (80), which weakens the forces of attraction
between oppositely charged ions and makes them free to conduct electricity. The
dissociated ions are further stabilized by their hydrogen. For example, NaCl conducts

64
electricity in fused state due to complete dissociation of it into ions. It must be noted
that there is difference between dissociation and ionization because degree of ionization
depends upon polarity and strength of the bond and extent of its solvation. Dissociation
mainly gives information about separation of ions in water already existing as such. But
they are interchangeable.

Faraday was born near London in a middle class family. He was an apprentice to a kind
bookbinder at the age of 14. There, he got good opportunity of reading books, he
binded. Fortunately, he assisted Davy in laboratory and gained
much more from the experience of coming contact to many
world famous scientists. He succeeded Davy as Director of Royal
Institution laboratories in 1825 and became first Fullerian
Professor of chemistry.

His first important work was on analytical chemistry. He also

experimented in the field of electricity and magnetism for a long

time. At last, his work led to establishment of modern field Michael Faraday (AD
theory. He also discovered the two laws of electrolysis in 1834. 1791-1867)
Faraday was very kind and modest person. He worked alone
and didn't have any assistant. He is very famous for his Christmas lecture on 'Chemical
History of a Candle' apart from his scientific experiments. He popularised science in
many ways including his Friday evening discourses which he founded at Royal
Institution. His 450 highly valued research paper have been published.

Arrhenius was born in Sweden. In 1884, his thesis based on conductivities of electrolytic
solutions presented in university of Uppsala was a distinguished one. He gained
experience and knowledge by traveling to different research centre in Europe. He was
appointed as professor of physics at University of Stockhome in 1895. After serving it
from 1897-1902, he continued his work on electrolytes. His one of the major

65
achievements is temperature dependence of rate of reaction, known as Arrhenius
equation.

He worked in various fields and made an important contribution

to immunochemistry, cosmology, origin of life and causes of ice
age. He was the first to discuss 'green house effect' He was
awarded noble prize in chemistry in 1903 for his theory of
electrolytic dissociation and its contribution in the development of
chemistry.

Svante August In highly developed societies, acids, bases and salts are
Arrhenius (AD indispensable compounds.
1859 - 1927)

The Arrhenius Theory

In 1680, Robert Boyle made the following observations:

 Acids dissolve many substances

 Acids change the colours of some natural dyes (indicators)

 Acids lose their characteristic properties when mixed with alkalis (bases)

By 1814 Gay Lussac concluded

 Acids neutralise bases

 Acids and bases can be defined only in terms of their reactions with one another.

In 1884, Svante Arrhenius presented his theory of electrolytic dissociation which led to
the Arrhenius theory of acid-base reactions.

 An acid is a substance that contains hydrogen and produces in aqueous

solution. So, according to Arrehenius theory, ionization of an acid in aqueous
solution can be represented by the following equation.

66
 HX(aq) H+(aq) + X-(aq)

Or HX + H2O(ℓ) H3O+(aq) + X-(aq)

A base is a substance that contains OH group and produces hydroxide

ions in aqueous solutions. As in case of acids, ionization of a base can be
represented as

MOH(aq) M+(aq) + OH-(aq)

 Neutralisation is defined as a combination of ions with ions to form H2O

molecules.
H+(aq) + OH-(aq) H2O(ℓ)

 The Arrhenius theory of acid-base behaviour satisfactorily explains the reactions

of protonic acids (those containing acidic hydrogen atoms) with metal
hydroxides (hydroxy bases).

 The major limitation of this theory is that many compounds don't contain or give
H+ or OH- ions in their aqueous solutions but still they can behave like an acid or
base. Thus, the limited scope of this theory led to other general theories of acid-
base behaviour.

Protonic

 The most common isotope of has no neutrons. Thus is a base proton. We

can use the terms hydrogen ion, proton and H+ interchangeably.

 Although Arrhenius described H+ ions as base ions (protons), actually these are
hydrated in aqueous solution and exist as where n is a small integer.

 This formation of H3O+ can be attributed to the small size (10-13 radius) of H+ ion
and its intense electric field which results into the biding of H+ ion with one of the
lone pairs of oxygen atom in H2O. This species has been detected in many

67
 compounds in the solid state like H3O+Cl-.

 The same above concept applies to ions and they also exist as hydrated
species like , , etc.

We represent hydrated hydrogen ion as hydronium ion or

H+ (H2O)n where n = 1

The hydrated hydrogen ion is the specie that gives an aqueous solution of acids their
characteristic acidic properties.

Hydronium ion,

Indispensable

Many acids, bases and salts occur in nature and serve a wide variety of purposes. From
our digestive juice (0.10 mol HCl per litre) to common salt, the list is endless. The table
below lists some important chemicals and their major uses.

Most common household liquids are acidic, including soft drinks, vinegar and fruit
juices. Most cleaning materials are basic.

68
S. No. Name Formula Uses

1. sulphuric acid H2SO4 Fertilisers and other chemicals

2. ammonia NH3 Fertilisers and other chemicals

lime (calcium oxide Manufacture of other

CaO,
3. and calcium chemicals, steel making, water
Ca(OH)2
hydroxide) treatment

4. phosphoric acid H3PO4 Fertilisers and detergents

other chemicals, pulp and

paper, soap and detergents
5. sodium hydroxide NaOH
aluminium manufacture,
textiles.

Fertilisers, explosives,
6. Nitric acid HNO3
plastics and lacquers

manufacture of glass,
Sodium carbonate,
7. Na2CO3 chemicals, detergents,
soda ash
paper and pulp

8. ammonium nitrate NH4NO3 Fertilisers and explosives.

Manufacture of chemicals,
9. hydrochloric acid HCl
rubber, metal cleaning

Fibres (polyesters), films,

10. terephthalic acid C8H6O4
bottles

11. ammonium sulphate (NH4)2SO4 Fertilisers

12. potash KOH, K2CO3 Fertilisers

13. sodium sulphate Na2SO4 paper, glass, detergents

Most common household liquids are acidic, including soft drinks, vinegar and fruit
juices. Most cleaning materials are basic.

69
The Bronsted-Lowry Theory

In 1923, J.N. Bronsted and T.M. Lowry independently presented logical extensions to
the Arrhenius theory. Since Bronsted's contribution was greater, the theory is called
Bronsted theory or Bronsted-Lowry theory.

 An acid is defined as a proton donor ( ) and a base is defined as a proton

acceptor.

 An acid-base reaction is the transfer of a proton from an acid to a base.

 Consider the complete ionisation of hydrogen chloride, a strong acid in water,

wherein water acts as a base or proton acceptor.

Step 1: Arrhenius description

Step 2:

Overall:

Bronsted-Lowry description

Now, consider ionisation of hydrogen fluoride, a weak acid. The reaction is

reversible.

70
 We describe Bronsted-Lowry acid-base reactions in terms of conjugate acid-base
pairs. These two species differ by a proton.

 The base that results when an acid donates its proton is called the conjugate
base of the acid.

 The acid that is formed when a base accepts a proton is called the conjugate acid
of the base.

71
 The stronger the acid, the weaker is its conjugate base.
The weaker the acid, the stronger is its conjugate base.

Consider ionisation of aqueous ammonia. Here NH3 acts as a weak Bronsted-Lowry

base and water as an acid.

Consider the reverse reaction. Here NH4+ is the conjugate acid of NH3 and
OH- is the conjugate base of water.

Water acts as an acid, H+donor, in its reaction with NH3, whereas it

acts as a base, (H+ acceptor) in its reaction with HF. Whether water acts
as an acid or as a base depends upon the other species present.

72
Autoionisation of Water

Pure water ionises very slightly to produce equal number of hydrated hydrogen ions
and hydroxide ions.

73
The members of each conjugate pair are designated by the same numerical subscript.

This autoionisation of water or self-ionisation is an acid-base reaction according to

Bronsted-Lowry theory.

Water is said to be amphiprotic, that is water molecules can both donate and accept
protons.

Amphoterism is a general term that describes the ability of a substance to react either as
an acid or as a base.

Amphiprotic behaviour describes the substance's ability to exhibit amphoterism by

accepting and by ionating a proton, H+.

Example:

, and NH3 are amphiprotic. Give the corresponding conjugate acid and
base for each of the species.

Solution:

Species Conjugate acid Conjugate base

H2O H3O+

H2CO3 CO32-

H2SO4 SO42-

NH3

The Lewis theory (1923)

G.N. Lewis presented the most comprehensive of the classic acid-base theories.

74
 An acid is any species that can accept an electron pari.
A base is any species that can make available, or donate an electron pair.

Reaction between boron trichloride and ammonia is a typical Lewis acid-base

reaction.

Co-ordinate covalent bond formation takes place when both electrons are furnished by
one atom or ion.

Lewis theory can be applied to autoionisation of water as:

75
Lewis acids generally

 contain only six electrons in the highest occupied energy level of the central atom
(open sextet structure) compounds of group IIIA examples: BCl3, BBr3, BF3 etc.

 are other ions and molecules which can expand the valence shell of the central
element.

For example, anhydrous tin (IV) chloride. The (group IVA) can utilise its vacant d orbitals.

acid base

Sn is sp3 hybridised Sn is sp3d3 hybridised

Tetrahedral shape Octahedral shape

76
 While Arrhenius acids and bases are also Bronsted-
Lowry acids and bases, REVERSE is NOT TRUE.

Bronsted-Lowry acids and bases are also Lewis

acids and bases, REVERSE it NOT TRUE.

9.7 Ionisation of Acids and Bases

9.7.1 Ionic Product for Water

In

since water is pure, its activity is 1. We do not include its concentration in the
equilibrium constant expression.

The equilibrium constant is called ionic product for water, Kw = [H3O +][ OH-]

In pure water at 25°C

[H3O+] = [OH–] = 1.0 10–7 mol L–1

Substituting these values in Kw expression

Kw= (1.0 10–7) (1.0 10–7)

Kw = 1.0 10–14 (at 25°C)

This expression is also valid for all dilute aqueous solutions at 25°C.

Value of Kw is different at different temperatures. It increases with the increase in

temperature.

77
9.7.2 pH Scale

Calculation of Ion Concentrations

To calculate concentrations of H3O+ and OH– ions in 0.050 M HNO3 solution,

 we write equation for ionisation of HNO3 (a strong acid)

 use Kw expression to find OH– ion concentration

Let us see step-wise:

Initial 0.050 M

Change due —0.050 M +0.050 M +0.050 M

to reaction

0M 0.050 M 0.050 M

[H3O+] = [NO3–] = 0.050 M

Kw= [H3O+] [OH–] = 1.0 10–14

Different temperatures

Kw at some temperatures

Temperature oC Kw
0
10
25
37
60

78
 Solution Conditions Temperature 25oC

Acidic [H3O+] > [OH–] [H3O+]>1.0 10–7 M; [OH–] < 1.0 10–7M

Neutral [H3O+] = [OH–] [H3O+] = 1.0 10–7 M; [OH–] = 1.0 10–7M

Basic [H3O+] < [OH–] [H3O+] < 1.0 10–7 M; [OH–] = 1.0 10–7M

The pH and pOH scale help to express the acidity and the basicity of dilute aqueous
solutions.

pH = –log[H3O+] or [H3O+] = 10–pH

pOH = - log[OH–] or [OH–] = 10–pOH.

where p = negative logarithm of the H3O+ concentration.

pKw= –log Kw

Relationship between pH and pOH in all dilute solutions at 25°C

[H3O+][OH–] = 1.0 10–14

Taking logarithm of both sides of the equation

log[H3O+] + log[OH-] = log (1.0 10-14)

Multiplying both sides by –1

(–log [H3O+]) + (–log[OH–]) = –log(1.0 10–14)

pH + pOH = 14.00

79
 Type of solution Condition Temperature at 25oC

Acidic [H3O+] > [OH–] [H3O+] > 1.0 10–7 M > [OH]
pH < pOH pH < 7.00 < pOH
Neutral [H3O+] = [OH–] [H3O] = 1.0 10–7 M = [OH–]
pH = pOH pH = 7.00 = pOH
Basic [H3O+] < [OH–] [H3O+] < 1.0 10–7 M < [OH–]

pH > pOH pH > 7.00 > pOH

pH of a solution can be determined by a pH meter or by indicator method.

9.7.3 Ionisation Constants for Weak Acids and Bases

Weak acids

Weak acids ionise only slightly in dilute aqueous solutions. Consider weak acid,
CH3COOH.

In water,

Real activity of pure water is essentially 1, and activity of each dissolved species is
numerically equal to its molar concentration. The ionisation constant of weak acid, Ka,
does not include a term for concentration of water.

General representation of monoprotic acid is as given below.

80
 Ka, Kb have to be calculated from experimentally determined data.

Degree of Dissociation

It is defined as the fraction of total concentration which exists in ionic state.

Let C be the molar concentration of a weak acid HA and α be its degree of dissociation,
then

But, For weak acids, α<<1 1–α 1

or α =

Method to find [H+]:

Since [H+] = C

pH for a Weak Acid:

81
  We can calculate Ka and pKa from the equilibrium concentration.

 We can calculate Ka from percent ionisation.

 We can calculate Ka from pH

Since ionisation constants are equilibrium constants for ionisation reactions, their
values indicate the extent to which weak electrolytes ionise.

At same concentrations, acids with larger ionisation constants ionise to a greater extent
(stronger acids).

HF > HNO2 > CH3COOH > HOCl > HCN

Consider order of base strengths of anions of these acids

F—<NO2–<CH3COO-< OCl–< CN–

The larger the value of Ka, smaller is the value of pKa stronger is the acid.

Strength of an acid is the same as reactivity of the acid. HF dissolves glass but
hydrofluoric acid is not a strong acid.

Weak bases

Consider ammonia in aqueous solution.

Degree of dissociation for weak bases:

As proceeding in a similar manner as in case of weak acids, we will get,

82
pH for a weak base:

9.7.4 Ionisation of Polybasic Acids and Bases

Polyprotic acids

Acids that furnish two or more hydronium ions per molecule. The ionisation occurs
step-wise one proton at a time. Acids like oxalic acid, sulphuric acid etc have more than
one ionisable proton per molecule of acid.

For example: Phosphoric acid

83
Ionisation constants of some common polyprotic acids (298 K)

Acid

Oxalic acid 5.9 10–2 6.4 10–5

Ascorbic acid 7.4 10–4 1.6 10–12

Sulphurous acid 1.7 10–2 6.4 10–8

Sulphuric acid Very large 1.2 10–2

Carbonic acid 4.3 10–7 5.6 10–11

Citric acid 7.4 10–4 1.7 10–5 4 10–7

Phosphoric acid 7.5 10–3 6.2 10–8 4.2 10–13

[H3O+] produced in step 1 is very large as compared with [H3O+] in successive steps.
Ionisation constants of some selected weak Acids and Bases.

Acid Ka

Hydrofluoric acid (HF) 3.5 10–4

Nitrous acid (HNO2) 4.5 10–4

Formic acid (HCOOH) 1.8 10–4

Niacin (C5H4NCOOH) 1.5 10–5

Acetic acid (CH3COOH) 1.74 10–5

Benzoic acid (C6H5COOH) 6.5 10–5

Hydrocyanic acid (HCN) 4.9 10–10

84
Phenol (C6H5OH) 1.3 10–10

Base Kb

Diethylamine (CH3)2NH 5.4 10–4

Triethylamine (C2H5)3N 6.45 10–5

Ammonia (NH3 or NH4OH) 1.77 10–5

Quinine (Plant product) 1.10 10–6

Pyridine (C5H5N) 1.77 10–9

Aniline (C6H5NH2) 4.27 10–10

Urea (NH2CONH2) 1.3 10–14

PH

In a pH value only the digit after the decimal point are significant. This is
because the digit before the decimal comes from the power of 10.

Substances pH range

Gastric contents (human) 1.6 – 3.0

Soft drinks 2.0 – 4.0

Lemon 2.2 – 2.4

Vinegar 2.4 – 3.4

Tomatoes 4.0 – 4.4

Beer 4.0 – 5.5

Cow’s milk 6.3 – 6.6

Saliva milk 6.5 – 7.5

Blood plasma (human) 7.3 – 7.5

Milk of magnesia 10.5

85
9.7.5 Hydrolysis of salts

It is commonly observed that different salts, on dissolution in water do not always form
neutral solutions. For example, an aqueous solution of copper sulphate is acidic
whereas the aqueous solution of sodium acetate is basic in character. However, salts of
strong acids and strong bases such as sodium chloride form neutral solutions. This is
due to the fact that a salt on dissolution in water undergoes dissociation to form ions.
These ions can ineteract with water molecules and thereby produce either an acidic or
an alkaline solution. This process is called hydrolysis. Thus hydrolysis is the reaction of
the anion/cation or both of the salt with water to produce an acidic or basic solution.

The solution formed by strong acids or bases are neutral or we can say that they have a
pH of 7. On the contrary, the solutions of salts formed by strong bases and weak acids
are basic in nature. While the solutions formed by weak bases and strong acids are
acidic in nature.

Hydrolysis is reverse of neutralization.

The equilibrium constant of such a reaction is called the hydrolysis constant. The
general hydrolysis equilibria and hydrolysis constants are given below.

Hydrolysis of anion (A–)

or

Hydrolysis of cation

86
The fraction of the total salt that gets hydrolysed at equilibrium is called degree of
hydrolysis. It is written as h.

Relation of Hydrolysis constant and and Hydrolysis of salts of weak acid and
strong base. In this case, the anion (A–) which is a stronger base than OH-, will undergo
hydrolysis and will give free OH– ions. Therefore, the resulting solution will be basic in
character having pH greater than 7. Examples of these types of salts are CH3COONa,
Na3PO4, etc.

Weak acid

The aqueous solution of a salt of weak acid and strong base is alkaline. For the general
reaction:

BA + H2O BOH + HA
Salt Strong base Weak acid

– –
or

– –
or

This is called anion hydrolysis.

Hydrolysis constant

The hydrolysis constant may be written as:

For weak acid HA,

87
So that,

Also Kw = [H+][OH–]

Multiplying equation (i) and (ii) and dividing by equation (iii), we get

... (1)

It is clear that the hydrolysis constant, Kh of the salt is inversely proportional to the
dissociation constant, Ka of the weak acid. Therefore, the weaker the acid, the greater is
the hydrolysis constant of the salt.

Example:
Calculate the hydrolysis constant of salt containing NO2— ions, Ka for HNO2 = 4.3 x 10—10.
Solution:

We Know that,

–
So, –

Degree of hydrolysis

Let the original concentration of the salt in the solution be c mole/litre and h is the
degree of hydrolysis at that concentration.

88
 – –

Initial conc. c 0 0

Conc. at equilibrium c (1 – h)

The hydrolysis constant,

If h is very small as compared to 1, we can assume 1 – h 1.

Kh = ch2

or

Substituting the value of Kh

... (2)

Example:
Calculate the degree of hydrolysis of N/10 solution of sodium acetate at 298 K.
Ka(CH3COOH) = 1.8 10—5

Solution:

( C = N/10 = 0.1N and in case of CH3COOH, Normality = Molarity)

h = 7.452x10—5

89
pH of the hydrolysed salt solution

[OH—] = ch

Substituting the value of h from equation (2)

Now, pH = –log [H+]

= –log [H+]

= –log

pH = – –

Now, – –

... (3)

Thus, knowing the molar concentration c of the solution, Ka and Kw, the pH of the
solution can be calculated.

Example:

Calculate the pH of an aqueous solution of 0.1 M acetic acid when it is titrated with a
solution of 0.1 M NaOH. Ka = 1.9 10-5.

90
Solution:

This solution forms a mixture containing weak acid and strong base, its pH can be
calculated as:

2. Hydrolysis of salt of strong acid and weak base. In this case, cation (B+) will
undergo hydrolysis and will give free H+ ions. Therefore, the resulting solution will be
acidic in character having pH less than 7. The common examples are NH4Cl, CuSO4,
AlCl3, etc. For example,

Weak base

Therefore, the aqueous solution of salt of strong acid and weak base will be acidic.

For the general reaction.

Salt

or

So, it is also called cationic hydrolysis.

Hydrolysis constant

The hydrolysis constant may be written as:

91
The following equilibrium also exists in solution

For weak base BOH,

and Kw = [H–] [OH–]

–
=1

Example:
Calculate hydrolysis constant for aniline mixture?

Kb for aniline = 4.6 10–10.

Solution:

For base,

Thus, the hydrolysis constant is inversely proportional to dissociation constant of the

base. Therefore, the weaker the base, the greater is the hydrolysis constant of the salt.

92
Degree of hydrolysis

Let the original concentration of the salt in the solution be c mol litre-1 and h is the
degree of hydrolysis at that concentration.

Initial conc. c 0 0
Conc. at equilibrium (1 – h) ch ch

Hydrolysis constant,

If h is very small in comparison to 1, we may assume, 1 - h 1, so that Kh = ch2

or

Substituting the value of Kh from equation (4)

pH of the hydrolysed salt solution

Now, [H+] = ch

Substituting the value of h from equation (5)

93
 – –

– – ... (6)

Example:

pKb for ammonia is 4.8. Calculate pH of 0.2 M aqueous solution of ammonia?

Solution:

3. Salt of weak acid and a weak base: In this case both the cation and anion undergo
hydrolysis to the same or different extents. The resulting solution may be neutral, acidic
or basic depending upon the relative strengths of acids and bases. Some common
examples of such salts are CH3COONH4, (NH4)2CO3, AlPO4, etc. The hydrolysis may be
written as:

Weak acid Weak base

94
For a general reaction:

Salt Weak base

–
or

Therefore, it involves anion hydrolysis as well as cation hydrolysis.

The hydrolysis constant, Kh may be written as

The following equilibria also exist in the solution for weak acid

For weak base

and Kw = [H+][OH–]

Multiplying and dividing by [H+] [OH–] in the equation for Kh we get

95
Degree of hydrolysis

Let the original concentration of the salt in the solution be c mole litre-1 and h is the
degree of hydrolysis.

–
Initial conc.
c c 0 0
Conc. at equilibrium c (1–h) c (1–h) ch ch

Since h is very small, it may be neglected in comparison to 1, so that 1 – h 1

In this case, the degree of hydroysis is independent of the concentration of the solution.
Further, the weaker the acid and the base, the greater is the degree of hydrolysis of the
salt.

Example:
Calculate the percentage hydrolysis of semi-normal solution of ammonium acetate,
given Ka = 1.75 10–5, Kb = 1.8 10–5. What will be the change in degree of hydrolysis
when 2 litre of water is added to one litre of above solution?

Solution:
Ammonium acetate is a salt of weak acid and weak base, we know that

96
The salt in the given question is salt of a weak acid and weak base, so its degree of
hydrolysis remains unaltered.

pH of the hydrolysed salt solution

We know that for the dissociation of a weak acid, HA

( 1–h 1)

or [H+] = Ka.h

Now, pH = – log [H+]

97
– – –

Example:
Calculate the pH of an aqueous solution of 1M ammonium acetate assuming complete
dissociation.

(Ka = 1.8 10–5 pKb = 4.8)

Solution:

Ka for CH3COOH = 1.8 10–5

pKa (CH3COOH) = 5 – log 1.8

= 5 – 0.2553 = 4.7447

Now, pH = –

=7+ –

= 6.97285
It is clear from the above equation that pH of the solution will depend upon the pK
values of the acid and base. According to equation (9),

If pKa < pKb, pH of the solution will be less than pKw and consequently solution will
be acidic.

If pKa > pKb, then pH of the solution will be more than pKw and hence solution will
be alkaline.

If PKa = pKb, pH of the solution will be equal to pKw and hence solution will be

neutral.

98
4. Salt of strong acid and strong base: In this case, neither the cation nor the anion
undergoes hydrolysis. Therefore, the resulting solution is neutral. For example, aqueous
–
solution of KCl is neutral. When dissolved in water, its ions and have no
–
tendency to react with the and ions of water. This is because, the possible
products of such reaction are KOH and HCl, which are themselves completely
–
dissociated. As a result, there is no change in the concentration of and ions an
hence the solution continues to remain neutral.

–
KCl (aq) +

–
H2O +

– –
(aq) + Cl(aq) + H2O (aq) (aq) + (aq) (aq)

Hence, it can be calculated that the salts of strong acids and strong bases do not
undergo hydrolysis and the resulting solution is neutral.

Let us sum up the important relations of hydrolysis of different salts.

Kh h
pH
Salt of Examples Hydrolysis Degrees of
of solution
constant hydrolysis
Weak acid and CH3COONa 7 + pKa + log c
strong base

Strong acid NH4Cl 7 – pKb – log c

and weak base

Weak acid and CH3COONH4 7 + pKa – pKb

weak base

Strong acid NaCl 7

and strong Does not undergo hydrolysis
base

99
9.7.6 Acid Base Titrations

When an aqueous solution of an acid such as HCl is added to an aqueous solution of

NaOH neutralization reaction takes place to form a salt and water.

HCl(aq) + NaOH(aq) NaCl(aq) + H2O (ℓ)

It may be noted that although the reaction is called neutralization, the solution may not
be always neutral.

This depends on the relative concentrations of H+ and OH– ions in solutions. If H+ ions
are in excess, the solution will be acidic, if OH– ions are in excess the solution will be
basic. This is known from the following observations:

(i) When a strong acid reacts with a strong base, a neutral solution is formed because
both are completely ionized and the reaction proceeds to completion. For example,

HCl(aq) + NaOH(aq) NaCl(aq) + H2O (ℓ)

(ii) When a strong acid reacts with a weak base, the solution formed will be acidic
because the weak base is not completely ionized. For example,

HCl(aq) + NH4OH(aq) NH4Cl(aq) + H2O

(iii) When a weak acid reacts with a strong base, the solution formed will be basic
because of the presence of free OH– ions

CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O (ℓ)

(iv) When a weak acid reacts with a weak base, the solution formed may give acidic,
basic or neutral solutions. This depends upon the strengths of the acid and base.
For exampleL

CH3COOH(aq) + NH4OH(aq) CH3COONH4(aq) + H2O (ℓ)

100
An acid-base titration is used in quantitative chemical analysis to determine the
concentration of an acid or a base. An aqueous solution of the acid is normally taken in
a graduated burette and a known volume of the base solution is taken in the titration
flask with the help of a pipette. A few drops of a substance called indicator is added to
give it a characteristic colour. The acid solution is now added dropwise with occasional
shaking till the solution undergoes a change in colour. This is known as end point or
equivalence point. So an indicator may be defined as "the substance which possesses a
certain colour in one medium and a different colour in the other medium".

Acid-Base Indicators

Acid-base indicators are substances which change colour according to the hydrogen ion
concentration of the solution to which they are added.

The object of an acid-base titration is to determine the amount of acid (or a base) which
is exactly equivalent chemically to the amount of some standard base (or an acid). The
point at which this equivalence is reached is called the end point. If both the acid and
the base are strong electrolytes, the resultant solution will be neutral at the end point
and have a pH of 7. However, if either the acid or the base is a weak electrolyte, the
solution at the equivalence point will be either slightly alkaline (pH>7) or slightly acidic
(pH>7). For any acid-base titration, the correct end point will be characterized by a
definite value of the H+ ion concentration (i.e. pH). The value will depend upon the
nature of the acid and the base and the concentration of the solution.

A large number of acid-base indicators are available which possess different colours
according to the H+ ion concentration of the solution. The chief characteristic of these
indicators is that the change from predominantly 'acid' colour to predominantly 'base'
colour is not sudden and abrupt, but takes place within a small interval of pH
(generally about 2 pH units). This is called colour-change interval of the indicator. The
position of the colur-change interval in the pH scale varies widely with different
indicators. Therefore, for most acid-base titrations we choose, an indicator which shows

101
a distinct colour change at a pH close to that of equivalence point. Some common
indicators along with their pH ranges are given in Table.

Colour

Indicator pH range Acid solution Base

solution

Cresol red 1.2 - 1.8 Red Yellow

Thymol blue 1.2 - 2.8 Red Yellow

Methyl yellow 2.9 - 4.0 Red Yellow

Methyl orange 3.1 - 4.4 Pink Yellow

Methyl red 4.2 - 6.3 Red Yellow

Litmus 5.0 - 8.0 Red Blue

Bromothymol blue 6.0 - 7.6 Yellow Blue

Phenol red 6.4 - 8.2 Yellow Red

Thymol blue (base) 8.1 - 9.6 Yellow Blue

Phenolphthalein 8.3 - 10.0 Colourless Pink

Alizarin yellow R 10.1 - 12.0 Blue Yellow

Acid-Base Indicator Behavior

The first successful theory was developed by Ostwald, which offered a simple
explanation for the colour change with change in pH. According to Ostwald, all acid-
base indicators are weak organic acids or bases which possess different colours in
unionized and ionized states. If indicator acid is represented as HIn and has its ionized
form In; then equilibrium in aqueous solution may be represented as:

102
 –

Unionised colour Ionised colour ... (i)

For a basic indicator,

Unionised colour Ionised colour ... (ii)

The unionized molecule has one colour (say colour A) while the ionized ion has another
colour (say colour B)

The equilibrium constant for a weak acid indicator may be written as:

–
... (iii)

where Kin is known as indicator constant.

…(iv)

the colour of the indicator changes from colour A to colour B at a particular point. This
is known as end point of the indicator at this point.

[H In] = [In]

Kind = [H+] = [H3O+]

–log Kind = – log [H+]

pKind = pH

Mixed Indicators
As already discussed, with ordinary acid-base indicators, the colour change is not sharp
and abrupt, but extends over 2 units of pH. However, sometimes, it is desirable to have
a sharp colour change over a narrow and selected range of pH. This can be achieved by

103
the use of mixture of indicators whose pKind values are close together and the
overlapping colours are complementary at an intermediate pH value.

For example, a mixture of 3 parts of phenolphthalein and 1 part of naphtholphthalein

shows a change in colour from pale rose to violet at pH = 8.9. The mixed indicator is
useful for the titration of phosphoric acid to diprotic stage. Similarly, a mixture of 3
parts of thymol blue and 1 part of cresol red shows a change in colour from yellow to
violet at pH = 8.3. This mixed indicator is useful for the titration of CO 32- to HCO3-
stage.

Some common mixed indicators are given below.

Some Common Mixed Indicators

Indicator mixture pH Colour change

Bromocresol green-methyl orange 4.3 Orange - Blue green

Bromocresol green-chlorophenol red 6.1 Pale green - Blue violet

Bromothymol blue-neutral red 7.2 Rose pink – Green

Bromothymol blue-phenol red 7.5 Yellow – Violet

Thymol blue-cresol red 8.3 Yellow – Violet

Thymol blue-phenolphthalein 9.0 Yellow – Violet

Thymolphthalein-phenolphthalein 9.9 Colourless – Violet

Universal Indicators

A universal indicator is a mixture of several indicators with a wide range of pH. These
are obtained by suitably mixing certain indicators, so that changes in colour may occur
over a considerable portion of the pH range; these mixtures behave like a single
indicator. However, these are not suitable for very accurate quantitative titrations.

104
These can be used for approximate pH of a solution. For example, a mixture of suitable
amounts of alcoholic solutions of phenolphthalein, methyl red, methyl yellow,
bromothymol blue and thymol blue in sodium hydroxide solution is yellow in colour.
This shows the following colour changes at different pH values:

pH 2 4 6 8 10
colour change Red Orange Yellow Green Blue

Several universal indicators with colour changes over different pH ranges are
commercially available.

During titrations, the pH of the reaction mixture changes constantly during the course
of the reaction. With the help of the titration curves we can choose the proper indicator
for a particular titration.

The four different types of titrations have already been discussed earlier. The titration
curves for each one of them can be shown as below.

I) Strong acid and strong base

NaOH(aq) + HCl(aq) NaCl(aq) + H2O (ℓ)

As the alkali is added the pH changes slowly in the beginning. But at equivalence
point pH changes rapidly from 3.5-10. Thus any indicator having the above pH
range can be used. So either phenolphthalein or methyl orange can be used as
indicator.

105
II) Titration of strong acid against weak base

HCl(aq) + NH4OH(aq) NH4Cl(aq) + H2O (ℓ)

In this case the pH changes from 3.5 to 7 at equivalence point. Methyl orange and
bromothymol blue are suitable indicators of this type of reaction. The range of
phenolphthalein is outside the vertical portion of the curve.

106
III) Titration of weak acid against strong base

CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(ℓ)

In this case pH changes from 7 to 11. So phenolphthalein is the suitable indicator.

IV) Titration of weak acid against weak base

CH3COOH(aq) + NH4OH(aq) CH3COONH4(aq) + H2O(ℓ)

In this there is no sharp increase in pH at equivalence point. So no indicator is

suitable. In this phenol-red is used. Such titrations are not commonly carried out in
the laboratories.

107
 STUDENT ACTIVITY – 4

Reversible Reactions: Acid-Base Indicators

Acid-base indicators are a quick and easy way to demonstrate reversible systems. Here
are a few examples using different indicators:

 Add a few drops of phenolphthalein to a test tube half-filled with distilled water.
To this colourless solution add a few drops of 0.1 M NaOH. The solution will
turn light pink. Adding additional base will cause the colour to deepen.

 Next add several drops of 0.1 M HCl. Swirl the test tube to mix. The solution will
turn colourless.

108
 Phenolphthalein Colour pH range

colourless 0-8

pink 8 - 12

colourless 12 and above

 Add about 1 mL of thymol blue to 100 mL of distilled water in an Erlenmeyer

flask, noting the colour. Divide this into two test tubes, using one as a control.
Thymol blue in distilled water is blue.

 Add a single drop of 0.1 M HCl to the test tube that is not the control. Swirl the
tube to ensure complete mixing. Continue adding HCl until a definite colour
change is observed and have students record the new colour.

 Continue adding more 0.1 M HCl until a second colour change occurs. Record.

 Reverse the colour change by the addition of 0.1 M NaOH. As with the HCl,
continue adding NaOH until two colour changes have been noted.

Thymol Blue Colour pH range

blue 9 and higher

green 8.5

yellow 2-8

red 0-2

109
 9.8 BUFFER SOLUTIONS

Generally pH of a solution changes when an acid or a base is added to it. But if a

solution contains a weak acid and its conjugate base or a weak base and its conjugate
acid, such a solution can resist change in pH and is called a buffer solution.

Hence a buffer solution can be defined as a solution which can resist a change in pH on
addition of a small amount of acid or base. The ability of a buffer solution to resist
change in pH is known as buffer action.

If the pH of the buffer solution is less than 7, it is called an acidic buffer and if the pH of
the buffer solution is greater than 7 it is called a basic buffer.

Acidic buffer Basic buffer

1) Acetic acid and sodium acetate 1) Ammonium hydroxide and

ammonium chloride

2) Formic acid and sodium format 2) Ammonium hydroxide and

ammonium nitrate

3) Phosphonic acid

Buffer action of acidic buffer

In an acidic buffer solution containing equimolar amounts of CH3COOH and

CH3COONa, acetic acid is not completely ionised as it is a weak electrolyte while
sodium acetate is completely ionised;

Now if we add HCl to the buffer solution it will ionise to give H3O+. This combines with
CH3COO– to form weakly ionized acetic acid.

110
Since H3O+ ions are neutralised by CH3COO– ions, there will be no change in pH. On
the other hand if we add a few drops of NaOH to the buffer solution, it provides OH–
ions. This reacts with H3O+ ions to form unionised water molecules. This would result
in the greater ionization of acetic acid in order to keep the H3O+ ions constant.

H3O+(aq) + OH–(aq) 2H2O(ℓ)

Therefore the pH of the solution remains unchanged.

Buffer action of basic buffer

In case of a buffer solution containing NH4OH and NH4Cl, NH4OH is not completely
ionised while NH4Cl is fully ionised.

When a few drops of HCl is added to the buffer solution, it will ionise to give H3O+ ion
which will combine with OH- ions to form H2O.

Therefore, the addition of HCl will not change the pH. On the other hand, when a few
drops of NaOH solution are added to the buffer solution, it would give OH– ions. These
OH– ions combine with ions present in the solution to form NH4OH, which is only
slightly ionised.

Hence, the addition of a base also will not change the pH.

111
9.8.1 Henderson – Hasseelbach Equation

pH of the Buffer solution (Henderson's equation)

Let us consider an acidic buffer consisting of weak acid HA and its salt NaA

Similarly for basic buffers.

A buffer solution has maximum buffer capacity when the ratio

Example:

Suggest suitable indicators for following titrations:

a) H2SO4 with NaOH

b) HCl with NH3

c) HCN with NaOH

112
Solution:

a) Given titration is of strong acid with strong base. So, litmus test or methyl orange
can be used as indicators.

b) This titration is of strong acid with weak base. So methyl red can be used.

c) This titration is of weak and strong base, so phenopthalein can be used.

Example:
A base X has a Kb of 5.1 x 10–8. In what amounts should 0.02 m HCl and 0.02 m base be
mixed to make 200 ml of a buffer of pH 7?

Solution:

For basic buffer,

If ‘a’ ml of HCl and ‘b’ ml of base are mixed.

a + b = 200

But a ml of HCl will neutralise a mL of base

[Base] = b – a

113
[Salt] = a

So volume of base = 200 – 50.05

= 149.95 mL

pH of a Buffer (when an acid or a base is added)

Although we say that pH of a buffer solution doesn't change on addition of an acid or

base. In actual, pH of a buffer solution do change by a small value when an acid or a
base is added to it.

1. Effect of addition of an Acid

Let us consider an acidic buffer HA/A–

where [Salt] = [A–]

[Acid] = [HA]

when XM HCl is added to it, H+ ions from HCl reacts with A- to give
undissociated acid as follows:

[Salt–x] [Acid+x]

pH of buffer decreases

114
2. Effect of addition of a Base:

Let us suppose XM NaOH is added to the buffer solution. So OH– ions from
NaOH will react with HA to produce salt and H2O.

pH of a buffer decreases.

Buffer capacity

It is defined as the number of moles of acid or base required by one litre of a buffer
solution for changing its pH by 1 unit.

Higher the amount of acid or base used to produce a definite change of pH in a buffer
solution, higher will be its buffer capacity.

Buffer capacity of a solution is maximum when both the components of buffer

solution are present in equivalent amount.

A given acid may be used for preparing buffer solutions having pH values in the
range of pKa 1.

The best buffer will have pH = pKa. For example, best buffer of acetic acid with
sodium acetate will be when CH3COOH and CH3COONa will be present in
equivalent amounts. Thus in such case.

pH = pKa = 4.8 pH limits = pka 1 = 3.8 to 5.8

115
Example:

When 0.005 mole of a strong acid is added to 250 mL of a buffer solution, its pH
decreases by 0.04 units. Calculate the buffer capacity of the solution.

Solution:

0.005 mole of acid is added to 250 mL or 0.020 mole of acid is added per litre of solution.

Applications of Buffers

1) In biological systems: The pH of the blood ranges between 7.36 – 7.42. It is

controlled by the buffer action of and H2CO3 present in the body.

2) In agriculture: The yield of the crop depends upon the pH of the soil. A mixture
of salts and organic acids present in the soil control the pH of the soil.

3) In food preservation: The control of the pH of the medium is very important in

the preservation of food.

STUDENT ACTIVITY – 5
A laboratory exercise is presented in which students make their own buffer.

Background information and instructions on how to create the lab are included, with
pre-requisites and post-instruction ideas offered.

Alkalosis or Acidosis

If this buffer system was absent from our blood, the eating acidic or basic foods would
cause the pH would swing too high (alkalosis) or too low (acidosis), and the result
could be deadly.

116
This lab will demonstrate the buffering solution found in your blood.

Our blood cannot tolerate a drastic shift in pH. It's a good thing, then, that human blood
contains a bufffer of carbonic acid, H2CO3, and sodium bicarbonate, NaHCO3. This
buffer regulates drastic shifts in the pH of our blood.

Pre-Lab Questions

1. What is a buffer?

2. What two parts are necessary in a buffer?

3. What does each part do?

4. Read through the procedure. Which setup is the control?

5. What is the variable in the experiment?

6. What question are we trying to understand by performing this experiment?

Procedure

Beaker #1: Unbuffered Solution

1. Place 50 ml of deionized water in a beaker and add 6 drops of universal pH

indicator. Note the color and record.

2. Add 3 drops of 1.0 M HCl. Note the new color and record the pH.
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3. Save this beaker & solution for comparison to situation #2.

Beaker #2: Buffered System

1. Make a buffer solution in a new beaker. Do this by putting 50 ml of 0.1 M

NaHCO3 solution in the beaker and blowing exhaled breath into the solution for
at least 2 minutes.

117
 2. Add 6 drops of universal pH indicator. Note the color and record the pH.

3. Add 3 drops of 1.0 M HCl as you did above and note the color and record the
pH.

4. Continue to add acid drop by drop, counting the drops (swirl to mix) until the
color matches the unbuffered solution from step 2 in situation #1. How many
drops did you use? Record.

Data Table

Beaker 1

1. Initial color and pH of beaker 1 _______________

2. Final color and pH of beaker 1 _______________

Beaker 2

2. Initial color and pH of beaker 2 _______________

3. pH and color of beaker 2 after HCl addition _______________

4. Number of drops of HCl added to beaker 2 _______________

Post-Lab Questions

1. Did the buffer system work? Give evidence.

2. Exhaled breath contains CO2. This carbon dioxide reacted with the water in the
beaker to form carbonic acid, H2CO3. Write the chemical reaction.

3. Write a reaction for how this buffer acts when an acid (contributes hydrogen
ions) is added.

4. Write a reaction for how this buffer would react if a base (hydroxide ions) were
added.

118
 1. In this lab, students are directed to make a buffer system that simulates one
found in human blood. The buffer should work, allowing students to add quite a
large amount of hydrochloric acid before they see a color (pH) change.

2. CO2 + H2O H2CO3

3. (adding an acid to the buffer creates more of the acidic

component already present in the buffer.)

4. (adding a base to the buffer produces more of the

bicarbonate ion, the basic component of the buffer.)

This activity naturally leads to a discussion of buffer capacity. How much acid can a
buffer neutralize? How much base? It also offers an opportunity to write equations
showing how the buffer reacts with the acidic and basic components of the added
solutions.

9.9 Solubility Equilibria of Sparingly Soluble Salt

9.9.1 Solubility Product and Common I on Affect

These concepts play an important role in the separation of basic radicals in the
qualitative analysis of different groups.

Common ion effect is the suppression of the degree of dissociation of a weak acid or
a weak base by the addition of a strong electrolyte containing a common ion.

This effect is also a consequence of a Le Chatelier's principle because by increasing the

concentration of one of the ions present in the solution, it will combine with the ion
having opposite charge and thus the resulting salt will get precipitated until K sp
becomes equal to Qsp. Similarly, by decreasing the concentration of one of the ions,
more salt can be dissolved in it until Ksp= Qsp.

119
The ionisation of a weak base NH4OH is suppressed by adding a small amount of
NH4Cl as shown below.

Ionisation of weak base NH4OH

–
Ionisation constant for a base,

On addition of solid NH4Cl the concentration of NH4+ ion increases. According to

Le-Chateliers principle the equilibrium will shift to the left and the weak base NH4OH
becomes more weak in the presence of its salt.

NH4Cl NH4+ + Cl– common ion Similarly, the ionisation of H2S can be suppressed by
the addition of a strong acid HCl.

Common ion
Example:

The solubility product, Ksp of PbBr2 is 8 10-5. If the salt is 70% dissociated in saturated
solution, find the solubility of salt?

Solution:

Solubility equilibrium of PbBr2 can be represented by:

x x 2x

Now, Ksp = [Pb2+] [Br–]2

8 10–5 = 4x3

x = 2.714 10–2 mol L–1

120
 –
So solubility when PbBr2 is 70% dissociated

= 1.8998 10–2 mol L–1

Solubility in gm/L = 1.8998 367 g/L

= 6.972 g/L

Qualitative analysis is based on the principle of solubility product and the

common ion effect and a brief description of the scheme of qualitative analysis is
given below.

Group I radicals: They are precipitated as chlorides due to the low value of solubility
products (Ag+, Hg2+ and Pb2+ ions)

Ksp(PbCl2) = 1.6 10–5

Ksp(AgCl) = 1.7 10–10

Group II radicals: They are separated as insoluble sulphides in acidic medium

(Hg2+, Pb2+ Cu2+, As3+, Sb3+, Sn2+). The solubility product of sulphides of these cations is
less than those of group IV sulphides. Due to the common ion effect, the concentration
of S2- decreases and the decreased concentration of S2- ions is sufficient to exceed the
solubility product of group II radicals but not of group IV cations
(Zn2+, Mn2+, Ni2+, Co2+).

Hence, group IV radicals are not precipitated along with the group II radicals.

Group III radicals: They are precipitated as their hydroxides by addition of an

ammoniacal solution containing ammonium chloride. The concentration of OH– of an
ammoniacal solution decreases with addition of NH4Cl because of the common ion
effect. Thus, only for least soluble hydroxides of Al3+, Cr3+ and Fe3+ the ionic product
exceeds the corresponding solubility products.

121
Group IV radicals: They are precipitated as insoluble sulphides in ammoniacal
solutions. In the presence of NH4OH, the concentration of S2– ion becomes larger when
H2S is passed through the solution due to removal of H+ ions with OH– ions to form
water and the equilibrium shifts in the forward direction as shown below.

Group V radicals: They are precipitated as insoluble carbonates in ammoniacal solution

containing ammonium chloride. The carbonates of Ba2+, Ca2+ and Sr2+ are precipitated
due to suppression of ionisation of (NH4)2CO3 due to common NH4+ ion. The solubility
product of the carbonates of group VI cations being much more than that of group V,
they are not precipitated.

H2S 2H+ + S2–

NH4OH NH4+ + OH–

H+ + OH– H2O(NH4)2S 2NH4+ + S2–

Group V radicals: They are precipitated as insoluble carbonates in ammoniacal solution

containing ammonium chloride. The carbonates of Ba2+, Ca2+ and Sr2+ are precipitated
due to suppression of ionisation of (NH4)2CO3 due to common NH4+ ion. The solubility
product of the carbonates of group VI cations being much more than that of group V,
they are not precipitated

122
 STUDENT WORKSHEETS

STUDENT WORKSHEET – 1

Q1. What are the characteristics common to the systems at equilibrium?

Q2. What is equilibrium? Which forces operating in the given equilibria becomes
constant at equilibrium:

a) Solid-liquid equilibrium

b) Liquid-gas equilibrium

c) Solid-solution equilibrium

d) Gas-solution equilibrium

Q3. Which of the following systems are at equilibrium:

(a) water boiling in an open vessel

(b) mercury and mercury vapour in a thermometer at constant temperature?

Q4. Which of the following favours maximum solubility of a gas in water?

Option 1: High pressure, high temperature

Option 2: High pressure, low temperature

Option 3: Low pressure, high temperature

Option 4: Low pressure, high temperature

Q5. In case of liquid gas equilibrium, the __________ of the gas above liquid
should be constant at equilibrium at a given temperature.

Option 1: pressure

Option 2: concentration

Option 3: solubility

Option 4: none of the above

123
Q6. For H2O(s) H2O(ℓ) equilibrium, the temperature at which two phases coexist
without any change of heat with surroundings is called

Option 1: melting point

Option 2: boiling point

Option 3: triple point

Option 4: none of the above

Q7. For dissolution of gases in liquids, ___________ of a gas in liquid is proportional

to the pressure of the gas over the liquid.

Option 1: concentration

Option 2: temperature

Option 3: density

Option 4: none of the above

124
 STUDENT WORKSHEET – 2

Q1. At equilibrium, the mass of each of the reactants and products remains constant.
Explain. Does this statement mean that the reaction has stopped?

Q2. List the characteristics of chemical equilibrium.

Q3. What type of chemical equilibria exist in the following chemical reactions?

a) H2O(ℓ) + H2O(ℓ) H3O+(aq) + OH-(aq)

b) 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

c) I2(aq) + I-(aq) (aq)

Q4. Under what conditions does a reversible reaction become irreversible?

Q5. H2(g) + I2(g) 2HI(g) is an example of

Option 1: homogeneous equilibrium

Option 2: heterogeneous equilibrium

Option 3: physical equilibrium

Option 4: none of the above

Q6. The reaction at equilibrium contains

Option 1: reactants only

Option 2: products only

Option 3: both reactants and products

Option 4: none of the above

Q7. At equilibrium, concentration of reactants and product is

Option 1: the same

Option 2: different

125
 Option 3: constant

Option 4: none of the above

Q8. In a chemical reaction, equilibrium is said to have been established when the

Option 1: temperature of the opposing reactants are equal

Option 2: concentration of reactants and products are constant

Option 3: opposing reactions cease

Option 4: velocities of opposing reactions become equal

Q9. BaCl2(aq) + Na2SO4(aq) BaSO4(s) + NaCl(aq) is an example of _____ reaction.

Option 1: reversible

Option 2: irreversible

Option 3: photochemical

Option 4: none of the above

126
 STUDENT WORKSHEET – 3

Q1. In which case is the reaction the fastest: k1 = 1015, k2 = 103 and k3 = 105?

Q2. a) What is meant by the Law of mass action?

b) Derive the expression for Kc for a general reaction: aA + bB cC + dD.

Q3. (a) What is the equilibrium constant expression for the following reaction:

Q4. What is the equilibrium constant (K') for the following equation,

if the equilibrium constant for the equation H2 + I2 2HI is K.

Q5. How are the equilibrium constants Kp and Kc related for the reaction

N2(g) + 3H2(g) 2NH3(g)

Q6. At some temperature and under a pressure of 4 atm, PCl5 is 10% dissociated.
Calculate the pressure at which PCl5 will be 20% dissociated temperature
remaining same.

Q7. What does the value of the equilibrium constant depend on? Give two factors.

Q8. Write the equilibrium constant expressions for the following reactions:

1.

2.

3.

Q9. What is the relationship between Kc and Kp?

Q10. The value of equilibrium constant Kc for the reaction 2NO(g) + O2(g) 2NO2(g)
is 0.25. What will be the value of the equilibrium constant K'c for
2NO2(g) 2NO(g) + O2(g)?

127
 STUDENT WORKSHEET – 4

Q1. If NaF is added to the equilibrium, Fe3+ + SCN- FeSCN2+ what would be the
intensity of the colour and in which direction will the equilibrium shift?

Q2. What are the conditions favourable for a better yield of NH3 in Haber's process?

Q3. 2SO2(g) + O2(g) 2SO3(g) + 193.2 kJ

What is the effect of (a) temperature (b) pressure and (c) concentration of SO2
and O2 (d) catalyst on the above reaciton.

Q4. For a reaction A(g) + B(g) 2C(g)+ H at chemical equilibrium, what is the
effect of

a) increase of temperature

b) increase of volume of reactants

c) increase of pressure

d) addition of catalyst

Q5. What conditions are favourable to check the dissociation of PCl5 in the reaction

Q6. Does pressure have any effect on the equilibrium concentration of NO(g) in the
following reaction?

N2(g) + O2(g) 2NO(g) – Q

Q7. State and explain Le Chatelier's principle.

Q8. What is the effect of adding an inert gas to a reaction mixture in equilibrium?

Q9. Pure NH3 is placed in a vessel at a temperature where its dissociation constant is
appreciable. At equilibrium.

128
 Option 1: Kp changes with temperature

Option 2: α doesn't change with pressure

Option 3: concentration ammonia changes with pressure

Option 4: concentration of hydrogen is more than that of nitrogen

Q 10. A catalyst, when added to a reaction mixture which is reversible,

Option 1: increases the rate of forward reaction

Option 2: has no effect

Option 3: helps in reaching equilibrium quickly

Option 4: increases the rate of backward reaction

Q 11. Dissociation of PCl5 PCl3 + Cl2 - Q is

Option 1: inversely proportional to the pressure applied

Option 2: not affected by pressure

Option 3: unpredictable

Option 4: directly proportional to the pressure applied

129
 STUDENT WORKSHEET – 5

Q1. Classify the following as acids and base and the concept (Lewis or Bronsted) for
classification.

(i) BF3

(ii) Na2CO3

(iii) HC

(iv) SiF4

Q2. Write down the conjugate acid and conjugate base of the following:

i) H2O
ii)
iii) NH3
iv)

Q3. Define the term 'acid' and 'base' according to each of the following concepts:

i) Arrhenius
ii) Bronsted–Lowry
iii) Lewis

Q4. What are the major limitations of Arrhenius and Bronsted–Lowry acid–base
concept?

Q5. a) Write the formula of conjugate acid and conjugate base of H2NCH2COOH

–
b) Why is ammonia treated as a base though it does not contain ions?

Q6. What is the Bronsted acid of ?

Q7. Give the conjugate pair of .

Q8. Theory of ionisation was given by

Option 1: Rutherford

130
 Option 2: Faraday

Option 3: Graham

Option 4: Arrehenius

Q9. Which of the following species is amphoteric?

Option 1: CO2

Option 2: C2H5 – OH

Option 3: C2H5–O–C2H5

Option 4: SO2

131
 STUDENT WORKSHEET – 6

Q1. What is the role of indicator in acid-base titrations?

Q2. Explain the following terms

a) Acid-base indicator

b) Range of an acid-base indicator

c) Titration

Q3. Why phenolphthalein cannot be used as an indicator for HCl and NH4OH
titration?

Q4. An acid having pH = 6 is diluted 1000 times. What will be the pH of the final
solution?

Q5. a) Calculate the pH of 0.001 N H2SO4 solution.

b) What is the effect of increase of temperature on ionic product of water?

Q6. Calculate the pH value of 10-8 M HCl solution.

Q7. What is the pH value of N/1000 HCl solution?

Q8. A weak ionised acid has a pH of 1. On dilution with water, its pH becomes 3.
How many times has the solution been diluted?

–
Q9. a) The of a water solution is 10-6 mol L-1. What is [H3O+]?

b) The [H3O+] of a water solution is 4.3 10-2 mol L-1. What is [OH-]?

Q10. When a weak acid is titrated against a weak base, the indicator used is

Option 1: Phenolphthaleia

Option 2: Methyl orange

132
 Correct Option 3: Phenol red

Option 4: None of the above

Q11. An acidic buffer is one which has a pH

Option 1: less than 7

Option 2: greater than 7

Option 3: equal to 7

Option 4: none of the above

133
 STUDENT WORKSHEET – 7

Q1. Define

(a) buffer solution

(b) buffer action

Q2. Calculate the pH of a solution obtained by mixing 50 mL of 0.1 M NaOH with

100 mL of 0.1 M CH3COOH. Ka for acetic acid is 1.8 10-6

Q3. Calculate the pH of the solution at end point when 50 mL of 0.1 M acetic acid is
titrated against 50 mL of 0.10 M NaOH solution. Ka for acetic acid is 1.8 10-6.

Q4. Describe the Hendersens equation for an acid buffer.

Q5. What are the applications of buffer solutions.

Q6. Describe the buffer action of an acidic buffer.

Q7. A basic buffer is one which has a pH

Option 1: equal to 7

Option 2: greater than 7

Option 3: less than 7

Option 4: None of the above

Q8. A buffer solution has maximum buffer capacity when

Option 1: the ratio =1

Option 2: the ratio =1

Option 3: both (a) and (b)

Option 4: None of the above

134
Q9. The buffer action of blood is due to

Option 1: H2CO3 and ion

Option 2: CO2 and H2CO3

Option 3: CO2 and

Option 4: None of the above

Q10. Which buffer solution will have pH greater than 7?

Option 1: NH4OH + NH4Cl

Option 2: HCOOH + HCOONa

Option 3: CH3COONH4

Option 4: CH3COOH + CH3COONa

135
 STUDENT WORKSHEET – 8

Q1. Define

a) Common ion effect

b) Solubility product

c) The solubility of CaF2 in water at 298 K is 1.7 10–3 grams per 100 mL of the
solution. Calculate the solubility product of CaF2

Q2. Why are the sulphides of group II precipitated by passing H2S gas through the
solution of these cations in presence of dil HCl?

Q3. Will AgCl be more soluble in aqueous solution or NaCl solution and why?

Q4. The solubility product of AgCl in water is 1.5 10–10. Calculate its solubility in
0.01 M NaCl aqueous solution.

Q5. PbCl2 has a solubility product of 1.7 10–8. Will a precipitate of PbCl2 form, when
0.01 mol of lead nitrate and 0.01 mol of potasium chloride are mixed and water
added upto one litre?

Q6. In the qualitative analysis of Group III, why is NH4Cl added along with NH4OH
to precipitate Fe3+, Cr3+ and Al3+. Why?

Q7. What is solubility and solubility product? Derive a relationship between them.
Give application of solubility product in qualitative analysis.

Q8. The solubility of AgI in NaI solution is less than that in pure water because.

Option 1: temperature of solution decreases

Option 2: of common ion effect

Option 3: AgI forms complex with NaI

Option 4: Ksp of AgI is less than that of NaI

136
Q9. Molar concentration of water is

Option 1: 550 104 mol L-1

Option 2: 55.5 mol L-1

Option 3: 55 103 mol L-1

Option 4: none of the above

Q10. Precipitation takes place when the ionic product _____ the solubility product.

Option 1: is less than

Option 2: equals

Option 3: exceeds

Option 4: none of the above

137
 Summary
A condition in which opposing forces are balanced and the macroscopic properties of
the system do not undergo any change is called Equilibrium state. Suppose in
conversion of liquid to vapour, it means number of molecules leaving the liquid to
vapour equals the number of molecules returning to the liquid from vapour.
Equilibrium can be established for both physical and chemical processes. Here rate of
forward reaction is equal to the rate of backward reaction.

Equilibrium constant Kc for a reaction aA+bB cC+dD can be expressed as:

. For a gaseous reaction equilibrium constant is expressed as Kp.

Le Chatelier's principle explains that any change in temperature, pressure, etc. will
lead to shift in the equilibrium in such direction which will reduce the effect of change.

Substances that conduct electricity in aqueous solutions are called electrolytes. Acid,
bases and salts are the electrolytes that produce anions and cations by ionization in their
aqueous solutions. The degree of ionization and common ion based on concentration
are discussed. pH of hydrogen ion concentration is introduced. Brief explanation of
Buffer solutions and their importance is also given. Sparingly soluble salts and the
equilibrium constant is introduced as solubility product constant.

138
 Crossword Puzzle

ACROSS

Hints

1 the suppression of the degree of dissociation of a weak acid or a weak base by

the addition of a strong electrolyte containing a common ion.

4 a solution that can resist change in pH

6 It is defined as a combination of protons with hydroxyl ions to form water

molecules.

8 Substances whose solution contain ions and conduct electric current by

migration of ions

9 Introduction of this substance to a system changes the reaction rate But cannot
shift the equilibrium in favour of either products or reactants.

11 The process where both the forward and the backward processes go on at the
same rate.

12 The two phases, solid – liquid, can co-exist only at a definite temperature
called

13 Acids that furnish two or more hydronium ions per molecule

14 The parameter on which the value of equilibrium constant depends

15 It is a general term that describes the ability of a substance to react either as an

acid or as a base

139
 DOWN

Hints

2 The magnitude this quantity gives an indication of the extent to which the
process proceeds before acquiring equilibrium.

3 no tendency of energy to flow into or out as heat with respect to

surroundings.

5 a mixture of several indicators with a wide range of pH

7 the ratio of concentrations or partial pressure to a standard concentration

10 the reaction of the anion/cation or both of the salt with water to produce an
acidic or basic solution.

140
141
 ANSWERS

C O M M O N I O N E F F E C T

Q H

B U F F E R S O L U T I O N U E

N I R

N E U T R A L I S A T I O N L M

V A I A

E L E C T R O L Y T E S C B L

R T R E

C A T A L Y S T I I Q

H A V U U

D Y N A M I C E Q U I L I B R I U M I

D I T C L

F R E E Z I N G P O I N T Y O I

O D N B

L P O L Y P R O T I C A C I D S R

Y C T I

S T E M P E R A T U R E A U

I T N M

S O T

A M P H O T E R I S M

142
 Common Misconceptions

 Often students think of equilibrium as static

 Students do not appreciate the fact that at melting point, boiling point etc there are
two phases in equilibrium
 Students often mix up the concepts of equilibrium constant and reaction quotient
 Although buffers resist the change in ph , but this is true only for small additions
of acid or base

143
 Additional Resource Links

www.chemguide.co.uk/physical/equilibria/introduction.html

www.ion.chem.usu.edu/~sbialkow/Classes/3600/.../Equilibrium/equil.html

www.adichemistry.com/.../equilibrium/introduction/chemical-equilibrium.html

www.sparknotes.com/economics/micro/.../equilibrium/summary.html

www.4college.co.uk/as/atm/Equilibrium.php

www.wiziq.com/tutorials/equilibrium-in-physical-processes

www.mikeblaber.org/oldwine/chm1046/notes/.../Equilib.htm

www.chemguide.co.uk/physical/equilibmenu.html

www.docbrown.info/page04/4_74revNH3.htm

www.wiziq.com/tutorial/9322-Chemical-equilibrium

www.chemed.chem.purdue.edu/genchem/.../bp/.../equilib.htm

www.chm.davidson.edu/java/lechatelier/lechatelier.html

www.rsc.org/chemsoc/timeline/pages/1884.html

www.academicearth.org/lectures/how-pushy-le-chateliers-principle

www.chm.davidson.edu/vce/equilibria/volume.html

www.chemguide.co.uk/physical/acidbaseeqia/theories.html

www.chemteam.info/AcidBase/Arrhenius-AcidBase.html

www.uwec.edu/lewisd/Chem321-0015/Acid-Base/Acid.htm

www.dwb4.unl.edu/Chem/CHEM869R/CHEM869RLinks/.../lavoisier.htm

144
www.elmhurst.edu/~chm/vchembook/184ph.html

www.parish-supply.com/phscale.htm

www.epa.gov/acidrain/measure/ph.html

www.osumex.com/_whatisph.php

www.chemguide.co.uk/physical/acidbaseeqia/buffers.html

www.delloyd.50megs.com/moreinfo/buffers2.html

www.wisegeek.com/what-is-a-buffer-solution.htm

www.chemcollective.org › Buffer Review

www.chemguide.co.uk/physical/ksp/introduction.html

www.science.uwaterloo.ca/~cchieh/cact/c123/ksp.html

https://chemistry.twu.edu/tutorial/KspSum.html;www.solubilityofthings.com/

145
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