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Solid State
Exercise - 2:
2
Solve all types of
1. CsBr crystallizes in a body
centered cubic lattice. The edge
length of unit cell is 436.6 pm.
Given that the atomic mass of
Cs = 133u and Br = 80u, the
exercise questions density of CsBr is:
based on the latest JEE (JEE 2019)
pattern.
(a) 42.5 g/cm3 (b) 0.425 g/cm3
(c) 4.25 g/cm3 (d) 8.5 g/cm3
Answer Key
3
CHAPTER-1: SOLID STATE
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TABLE OF CONTENTS
THERMODYNAMICS AND THERMOCHEMISTRY
Theory ................................................................................................................................................ 8
Solved Examples ............................................................................................................................... 26
Exercise - 1 : Basic Objective Questions........................................................................................... 38
Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 47

Exercise - 3 : Advanced Objective Questions ................................................................................. 56
Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 63
Answer Key ........................................................................................................................................ 166
CHEMICAL EQUILIBRIUM
Theory ................................................................................................................................................ 70
Solved Examples ............................................................................................................................... 80
Answer Key ........................................................................................................................................ 168

IONIC EQUILIBRIUM
Theory ................................................................................................................................................ 117

Solved Examples ............................................................................................................................... 129

Answer Key ........................................................................................................................................ 170

THERMODYNAMICS
AND
THERMOCHEMISTRY

Chapter 10
THERMODYNAMICS AND THERMOCHEMISTRY
1. INTRODUCTION 2.2.2 Closed System
It is the study of flow of energy. It encompasses the study of flow In a closed system, there is no exchange of matter, but exchange
of heat as well as mass. of energy is possible between system and the surroundings. The
presence of reactants in a closed vessel made of conducting
The law of thermodynamics deals energy changes of macroscopic
material. i.e., Copper or steel, is an example of a closed system.
systems involving a large number of molecules rather than
microscopic systems containing a few molecules.
Thermodynamics is not concerned about how and at what rate
these energy transformations are carried out, but is based on
initial and final states of a system undergoing the changes.
2. THERMODYNAMIC TERMS
2.1 System and The Surroundings

A system in the thermodynamics refers to that part of universe in
which observations are made and remaining universe constitutes
the surroundings. The surroundings include everything other
than the system. System and the surroundings together constitute
the universe. Closed system
The Universe = The System + The Surrounding
2.2.3 Isolated System
2.2 Types of System
In an isolated system, there is no exchange of energy or matter
2.2.1 Open System between the system and the surroundings. The presence of
reactants in a thermos flask or any other closed insulated vessel
In an open system, there is exchange of energy and matter between
is an example of an isolated system.
system and surroundings. The presence of reactants in an open
beaker is an example of an open system.
Here the boundary is an imaginary surface enclosing the beaker
and reactants.
Isolated system
Open system
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Thermodynamics and Thermochemistry

THERMODYNAMICS AND THERMOCHEMISTRY 10
2.3 State of a System
In thermodynamics, state of the system defined by state functions

and state variables.
2.3.1 State Functions
These physical quantities whose value depend only upon the

status of the the system and does not depend upon the path by
which this state has been attained are said to be state function. In
other words, if the physical quantity depends only upon the initial Extensive and intensive properties
state and final state of the system independent of the path by
2.5 Thermodynamic Processes
which this change had been brought upon is known as a state
function. Some common state functions are pressure (p), volume Let us consider a system having P1V1 and T1 state functions if T1
(V), temperature (T), internal energy (U), enthalpy (H), entropy is chaged to T2 then the resulting system is characterized by state
(S), etc. functions P1V1 and T2 and the process of changing state is called
thermodynamic process. A thermodynamic process can be defined
2.3.2 State Variables as a process having change in state of system. These are of
If any of P, V or T is changed, it act as state variable and the other following types:
which depends on first one are state functions. 2.5.1 Isothermal Process
2.3.3 Path Functions The thermodynamic process in which temperature remains
constant throughout is called isothermal process.
Functions, which are associated with the path they carried
through, are called path functions. Values of path functions varies 2.5.2 Adiabatic Process
if the followed path is different. The common path funtions are
The thermodynamic process in which heat exchange between
heat and work.
system and surrounding is not possible.
2.4 Extensive and Intensive Properties 2.5.3 Isobaric Process
In thermodynamics, a distinction is made between extensive The thermodynamic process occurrring at constant pressure is
properties and intensive properties. An extensive property is a called isobaric process.
property whose value depends on the quantity or size of matter
2.5.4 Isochoric Process
present in the system. For example, mass, volume, internal energy,
enthalpy, heat capacity, etc. are extensive properties. The thermodynamic process occurring at constant volume is called
isochoric process.
Those properties which do not depend on the quantity or size of
matter present are known as intensive properties. For example 2.5.5 Cyclic Process
temperature, density, pressure etc. are intensive properties. The therymodynamic process having same initial and final state
is called cyclic process.
Example
2.6 Thermodynamic Equilibrium
A container having the volume V, contains water at temperature
25ºC . If we put a partition exactly in the middle, each part will have A system is said to be under thermodynamic equilibrium when
a volume V/2, but the temperature will remain same, i.e, 25ºC. none of the state variables are changing and it satisfies the three
equilibriums.
2.6.1 Mechanical Equilibrium
There is no mechanical motion and the pressure and the volume
of the system are not changing.
2.6.2 Thermal Equilibrium
There is no flow of heat and the temperature and the system does
not change with time.
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2.6.3 Chemical Equilibrium
If any chemical reaction is taking place in the system then the rate
of forward reaction is equal to the rate of backward reaction which
means that the overall moles of the system is constant.
3. ZEROTH LAW OF THERMODYNAMICS
This statement just says that, if body 'A' is in thermal equilibrium

with body 'B' and body 'B' is in thermal equilibrium with body 'C'
then body 'A' will also be in thermal equilibrium with body 'C' and
all three will be in thermal equilibrium with each other. Adiabatic system
Let us call the initial state of the system as state A and its
temperature as TA. Let the internal energy of the system in state A
be called UA. We can change the state of the system in two different
ways.
First way: We do some mechanical work, say 1 kJ, by rotating a
set of small paddles and thereby churning water. Let the new
state be called B state and its temperature, as TB . It is found that
TB > TA and the change in temperature, T = TB –TA. Let the
internal energy of the system in state B be UB and the change in
Zeroth law of thermodynamics internal energy, U =UB – UA.
4. INTERNAL ENERGY Second way: We now do an equal amount (i.e., 1 kJ) electrical
A thermodynamic system containing some quantitiy of matter is work with the help of an immersion rod and note down the
itself associated with a certain quantity of energy. It is the sum temperature change. We find that the change in temperature is
of all different types of energies associated with atoms and same as in the earlier case, say, TB – TA.
molecules such as electronic energy (Ee), nuclear energy (En), In fact, the experiments in the above manner were done by J. P.
chemical bond energy (Ec), potential energy (Ep) and kinetic energy Joule between 1840–50 and he was able to show that a given
(Ek). This total energy of a system always implies internal energy amount of work done on the system, no matter how it was done
represented by the symbol ‘U’. Thus (irrespective of path) produced the same change of state, as
U = Ee + En + Ec + Ep + Ek measured by the change in the temperature of the system.
The change in internal energy can be brought about whenever So, the adiabatic work, wad required to bring about a change of
heat is absorbed or realeased by the system, work is done on or state is equal to the difference between the value of U in one state
by the system or matter enters or leaves the system. and that in another state,  U i.e.,
 U = U2 – U1 = wad
5. CONCEPT OF HEAT AND WORK
Therefore, internal energy, U, of the system is a state function.
5.1 Thermodynamic Work
By conventions of IUPAC in chemical thermodynamics. The
Let us first examine a change in internal energy by doing work. positive sign expresses that wad is positive when work is done on
We take a system containing some quantity of water in a thermo the system and the internal energy of system increases. Similarly,
flask or in an insulated beaker. if the work is done by the system, wad will be negative because
Let us bring the change in the internal energy of the system by internal energy of the system decreases.
doing some work on it.
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5.2 Heat Now the final internal enerygy U2 is given by
We can also change the internal energy of a system by transfer of U2 = U 1 + q + w
heat from the surroundings to the system or vice-versa without or U2 – U1 = q + w
expenditure of work. This exchange of energy, which is a result of
temperature difference is called heat, q. Let us consider bringing or  U = q + w
about the same change in temperature by transfer of heat through i.e., change in internal energy = Heat absorbed + Work done on
thermally conducting walls instead of adiabatic walls. the system
For a given change in state, q and w can vary depending on how
the change is carried out. However q + w =  U will depend only
on initial and final state. It will be independent of the way the
change is carried out. If there is no transfer of energy as heat of
energy as heat or as work (isolated system) i.e., if w = 0 and q = 0,
then  U = 0.
The equation,  U = q + w is a mathematical statement of the first

law of thermodynamics which states that, “Energy can neither
be created nor be destroyed although it may be changed from one
form to another”.
From this statement it follows that total energy of the universe,
i.e., system and surroundings taken together is always constant
Non-adiabatic system
during any physical or chemical process.
We take water at temperature, TA in a container having thermally
conducting walls, it in a huge heat reservoir at temperature, TB.The 7. CONCEPT OF REVERSIBILITY
heat absorbed by the system (water), q can be measured in terms
of temperature difference , TB – TA. In this case change in internal A process whose direction can be changed by an infinitesimal
energy, change to the system or surroundings and which can be reversed
by retracing the original path and the system is restored to the
 U= q, when no work is done at constant volume. By conventions initial state. The driving force of a reversible process is very-very
of IUPAC in chemical thermodynamics. The q is positive, when small and such a process is extremely slow. For a process to be
heat is transferred from the surroundings to the system and the reversible there must not be any dissipative forces and also the
internal energy of the system increases and q is negative when system should be in a Quasi Static State.
heat is transferred from system to the surroundings resulting in
decrease of the internal energy of the system. 7.1 Quasi Static State
A quasi static state means that the system seems to be static at all
6. FIRST LAW OF THERMODYNAMICS
intervals of time but actually is not. The motion is so slow that it
Let us consider the general case in which a change of state is is almost impossible to detect the motion and the system seems
brought about both by doing work nad transfer of heat. The to be in equilibrium with the surroundings at all instants of time.
change in internal energy for this case can be written as
7.2 Irrversible Process
U=q+w
Processes other than reversible processes are known as
Lets simplify it through a diagrammatic representation of system irreversible process as these processes do not meet the
undergoing changes. requirements of reversibilty. So it can be defined as “When a
process goes from initial to final state in a single step and can not
be carried out in the reverse order, it is said to be an irreversible
process”.
First law of thermodynamics
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Difference between Reversible Process and Irreversible Process
S.NO. Reversible Process Irreversible process
1. It takes place in infinite number of It takes place in single step
number of infinitesimally small steps and
it would take infinite time to occur
2. It is imaginary as it assumes the presence It is real and can be performed actually
of, frictionless and weightless piston
3. It is in the state of equilibrium at all the It is an equilibrium state only at the
stages of operation initial and final stages of the
operation
4. All changes are reversed when the After the occurring of the process
process is carried out in reversible changes do not return to the initial
direction state by themselves
5. It is extremely slow. It proceeds at measureable speed.
6. Work done by a reversible process is Work done in irreversible process is
greater than the corresponding smaller than the corresponding
irreversible process reversible process.
8. EXPANSION WORK
First of all, let us concentrate on the nature of work a system can
do. We will consider only pressure-volume work.
For understanding pressure-volume work, let us consider a
cylinder which contains one mole of an ideal gas fitted with a
frictionless piston. Total volume of the gas is Vi and pressure of
the gas inside is p. If external pressure is pex which is greater than
p, piston is moved inward till the pressure inside becomes equal
to pex. Let this change be achieved in a single step and the final
volume be Vf. During this compression, suppose piston moves a
distance, l and is cross-sectional area of the piston is A.
then, volume change    A  V   Vf  Vi 
force
We also know, pressure 
area Work done on an ideal gas in a cylinder when it is compressed
Therefore, force on the piston = pex . A by a constant external pressure
If w is the work done on the system by movement of the piston The negative sign of this expression is required to obtain
then conventional sign for w, which will be positive. It indicates that in
case of compression work is done on the system. Here (Vf – Vi)
w = force × distance  pex .A. will be negative and negative multiplied by negative will be
= pex . (–  V) = – pex  V = – pex (Vf – Vi) positive. Hence the sign obtained for the work will be positive.
If the pressure is not constant at every stage of compression, but
changes in number of finite steps, work done on the gas will be
summed over all the steps and will be equal to -  p  V
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Now, the pressure of the gas (pin which we can write as p now) can
be expressed in terms of its volume through gas equation. For n
mol of an ideal gas i.e., pV = nRT.
nRT
p
V
Therefore, at constant temperature (isothermal process),
Vf
dV V
w rev    nRT   nRT ln f
Vi
V Vi
P-V plot when pressure is not constant and changes in finite
steps Vf
If the pressure is not constant but changes during the process w rev  2.303nRT log
Vi
such that it is always infinitesimally greater than the pressure of
the gas, then, at each stage of compression, the volume decreases Work in Cyclic Process
by an infinitesimal amount, dV. In such a case we can calculate the
work done on the gas by the relation A cyclic process is one which comes back to its initial state. The
graph of a cyclic process is always a closed graph. For a cyclic
Vf
process, Unet = 0 and qnet = – wnet.
w    p ex dV
Vi Isothermal Free Expansion of an Ideal Gas
Here, pex at each stage is equal to (Pin + dp) in case of compression. For isothermal (T = constant) expansion of an ideal gas into
In an expansion process under similar conditions, the external vacuum ; w = 0 since pex = 0. Also, Joule determined experimentally
pressure is always less than the pressure of the system i.e., pex = that q = 0; therefore,  U = 0
(pin– dp). In general case we can write, pex = (pin + dp). Such
processes are called reversible processes. Equation,  U = q + w can be expressed for isothermal irreversible
and reversible changes as follows:
1. For isothermal irreversible change
q = – w = pex (Vf –Vi )
2. For isothermal reversible change
Vf
q   w  nRT ln
Vi
Vf
 2.303nRT log
Vi
3. For adiabatic change, q = 0,  U = wad

P-V plot when pressure is not constant and changes in infinite
steps 8.1 Work Done in Various Types of Thermodynamic Processes
Vf Vf 8.1.1 Isothermal Process

w    pex dV     pin  dp  dV
These processes are the ones in which the temperature is constant
Vi Vi
throughout the process.
Since dp × dV is very small we can write U = 0; H = 0
Vf
w    pin dV V  P 
w  2.303nRT log  2   2.303nRT log  1 
Vi
 V1   P2 
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8.1.2 Adiabatic Process 9.1.1 Molar Heat Capacity at Constant Pressure
These processes are the ones in which the heat exchanged with The molar heat capacity of a system at constant pressure (Cp) is
the surroundings is zero. Such processes are generally defined the amount of heat needed to raise the temperature of one mole
by the equations: gas by 1K. at constant pressure.
TV–1 = constant, TP1– = constant, PV = constant. qp
Cp 
q=0  w = U nT
 P V  P V  nRT 9.1.2 Molar Heat Capacity at Constant Volume

U  nC V T   2 2 1 1  
  1   1 The molar heat capacity of a system at constant volume (CV) is
the amount of heat needed to raise the temperature of one mole
H = nCPT gas by 1K. at constant volume.
8.1.3 Isochoric Process
qv
Cv 
These processes are the ones in which the volume remains nT
constant. Since the change in volume is zero therefore we can say
Heat Capacities of Different Types of Gases
that
Types of gas Cv Cp = Cp/Cv
w=0 Monoatomic 3R/2 5R/2 5/3 = 1.67
U = nCVT = qV Diatomic 5R/2 7R/2 7/5 = 1.4
8.1.4 Isobaric Process Non-linear Polyatomic 3R 4R 4/3 = 1.34
These are the processes in which the pressure remains constant 9.1.3 Relation between Cp and CV
(dp = 0) We know that : H = nCpT and U = nCVT
w = – PV = – nRT for 1 mole (n = 1) of an ideal gas
H = nCPT H = U + PV  U + RT
NOTE Putting H = CpT and U = CVT
All these processes are happening on a system containing an CpT = CVT + RT
ideal gas therefore we can apply PV = nRT at any stage that we Cp = CV + R
find suitable.
9.2 Polytropic Process
9. HEAT CAPACITY OF A SYSTEM
It is a generalized form of any thermodynamic process which has
The heat capacity (C) of the system is the amount of heat needed
a form PVn = constant where n is a real number. For an isothermal
to raise the temperature of the system by 1K.
process n = 1 and for an adiabatic process n = . The heat capacity
q of a polytropic process can be calculated using the first law of
C thermodynamics and comes out to be :
T
9.1 Molar Heat Capacity R
C  CV 
The molar heat capacity of a system (CM) is the amount of heat n 1
needed to raise the temperature of one mole gas by 1K.
10. GRAPH TRANSFORMATION
q
CM 
nT When a thermodynamic process is plotted in terms of two state
variable it can be transformed into a graph involving the other
state variable by doing the following
1. Identify the type of curve given, whether it is P-V, V-T or P-T
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graph. 11. ENTHALPY (H)
2. Then, Identify every step of the process According to the first law of thermodynamics
3. Then one by one convert every step into the required graph U  q p  pV at constant pressure, where qp is heat absorbed
bearing in mind critical points like, an expansion process will
by the system and pV represent expansion work done by the
remain an expansion process and so on.
system.
4. A cyclic process should remain cyclic whichever graph we Let us represent the initial state by subscript 1 and final state by
make. subscript 2. We can rewrite the equation as:
U2 – U1 = qp – p (V2 – V1)
On rearranging, we get
qp = (U2 + pV2) – (U1 + pV1)
Now we can define another thermodynamic function, the enthalpy
as: H = U + pV
so, equation becomes
P-V and P-T graphs of cyclic process
qp = H2 – H1 =  H
NOTE
From the given P–V graph. Hence, H  U  pV
Process 12 is isothermal expansion; 23 adiabatic expansion; It is important to note that when heat is absorbed by the system
34 isothermal compression & 41 adiabatic compression. at constant pressure, we are actually measuring changes in the
enthalpy.
Graphical representation of various thermodynamic processes
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Remember H = qp, heat absorbed by the system at constant
pressure.
H is negative for exothermic reactions and H is positive for
endothermic reactions.
Let us consider a reaction involving gases. If VA is the total volume
of the gaseous reactants, VB is the total volume of the gaseous
products, nA is the number of moles of gaseous reactants and nB
is the number of moles of gaseous products, all at constant
pressure and temperature, then using the ideal gas law, we write,
pVA  n A RT
and pVB  n B RT
Thus, pVB – pVA = nBRT – nART = (nB –nA)RT

or p (VB – VA) = (nB – nA) RT Bomb calorimeter
or p  V =  ngRT
T Here, a steel vessel (the bomb) is immersed in a water bath to
ensure that no heat is lost to the surroundings. A combustible
Here,  ng refers to the number of moles of gaseous products substance is burnt in pure dioxygen supplied in the steel bomb.
minus the number of moles of gaseous reactants. Heat evolved during the reaction is transferred to the water around
the bomb and its temperature is monitored. Since the bomb
This gives the relation, H = U  n g RT calorimeter is sealed, its volume does not change. Under these
conditions, no work is done as the reaction is carried out at
12. CALORIMETRY: MEASUREMENT OF U AND H constant volume in the bomb calorimeter. Temperature change of
the calorimeter produced by the completed reaction is then
We can measure energy changes associated with chemical or converted to q V, by using the known heat capacity of the
physical processes by an experimental technique called calorimetry. calorimeter.
In calorimetry, the process is carried out in a vessel called
calorimeter, which is immersed in a known volume of a liquid. 12.2 H Measurements
Knowing the heat capacity of the liquid in which calorimeter is Measurement of heat change at constant pressure (generally
immersed and the heat capacity of calorimeter, it is possible to under atmospheric pressure) can be done in a calorimeter shown
determine the heat evolved in the process by measuring in the figure below.
temperature changes. Measurements are made under two different
conditions:
i) at constant volume, qV
ii) at constant pressure, qp
12.1 U Measurements
For chemical reactions, heat absorbed at constant volume, is
measured in a bomb calorimeter.
Coffee cup calorimeter
We know that H = q p (at constant p) and, therefore, heat

absorbed or evolved, qp at constant pressure is also called the
heat of reaction or enthalpy of reaction, H .
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In an exothermic reaction, heat is evolved, and system loses heat With partition we can pick the molecules of gas with surety that it
to the surroundings. Therefore, qp will be negative and H will is from gas A or gas B. But, if we were to pick up molecules from
also be negative. Similarly in an endothermic reaction, heat is container when partition is removed, we are not sure whether the
absorbed, qp is positive and H will be positive. molecules picked are of gas A or gas B. We say that the system
has become less predictable or more chaotic.
13. NEED FOR SECOND LAW At this point, we introduce another thermodynamic function,
entropy denoted as S. The above mentioned disorder is the
13.1 Spontaneous Process
manifestation of entropy. S is independent of path. For a given
A spontaneous process is one which happens on its own. Example, substance, the crystalline solid state is the state of lowest entropy
heat always flows spontaneously from higher temperature to lower (most ordered), The gaseous state is state of highest entropy.
temperature.
Whenever heat is added to the system, it increases molecular
The first law talks about the conservation of energy in a process motions causing increased randomness in the system. Thus heat
but does not speak of the feasibility of a process. It does not tell (q) has randomising influence on the system. Therefore S is
whether a process will happen on its own i.e. whether the process related with q and T for a reversible reaction as :
is spontaneous or not.
qrev
According to first law any process where energy remains S 
T
conserved is feasible, but this is not true for all processes. Hence,
The total entropy change (Stotal) for the system and surroundings
we need some other basis for feasibility of a process.
of a spontaneous process is given by
13.2 Entropy and Spontaneity
Stotal = Ssystem + Ssurr > 0
Let us consider diffusion of two gases into each other in a closed
When a system is in equilibrium, the entropy is maximum, and the
container which is isolated from the surroundings as shown in
change in entropy, S = 0.
fig. (a) and (b).
We can say that entropy for a spontaneous process increases till
The two gases, say, gas A and gas B are represented by blue dots
it reaches maximum and at equilibrium the change in entropy is
and pink dots respectively and separated by a movable partition
zero. Since entropy is a state property, we can calculate the change
fig. (a) When the partition is withdrawn the gases begin to diffuse
in entropy of a reversible process by.
into each other and after a period of time, diffusion will be complete
fig (b). q sys,rev
S 
T
We find that both for reversible and irreversible expansion for an
ideal gas, under isothermal conditions, U = 0, but Stotal i.e.,
Ssys + Ssurr is not zero for irreversible process. Thus, U does
not discriminate between reversible and irreversible process,
whereas S does.
13.3 Entropy change in Thermodynamic Processes
The entropy changes in a thermodynamic process can be
mathematically calculated by the equation:
T   V2 
S  nC V n  2   nRn  
 T1   V1 
This expression can be simplified for the four processes studied
earlier as :
 V2 
Diffusion of two gases For Isothermal Process: S  nRn  V 
 1
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 T2  constant i.e. STotal = 0
For Isochoric Process: S  nCV n  T 
 1
15. GIBBS FREE ENERGY AND SPONTANEITY
 T2 
For Isobaric Process: S  nCP n  T  We have seen that for a system, it is the total entropy change,
 1 Stotal which decides the spontaneity of the process. It is clear
from the discussion in previous sections that neither decrease in
For Adiabatic Process: S  0  q rev  0 
enthalpy nor increase in entropy alone can determine the direction
of spontaneous change.
13.4 Entropy Change During Phase Transition
For this purpose, we define a new thermodynamic function the
Entropy of Fusion Gibbs energy or Gibbs function, G, as
G = H – TS
H fusion
Sfusion  Sliquid  Ssolid  Gibbs function, G is an extensive property and a state function.
Tf
The change in Gibbs energy for the system, Gsys can be written
Entropy of Vapourisation as
H vapour G sys  H sys  TSsys  Ssys T

Svapour  Svapour  Sliquid 
Tbp
At constant temperature,  T = 0
Entropy of Sublimation
 G sys  H sys  TSsys
H sub
Ssub  Svapour  Ssolid 
Tsub Usually the subscript ‘system’ is dropped and we simply write
this equation as
Important points to Remember:
1. Entropy of a system remains constant in a reversible adiabatic G  H  T S
process. Therefore, it is also known as isoentropic process. This equation is known as the Gibbs equation, one of the most
2. Entropy of an ideal gas will always increase in isothermal important equations in chemistry. Here, we have considered both
expansion. terms together for spontaneity: energy (in terms of H) and
entropy (S, a measure of disorder) as indicated earlier.
3. In a reversible adiabatic process the entropy of both system Dimensionally if we analyse, we find that G has units of energy
and surroundings remains the same and there is no overall because, both H and the TS are energy terms, since TS = (K)
change in entropy as well. (J/K) = J.
SSystem = SSurroundings = STotal = 0 Now let us consider how G is related to reaction spontaneity.
4. In a reversible isothermal expansion the entropy of We know,
surroundings will always decrease to balance the increase in
system’s entropy to make the overall entropy constant. Stotal  Ssys  Ssurr
5. In free expansion the entropy of the system always increases If the system is in thermal equilibrium with the surrounding, then
and that of surrounding remains constant. Free expansion is the temperature of the surrounding is same as that of the system.
both isothermal and adiabatic and is irreversible. Also, increase in enthalpy of the surrounding is equal to decrease
in the enthalpy of the system.
14. SECOND LAW OF THEROMODYNAMICS
Therefore, entropy change of surroundings,
“The entropy of an isolated system/Universe tends to increase.”
or H surr H sys
“In a spontaneous process the entropy of the universe increases.” Ssurr  
T T
STotal  SSystem  SSurrounding  0
(for a sponataneous change)
Thus, in a reversible process the entropy of the Universe remains
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temperature is lowered, the entropy decreases.
 H sys 
Stotal  Ssys   The absolute entropy of a perfectly crystalline substance at
 T 
absolute zero temperature is zero.
Rearranging the above equation: This is called third law of thermodynamics. This is so because
there is perfect order in a crystal at absolute zero. The statement
TStotal  TSsys  H sys
is confined to pure crystalline solids because theoretical
For spontaneous process, Stotal > 0 , so arguments and practical evidences have shown that entropy of
solutions and super cooled liquids is not zero at 0 K. The
TSsys  H sys  0 importance of the third law lies in the fact that it permits the
calculation of absolute values of entropy of pure substance from
   H sys  TSsys   0 thermal data alone.
Using equation , the above equation can be written as q rev

For a pure substance, this can be done by summing
T
–G > 0
increments from 0 K to 298 K.
GH – TS < 0
Hsys is the enthalpy change of a reaction, TSsys is the energy 17. THERMOCHEMICAL EQUATIONS
which is not available to do useful work. So G is the net energy A chemical equation which gives us all the information like energy
available to do useful work and is thus a measure of the ‘free changes associated with a chemical reaction and phases of various
energy’. For this reason, it is also known as the free energy of the reactants and products is called thermochemical equation.
reaction.
For a chemical reaction, HReaction = HProducts – HReactants
G gives a criteria for spontaneity at constant pressure and
temperature. The change in enthalpy during a chemical reaction occurs due to
breaking and making of bonds.
(i) If G is negative (< 0), the process is spontaneous.
Also, H = U + ngRT.
(ii) If G is positive (> 0), the process is non spontaneous.
All reactions can be categorized into one of the following two
Effect of Temperature on Spontaneity categories :
fHº fSº fGº Description 17.1 Endothermic Reactions

– + – Spontaneous at all temperatures These are chemical reactions which absorb energy.
+ – + Nonspontaneous at all tempertures
(H = positive)
– – + (at high T) Nonspontaneous at high temeprature
– – – (at low T) Spontaneous at low temperature
+ + + (at low T) Non-spontaneous at low temperature
+ + – (at high T) Spontaneous at high temperature
16. THIRD LAW OF THERMODYNAMICS

Molecules of a substance may move in a straight line in any
direction, they may spin like a top and the bonds in the molecules
may stretch and compress. These motions of the molecule are Fig. 10.17: Enthalpy diagram for endothermic reactions
called translational, rotational and vibrational motion respectively. CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g)
When temperature of the system rises, these motions become
more vigarous and entropy increases. On the other hand when H = – 890 kJ/mol
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17.2 Exothermic Reactions gaseous state at a constant temperature and standard pressure
(1 bar).
These are chemical reactions which release energy.
For example: Solid CO2 or ‘dry ice’ sublimes at 195 K
H = negative)
CO 2  s   CO 2  g  ; sub H   25.2kJmol –1
Naphthalene sublimes slowly and for this sub H   73.0kJmol1
18. ENTHALPIES OF REACTIONS

Enthalpy change can be calculated for all reactions and is
sometimes called the Heat of Reaction. Let’s take a look at various
types of reactions and enthalpy changes associated with them :
Enthalpy diagram for exothermic reaction H oRe action   H oPr oduct   H oReactants
18.1 Enthalpy of Formation

17.3 Enthalpy Change During Phase Transformation
It is the heat absorbed or released when one mole of a compound
17.3.1 Enthalpy of fusion (Symbol fusHº)
is formed from its constituent elements under their standard
The heat change (or enthalpy change) that is accompanied when elemental forms. The enthalpy for formation of the following
one mole of a solid substance undergoes melting in standard substances is taken to be zero under 1 bar pressure and 298 K.
state is called standard enthalpy of fusion or molar enthalpy of
Hfo (O2, g) = 0; Hfo (S, Rhombic) = 0

fusion,  fus H Hfo (C, graphite) = 0; Hfo (P, white) = 0
For example, ice requires heat for melting. Normally this melting Hfo (Br2, l) = 0; Hfo (H2, g) = 0
takes place at constant pressure, i.e., atmospheric pressure and
during the phase transition, temperature remains constant (273K). 18.2 Enthalpy of Combustion
It is the heat released when one mole of a substance undergoes
H 2 O  s   H 2 O  l  ;  fus H   6.00kJmol1 combustion in presence of oxygen.
If process is reversed, an equal amount of heat is given off to the CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g) H = – 890 kJ/mol
surroundings. 18.3 Enthalpy of Neutralization
17.3.2 Enthalpy of vaporization (Symbol vapHº) It is the heat released or absorbed when one equivalent of an acid
undergoes neutralisation with one equivalent of a base. e.g.
The enthalpy change (or heat change) when one mole of liquid at
H+ (aq) + OH– (aq)  H2O (l ) H = – 57.3 kJ/mol
constant temperature and under pressure (1 bar) undergoes
vaporization is called standard enthalpy of vaporization or molar 18.4 Enthalpy of Solution

enthalpy of vaporization,  vap H . It is the heat released or absorbed when 1 mole of a compound is
dissolved in excess of a solvent (water).
For example, water requires heat for evaporation, at constant
MgSO4 (s) + H2O (excess) Mg2+ (aq) + SO42– (aq)
temperature of its boiling point Tb and at constant pressure
HoSol = – 91.211 kJ/mol
H 2 O  l   H 2 O  g  ;  vap H   40.79kJmol 1 18.5 Enthalpy of Hydration
17.3.3 Enthalpy of sublimation (Symbol subHº) It is the energy released or absorbed when 1 mole of anhydrous
or partially hydrated salt undergoes hydration by the addition of
Sublimation is the process when a solid changes directly into water of crystallisation. e.g.
gaseous state without changing into liquid state. The change in CuSO4(s) + 5H2O(l)  CuSO4. 5H2O(s) Hhyd = –78.9 kJ/mol
state occurs at a temperature below its melting point. In this case
the enthalpy of sublimation is defined as the change in enthalpy
when one mole of a solid substance is directly converted into the
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18.6 Lattice Enthalpy
The lattice enthalpy of an ionic compound is the enthalpy change
which occurs when one mole of an ionic compound dissociates
into its ions in gaseous state. It is denoted by  lattice H Resonating structures of benzene
For example: The difference of 151 kJ gives the resonance energy of benzene.
NaCl  s   Na 
 g   Cl  g  ;

 lattice H  788kJ mol 1
19. HESS LAW
Relationship of solH,latticeH and hydH “If a reaction takes place in several steps then its standard reaction
 sol H   lattice H   hyd H enthalpy is the sum of the standard enthalpies of the intermediate
reactions into which the overall reaction may be divided at the
18.7 Bond Dissociation Enthalpy same temperature”. This is called the Hess law of constant heat
summation
The energy needed to break the bonds of one mole molecules is
called the bond dissociation Enthalpy of the substance. It is defined
per mol of molecule.
e.g. Bond dissociation enthalpy of H2 is 436 kJ/mol
H 2 (g)  2H(g) H  436 kJ / mole
18.8 Heat of Atomization

It is defined as the energy required to convert any substance to
gaseous atoms. This is defined per mol of the gaseous atoms. For Representation of Hess law
example heat of atomisation of H will be 218 kJ/mol atoms. 19.1 Born Haber Cycle
The entire thermodynamics process of formation of an ionic crystal
H 2 (g)  2H(g) H  436 kJ / mole lattice is called Born Haber cycle. An ionic compound is formed
from its constituents through a series of steps involving
For diatomic molecules bond dissociation energy and heat of conversion of atoms/molecules into gaseous phase for ion
atomization are same. formation, ionisation and electron gain to form ions and then the
reaction of gaseous ions to form solid lattice
18.9 Resonance Energy
Generally there is a good agreement between the enthalpies of
formation as calculated from bond energies and those determined
experimentally. However, if a compound exhibits resonance, there
is a considerable difference between the two values. This difference
gives a measure of the resonance energy of the compound. As an
example, we may consider the dissociation of benzene:
C6 H 6 (g)  6C(g)  6H(g)
Assuming that benzene ring consists of three single and three
double bonds (Kekule’s structure), the calcualted dissociation
energy comes out to be 5384.1 kJ as illustrated below:
H g  3( H C  C )  3( H C  C )  6( H C  H )
 3  347.3  3  615.0  6  416.2  5384.1 kJ mol1
The experimental value is known to be 5535.1 kJ mol-1. Evidently,
the actual energy required for the dissociation of benzene is 151
kJ more than the calcualted value. This clearly show that the
acutal structure of benzene is more stable than the Kekule structure
by 151 kJ. The actual structure of benzene is known to be the
resonance hybrid of the two Kekule structures.
Born Haber Cycle of NaCl
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20. KIRCHHOFF EQUATION 21. GIBBS ENERGY CHANGE AND EQUILIBRIUM
The enthalpy of any process, whether physical or chemical, varies Gibbs energy for a reaction in which all reactants and products
with temperature. The influence of temperature can be worked are in standard state,  r G is related to the equilibrium constant
out as follows: of the reaction as follows:
H reaction   H products  H reactants 0   r G  RT  ln K
Differentiating with respect to temperature, keeping pressure Or  r G   RT ln K

constant, we have
Or  r G   2.303RT log K
 dH   dH product   dH reactant 
        C P product   CP reactant We also know that
 dT P  dT  P  dT P
 r G   r H  T r S  RT ln K
If C P = Sum of heat capacities of products – Sum of heat
For strongly endothermic reactions, K is smaller while for
capacities of reactants, then
exothermic reactions, K is much larger than 1.
d  H   CP dT
This equation is called the Kirchhoff equation. It states that the

variation of H of a reaction as temperature at constant pressure
is equal to C P of the system.
The temperature-dependence of enthalpy of reaction at constant

volume is given by
d  U   CV dT
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SUMMARY
 System: A part of universe which is under investigation.  Enthalpy (H): It is sum of internal energy and pressure-
volume energy of the system at a particular temperature and
 Surroundings: The rest of the universe which is not a part
pressure. It is also called heat content (H = U + PV).
of the system.
 Enthalpy change ( ΔH ): It is the measure of heat change
 State of the system: The conditions of existence of a system
when its macroscopic properties have definite values. taking place during the process at constant temperature and
constant pressure.
 State functions: The thermodynamic quantities which
depend only on the initial and final state of the system. q p  H
 Energy is exchanged between the system and the Enthalpy H and internal energy change (U) are related as
surroundings as heat if they are at different temperatures.
H  U  PV
 The properties of the system whose value is independent
of the amount of substance are called intensive properties, H  U  n g RT
e.g., temperature, pressure, viscosity, surface tension,
dielectric, specific heat capacity.
Where n g  Gaseous moles of products – Gaseous moles
 The properties of the system whose value depends upon of reactants
the amount of substance present in the system are called
extensive properties. e.g., mass, volume, surface area,
energy, enthalpy, entropy, free energy, heat capacity.

Θ
 
Enthalpy of reaction Δr H : The enthalpy change
accompanying a chemical reaction when the number of moles
 Work is also a mode of transference of energy between
of reactants react to give the products as given by the
system and the surroundings. Work done by the system on
balanced chemical equation.
the surroundings is given by PV.
 Internal energy (U): The energy associated with the system 

Θ
 
Standard enthalpy of formation Δf H : The enthalpy
at a particular conditions of temperature and pressure. change accompanying the formation of one mole of the
 Internal energy change ( ΔU ): It is a measure of heat change compound from its element at standard conditions and all
occurring during the process at constant temperature and the substances being in their standard states.
constant volume.
As a convention, the  f H of every element is assumed to
q v  U be zero.
 First law of thermodynamics: It states that the energy of
the universe always remains constant during chemical and

Θ
 
Enthalpy of combustion Δc H : The amount of heat
physical changes. Mathematically. change when 1 mole of the substance is completely burnt in
U  q  w excess of oxygen or air.  c H  is always negative.
 Internal energy of an ideal gas depends only on temperature.

Therefore, in an isothermal process involving ideal gas,
  Θ

Enthalpy of solution Δsol H : The enthalpy change when
U  0 . one mole of a substance is dissolved in large excess of

solvent so that further dilution does not give any further
 Work of expansion, w  –PV . enthalpy change.
 Work of expansion in vacuum.  Enthalpy of hydration: It is the enthalpy change during the
hydration of 1 mole of anhydrous salt to a specific hydrate.
pext  0, w  0
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 Hess law: The enthalpy change in a particular reaction is the  Gibbs energy: Gibbs energy is the energy in a system that
same whether the reaction takes place in one step or in a can be converted into useful work
number of steps. G   w useful
 Bond enthalpy: The average amount of energy required to G  H  T S
break one mole of the bonds of a particular type in gaseous
For a spontaneous process G  0
molecules.
For a non - spontaneous process G  0
q rev For a process at equilibrium G  0
 Entropy: S 
T  Relation of Gibbs energy and equilibrium constant:
 r G    2.303R T log K
  r Sº  Sº (products) – Sº (reactants)
i.e., Stotal  Ssys  Ssurr must be positive
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SOLVED EXAMPLES
Example - 1 Example - 4
Calculate the internal energy change in each of the A 5-litre cylinder contained 10 moles of oxygen gas at 27oC.
following cases : Due to sudden leakage through the hole, all the gas escaped
into the atmosphere and the cylinder got empty. If the
(i) A system absorbs 15 kJ of heat and does 5 kJ of work.
atmospheric pressure is 1.0 atmosphere, calculate the work
(ii) 5 kJ of work is done on the system and 15 kJ of heat is done by the gas. (1 L atm = 101.3 J)
given out by the system.
Sol. Vinitial = 5L, T = 27oC = 27 + 273 K = 300 K
Sol. (i) Here, q = +15 kJ
w = – 5 kJ nRT 10  0.0821 300
Vfinal =   246.3L
P 1.0
 According to first law of thermodynamics,
U = q + w = 15 + (–5) = 10 kJ V = Vfinal – Vinitial = 246.3 – 5 = 241.3 L
Thus, internal energy of the system increases by 10 kJ. wexp = – PV = – 1 × 241.3 L atm
(ii) Here, w = + 5 kJ = – 241.3 × 101.3 J = – 24443.7 J.
q = – 5 kJ
Example - 5
 According to first law of thermodynamics,
U = q + w = – 15 + (+ 5) = – 10 kJ Two moles of an ideal gas initially at 27 oC and one
atmospheric pressure are compressed isothermally and
Thus, the internal energy of the system decreases by 10 kJ.
reversibly till the final pressure of the gas is 10 atm. Calculate
Example - 2 q, w and U for the process.
Sol. Here, n = 2 moles, T = 27oC = 300 K, P1 = 1 atm, P2 = 10 atm
Calculate w, q and U when 0.75 mol of an ideal gas expands
isothermally and reversibly at 27oC from a volume of 15 L to P1
25 L. w = –2.303 n RT log
P2
Sol. For isothermal reversible expansion of an ideal gas,
V2 1 1
w = – 2.303 nRT log V Putting n = 0.75 mol, V1 = 15 L, V2 = 2.303  2  8.314 JK mol–1 × 300 K × log = 11488 J
1 10
= 25 L, T = 27 + 273 = 300 K and R = 8.314 J K–1 mol–1, we get
For isothermal compression of ideal gas, U = 0
25
w = – 2.303 × 0.75 × 8.314 × 300 log  955.5 J Further, U = q + w  q = – w = – 11488 J.
15
(–ve sign represents work of expansion)
Example - 6
For isothermal expansion of an ideal gas, U = 0
U = q + w gives q = – w = + 955.5 J. 10g of argon gas is compressed isothermally and reversibly
at a temperature of 27ºC from 10L to 5L. Calculate q, W, U
Example - 3 and H for this process. R = 2.0 cal K–1 mol–1. log10 2 = 0.30
Atomic wt. of Ar = 40
Carbon monoxide is allowed to expand isothermally and
reversibly from 10 m3 to 20 m3 at 300 K and work obtained is V2
Sol. w = – 2.303 nRT log10
4.754 kJ. Calculate the number of moles of carbon monoxide. V1
V2
Sol. w = – 2.303 n RT log 10 5
V1 = – 2.303 × × 2 × 300 log10
40 10
20 w = 103.991 cal
– 4754 = – 2.303 × n × 8.314 × 300 log .
10
U = 0 ; H = 0 (Constant temperature)
This given n = 2.75 moles.  q = U – w q = – w = – 103.991 cal

A gas present in a cylinder fitted with a frictionless piston The state of a mole of an ideal gas changed from state A
expands against a constant pressure of 1 atm from a volume (2p, v) through four different processes and finally returns
of 2 litre to a volume of 6 litre. In doing so, it absorbs to initial State A reversibly as shown below.
800 J heat from surroundings. Determine increase in internal
energy of process.
Sol. Since, work is done against constant pressure and thus,
irreversible.
Given, V = (6 – 2) = 4 litre; P = 1 atm
 w = – 1 × 4 litre-atm = – 4 × 1.01325 × 102 J
= 405.3 J
Now from first law of thermodynamics
q = U – w
800 = U + 405.3  U = 394.7 Joule
Calculate the total work done by the system and heat
Example - 8 absorbed by the system in the cyclic process.
5 moles of an ideal gas at 300 K are expanded isothermally Sol. State A to State B (Isobaric expansion)
from an initial pressure of 500 Pa to a final pressure of 100 Pa Pressure is held constant at 2p and the gas is heated until
against a constant external pressure of 100 Pa. Calculate w, the volume v becomes 2v.
q, U and H for the process. What will be the difference if  W1 = – pV = – 2p (2v – v) = – 2pv
the same process is carried out irreversibly ? What are the
State B to State C (Isochoric process)
values of w, q, U, H for the irreversible process ?
Volume is held constant at 2v and the gas is cooled until
Sol. For an isothermal irreversible expansion :
the pressure 2p reaches p.
U = H = 0
W2 = 0 ( V = 0)
w = – Pext (V2–V1)
State C to State D (Isobaric compression)
V2 and V1 can be calculated from ideal gas equation.
Pressure is held constant at p and the gas is further cooled
V1 = nRT/P1 = 5 × 8.314 × 300/500 = 24.9 m3 until the volume 2v becomes v.
V2 = nRT/P2 = 124.7 m3 W3 = – p (v – 2v) = pv
Therefore, w = – 100 × (124.5 – 24.9) State D to State A (Isochoric process)
= – 9980 J Volume is held constant at v and the gas is heated until the
q = + 9980 J pressure p reaches 2p.
If this process is done reversibly then the internal and W4 = 0 ( V = 0)
external pressure should be same throughout. Total work done by the gas = W = W1 + W2 + W3 + W4
U = H = 0 (temperature is constant) or W = – 2pv + 0 + pv + 0 = – pv (= area ABCD)
w = – nRT ln (V2/V1) As the process is cyclic E = 0
= – 5 × 8.314 × 300 × ln 5 q = – w q = + pv
= – 20071.3 J where q is the heat absorbed in the cylic process.
q = + 20071.3 J

Example - 10 Total work, W = – 2026.5 + 0 + 1404.07

Two mole of a perfect gas undergo the following processes: = – 622.43 J
(a) a reversible isobaric expansion from For cyclic process : U = 0
(1.0 atm, 20.0L) to (1.0 atm, 40.0L).  q=–w
(b) a reversible isochoric change of state from q = + 622.43 J
(1.0 atm, 40.0L) to (0.5 atm, 40.0L) Example - 11
(c) a reversible isothermal compression from
Calculate the amount of work done in each of the following
(0.5 atm, 40.0L) to (1.0 atm, 20.0L).
cases :
(i) sketch with labels each of the processes on the same
P-V diagram. (i) One mole of an ideal gas contained in a bulb of 10
litre capacity at 1 bar is allowed to enter into an
(ii) Calculate the total work (w) and the total heat change
evacuated bulb of 100 litre capacity.
(q) involved in the above processes.
(iii)What will be the value of U, H and S for the (ii) One mole of a gas is allowed to expand from a volume
overall process ? of 1 litre to a volume of 5 litres against the constant
external pressure of 1 atm (1 litres atm = 101.3 J) Calculate
Sol. The overall process is cyclic one, i.e., initial state is regained,
the internal energy change (U) in each case if the process
thus U = 0; H = 0 and S = 0.
were carried out adiabatically.
Sol. (i) w = –Pext × V
As expansion takes place into the evacuated bulb, i.e.,
against vacuum, Pext = 0. Hence, w = 0.
For adiabatic process, q = 0 U = q + w = 0 + 0 = 0.
(ii) V = V2 – V1 = 5 – 1 = 4 litres
P = 1 atm  w = – PV
= –1 × 4 litre atm = – 4 litres atm
= – 4 × 101.3 J = – 405.2 J (1 L – atm = 101.3J)
Now, total work W = WAB + WBC + WCA
The negative sign implies that the work is done by the
WAB = – P (VB – VA) system.
= – 1 (40 – 20) = – 20L atm For adiabatic process, U = q + w = 0 – 405.2 J = – 405.2 J.
= – 20 × 1.01325 × 102 J
Example - 12
= – 2026.5 J
WBC = 0 (Isochoric) 5.6 dm3 of an unknown gas at S.T.P. required 52.25 J of heat
to raise its temperature by 10oC at constant volume. Calculate
VA Cv, Cp and  of the gas
WCA = – 2.303 nRT log10 V
C Sol. The 22.4 dm3 of a gas at S.T.P. = 1 mol
n = 2 mol.
1
At point C : P = 0.5 atm, V = 40L  5.6 dm3 of the gas at S.T.P. =  5.6  0.25 mol
22.4
PV = nRT
Thus, for 10o rise, 0.25 mol of the gas at constant volume
0.5  40 require heat = 52.25 J
T = (0.0821) (2) = 121.8 K.  For 1o rise, 1 mol of the gas at constant volume will require
 20  52.25
WCA = – 2.303 (2) (8.314) (121.8) log10   heat =  20.9
 40  10  0.25
= 1404.07 J

 Cv = 20.9 J K–1 mol–1

V1  V2
Now, Cp = Cv + R = 20.9 J K–1 mol–1 + 8.314 J K–1 mol–1 = 29.214 Ssystem = nR ln V1 > 0  V1 + V2 > V1
J K–1 mol–1
Ssurr = 0  qsurr. = 0
Cp29.214
   = 1.4 Suniv > 0
Cv 20.9
Example - 15
Example - 13
1.0 mol of an ideal gas, initially present in a 2.00 L insulated
A heated copper block at 130oC loses 340 J of heat to the cylinder at 300 K is allowed to expand against vacuum to
surroundings which are at room temperature of 32oC. 8.00 L. Determine W, E, H, Suniv and G .
Calculate
(i) the entropy change of the system (copper block)
(ii) the entropy change in the surroundings Sol.
(iii) the total entropy change in the universe due to this
process W = – pext V = 0, q = 0, E = 0 = H
Assume that the temperature of the block and the  Tf = 300 K
surroundings remains constant.
V2
Sol. Tsystem = 130o C = 130 + 273 K = 403 K, Tsurr = 32oC = 32 + 273 Ssys = R ln V = R ln 4 = 11.52 JK–1
1
K = 305 K qsystem = – 340 J, qsurr = + 340 J
Ssurr = 0  qsys = qsurr = 0
qsystem 340 J –1
(i) Ssystem    -0.84 JK -1 Suniv = 11.52 JK
Tsystem 403K
G = – TSuniv = – 300 × 11.52 = – 3456 J/mol.
qsurr 340 J Example - 16

(ii) Ssurr    +1.11 J K -1
Tsurr 305 K
The heat of combustion of benzene in a bomb calorimeter
(iii) Stotal or Suniverse = Ssystem + Ssurr = – 0.84 + (+1.11) (i.e., constant volume) was found to be 3263.9 kJ mol–1 at
J K–1 = 0.27 J K–1 25oC. Calculate the heat of combustion of benzene at
constant pressure.
Example - 14 Sol. The reaction is:
An ideal gas is originally confined to a volume V1 in an 1
C 6 H 6   7 O 2 
 6CO 2  g   3H 2 O   
insulated container of volume V1 + V2. The remainder of 2 g 
the container is evacuated. The portion is then removed
In this reaction, O2 is the only gaseous reactant and CO2 is
and the gas expands to fill the entire container. If the initial
the only gaseous product.
temperature of the gas was T, what is the final temperature.
Also predict qualitatively, the entropy change of system,
surroundings and the universe. 1 1 3
 n g  n p  n r  6  7
 1  
2 2 2
Also, we are given U (or qv) = – 3263.9 kJ mol–1
T = 25oC = 298K
8.314
R = 8.314 J K–1 mol–1 = kJ K 1 mol 1
1000
Sol. This is a process of adiabatic free expansion of an ideal
gas. The internal energy does not change thus the
temperature also stays the same, i.e., the final temperature
is still T.

So mass of solution = 700g

H (or qp) = U + ng RT = – 3263.9 kJ mol–1 +
Specific heat = 4.18 J K–1 g–1
 3   8.314 
  mol   kJ K 1 mol 1   298K  Q 2284
 2   1000  Q  m  C   T  T   = 0.78ºC
m  C 700  4.18
= – 3263.9 – 3.7 kJ mol–1 = – 3267.6 kJ mol–1. In case (ii), heat produced = 4.568 kJ = 4568 J
Total mass of the solution = 200 + 400 = 600 g
Example - 17 Q 4568
 T   = 1.82ºC
m  C 600  4.18
Calculate the amount of heat evolved when Example - 18
(i) 500 cm3 of 0.1 M hydrochloric acid is mixed with 200 cm3
of 0.2 M sodium hydroxide solution Calculate the enthalpy change accompanying the
(ii) 200 cm3 of 0.2 M sulphuric acid is mixed with 400 cm3 of transformation of C (graphite) to C(diamond). Given that
0.5 M potassium hydroxide solution. the enthalpies of combustion of graphite and diamond are
393.5 and 395.4 kJ mol–1 respectively.
Assuming that the specific heat of water is 4.18 J K–1 g–1
and ignoring the heat absorbed by the container, Sol. Remember, enthalpy of combustion is always negative we
thermometer, stirrer etc., what would be the rise in are given
temperature in each of the above cases ?
(i) C (graphite) + O2 (g) 
 CO2(g) ; c Ho = – 393.5 kJ
0.1 mol –1
Sol. (i) moles of HCl =  500 = 0.05 = 0.05 mole of H+ ions
1000
(ii) C (diamond) + O2 (g) 
 CO2(g) ; c Ho = – 395.4 kJ
0.2
200 cm3 of 0.2 M NaOH   200 mol–1
1000
mole of NaOH = 0.04 mole = 0.04 mole of OH– ions We aim at C(graphite) 
 C(diamond), trans Ho = ?
Thus, 0.04 mole of H+ ions will combine with 0.04 mole of Subtracting eqn. (ii) from eqn. (i), we get
OH– ions to from 0.04 mole of H2O and 0.01 mole of H+ ions
will remain unreacted. C(graphite) – C(diamond) 
 0;
 Heat evolved when 1 mole of H+ ions combine with 1 r Ho = – 393.5 – (–395.4) = + 1.9 kJ
mole of OH– ions = 57.1 kJ. or
 Heat evolved when 0.04 mole of H ions combine with
+
C(graphite) 
 (diamond) ; trans H = + 1.9 kJ
0.04 mole of OH– ions = 57.1 × 0.04 = 2.284 kJ
Example - 19
(ii) 200 cm of 0.2 M H 2 SO 4  0.2  200 mole of
3
1000 Calculate the enthalpy of hydration of anhydrous copper

H2SO4 = 0.04 mole of H2SO4 = 0.08 mole of H+ ions sulphate (CuSO 4 ) into hydrated copper sulphate
(CuSO4.5H2O). Given that the enthalpies of solutions of
0.5 anhydrous copper sulphate and hydrated copper sulphate
400 cm3 of 0.5 M KOH   400 mole of KOH = 0.2 mole are –66.5 and + 11.7 kJ mol–1 respectively
1000
of KOH = 0.2 mole of OH– ions Sol. We are given
Thus, 0.08 mole of H+ ions will neutralize 0.08 mole of OH– (i) CuSO4 (s) + aq 
 CuSO4 (aq) ;
ions. (out of 0.2 mole of OH– ions) to form 0.08 mole of H2O.
sol H1 = – 66.5 kJ mol–1
Hence, heat evolved = 57.1 × 0.08 = 4.568 kJ
In case (i), heat produced = 2.284 kJ = 2284 J (ii) CuSO4.5H2O (s) + aq 
 CuSO4 (aq) ;
Total volume of the solution = 500 + 200 = 700 mL sol H2 = + 11.7 kJ mol–1
Assuming density of solution = 1g/mL

We aim at CuSO4 (s) + 5H2O (l) 

 CuSO4.5H2O(s) ; 1 1
(iv) K (s)  O 2  g   H 2  g   aq 

hyd H = ? 2 2
H = H1 – H2 = – 66.5 – (+11.7) = – 78.2 kJ/mol KOH (aq), H = – 487.4 kJ mol–1
Example - 20  KCl (aq), H = + 18.4 kJ mol–1

(v) KCl (s) + aq 
Calculate the enthalpy of formation of methane, given that 1

the enthalpies of combustion of methane, graphite and Sol. We aim at : K(s) + Cl 2  g  
 KCl  s  ,  f H  ?
2
hydrogen are 890.2 kJ, 393.4 kJ and 285.7 kJ mol –1
respectively. In order to get this thermochemical equation, we follow the
Sol. Remember : Enthalpy of combustion is always negative. following two steps :
We are given : Step 1. Adding Eqns. (iii) and (iv) and subtacting Eq. (v). we
have
 CO2 + 2 H2O, H = – 890.2 kJ mol–1
(i) CH4 + 2O2 
1 1
K (s) + Cl 2(g )  H 2(g )  O 2(g )  
 KCl  s  
 CO2, H = – 393.4 kJ mol
(ii) C + O2  –1 2 2
HCl (aq) + KOH (aq) – KCl (aq)
1
 H 2 O, H  285.7 kJ mol1
(iii) H 2  O2  H = – 487.4 + (–164.4) – (18.4) = – 670.2 kJ mol–1 ... (vii)
2
Step 2. To cancel out the terms of this equation which do not
 CH4, H = ?
We aim at : C + 2H2  appear in the required equation (vi), add eqn. (i) to eqn. (vii)
In order to get this thermochemical equation, multiply eqn. and subtract eqn. (ii) from their sum. This gives
(iii) by 2 and add it to eqn. (ii) and then subtract eqn. (i) from 1
their sum. We get : K  s   Cl 2  g  
 KCl  s  ;
2
C + 2 H2 
 CH4,
fH = 670.2  57.3   286.2  = – 441.3 kJ
H = – 393.4 + 2 (–285.7)
– (–890.2) kJ mol–1 = –74.6 kJ mol–1 Example - 22
Hence, the heat of formation of methane is : The combustion of 1 mole of benzene takes place at 298 K
f H = –74.6 kJ mol–1 and 1 atm. After combustion, CO2(g) and H2O(l) are produced
and 3267.0 kJ of heat is liberated. Calculate the standard
Example - 21 enthalpy of formation, f Ho of benzene. Standard enthalpies
of formation of CO2 (g) and H2O (l) are – 393.5 kJ mol–1 and
Calculate the heat of formation of KCl from the following –285.83 kJ mol–1 respectively.
data :
 C6H6    , H = ?
Sol. Aim : 6 C (s) + 3 H2(g) 
(i) KOH (aq) + HCl (aq) 
 KCl (aq) + H2O
Given :
   , H = – 57.3 kJ mol–1
15
(i) C6H6 (l) + O   6 CO2(g) + 3 H2O (l), H
1 2 2(g)
(ii) H2 (g) + O 2  g  
 H 2O    ,
2 = –3267.0 kJ mol–1
1
H = 286.2 kJ mol
 CO2 (g), H = – 393.5 kJ mol–1
(ii) C (s) + O2 (g) 
1 1
(iii) H 2  g   Cl 2  g   aq 
 HCl  aq  , 1
2 2 (iii) H2 (g) +  H2O (l), H = –285.83 kJ mol–1
O 2  g  
2
H = – 164.4 kJ mol–1

In order to get the required thermochemical equation, Example - 25

multiply Eq. (ii) by 6 and Eq. (iii) by 3 and subtract Eq.
(i) from their sum, i.e. operating 6 × Eqn. (ii) + 3 × Eqn. Enthalpy of solution (H) for BaCl2.2H2O and BaCl2 are 8.8
(iii) – Eqn. (i), we get and –20.6 kJ mol–1 respectively. Calculate the heat of
hydration of BaCl2 to BaCl2.2H2O.
6C (s) + 3H2 (g) 
 C6H6 (l) ; Sol. We are given
H = 6 (–393.5) + 3 (–285.83) – (–3267.0)
 BaCl2(aq), sol H1o = 8.8 kJ mol–1
(i) BaCl2.2H2O (s) + aq 
= – 2361 – 857.49 + 3267.0 = 48.51 kJ mol–1
Thus, the enthalpy of formation of benzene is  BaCl2(aq), sol H o2 = – 20.6 kJ mol–1
(ii) BaCl2 (s) + aq 
f H = – 48.51 kJ mol–1 We aim at
Example - 23
 BaCl2.2H2O (s), hyd Ho = ?
BaCl2 (s) + 2H2O 
Calculate the enthalpy of combustion of ethylene (gas) to H = H2 – H1 = – 29.4 kJ mol–1
form CO2 (gas) and H2O (gas) at 298 K and 1 atmospheric
pressure. The enthalpies of formation of CO2, H2O and C2H4 Example - 26
are –393.5, –241.8, + 52.3 kJ per mole respectively.
Calculate the enthalpy of hydrogenation of ethylene, given
Sol. We are given :
that the enthalpy of combustion of enthylene, hydrogen
and ethane are – 1410.0, – 286.2 and – 1560.6 kJ mol–1
(i) C(s) + O2(g) 
 CO2(g), H1o = – 393.5 kJ mol–1
respectively at 298 K.
1
(ii) H 2  g   O 2(g )  
 H2O(g), H o2 = – 241.8kJ mol–1 Sol. We are given (i) C2H4 (g) + 3O2 (g) 
 2CO2(g) + 2H2O (l),
2
H = – 1410 kJ mol–1
(iii) 2C (s) + 2H2(g) 
 C2H4(g), H 3o = + 52.3 kJ mol–1
1
(ii) H2 (g)  O 2  g  
 H2O (l), H = – 286.2 kJ mol–1
We aim at : C2H4(g) + 3O2(g) 
 2CO2(g) + 2H2O(g) 2
H = – H3 + 2H1 + 2H2 1

(iii) C 2H 6 (g) + 3 O2  g  
 2CO2  g  + 3H 2 O (l),
2
= –1322.9 kJ mol–1
H = – 1560.6 kJ mol–1
Example - 24
 C2H6 (g), H = ?
We aim at: C2H4 + H2(g) 
Given the following thermochemical equations:
Equation (i) + Equation (ii) – Equation (iii) gives
 SO2 (g), H = – 297.5 kJ mol–1
(i) S (rhombic) + O2 (g) 
 SO2 (g), H = – 300.0 kJ mol–1
(ii) S(monoclinic) + O2  C2H4 (g) + H2 (g) 
 C2H6 (g),
Calculate H for the transformation of one gram atom of H = – 1410.0 + (–286.2) – (1560.6) = – 135.6 kJ mol–1
rhombic sulphur into monoclinic sulphur.
Example - 27
Sol. We aim at
S (rhombic)  S (monoclinic), H = ? The thermite reaction used for welding of metals involves
Equation (i)  Equation (ii) gives the reaction
S(rhombic) – S(monoclinic) 
 0, 2 Al (s) + Fe2O3 (s) 
 Al2O3 (s) + 2Fe (s)
H = -297.5 – (–300.0) = 2.5 kJ mol–1
What is Ho at 25oC for this reaction ? Given that the standard
or heats of formation of Al 2 O 3 and Fe 2 O 3 are
 S(monoclinic), H = + 2.5 kJ mol–1
S(rhombic)  – 1675.7 kJ and –828.4 kJ mol–1 respectively.
Thus, for the transformation of one gram atom of rhombic
sulphur into monoclinic sulphur, 2.5 kJ mol–1 of heat is Sol. We aim at 2Al (s) + Fe2O3(s) 
 Al2O3 (s) + 2Fe
absorbed. (s), r Ho = ?
r H = Sum of f Ho of products – Sum of

f Ho of reactants Example - 30
=[f Ho (Al2O3) + 2 × f Ho (Fe)] –
The thermochemical equation for solid and liquid rocket
[2 × f Ho (Al) + f Ho (Fe2O3)]
fuel are given below :
= [–1675.7 + 0] – [0 + (–828.4)] = – 847.3 kJ mol–1
1
2Al  s   1 O 2  g  
 Al2 O3  s  ;
Example - 28 2
The heat evolved in the combustion of methane is given H  1667.8 kJ mol1

by the equation : 1
H 2  g   O 2  g  
 H 2 O 1 ;
 CO2(g) + 2H2O (l), H = – 890.3 kJ mol
CH4 (g) + 2O2 (g)  –1
2
(a) How many grams of methane would be required to H  285.9 kJ mol1
produce 445.15 kJ of heat of combustion ?
(a) If equal masses of aluminium and hydrogen are used,
(b) How many grams of carbon dioxide would be formed which is a better rocket fuel ?
when 445.15 kJ of heat is evolved ? (b) Determine H for the reaction :
(c) What volume of oxygen at STP would be used in the
combustion process (a) or (b) ? 1
 2Al (s) + 1 O 2  g  .
Al2O3(s) 
Sol. (a) From the given equation. 2
890.3 kJ of heat is produced from 1 mole of CH4, i.e., Sol. (a) From the first given equation,
12 + 4 = 16 g of CH4 2 moles of Al (i.e., 2 × 27 g = 54 g) on combustion give heat
 445.15 kJ of heat is produced from 8 g of CH4 = 1667.8 kJ
(b) From the given equation, when 890.3 kJ of heat is
1667.8
evolved, CO2 formed = 1 mole = 44 g  1 g of Al on combustion gives heat   30.9 kJ
54
 When 445.15 kJ of heat is evolved, CO2 formed = 22 g
(c) From the equation, O 2 used in the production of From the second given equation, 1 mole of H2 (= 2 g) on
890.3 kJ of heat = 2 moles = 2 × 22.4 litres at STP combsution gives heat = 285.9 kJ
= 44.8 litres at STP 285.9
1 g of H2 on combustion gives heat   142.95 kJ
Hence, O2 used in the production of 445.15 kJ of heat = 22.4 2
litres at STP. Thus, H2 is a better rocket fuel.
Example - 29 (b) Writing the reverse of the first reaction, we have

1
From the thermochemical equation, Al2 O3  s  
 2Al  s   1 O 2  g  ; H  1667.8 kJ mol 1
2
1 Thus, for the reaction given in part (b) of the problem,
C6 H 6     7 O 2  g  
 3H 2 O     6CO 2 (g),
2 H = + 1667.8 kJ mol–1
cH = – 3264.64 kJ mol–1, Example - 31

calculate the energy evolved when 39 g of C6H6 are burnt in
When 1 g liquid naphthalene (C10H8) solidifies. 149 joules
an open container.
of heat is evolved. Calculate the enthalpy of fusion of
Sol. From the given equation, naphthalene.
When 1 mole of C6H6 (78 g of C6H6) is burnt, heat evolved = Sol. Molar mass of naphthalene (C10H8) = 128 g mol–1
3264.64 kJ
When 1 g of liquid naphthalene solidified, heat evolved =
3264.64 149 joules.
 When 39 g of C6H6 is burnt, heat evolved =  39
78 When 1 mole, i.e., 128 g of naphthalene solidifies, heat
= 1632.32 kJ evolved = 149 joules.
When 1 mole, i.e., 128 g of naphthalene solidifies, heat
evolved = 149 × 128 joules = 19072 joules

Since fusion is reverse of solidification, therefore, heat Sol. r H = B.E. (Reactants) – B.E. (Products)
absorbed for fusion of one mole of naphthalene = 19072 = [B.E. (H2) + B.E. (Br2)] – 2 B.E. (HBr) =
joules.
435 + 192 – 2 × 364 = – 101 kJ
i.e., Enthalpy of fusion (fus H) = + 19072 joules/mole
Example - 35
Example - 32
Propane has the structure H3C–CH2 –CH3. Calculate the
The heat evolved in the combustion of glucose is shown in
change in enthalpy for the reaction:
the equation :
 6CO2 (g) + 6 H2O (g), c H
C6H12O6 + 6O2 (g)  C3H8 (g) + 5 O2 (g) 
 3 CO2 (g) + 4 H2O (g)
= – 2840 kJ mol–1 Given that average bond enthalpies are:
What is the energy requirement for production of 0.36 g of C–C C–H C = O O = O O–H
glucose by the reverse reaction ? 347 414 741 498 464 kJ mol–1
Sol. The given equation is :
C6H12O6 + 6O2(g) 
 6CO2(g) + 6H2O (g) ; Sol. +5 O=O3O=C=O+4H–O–H
r H = – 2840 kJ mol–1
Writing the reverse reaction, we have H = (2eC–C + 8eC–H + 5eO=O) – (6eC=O + 8eO–H)
= 2 (347) + 8 (414) + 5 (498) – 6 (741) – 8 (464)
6CO2 (g) + 6H2O(g)   C6H12O6 (s) + 6O2(g) ;
= – 1662 kJ mol–1
r H = + 2840 kJ mol–1
Thus, for production of 1 mole of C6H12O6 (= 72 + 12 + 96 = Example - 36

180 g), heat required (absorbed) = 2840 kJ.
Calculate the entropy change involved in conversion of
 For production of 0.36 g of glucose, heat absorbed = one mole (18 g) of solid ice at 273 K to liquid water at the
2840 same temperature (latent heat of fusion = 6025 J mol–1).
 0.36  5.68kJ
180
f H
Sol. Entropy change for ice  water is given by  f S 
Example - 33 Tf
Calculate the bond energy of C–H bond, given that the Here, f H = 6025 J mol–, Tf = 273 K 
heat of formation of CH4, heat of sublimation of carbon and
6025 J K 1 mol1
heat of dissociation of H2 are – 74.8, + 719.6 and 435.4 kJ f S   22.1 JK 1mol 1.
mol–1 respectively. 273K
Sol. Here, we are given
Example - 37
 CH4(g), r H = – 74.8 kJ
C (s) + 2H2 (g)  o
Calculate the entropy change involved in the conversion of
H = esub(C) + 2eH–H – 4eC–H one mole of liquid water at 373 K to vapour at the same
– 74.8 = 719.6 + 2 (435.4) – 4eC–H temperature (latent heat of vaporization of water
vap H = 2.257 kJ/g)
eC–H = 416.3 kJ/mol
Sol. For the conversion of water  vapour, the entropy change
Example - 34
 vap H
is given by vap S =
Calculate the enthalpy change for the reaction Tb
H2 (g) + Br2 (g) 

 2HBr (g) Here, vap H = 2.257 kJ/g = 2.257 × 18 kJ/mol =
Given that the bond enthalpies of H–H, Br–Br, H–Br are 40.626 kJ/mol, Tb = 373 K
435, 192 and 364 kJ mol–1 respectively.

and – 237.2 kJ mol–1 respectively. Predict the feasibility of

40.626 kJ mol1 the above reaction at the standard state.
 vap S =  0.1089 kJ K–1 mol–1
373 K
Sol. Here, we are given
= 108.9 J K–1 mol–1. f Go (NH3) = – 16.8 kJ mol–1
f Go (NO) = + 86.7 kJ mol–1
Example - 38
f Go (H2O) = – 237.2 kJ mol–1
At 0oC, ice and water are in equilibrium and H = 6.00 kJ  r Go =  f Go (Products) –  f Go (Reactants) = [14 × f
mol–1 for the process H2O (s)  H2O (l). What will be S Go (NO) + 6 × f Go (H2O)] – [4 × f Go (NH3)
and G for the conversion of ice to liquid water ? + 5 × f Go (O2)]
Sol. Since the given process is in equilibrium, G = 0 = [4 × (86.7) + 6 × (–237.2)] – [4 × (– 16.8) + 5 × 0]
Putting this value in the relationship, G = H – TS, we = – 1009.2 kJ
get
Since r G is negative, the process is feasible.
o
H
0 = H – TS or TS = H or S = Example - 41
T
We are given H = 6.0 kj mol–1 = 6000 J mol–1 and Calculate the entropy change for the rusting of iron
T = 0oC = 273 K according to the reaction :
 
6000 J mol1  2 Fe2O3 (s), Ho = –1648 kJ mol–1
4 Fe (s) + 3 O2 (g) 
 21.98 J K –1 mol –1
273K Given that the standard entropies of Fe, O2 and Fe2O3 are
27.3, 205.0 and 87.4 J K–1 mol–1 respectively. Will the reaction
Example - 39 be spontaneous at room temperature (25oC) ? Justify your
answer with appropriate calculations.
A + B 
 C + D ; H = – 10,000 J mol–1, Sol. r So =  So (Products) –  So (Reactants) =
S = – 33.3 J mol–1 K–1 2 So (Fe2O3) – [4 So (Fe) + 3 So (O2)]
(i) At what temperature the reaction will occur = 2 × 87.4 – [4 × 27.3 + 3 × 205.0] J K–1 mol–1 =
spontaneously from left to right ? – 549.4 J K–1 mol–1
(ii) At what temperature, the reaction will reverse? This is the entropy change of the reaction, i.e., system
Sol. G = H – TS (Ssystem)
At equilibrium, G = 0 so that H = TS or Now, rGo = r Ho – Tr So
= – 1648000 J mol–1 – 298 K × (–549.4 J K–1 mol–1)
1
H 10000 J mol = – 1648000 + 163721 J K–1 mol–1 =
T   300.03K
S 33.3JK 1 mol1 – 1484279 J K–1 mol–1
(i) For spontaneity from left to right. G should be –ve for As Go is –ve, the reaction is spontaneous.
the given reaction. This will be so if T < 300.3 K Example - 42
(ii) For reverse reaction to occur, G should be +ve forward
reaction. This will be so if T > 300.3 K. Calculate the standard enthalpy of formation of CH3OH (l)
from the following data :
Example - 40
3
(i) CH 3OH     O 2  g  
 CO 2  g  
Calculate the standard free energy change for the reaction, 2
2 H 2 O    ;  r H o  726 kJ mol1
4NH3 (g) + 5O2 (g) 
 4NO (g) + 6H2O (l)
Given that the standard free energies of formation (f Go)
for NH 3 (g), NO (g) and H 2O (l) are – 16.8, + 86.7

1
(ii) C  s   O 2  g  
 CO 2  g  ;  c H o  (ii) CO (g) + O 2  g  
 (g); r Ho = – 283.0 kJ mol–l
2
– 393 kJ mol–l
1
Sol. We aim at : C (s) + O 2  g  
 CO  g  ;  f H o  ?
1 2
(iii) H 2  g   O 2  g  
 H2 O    ; f Ho 
2 Subtracting eqn. (ii) from eqn. (i), we get
– 286 kJ mol .
–1
1
1 C (s) + O 2  g   CO  g  
 0;
Sol. Aim : C (s) + 2H2 (g)  O 2  g  
 CH 3OH    , 2
2
r Ho = –393.5 – (– 283.0) = – 110.5 kJ mol–1
o
f H  ?
1
or C  s   O2  g  
 CO  g  ;  r Ho  110.5kJ.
Eqn. (ii) + 2 × Eqn. (iii) – Eqn. (i) gives the required eqn. with 2
H = – 393 + 2 (–286) – (– 726) kJ mol–1 =
 Heat of formation of CO is : f Ho = – 110.5 kJ mol–1
– 239 kJ mol .
–1
Example - 45
Example - 43
Determine whether or not, it is possible for sodium to reduce
Calculate enthalpy of formation of methane (CH4) from the aluminium oxide to aluminium at 298 K. Given that G 0f of
following data : Al2O3 at 298 K = – 1582 kJ mol–1; G 0f of Na2O(s) at 298 K
= –377 kJ mol–1.
 CO2(g), r Ho = – 393.5 kJ mol–1
(i) C (s) + O2 (g) 
Sol. The given reaction is :
1 Al2O3 (s) + 6Na(s) 3Na2O (s) + 2Al(s)
(ii) H 2  g   O2  g  
 H2 O    ,
2
Hence, Gº = 3 × G 0f (Na2O) – G 0f (Al2O3)
r H = – 285.8 kJ mol
o –1
(Gº for Na and Al = 0)

 CO2 (g) + 2 H2O (  ),
(iii) CH4 (g) + 2O2 (g)  = 3 × (– 377) – (– 1582) = 451 kJ mol–1
r Ho = –890.3 kJ mol–1 The reaction cannot occur since Gº (298 K) is positive.
 CH4 (g) ; f Ho = ?
Sol. We aim at : C (s) + 2 H2 (g)  Example - 46
Multiplying eqn. (ii) with 2, adding to eqn. (i) and then The heat librerated on complete combustion of 7.8g
subtracting eqn. (iii) from the sum, i.e., operating eqn. (i) + benzene is 327 kJ. This heat has been measured at
2 × eqn. (ii) – eqn. (iii), we get constant volume at 27ºC. Calculate heat of combustion
of benzene at constant pressure at 27ºC.
 0; r Ho = – 393.5 +
C (s) + 2 H2 (g)  CH4 (g)  (R = 8.3 J mol–1 K–1).
2 (–285.8) – (–890.3) = 74.8 kJ mol–1
15
Sol. C6H6 (l ) + O (g) 6CO2(g) + 3H2O (l )
 CH4 (g); f Ho = – 74.8 kJ mol–1
or C (s) + 2 H2 (g)  2 2
Hence, enthalpy of formation of methane is : 15 3
n = 6 – 
f H = – 74.8 kJ mol
o –1 2 2
327  78
Example - 44 Also, U per mol = – = – 3270 kJ
7 .8
Now, H = U + nRT
Calculate the enthalpy of formation of carbon monoxide
(CO) from the following data :  3
= – 3270 +    × 8.3 × 300 × 10–3
 2
 CO2 (g); r Ho = – 393.5 kJ mol–l
(i) C (s) + O2 (g) 
H = – 3273.735 kJ

Example - 47
Sol. Aim equation : 12C (s) + 11 H2 (g)  C12 H22 O11 (s)
H = ?
Calculate standard heat of formation of CS2. Given that
standard heat of combustion of C, S and CS2 are – 393.3, H = 12H2 + 11 H3 – H1
– 293.72 and – 1108.76 kJ mol–1. = 12 (–393) + 11 (–286) – (–5644)
Sol. We have to find H for = –2218 kJ/mol
C + 2S CS2; H = ?
Example - 50
Given, C + O2 CO2; H = – 393.3 kJ ......... (1)
S + O2 SO2; H = – 293.72 kJ ........ (2) The standard molar enthalpies of formation of cyclohexane
(l) and benzene (l ) at 25ºC are – 156 and + 49 kJ mol–1
CS2 + 3O2 CO2 + 2SO2 ; H = – 1108.76 kJ ......... (3)
respectively. The standard enthalpy of hydrogenation of
Multiply Eq. (2) by 2 and add in Eq. (1) cyclohexene (l ) at 25ºC is – 119 kJ mol–1. Use these data to
C + 2S + 3O2 CO2 + 2SO2; H = – 980.74 kJ .......... (4) estimate the magnitude of the resonance energy of benzene.
Subtract Eq. (3) from Eq. (4) Sol. Enthalpy of formation of 3 carbon-carbon double bonds
C + 2S CS2; H = + 128.02 kJ Hf (Cyclohexane) – Hf (Benzene)
Hf of CS2 = + 128.02 kJ = – 156 – (+49) kJ
Example - 48 = – 205 kJ.
Given, that,
Estimate the average S–F bond energy in SF6. The standard
heat of formation value of SF6(g), S (g) and F (g) are : – 1100, 275 Cyclohexene + H2 Cyclohexane ; H = – 119 kJ
and 80 kJ mol–1 respectively. Theoretical enthalpy of formation of 3 double bonds in
Sol. H = Hsub(s) + 6HF – 6HS–F benzene ring
–1100 = 275 + 6 (80) – 6HS–F = 3 × (– 119) kJ = – 357 kJ.
HS–F = 309.17 kJ/mol  resonance energy of benzene = – 357 – (– 205) kJ
Example - 49 = – 152 kJ mol–1.
From the following themochemical equations, calculate the

enthalpy of formation of cane sugar (C12H22O11) :
(i) C12H22O11 (s) + 12 O2(g) 12 CO2(g) + 11 H2O (l)
rH1 = – 5644 kJ mol–1
(ii) C (s) + O2 (g) CO2(g) rH2 = – 393 kJ mol–1
(iii) H2(g) + 1/2 O2(g) H2O (l) rH3 = – 286 kJ mol–1

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
Introduction of Thermodynamics 9. What is the change in internal energy when a gas contracts
from 377 mL to 177 mL under a constant pressure of 1520
1. Which of the following is not a state function ?
torr, while at the same time being cooled by removing 124
(a) Heat (b) Internal energy J heat?
(c) Enthalpy (d) Entropy (a) 40.52 J (b) –83.48 J
2. Which of the following quantities is not a state function ? (c) –248 J (d) None of these
(a) Temperature (b) Entropy 10. A given mass of gas expands from the state A to the state
(c) Enthalpy (d) Work B by three paths 1, 2 and 3 as shown in the figure. If w1, w2
and w3 respectively be the magnitudes work done by the
3. Which of the following is not an intensive property ?
gas along three paths then :
(a) Entropy (b) Pressure
(c) Temperature (d) Molar volume
4. Which of the following is a state function and also an
extensive property?
(a) Internal energy (b) Pressure
(c) Molar heat capacity (d) Temperature
(a) w1 > w2 > w3 (b) w1 < w2 < w3
5. Warming ammonium chloride with sodium hydroxide in a
(c) w1 = w2 = w3 (d) w2 < w3 < w1
test tube is an example of :
11. An ideal gas is taken around the cycle ABCA as shown in
(a) Closed system (b) Isolated system
P-V diagram
(c) Open system (d) None of these
The net work done by the gas during the cycle is equal to :
6. A tightly closed thermoflask contains some ice cubes. This
constitutes
(a) closed system (b) open system
(c) isolated system
(d) Non-thermodynamic system
Internal Energy, Concept of Heat and Work
7. A sample of gas changes from P1, V1 and T1 to P2, V2 and T2
(a) 12 P1V1 (b) 6P1V1
by one path and then back to P1, V1 and T1, U for the
process is : (c) 5P1V1 (d) P1V1
(a) Infinite (b) > 0 12. An ideal gas is taken through the cycle A  B  C  A
as shown in fig. If the net heat supplied to the gas in cycle
(c) < 0 (d) equal to 0
is 5 J, the work done by the gas in the process C  A.
8. Which of the following changes would definitely increase
the internal energy of a system?
(a) The system gains heat and performs work.
(b) The system gains heat and has work performed on it.
(c) The system loses heat and performs work.
(d) The system loses heat and has work performed on it.
(a) –5 J (b) –10 J
(c) –15 J (d) –20 J

13. In a system where E = –51.0 kJ, a piston expanded against 20. A heat engine carries one mole of an ideal mono-atomic
a pext of 1.2 atm giving a change in volume of 32.0 L. What gas around the cycle as shown in figure, the amount of
was the change in heat of this system? heat added in the process AB and heat removed in the
(a) –36 kJ (b) –13 kJ process CA are:
(c) –47 kJ (d) 24 kJ

First Law of Thermodynamics
14. A system absorb 10 kJ of heat at constant volume and its
temperature rises from 27°C to 37°C. The value of U is
(a) 100 kJ (b) 10 kJ
(c) 0 (d) 1 kJ
15. As per the First Law of thermodynamics, which of the (a) qAB = 450 R and qCA = –450 R
following statement would be appropriate : (b) qAB = 450 R and qCA = –225 R
(a) Energy of the system remains constant (c) qAB = 450 R and qCA = –375 R
(b) Energy of the surroundings remains constant (d) qAB = 375 R and qCA = –450 R
(c) Entropy of the universe remains constant 21. An ideal gas receives 10 J of heat in a reversible isothermal
(d) Energy of the universe remains constant expansion. Then the work done by the gas :
16. A sample of liquid in a thermally insulated container (a (a) would be more than 10 J
calorimeter) is stirred for 2 hr. by a mechanical linkage to a (b) 10 J
motor in the surrounding, for this process;
(c) would be less than 10 J
(a) w < 0; q = 0; U = 0 (b) w > 0; q > 0; U > 0
(d) cannot be determined
(c) w < 0; q > 0; U = 0 (d) w > 0; q = 0; U > 0
22. The maximum work obtained by an isothermal reversible
17. For a particular process q = –10 kJ and w=25 kJ. Which of expansion of 1 mole of an ideal gas at 27°C from 2.24 to
the following statements is true? 22.4 L is (R = 2 cal)
(a) Heat flows from the surroundings to the system. (a) – 1381.8 cal (b) – 600 cal
(b) The system does work on the surroundings. (c) –138.18 cal (d) – 690.9 cal
(c) E= –35 kJ 23.
o
2 mole of an ideal gas at 27 C expands isothermally and
(d) None of the above is true reversibly from a volume of 4 litres to 40 litre. The work
done (in kJ) is:
Reversible and Irreversible Work
(a) w = –28.72 kJ (b) w = –11.488 kJ
18. In an isothermal expansion of an ideal gas
(c) w = –5.736 kJ (d) w = –4.988 kJ
(a) q = 0 (b) V = 0
24. 5 mole of an ideal gas expand isothermally and irreversibly
(c) U = 0 (d) w = 0
from a pressure of 10 atm to 1 atm against a constant
19. Two moles of Helium gas undergo a reversible cyclic external pressure of 1 atm. wirr at 300 K is:
process as shown in figure. Assuming gas to be ideal.
(a) –15.921kJ (b) –11.224 kJ
What is the work for the process C to D ?
(c) –110.83 kJ (d) None of these
25. 10 mole of ideal gas expand isothermally and reversibly
from a pressure of 10 atm to 1 atm at 300 K. What is the
largest mass which can lifted through a height of 100 meter?
(a) 31842 kg (b) 58.55 kg
(c) 342.58 kg (d) None of these
(a) –800 Rn2 (b) zero
(c) +200 Rn2 (d) –600 Rn2

26. Which of the following statement is true? 33. During the adiabatic expansion of an ideal gas against
(a) A thermodynamic process is defined by initial and atmospheric pressure, the internal energy will
final states. (a) Increase (b) decrease
(b) E=0 for a reversible phase change at constant T and (c) stay the same (d) Impossible to say
P. 34. One mole of an ideal gas expands reversibly and
(c) q must be zero for an isothermal process. adiabatically from a temperature of 27oC. If the work done
(d) A reversible adiabatic process is also isoentropic. during the process is 3 kJ, then final temperature of the
gas is:(CV = 20 J/K )
27. In the thermodynamic sense of the word, an irreversible
process (a) 100 K (b) 150 K
(a) does the same work (but of opposite sign) as a (c) 195 K (d) 255 K
reversible process Enthalpy of a System
(b) violates the 1st law of thermodynamics, unlike a 35. For a chemical reaction at constant P and V, H is equal to
reversible process
(a) U (b) zero
(c) involves non-ideal gases (as opposed to ideal gases
(c) U + PV (d) p/T
in a reversible process)
36. For an endothermic reaction, S is positive. The reaction
(d) exchanges the same amount of heat (but of opposite
is :
sign) as a reversible process.
(a) feasible when TS > H
Heat Capacity of a System, Adiabatic Process and
(b) feasible when H > TS
Poisson’s Ratio
(c) feasible at all temperatures
28. Molar heat capacity of water in equilibrium with ice at
constant pressure is (d) not feasible at all
(a) zero (b)  37. Which of the following conditions is not favourable for
the feasibility of a process ?
(c) 40.45 kJ K–1 mol–1 (d) 75.48 J K–1 mol–1
(a) H = –ve, TS = –ve and TS < H
29. Ice–Water mass ratio is maintained as 1 : 1 in a given
system containing water in equilibrium with ice at constant (b) H = +ve, TS = +ve and TS > H
–1 –1
pressure. If CP (ice) = CP (water) = 4.18 J mol K molar (c) H = –ve, TS = +ve and H > TS
heat capacity of such a system is (d) H = +ve, TS = +ve and H > TS
(a) Zero (b) Infinity 38. In which of the following cases, the reaction is
–1 –1 –1 –1
(c) 4.182 JK mol (d) 75.48 JK mol spontaneous at all temperatures ?
30. In an adiabatic expansion of an ideal gas (a) H > 0, S > 0 (b) H < 0, S > 0
(a) T = 0 (b) w = 0 (c) H < 0, S < 0 (d) H > 0, S < 0
(c) q = 0 (d) U = 0 39. Which of the following is true for the reaction ?
31. The temperature of the system decreases in an  H2O(g) at 100°C and 1 atm pressure
H2O() 
(a) Isothermal compression (b) Isothermal expansion
(a) S = 0 (b) H = TS
(c) Adiabatic compression (d) Adiabtic expansion
(c) H = U (d) H = 0
32. 1 mole of NH3 gas at 27°C is expanded in reversible adiabatic
condition to make volume 8 times ( = 1.33). Final 40. For the reaction :
temperature and work done by the gas respectively are : C  s   O2  g  
 CO 2  g 
(a) 150 K, 900 cal (b) 150 K, 400 cal (a) H < U (b) H > U
(c) 250 K, 1000 cal (d) 200 K, 800 cal (c) H = U (d) H = 0

41. For which of the following reactions, H is greater than (c) H is +ve, S is –ve
U ?
(a) N2(g) + 3H2(g)  2NH3(g) (d) Both H and S are –ve.
(b) CH4(g) + 2O2(g)   CO2(g) + 2H2O(l) Second Law of Thermodynamics

(c) PCl5(g) 
 PCl3(g) + Cl2(g) 50. The statement “A heat engine always loses some of its
heat energy to the surroundings.” is an example of which
(d) HCl(aq) + NaOH(aq) 
 NaCl(aq) + H2O(aq)
of the following laws?
42. For the reaction,
(a) The Law of Corresponding States
PCl5  g  
 PCl3  g   Cl 2  g 
(b) The Zeroth Law of Thermodynamics
(a) H = U (b) H > U
(c) H < U (d) None of these (c) The First Law of Thermodynamics
43. (U – H) for the formation of NH3 from N2 and H2 is : (d) The Second Law of Thermodynamics
(a) RT (b) 2 RT
51. The entropy of the universe
1
(c) -2 RT (d) RT T (a) tends towards a maximum
2
44. The difference between heats of reaction at constant (b) tends towards a minimum
pressure and constant volume for the reaction.
(c) tends to be zero
2C2H6(l) + 15O2(g) 
 12CO2(g) + 6H2O(l) at 25°C is
(d) remains constant
(a) –7.43 kJ (b) +3.72 kJ
(c) –3.72 kJ (d) 7.43 kJ 52. Heat cannot by self flow from a body at lower temperature
45. For the reaction : to a body at higher temperature a statement of
consequence of:
C2 H 4  g   3O2  g  
 2CO 2  g   2H 2 O   
at 298 K, U = – 1415 kJ. (a) 1st law of thermodynamics
–1
If R = 0.0084 kJ K , then H is equal to (b) 2nd law of thermodynamics
(a) –1400 kJ (b) –1410 kJ
(c) conservation of momentum
(c) –1420 kJ (d) –1430 kJ
46. The difference between H and E on a molar basis for (d) conservation of mass
the combustion of methane gas at 300K (kelvin) would be : 53. When steam condenses to water at 90oC, the entropy of
(a) zero (b) –RT the system decreases. What must be true if the second
(c) –2RT (d) –3RT law of thermodynamics is to be satisfied?
47. Consider the reaction at 300 K (a) Entropy of the universe also decreases.
H2(g) + Cl2 (g) 
 2HCl(g); Hº = –185 kJ (b) Entropy of the surroundings also decreases.
If 2 mole of H2 completely react with 2 mole of Cl2 to form (c) Entropy of the surroundings increases to same extent
HCl. What is U° for this reaction ?
to which entropy of the system decreases.
(a) 0 (b) –185 kJ
(c) 370 kJ (d) –370 kJ (d) Increase in entropy in the surroundings is greater than
decrease in entropy of the system.
48. In an endothermic reaction
(a) H is negative
Entropy and Spontaneity
(b) Heat is given to the surroundings 54. Which of the following has highest entropy ?
(c) Enthalpy of the reactants is less than that of the (a) Mercury (b) Hydrogen
products (c) Water (d) Graphite
(d) E is negative 55. For a reversible process at equilibrium, the change in
entropy may be expressed as :
49 For the process : CO2(s) 
 CO2(g)
q rev
(a) Both H and S are +ve (a) S = Tqrev (b) S 
T
(b) H is –ve, S is +ve H
(c) S   (d) S = G
T

56. Entropy is a measure of  5 

64. When two mole of an ideal gas  Cp,m.  R  heated from
(a) disorder  2 
300 K to 600 K constant pressure. The change in entropy
(b) internal energy of gas (S) is :
(c) efficiency 3 3
(a) R n 2 (b)  R n 2
(d) useful work done by the system 2 2
5
57. When a solid is converted directly into gaseous state, the (c) 5 R n 2 (d) R n 2
process is called sublimation. The entropy change during 2
the process is : 65. In the above question calculate Sgas if process is carried
out at constant volume :
(a) zero (b) negative
3
(c) positive (d) may be negative or zero (a) 5 R n 2 (b) R n 2
2
58. The enthalpy of vaporisation of a substance is (c) 3 R n 2 (d) – 3 R n 2
–1
8400 J mol and its boiling point is –173ºC. The entropy 66. The entropy change when two moles of ideal monoatomic
change for vaporisation is : gas is heated from 200°C to 300°C reversibly and
(a) 84 J mol K
–1 –1
(b) 21 J mol K
–1 –1 isochorically ?
3  300  5  573 
R n  R n 
–1 –1 –1 –1
(c) 49 J mol K (d) 12 J mol K (a)  (b) 
2  200  2  273 
59. The enthalpy of vaporisation of a compound AB at its
 573  3  573 
(c) 3R n  (d) R n 
–1
boiling point (127°C) is 6.4 kJ mol . Its entropy of  
vaporisation is :  473  2  473 
–1 –1
If one mole of an ideal gas  Cp.m.  R  is expanded
(a) 2.56 kJ mol (b) 16 J mol 5
67.
–3
(c) 16 × 10 J mol
–1 3
(d) 1.6 × 10 kJ mol
–1
 2 
60. The entropy change for the conversion of 1 mol of –tin isothermally at 300 K until it’s volume is tripled, then
(at 13°C, 1 atm) to 1 mol of –tin (13°C, 1 atm), if enthalpy change in entropy of gas is :
–1
of transition is 2.095 kJ mol is : (a) zero (b) infinity
5
(c) R n 3
–1 –1 –1 –1
(a) 7.32 J mol K (b) 14.62 J K mol (d) R n 3
–1 –1
2
(c) 56.3 J mol K (d) 0
68. When one mole of an ideal gas is compressed to half of its
61. The following data is known about the melting of a initial volume and simultaneously heated to twice its initial
–1 –1 –1
compound AB. H = 9.2 kJ mol . S = 0.008 kJ K mol . Its temperature, the change in entropy of gas (S) is :
melting point is :
(a) Cp,m ln2 (b) Cv,m ln2
(a) 736 K (b) 1050 K
(c) R ln2 (d) (Cv,m –R) ln2
(c) 1150 K (d) 1150°C
69. Two mole of a monoatomic ideal gas is expanded
62. When potassium chloride is dissolved in water irreversibly and isothermally at T Kelvin until its volume
(a) Entropy increases is doubled and q joules of heat is absorbed from
surrounding. Stotal (J/K) (system + surrounding) is :
(b) Entropy decreases
(a) zero (b) 2 Rln2–q/T
(c) Entropy increases and then decreases
(c) 3Rln2–q/T (d) –2 Rln2 + q/T
(d) Free energy increases
70. One mole of an ideal diatomic gas (Cv = 5 cal) was
63. Which of the following processes is not accompanied by
transformed from initial 25°C and 1 L to the state when
increase of entropy ?
temperature is 100°C and volume 10 L. The entropy change
(a) dissolution of NH4Cl in water of the process can be expressed as (R = 2 calories/mol/K)
(b) burning of rocket fuel 298 373
(a) 3n  2 n10 (b) 5n  2 n10
(c) sublimation of dry ice 373 298
(d) condensing steam 373 1 373 1
(c) 7n  2 n (d) 5n  2 n
298 10 298 10

71. A reaction has H = – 33 kJ and S = +58 J/K. This reaction (a) should always be negative
would be : (b) should always be positive
(a) spontaneous below a certain temperature (c) will be equal to twice the energy of combination
(b) non-spontaneous at all temperature (d) may be positive or negative
(c) spontaneous above a certain temperature 78. Which of the following pairs has heat of neutralisation
(d) spontaneous at all temperature equal to –57.1 kJ ?
72. Calculate the entropy change (J/mol K) of the given (a) HNO3,KOH (b)HCl, NH4OH
reaction. The molar entropies [J/K–mol] are given in (c) H2SO4,NH4OH (d) CH3COOH,NaOH
brackets after each substance.
79. Which of the following neutralisation reactions is most
2 Pb S(s) [91.2] + 3O2(g)[205.1] 
 exothermic ?
(a) HCl and NaOH
2PbO(s) [66.5] + 2SO2(g)[248.2]
(b) HCN and NaOH
(a) –113.5 (b) –168.3
(c) HCl and NH4OH
(c) +72.5 (d) –149.2
(d) CH3COOH and NH4OH
o o
73. Given rS = –266 and listed [ Som values] calculate S for
80. The enthalpy change for the reaction,
Fe3O4(s) :
H 2 O  s  
 H 2 O    is called
4Fe3 O 4 (s)[.......]  O 2 (g)[205]  6Fe 2 O3 (S)[87]
(a) Enthalpy of formation
(a) +111.1 (b) 
(b) Enthalpy of fusion
(c)  (d) 248.25
(c) Enthalpy of vaporisation
Gibb’s Energy, Enthalpy of reactions/processes
(d) Enthalpy of transition
74. For a reaction to be spontaneous at all temperatures
81. The enthalpies of formation of N2O and NO at 298 K are 82
(a) G and H should be negative –1
and 90 kJ mol . The enthalpy of the reaction :
(b) H = G = 0
N 2 O  g   ½O 2  g  
 2NO  g 
(c) G and H should be positive
(d) H < G (a) –8 kJ (b) 98 kJ
75. For isothermal expansion in case of an ideal gas : (c) –74 kJ (d) 8 kJ
(a) G = S (b) G = H 82. The enthalpies of solution of anhydrous CuSO4 and

–1
CuSO4.5H2O are –15.89 and 2.80 k cal mol respectively.
(c) G = – T.S (d) None of these
The enthalpy of hydration of CuSO4 to CuSO4.5H2O is :
76. For the reaction at 300 K
(a) –18.69 kcal (b) 13.09 kcal
A(g) + B(g) 
 C(g) (c) –13.09 kcal (d) 18.69 kcal
U = –3.0 kcal S = –10.0 cal/K 83. Calculate the heat required to make 6.4 Kg CaC2 from CaO(s)
–1
(R  2 cal mol K )
–1 and C(s) from the reaction :
G is : CaO(s) + 3 C(s) 
 CaC2(s) + CO(g) given that
(a) –600 cal (b) –3600 cal
 f H º  CaO  = –151.6 kcal,  f H º  CaC 2  = –14.2kcal.
(c) 2400 cal (d) 3000 cal
77. The enthalpies of elements in their standard states are  f H º  CO  = –26.4 kcal.
taken as zero. Hence the enthalpy of formation of a (a) 5624 kcal
4
(b) 1.11 × 10 kcal
compound 3
(c) 86.24 × 10 (d) 1100 kcal

84. Given : (a) –297.1 kJ (b) 493.7 kJ
H2(g) + ½O2(g)  H2O(g) + q1 (c) –493.7 kJ (d) 297.1 kJ
–2
H2(g) + ½O2(g)  H2O (l) + q2 90. The standard heat of formation at 101.3 kNm and 298 K is
The enthalpy of vaporisation of water is equal to arbitrarily taken to be zero for :
(a) q1 + q2 (b) q1 – q2 (a) gaseous bromine atoms
(c) q2 – q1 (d) q1q2 (b) gaseous bromine molecules

(c) liquid bromine
If CH3COOH + OH 
 CH COO– + H O + x kJ
–
85. 3 2
(d) solid bromine.
H + OH   H O + y kJ
+ –
2
The enthalpy change for the reaction : 91. The enthalpy of formation of two compounds A and B are
–84 kJ and –156 kJ respectively. Which one of the following
CH COOH   CH COO– + H+ is
3 3 statements is correct ?
(a) x + y (b) x – y
(a) A and B are endothermic compounds
(c) y – x (d) x – y/2
(b) A is more stable than B
86. Which of the following reactions represents enthalpy of
(c) A is less stable than B
formation of AgCl ?
(d) Both A and B are unstable
(a) Ag   aq   Cl   aq  
 AgCl  s 
92. When 0.5 g of sulphur is burnt to SO2 4.6 kJ of heat is
1 liberated. What is the enthalpy of formation of sulphur
(b) AgCl  s  
 Ag  s   Cl2  g 
dioxide ?
2
(c) Ag  s   AuCl  s  
 AgCl  s   Au  s  (a) –147.2 kJ (b) +147.2 kJ
(c) +294.4 kJ (d) –294.4 kJ
1
(d) Ag  s   Cl2  g  
 AgCl  s  . 93.
–1
The heat of formation of Fe2O3(s) is –824.2 kJ mol . H for
2
the reaction.
87. Which of the following equations represents standard heat
of formation of methane ? 2Fe2 O3  s  
 4Fe  s   3O2  g  is :
(a) C (diamond) + 2H2(g) 
 CH4(g) (a) –412.1 kJ (b) –1648.4 kJ
(b) C (graphite) + 2H2(g) 
 CH4(g) (c) –3296.8 kJ (d) 1648.4 kJ

(c) C (diamond) + 4H(g)  94. The H for the reaction,
 CH4(g)
(d) C (graphite) + 4H(g) 
 CH4(g) 4S(s) + 6O2 (g) 
 4 SO3(g)
88. For the reaction, is –1583.2 kJ. Standard enthalpy of formation of sulphur
trioxide is :
2H 2 O  g  
 2H 2  g   O 2  g  H = 571.6 KJ
(a) –3166.4 kJ (b) 3166.4 kJ
f H of water is : (c) –395.8 kJ (d) 395.8 kJ
(a) 285.8 kJ (b) –285.8 kJ 95. Calculate the heat of formation of PCl5(s) from the following
(c) 1143.2 kJ (d) –1143.2 kJ data :
89. H for the reaction, 2P(s) + 3Cl2(g)   2PCl3(l) H = –151.8 kcal
1 PCl3(l) + Cl2(g) 
 PCl (s) H = –32.8 kcal
 SO3  g 
SO 2  g   O 2  g   H = –98.3 kJ
5
2 (a) –108.7 kcal (b) 108.7 kcal

If the enthalpy of formation of SO3(g) is –395.4 kJ then the (c) –184.6 kcal (d) 184.6 kcal
enthalpy of formation of SO2(g) is :

102. The enthalpy of neutralisation of NH4OH and HCl is :

96. If S + O2 
 SO2 H = –298.2 kJ –1 –1
(a) 57.1 kJ mol (b) < 57.1 kJ mol
1
SO 2  O 2 
 SO3 H = –98.2 kJ (c) > 57.1 kJ mol
–1
(d) zero
2 –1
103. The heat of neutralisation of NaOH and HCl is 57.3 kJ mol .
 H 2SO4 H = –130.2 kJ
SO3  H 2 O 
The amount of heat liberated when 0.25 mol of H2SO4 reacts
1 with 1 mole of NaOH is
H 2  O 2   H2O H = –287.3 kJ
2 (a) 57.3 kJ (b) 14.325 kJ
the enthalpy of formation of H2SO4 at 298 K will be (c) 28.65 kJ (d) 114.6 kJ
(a) –433.7 kJ (b) –650.3 kJ 104. The heat of neutralisation of strong base and strong acid
(c) +320.5 kJ (d) –813.9 kJ is 57.0 kJ. The heat released when 0.5 mol of HNO3 is
97. The enthalpies of combustion of carbon and carbon added to 0.2 mol of NaOH solution is :
–1
monoxide are –393.5 and –283.0 kJ mol respectively. The (a) 57.0 kJ (b) 11.40 kJ
enthalpy of formation of carbon monoxide is : (c) 28.5 kJ (d) 34.9 kJ
(a) –676.5 kJ (b) 110.5 kJ 105. In which of the following neutralisation reaction, the heat
(c) –110.5 kJ (d) 676.5 kJ of neutralisation will be highest ?
98. On combustion, carbon forms two oxides CO and CO2. (a) NH4OH and H2SO4 (b) HCl and NaOH
Heat of formation of CO2 is –393.5 kJ and that of CO is – (c) CH3COOH and KOH (d) CH3COOH and NH4OH
110.5 kJ. Heat of combustion of CO is :
106. The enthalpies of neutralization of a weak base AOH and
(a) –393.5 kJ (b) –504.0 kJ a strong base BOH by HCl are –12250 cal/mol and –13000
(c) –283.0 kJ (d) 2830.0 kJ cal/mol respectively. When one mole of HCl is added to a
99. Which of the following compounds will absorb maximum solution containing 1 mole of AOH and 1 mole of BOH,
the enthalpy change was –12500 cal/mol. In what ratio is
quantity of heat when dissolved in the same amount of
the acid distribution between AOH and BOH?
water. The enthalpies of solution of these compounds at
(a) 2:1 (b) 2:3
25°C in kJ/mole are given in brackets ?
–1 –1 (c) 1:2 (d) None of these
(a) P (H = –32.6 kJ mol ) (b) Q (H = –17.3 kJ mol )
–1 –1 107. In what proportion 1 M NaOH and 0.5M H2SO4 are mixed
(c) R (H = +2.56 kJ mol ) (d) S (H = +25.6 kJ mol )
so as to release maximum amount of energy and to form
100. Which of the following salts will have maximum cooling 100 mL solution ?
effect when 0.5 mole of the salt is dissolved in same amount
(a) 33 and 67 (b) 67 and 33
of water. Integral heat of solution at 298 K is given for
each salt ? (c) 40 and 60 (d) 50 and 50
(a) KNO3
–1
(H = 35.4 kJ mol ) 108. The enthalpies of combustion of rhombic sulphur and
–1
–1 monoclinic sulphur are –295.1 and –296.4 kJ mol
(b) NaCl (H = 5.35 kJ mol )
respectively. The enthalpy of allotropic transformation of
–1
(c) HBr (H = –83.3 kJ mol ) monoclinic to rhombic sulphur is :
–1
(d) KOH (H = –55.6 kJ mol ) (a) 1.3 kJ (b) –1.3 kJ
101. The enthalpy of neutralisation of HCl by NaOH is –57.1 kJ (c) –591.5 kJ (d) 0
–1
and that of HCN by NaOH is –12.1 kJ mol . The enthalpy
109. Which of the following enthalpies is always negative ?
of ionization of HCN is :
(a) Enthalpy of solution
(a) –69.2 kJ (b) –45.0 kJ
(b) Enthalpy of combustion
(c) 69.2 kJ (d) 45.0 kJ
(c) Enthalpy of sublimation
(d) Enthalpy of formation

–1 –1
110. In the reaction : (a) 498 kJ mol (b) 463 kJ mol
–1 –1
CO 2  g   H 2  g  
 CO  g   H 2 O  g  H = 2.8 kJ (c) 428 kJ mol (d) 70 kJ mol
115. Calculate the heat of the reaction
then H represents
(a) heat of formation (b) heat of reaction CH2 = CH2(g) + H2(g) 
 CH3CH3(g)
(c) heat of solution (c) heat of combustion given that bond energy of C – C, C = C, C – H and H – H is
111. Using the following energy values, determine the lattice 80, 145, 98 and 103 kcal.
–1 –1
energy of KF(s): (a) –28 kcal mol (b) –5.6 kcal mol
–1 –1 –1
Property Energy (kJ mol ) (c) –2.8 kcal mol (d) –56 kcal mol
Hatomization of K(s) 90 116. The enthalpy change for the following reaction is 368 kJ.
Hatomization of F2(s) 158 Calculate the average O–F bond energy.
Hf of KF(s) –567 OF2 (g)  O(g)  2F(g)
IE of K(s) 419 (a) 184 kJ/mol (b) 368 kJ/mol
EA of F(g) 328 (c) 536 kJ/mol (d) 736 kJ/mol
(a) 51 kJ (b) + 827 kJ 117. The enthalpy change for the reaction,
(c) + 1145 kJ (d) + 1483 kJ C2H6(g)  2C(g) + 6H(g) is X kJ. The bond energy of C–H
112. The lattice enthalpy and hydration enthalpy of four bond is:
compounds are given below: X X
(a) (b)
Compound Lattice enthalpy Hydration enthalpy 2 3
X
(kJ/mol) (kJ/mol) (c) (d) data insufficient
6
P +780 –920 o
118. Based on the values of B.E. given, fH of N2H4(g) is:
Q +1012 –812 –1 –1
Given: N–N = 159 kJ mol ; H–H = 436 kJ mol
R +828 –878
N  N = 941 kJ mol , N–H = 398 kJ mol
–1 –1
S +632 –600 –1 –1
(a) 711 kJ mol (b) 62 kJ mol
The pair of compounds which is soluble in water is –1 –1
(c) –98 kJ mol (d) –711 kJ mol
(a) P and Q (b) Q and R
119. The dissociation energy of CH4 and C2H6 are respectively
(c) R and S (d) P and R 360 and 620 kcal/mole. The bond energy of C–C is
Bond Dissociation Enthalpy (a) 260 k cal/mole (b) 180 k cal/mole
113. The standard enthalpies of formation of HCl(g), H(g) and (c) 130 k cal/mole (d) 80 k cal/mole
–1
Cl(g) are –92.2, 217.7 and 121.4 kJ mol respectively. The 120. An imaginary reaction X  Y takes place in three steps
bond dissociation energy of HCl is :
X  A, H = –q1; B  A, H = –q2, B  Y,, H = –q3
(a) +431.3 kJ (b) 236.9 kJ
If Hess’ law is applicable, then the heat of the reaction
(c) –431.3 kJ (d) 339.1 kJ (X  Y) is:
114. The enthalpy changes at 25°C in successive breaking of (a) q1–q2+q3 (b) q2–q3–q1
O–H bonds of water are :
(c) q1–q2–q3 (d) q3–q2–q1
H2O(g) 
 H(g) + OH(g) H = 498 kJ mol–1
OH(g) 
 H(g) + O(g) –1
H = 428 kJ mol
the bond enthalpy of the O–H bond is :

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

1. A reaction is non-spontaneous at the freezing point of 7. The enthalpy change for a reaction does not depend upon
water but is spontaneous at the boiling point of water, the (2003)
then (2002)
(a) physical state of reactants and products
H S
(b) use of different reactants for the same product
(a) + ve + ve
(c) nature of intermediate reaction steps
(b) – ve – ve
(d) difference in initial or final temperatures of involved
(c) – ve + ve substances
(d) + ve – ve 8. The enthalpies of combustion of carbon and carbon
2. A heat engine absorbs heat q1 from a source at temperature monoxide are – 393.5 and – 283 kJ mol–1 respectively. The
T1 and heat q2 from a source at temperature T2. Work done enthalpy of formation of carbon monoxide per mole is
is found to be J (q1 + q2). This is in accordance with (2004)
(2002) (a) 110.5 kJ (b) 676.5 kJ
(a) First law of thermodynamics (c) – 676.5 kJ (d) – 110.5 kJ
(b) Second law of thermodynamics 9. An ideal gas expands in volume from 1 × 10–3 m3 to
(c) Joules equivalent law 1 × 10–2 m3 at 300 K against a constant pressure of
1 × 105 Nm–2. The work done is (2004)
(d) None of the above
(a) – 900 J (b) – 900 kJ
3. Heat required to raise the temperature of 1 mole of a
substance by 1º is called (2002) (c) 270 kJ (d) 900 kJ
(a) specific heat (b) molar heat capacity 10. For a spontaneous reaction the G, equilibrium constant
(K) and Eºcell will be respectively (2005)
(c) water equivalent (d) specific gravity
(a) –ve, >1, –ve
4. The correct relationship between free energy change in a
reaction and the corresponding equilibrium constant Kc is (b) –ve, <1, –ve
(2003) (c) +ve, >1, –ve
(a) G = RT ln Kc (b) –G = RT ln Kc (d) –ve, >1, + ve
(c) Gº = RT ln Kc (d) – Gº = RT ln Kc 11. If the bond dissociation energies of XY, X2 and Y2 (all
diatomic molecules) are in the ratio of 1 : 1 : 0.5 and Hf for
5. If at 298 K the bond energies of C—H, C—C, C C and
the formation of XY is –200 kJ mol–1. The bond dissociation
H—H bonds are respectively, 414, 347, 615 and
energy of X2 will be (2005)
435 kJ mol–1, the value of enthalpy change for the reaction,
(a) 400 kJ mol–1 (b) 300 kJ mol–1
H2C CH2(g) + H2(g) H3C —CH3(g) at 298 K will be
(2003) (c) 800 kJ mol–1 (d) None of these
(a) + 250 kJ (b) – 250 kJ 12. Consider the reaction : N2 + 3H2  2NH3 carried out at
constant temperature and pressure. If H and E are the
(c) + 125 kJ (d) – 125 kJ
enthalpy and internal energy changes for the reaction,
6. The internal energy change when a system goes from state which of the following expressions is true ? (2005)
A to B is 40 kJ/mol. If the system goes from A to B by a
(a) H > E
reversible path and returns to state A by an irreversible
path, what would be the net change in internal energy ? (b) H < E
(2003) (c) H = E
(a) 40 kJ (b) > 40 kJ (d) H = 0
(c) < 40 kJ (d) zero

13. The standard enthalpy of formation (Hºf) at 298 K for Sº do not change with temperature, temperature above
methane, CH4(g) is – 74.8 kJ mol–1. which conversion of limestone to lime will be spontaneous
The additional information required to determine the is (2007)
average energy for C—H bond formation would be (a) 1008 K (b) 1200 K
(2006) (c) 845 K (d) 1118 K
(a) the dissociation energy of H 2 and enthalpy of 18. Identify the correct statement regarding a spontaneous
sublimation of carbon process. (2007)
(b) latent heat of vaporisation of methane (a) For a spontaneous process in an isolated system, the
(c) the first four ionisation energies of carbon and electron change in entropy is positive
gain enthalpy of hydrogen (b) Endothermic processes are never spontaneous
(d) the dissociation energy of hydrogen molecule, H2 (c) Exothermic processes are always spontaneous
14. The enthalpy changes for the following processes are listed (d) Lowering of energy in the reaction process is the only
below : criterion for spontaneity
Cl2 (g)  2Cl(g), 242.3 kJ mol–1 19. Assuming that water vapour is an ideal gas, the internal
I2(g)  2I(g), 151.0 kJ mol–1 energy change (E) when 1 mole of water is vaporised at 1
ICl (g)  I(g) + Cl (g), 211.3 kJ mol–1 bar pressure and 100ºC, (Given : molar enthalpy of
vaporisation of water at 1 bar and 373 K = 41 KJ mol–1 and
I2(s)  I2(g), 62.76 kJ mol–1
R = 8.3 J mol–1 K–1) will be (2007)
Given that the standard states for iodine and chlorine are
(a) 4.100 kJ mol–1 (b) 3.7904 kJ mol–1
I2(s) and Cl2(g), the standard enthalpy of formation of
ICl (g) is (2006) (c) 37.904 kJ mol–1 (d) 41.00 kJ mol–1
(a) – 14.6 kJ mol–1 (b) – 16.8 kJ mol–1 20. Standard entropy of X2, Y2 and XY3 are 60, 40 and
50 JK–1 mol–1, respectively. For the reaction,
(c) + 16.8 kJ mol–1 (d) + 244.8 kJ mol–1
15. (H – E) for the formation of carbon monoxide (CO) from 1 3
X 2  Y2  XY3 , H   30 kJ, to be at equilibrium,
its elements at 298 K is (R=8.314 JK–1 mol–1) (2006) 2 2
(a) – 1238.78 J mol–1 the temperature will be (2008)
(b) 1238.78 J mol–1 (a) 1250 (b) 500 K
(c) – 2477.57 J mol–1 (c) 750 K (d) 1000 K
(d) 2477.57 J mol–1 21. Oxidising power of chlorine in aqueous solution can be
determined by the parameters indicated below :
16. An ideal gas is allowed to expand both reversibly and
irreversibly in an isolated system. If T i is the initial 1 o
1  H  EA Ho
2 diss  Cl(g) 
Cl2 (g)  
temperature and Tf is the final temperature, which of the
2
following statements is correct ? (2006)
 Ho 
(a) (Tf)irrev > (Tf)rev Cl (g) 
hyd
 Cl (aq)
(b) Tf > Ti for reversible process but Tf = Ti for irreversible 1
The energy involved in the conversion of Cl (g) to
process 2 2
o
(c) (Tf)rev = (Tf)irrev Cl– (aq) will be (using the data, diss H Cl2  240 kJ mol 1
o 1
(d) Tf = Ti for both reversible and irreversible processes  EA HoCl  349kJ mol1 ,  hyd H Cl  381 kJ mol )
17. In conversion of limestone to lime, (2008)
CaCO3(s)  CaO (s) + CO2 (g) (a) + 152 kJ mol–1 (b) – 610 kJ mol–1
the values of Hº and Sº are + 179.1 kJ mol–1 and 160.2 J/K (c) – 850 kJ mol–1 (d) + 120 kJ mol–1
respectively at 298 K and 1 bar. Assuming that Hº and

22. On the basis of the following thermochemical data 27. The value of enthalpy change (H) for the reaction
[Gº H+ (aq) = 0] C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l),
 H (aq) + OH (aq); H = 57.32 kJ
H2O(l)  + –
at 27ºC is – 1366.5 kJ mol–1. The value of internal energy
1 change for the above reaction at this temperature will be
H2(g) + O (g) 
2 2  H2O(l); H = – 286.02 kJ
(2011)
The value of enthalpy of formation of OH– ion at 25ºC is
(a) – 1371.5 kJ (b) – 1369.0 kJ
(2009)
(c) – 1364.0 kJ (d) – 1361.5 kJ
(a) – 22.88 kJ (b) – 228.88 kJ 28. The entropy change involved in the isothermal reversible
(c) + 228.88 kJ (c) – 343.52 kJ expansion of 2 moles of an ideal gas from a volume of
23. In a fuel cell methanol is used as fuel and oxygen gas is 10 dm3 to a volume of 100 dm3 at 27º C is (2011)
3 (a) 38.3 J mol–1K–1 (b) 35.8 J mol–1K–1

used as an oxidiser. The reaction is CH3OH(l) + O (g)
2 2 (c) 32.3 J mol–1K–1 (d) 42.3J mol–1K–1
  CO2(g) + 2H2O(l). At 298 K standard Gibb’s energies 29. For complete combustion of ethanol,
of formation for CH3OH(l), H2O (l) and CO2(g) are – 166.2,
C2 H5 OH(l )  3O 2 (g)  2CO 2 (g)  3H 2 O(l ),
–237.2 and –394.4 kJ mol –1 respectively.
If standard enthalpy of combustion of methanol is the amount of heat produced as measured in bomb
– 726 kJ mol–1, efficiency of the fuel cell will be (2009) calorimeter, is 1364.47 kJ mol–1 at 25ºC. Assuming ideality
(a) 80% (b) 87% the Enthalpy of combustion,  CH, for the reaction will be:
(c) 90% (d) 97%
(R = 8.314 kJ mol–1) (2014)
24. For a particular reversible reaction at temperature T, H
and S were found to be both +ve. If Te is the temperature (a) –1361.95 kJ mol–1 (b) –1460.50 kJ mol–1
at equilibrium, the reaction would be spontaneous when (c) – 1350.50 kJ mol–1 (d) – 1366.95 kJ mol–1
(2010) 30. The standard enthalpy of formation of NH3 is –46.0 kJ
(a) Te > T (b) T > Te mol–1. If the enthalpy of formation of H2 from its atoms is
(c) Te is 5 times T (d) T = Te –436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the average
25. The standard enthalpy of formation of NH3 is – 46.0 kJ mol .
–1
bond enthalpy of N — H bond in NH3 is:
If the enthalpy of formation of H 2 from its atoms is
(Online 2014 Set - 1)
– 436 kJ mol–1 and that of N2 is –712 kJ mol–1, the average
bond enthalpy of N—H bond in NH3 is (2010) (a) – 1102 kJ mol–1 (b) – 964 kJ mol–1
(a) – 964 kJ mol–1 (b) + 352 kJ mol–1 (c) + 352 kJ mol–1 (d) + 1056 kJ mol–1
(c) + 1056 kJ mol–1 (d) – 1102 kJ mol–1 31. The molar heat capacity (Cp) of CD2O is 10 cals at 1000K.
26. Consider the reaction The change in entropy associated with cooling of 32g
4NO2(g) + O2(g)  2N2O5(g), rH = – 111 kJ. If N2O5(s) is of CD2O vapour from 1000 K to 100 K at constant
formed instead of N2O5(g) in the above reaction, the rH pressure will be: (Online 2014 Set - 2)
value will be
(D = deuterium, at. Mass = 2 u)
(Given, H of sublimation for N2O5 is 54 kJ mol–1) (2011)
(a) 2.303 cal deg–1 (b) 23.03 cal deg–1
(a) – 165 kJ (b) + 54 kJ
(c) –23.03 cal deg–1 (d) –2.303 cal deg–1
(c) +219 kJ (d) – 219 kJ

32. The entropy (So) of the following substances are: 37. For a reaction, A(g)  A(l); H = –3RT. The correct
CH4 (g) 186.2 J K–1 mol–1 statement for the reaction is : (Online 2017 Set - 1)
O2 (g) 205.0 J K–1 mol–1 (a)  H =  U  0 (b)  H =  U = 0
CO2 (g) 213.6 J K–1 mol–1 (c)  H <  U (d) H > U
H2O (l) 69.9 J K mol
–1 –1
38. What is the value of change in internal energy at 1 atm
The entropy change (S ) for the reaction
o in the process?
CH4(g) + 2O2(g)  CO2(g) + 2H2O (l) is: H 2 O(, 323K)  H 2 O(g, 423K)
(Online 2014 Set - 2) Given :
(a) –37.6 J K–1 mol–1 (b) –312.5 J K–1 mol–1
C v,m (H 2 O, )  75.0 JK 1mol1 ;
(c) –242.8 J K–1 mol–1 (d) –108.1 J K–1 mol–1
33. The H and S for a reaction at one atmospheric pressure Cp,m (H 2 O, g)  33.314 JK 1mol1 ;
are +30.558 kJ and 0.066 kJk–1 respectively. The temperature
at which the free energy change will be zero and below of Hvap at 373 K = 40.7 kJ/mol (Online 2017 Set - 1)
this temperature the nature of reaction would be
(a) 42.91 kJ/mol (b) 43086 kJ/mol
(c) 42.6 kJ/mol (d) 49.6 kJ/mol
(a) 483 K, spontaneous (b) 443 K, spontaneous
39. An ideal gas undergoes isothermal expansion at constant
(c) 463 K, spontaneous (d) 463 K, non-spontaneous
pressure. During the process :
34. A reaction at 1 bar is non-spontaneous at low temperature
but becomes spontaneous at high temperature. Identify
the correct statement about the reaction among the (a) enthalpy increases but entropy decreases.
following : (Online 2016 Set - 1) (b) enthalpy remains constant but entropy increases.
(a) Both “H and “S are negative. (c) enthalpy decreases but entropy increases.
(b) Both “H and “S are positive. (d) Both enthalpy and entropy remain constant.
(c) “H is positive while “S is negative. 40. A gas undergoes change from state A to state B. In this
(d) “H is negative while “S is positive process, the heat absorbed and work done by the gas is
5J and 8J, respectively. Now gas is brought back to A by
35. For the reaction, A(g) + B(g)  C(g) + D(g), H° and S°
another process during which 3J of heat is evolved. In
are respectively, –29.8 kJ mol–1 and –0.100 kJ K–1 mol–1 at
this reverse process of B to A : (Online 2017 Set - 2)
298 K. The equilibrium constant for the reaction at
298 K is : (Online 2016 Set - 1) (a) 10J of the work will be done by the gas.
(a) 1.0 × 10–10 (b) 1.0 × 1010 (b) 6J of the work will be done by the gas.
(c) 10 (d) 1 (c) 10J of the work will be done by the surrounding on
gas.
36. lf 100 mole of H2O2 decompose at 1 bar and 300 K, the
work done (kJ) by one mole of O2(g) as it expands against (d) 6J of the work will be done by the surrounding on
1 bar pressure is : gas.
 2H 2 O(l)  O2 (g) (R  8.3 JK 1 mol 1 ) 41. U is equal to : (2017)

2H 2 O2 (l) 
(Online 2016 Set- 2) (a) Isobaric work (b) Adiabatic work
(a) 62.25 (b) 124.50 (c) Isothermal work (d) Isochoric work
(c) 249.00 (d) 498.00

42. Given 46. fG0 at 500 K for substance ‘S’ in liquid state and gaseous
state are +100.7 kcal mol -1 and +103 kcal mol -1 ,
C(graphite) + O2 (g)  CO2(g) ; rH° = –393.5 kJ mol–1 respectively. Vapour pressure of liquid ‘S’ at 500 K is
approximately equal to : (R = 2 cal K-1 mol-1)
1
H 2 (g)  O 2 (g)  H 2 O(l); rH° = – 285.8 kJ mol–1 (Online 2018 Set - 2)
2
(a) 0.1 atm (b) 1 atm
CO2(g) + 2H2O(l)  CH4(g) + 2O2(g);
(c) 10 atm (d) 100 atm
rH° = +890.3 kJ mol–1
47. Given
Based on the above thermochemical equations, the (i) 2Fe2O3(s)  4Fe(s) + 3O2(g); rG0
value of rH° at 298 K for the reaction = + 1487.0 kJ mol-1
C(graphite) + 2H2(g)  CH4(g) will be : (2017) (ii) 2CO(g) + O2(g)  2CO2(g) ; = -514.4 kJ mo l-1
(a) + 144.0 kJ mol –1
(b) –74.8 kJ mol –1 Free energy change, for the reaction
(c) –144.0 kJ mol –1
(d) +74.8 kJ mol–1 2Fe2O3(s) + 6CO(g)  4Fe(s) + 6CO2(g) will be :
43. The combustion of benzene (I) gives CO2(g) and H2O(l). (a) -112.4 kJ mol-1 (b) -56.2 kJ mol-1
Given that heat of combustion of benzene at constant (c) -168.2 kJ mol-1 (d) -208.0 kJ mol-1
volume is –3263.9 kJ mol–1 at 25°C; heat of combustion (in 48. For which of the following processes, S is negative ?
kJ mol ) of benzene at constant pressure will be:
–1
(R = 8.314 JK–1 mol–1) (2018) (a) H2(g)  2H(g)

(b) N2(g, 1 atm)  N2(g, 5 atm)
(a) – 3267.6 (b) 4152.6
(c) C(diamond)  C(graphite)
(c) –452.46 (d) 3260 (d) N2(g, 273 K)  N2(g, 300 K)
44. For which of the following reactions, H is equal to U? 49. At 320 K, a gas A2 is 20 percent dissociated to A(g).
(Online 2018 Set - 1) The standard free energy change at 320 K and 1 atm in
J mol-1 is approximately :
(a) N2(g) + 3H2(g)  2NH3(g)
(R=8.314 JK–1 mol–1; ln 2=0.693; ln 3=1.098)
(b) 2HI(g)  H2(g)  l2(g)
(c) 2NO2(g)  N2O4(g)
(a) 4763 (b) 2068
(d) 2SO2(g) + O2(g) 2SO3(g)
(c) 1844 (d) 4281
45. An ideal gas undergoes a cyclic process as shown in
Figure. 50. Consider the reversible isothermal expansion of an ideal
gas in a closed system at two different temperatures T1
and T2(T1 < T 2). The correct graphical depiction of the
dependence of work done (w) on the final volume (V)
is: (2019)
UBC = –5 kJ mol–1, qAB = 2 kJ mol–1

(a) (b)
WAB = –5 kJ mol–1, WCA = 3 kJ mol–1
Heat absorbed by the system during process CA is :
(a) -5 kJ mol -1
(b) +5 kJ mol-1
(c) 18 kJ mol-1 (d) -18 kJ mol-1 (c) (d)


 T1  T2  2 
51. The entropy change associated with the conversion of 1
  T1  T2  2  
C ln
1 kg of ice at 273 K to water vapours at 383 K is: (a) p  4T T 
C ln (b) p  4T T 
 1 2   1 2

(Specific heat of water liquid and water vapour are 4.2 kJ
K–1 kg–1 and 2.0 kJ K–1 kg–1: heat of fusion and   T1  T2     T1  T2  
(c) 2C p ln  4T T  (d) 2C p ln  2T T 
vaporisation of water are 334 kJ kg–1 and 2491 kJ kg–1.  1 2   1 2 
respectively). (2019) 56. For the chemical reaction X  Y the standard

reaction Gibbs energy depends on temperature T(in K)
(log 273 = 2.436, log 373 = 2.572, log 383= 2.583) 3
as  r Gº  ln kJmol   120  T .
1
(a) 790kJ kg 1 K 1 (b) 2.64kJ kg 1 K 1 8

The major component of the reaction mixture at T is:
(c) 8.49kJ kg 1 K 1 (d) 9.26kJ kg 1 K 1 (2019)
(a) Y if T = 300 K (b) Y if T = 280 K
52. A process has H  200J mol 1 and
(c) X if T = 350 K (d) X if T = 315 K
S  40J K 1 mol 1 . Out of the values given below,,
choose the minimum temperature above which the 57. The reaction MgO  s   C  s   Mg  s   CO  g  , for
process will be spontaneous: (2019)
which Hº  491.1kJ mol –1 and Sº  198.0 K 1 mol –1 ,
(a) 20 K (b) 12 K
is not feasible at 298 K. Temperature above which
(c) 5 K (d) 4 K reaction will be feasible is
53. The process with negative entropy change is: (2019) (2019)
(a) 2040.5 K (b) 1890.0 K
(a) Dissociation of CaSO4(s) to CaO(s) and SO3(g)
(c) 2480.3 K (d) 2380.5 K
(b) Sublimation of dry ice
58. The standard reaction Gibbs energy for a chemical
(c) Dissolution of iodine in water
reaction at an absolute temperature T is given
(d) Synthesis of ammonia from N2 and H2
by  r G o  A  BT Where A and B are non-zone
54. An ideal gas undergoes isothermal compression from 5 constants. Which of the following is TRUE about this
m3 to 1 m3 against a constant external pressure of reaction? (2019)
4 Nm–2. Heat released in this process is used to increase (a) Exothermic if B < 0
the temperature of 1 mole of Al. If molar heat capacity of
(b) Endothermic if A > 0
Al is 24J mol–1 K–1 the temperature of Al increases by:
(c) Endothermic if A < 0 and B < 0
(2019)
(d) Exothermic if A > 0 and B < 0
3
(a) K (b) 2 K
2 59. Which one of the following equations does not
2 correctly represent the first law of thermodynamics for
(c) K (d) 1 K
3
the given processes involving an ideal gas? (Assume
55. Two blocks of the same metal having same mass and at
non-expansion work is zero) (2019)
temperature T1, and T2, respectively, are brought in
(a) Cyclic process: q = –w
contact with each other and allowed to attain thermal
equilibrium at constant pressure. The change in (b) Adiabatic process: U   w
entropy, S , for this process is: (2019) (c) Isochoric process: U  q
(d) Isothermal process: q   w

60. 5 moles of an ideal gas at 100 K are allowed to undergo (a) 2.85 (b) 5.7
reversible compression till its temperature becomes 200 (c) 22.8 (d) 11.4
K. If Cv = 28J K–1 mol–1, calculate and for this process. 66. If enthalpy of atomisation for Br2(l) is x kJ /mol and bond
(R = 8.0 Jk–1 mol–1) (2019) enthalpy for Br2 is y kJ/mol, the relation between them :
(a) U  14kJ;   pV   18 kJ (2020)
(b) U  14kJ;   pV   0.8kJ (a) is x > y (b) is x < y

(c) is x = y (d) does not exist
(c) U  14kJ;   pV   4 kJ
67. The true satement amongst the following (2020)
(d) U  14kJ;   pV   8.0 kJ
(a) S is a function of temeprature but S is not a function
61. Among the following, the set of parameters that of temperature
represents path functions, is: (2019) (b) Both S and S are functions of temperature
I. q + w II. q (c) Both S and S are not functions of temperature
III. w IV. H – TS (d) S is not a function of temperature but S is a function
of temperature
(a) II and III (b) II, III and IV
68. For one mole of an ideal gas, which of these statements
(c) I and IV (d) I, II and III must be true? (2020)
62. During compression of a spring the work done is 10 kJ (i) U and H each depends only on temeprature.
and 2 kJ escaped to the surroundings as heat. The (ii) Compressiblity factor z is not equal to 1
change in internal energy, U (in kJ) is: (2019) (iii) Cp.m - Cv,m = R
(a) –12 (b) –8 (iv) du = CvdT for any process

(a) (i), (iii) and (iv) (b) (i) and (iii)
(c) 8 (d) 12
(c) (iii) and (iv) (d) (ii), (iii) and (iv)
63. A process will be spontaneous at all temperature if:
69. The process that is not endothermic in nature is: (2020)
(2019)
(a) H (g)  e   H (g)

(a) H  0and S  0  
(b) Na (g)  Na (g ) e
(b) H  0 and S  0
(c) Ar(g)  e   Ar(g)

(c) H  0and S  0 
(d) O(g)  e   O(g)
2
(d) H  0 and S  0
Numerical Value Type Questions
64. The difference between H and U  H  U  , 70. For the reaction A(l)  2B(g)
when the combustion of one mole of heptane(l) is
carried out at a temperature T, is equal to: (2019) U  2.1kcal, S  20 Cal K 1 at 300 K, Hence G in
kcal (numeric value) is (2020)
(a) –4 RT (b) –3 RT
71. The standard heat of formation ( f H 298o ) of ethane (in
(c) 4 RT (d) 3 RT
kJ/mol), if the heat of combustion of ehtane, hydrogen
65. Enthalpy of sublimation of iodine is 24 cal g–1 at 200oC. and graphite are -1560, -393.5 and -286 kJ/mol, respectively,
If specific heat of I2(s) and I2(vap) are 0.055 and 0.031 is __________. (2020)
cal g–1 K–1 respectively, then enthalpy of sublimation of
iodine at 250oC in cal g–1 is: (2019)

72. The magnitude of work done by gas that undergoes a 3

reversible expansion along the path ABC shown in figure NH 2 CN(s)  O2 (g)  N 2 (g)  O 2 (g)  H 2 O(l)
2
is ________. (2020) is _____ kJ. (Rounded off to the nearest integer)
[Assume ideal gas and R = 8.314 J mol-1 K-1]
(2021-02-25/Shift - 1)
79. Five moles of an ideal gas at 293 K is expanded isothermally
from an initial pressure of 2.1 MPa to 1.3 Mpa against at
constant external pressure 4.3 MPa. The heat transferred
73. At constant volume, 4 mol of an ideal gas when heated in this process is ______ kJ mol-1. (Rounded-off to the
from 300 to 500 K changes its internal energy by 5000 J. nearest integer) [Use R = 8.314 J mol-1 K-1]
The molar heat capacity at constant volume is _____ . (2021-02-25/Shift - 2)
(2020) 80.  C  D
For a chemical reaction A  B 
74. The internal energy change (in J) when 90 g of water
unergoes complete evaporation at 100oC is (  r H  80 kJ mol1 ) the entropy change  r S
depends on the temperature T (in K) as
(Given : H vap for water at 373 K = 41 kJ / mol, R = 8.314  r S  2T(JK 1mol1 ).
JK-1 mol-1) (2020) Minimum temperature at which it will become
75. The heat of combution of ethanol into carbon dioxide and sponatneous is ________ K. (Integer)
water is -327 kcal at constant pressure. The heat evolved (2021-02-26/Shift - 1)
(in cal) at constant volume and 27oC (if all gases behave
81. The
Theaverage
averageS-F
S- Fbond
bondenergy
energyininkJ
kJmol
mol-1-1 of SF6 is ______.
ideally) is (R = 2 cal mol-1 K-1) .......... . (2020)
(Rounded off to the nearest integer)
76. For a dimerization reaction, 2A(g)  A 2 (g) at 298 K, [Given : The values of standard enthalpy of formation of
 1
U  20 kJ mol , S  30 kJ mol , 1
then the SF6(g), S(g) and F(g) are -1100, 275 and 80 kJ mol-1
respectively.] (2021-02-26/Shift - 2)
G  will be ....... j. (2020)
82. At 25oC, 50 g of iron reacts with HCl to form FeCl2, The
77. During which of the following processes, does entropy evolved hydrogen gas expands against a constant
decrease? pressure of 1 bar. The work done by the gas during this
(A) Freezing of water to ice at 0oC expansion is (Round off to the Nearest Integer).
(B) Freezing of water to ice at - 10oC [Given : R = 8.314 J mol-1 K-1. Assume, hydrogen is an
ideal gas] (2021-03-16/Shift - 2)
(C) N 2 (g)  3H 2 (g)  2NH 3 (g)
[Atomic mass of Fe is 55.85 u]
(D) Adsorption of CO(g) on lead surface.
83. The standard enthalpies of formation of Al2O3 and CaO
 
(E) NaCl(s)  Na (aq)  Cl (aq) are -1675 kJ mol-1 and -635 kJ mol-1 resepectively
Choose the correct answer from the options given For the reaction
below : (2021-03-17/Shift - 2) 3CaO + 2Al  3Ca + Al2O3 the standard reaction enthalpy
(a) (A), (C) and (E) only  r H o  ........kJ (2021-03-17/Shift - 1)
(b) (A), (B), (C) and (D) only (Round off to the Nearest Integer).
(c) (A) and (E) only
84. For the reaction C 2 H 6  C 2 H 4  H 2 the reaction
(d) (B) and (C) only
78. The reaction of cyanamide, NH2CN(s) with oxygen was enthalpy  r H  ..........kJ mol-1. (Round off to the Nearest
run in a bomb calorimeter and U was found to be Integer) . [Given : Bond enthalpies in kJ mol-1 : C - C = 347,
-742.24 kJ mol-1. The magnitude of H 298 for the reaction C = C = 611; C - H = 414, H - H = 436]
(2021-03-18/Shift - 1)

85. An average person needs about 10000 kJ energy per day.

92. For water  vap H  41kJmol1 at 373 K and 1 bar pressure.
The amount of glucose (molar mass = 180.0 g mol-1) needed
to meet this energy requirement is _____ g. (nearest Assuming that water vapour is an ideal gas that occupies
a much larger volume than liquid water, the internal energy
integer) (Use :  C H(glucose)  2700 kJ mol1 )
change during evaporation of water is ____ kJ mol-1
(2021-07-20/Shift - 1) [Use : R = 8.3 J mol-1 K-1] (2021-08-26/Shift - 2)
86. For a given chemical reaction A  B at 300 K the free 93. 200 mL of 0.2 M HCl is mixed with 300 mL of 0.1 M NaOH.
energy change is -49.4 kJ mol-1 and the enthalpy of reaction The molar heat of neturalization of this reaction is
is 51.4 kJ mol-1. The entropy change of the reaction is -57.1 kJ. The increase in temperature in oC of the system
_____ J K-1 mol-1. (2021-07-20/Shift - 2) on mixing is x × 10-2. The value of x is ______. (Nearest
87. If the standard molar enthalpy change for combustion of integer) [Given : Specific heat of water = 4.18 J g-1 K-1
graphite powder is 2.48 × 102 kJ mol-1, the amount of heat Density of water = 1.00 g cm-3] Assume no volume change
generated on combustion of 1 g of graphite powder is on mixing) : (2021-08-27/Shift - 1)
_____kJ. (Nearest Integer) (2021-07-22/Shift - 2) 94. Data given for the following reaction is as follows :
88. At 298 K, the enthalpy of fusion of a solid (X) is 2.8 kJ FeO (s)  C (graphite)  Fe(s )  CO (g )
mol-1 and the enthalpy of vaporization of the liquid (X)
Substance H o (kJ mol 1 ) So (J mol 1K 1 )
in kJ mol-1 is _______ . (in nearest integer)
(2021-07-25/Shift - 1) FeO(s) -266.3 57.49
89. A system does 200 J of work and at the same time absorbs C(graphite) 0 5.74
150 J of heat. The magnitude of the change in interval Fe(s) 0 27.28
energy is ________ J. (2021-07-25/Shift - 2)
CO(g) -110.5 197.6
90. When 400 mL of 0.2 M H2SO4 solution is mixed with 600
mL of 0.1 M NaOH solution, the increase in temperature The minimum temperature in K at which the reaction
of the final solution is ______ × 10-2 K. (Round off to the becomes spontaneous is _______. (Integer answer)
nearest integer). (2021-07-27/Shift - 2)
(2021-08-27/Shift - 2)
1
[Use : H (aq) + OH (aq)  H2O :  r H  57.1 kJ mol ]
+ -
95.  N 2 O4 (g), when

For the reaction 2NO 2 (g) 
Specific heat of H2O = 4.18 J K g
-1 -1
1
Density of H2O = 1.0 g cm-3 S  176.0JK 1 and H  57.8 kJ mol , the
magnitude of G at 298 K for the reaction is ____ kJ
Assume no change in volume of solution on mixing.
mol-1. (Nearest integer) (2021-09-01/Shift - 2)
91. For water at 100oC and 1 bar,
 vap H   vap U  ___________ 102 Jmol1
(Round off to the Nearest Integer. Use:R = 8.31J mol-1 K-1
Assume volume of H2O(l) is much smaller than volume of
H2O (g). Assume H2O(g) treated as an ideal gas).
(2021-07-27/Shift - 1)

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only One Correct Option] (a) 104 kcal (b) 10.4 kcal
1. An ideal gas at constant temperature and pressure (c) 1040 kcal (d) 1.04 kcal
expands, then its 8. Consider an ideal gas. When dw = 0 and dq < 0,
(a) Internal energy remains same (a) the temperature will decrease
(b) Internal energy decreases (b) the volume will increase
(c) Internal energy increases (c) the pressure will remain constant
(d) Entropy first increases and then decreases
(d) the temperature will increase
2. The internal energy of a substance
9. When heat is supplied to an ideal gas in an isothermal
(a) Increases with increase in temperature process, the
(b) Decreases with increase in temperature (a) gas will do positive work
(c) Can be calculated by the relation E = mc2 (b) gas will do negative work
(d) Remains unaffected with change in temperature (c) kinetic energy of the gas will increase
3. Which of the following is correct ? (d) gas will not obey the law of conservation of energy
CP 10. The magnitudes of enthalpy changes for irreversible
(a) CP – CV = R (b) C  
V adiabatic expansion of a gas from 1L to 2L is H1 and
(c) CP > CV (d) All of these for reversible adiabatic expansion for the same expansion
4. CP for monoatomic gas is is H2. Then
(a) 5/2 R (b) 3/2 R (a) H1 > H2
(c) 7/2 R (d) R (b) H1 < H2
5. Standard molar enthalpy of formation of CO2 is equal to (c) H1 = H2, enthalpy being a state function
(a) zero (d) H1 = E1 & H2 = E2 where E1 & E2 are
(b) the standard molar enthalpy of combustion of magnitudes of change in internal energy of gas in
gaseous carbon these expansions respectively.
(c) the sum of standard enthalpies of formation of CO and 11. A liquid which is confined inside an adiabatic piston is
O2 suddenly taken from state 1 to state 2 by a single stage
process. If the piston comes to rest at point 2 as shown.
(d) the standard molar enthalpy of combustion of
Then the enthalpy change for the process will be :
carbon (graphite)
6. The mathematical expression for the standard enthalpy
of sublimation is given by
(a) Hº (sublimation) = Hº (fusion) – 2Hº
(vaporization)
(b) Hº (sublimation) = Hº (fusion) – Hº
(vaporization)
(c) Hº (sublimation) = Hº (fusion) + Hº
(vaporization)
(d) Hº (sublimation) = Hº (combustion) + Hº
(dissociation)
2 P0 V0 3P0 V0
7. Energy required to dissociate 4g of gaseous hydrogen (a) H    1 (b) H    1
into free gaseous atoms is 208 kcal at 25°C. The bond
energy of H — H bond will be (c) H = – P0 V0 (d) None of these

12. A gas expands adiabatically at constant pressure such If Cv , m  21.686  103 T , then H for the process is :
–1/2
that T  V . The value of (Cp,m/Cv,m) of the gas will
be : (a) 3000 J (b) 3350 J
(a) 1.30 (b) 1.50 (c) 3700 J (d) 30350 J
(c) 1.70 (d) 2 19. For an ideal gas undergoing adiabatic expansion
13. 1 mole of an ideal gas A (Cv,m = 3 R) and 2 mole of an in vaccum,
 3  (a) U = 0 (b) q = 0
ideal gas B  C v,m  R  are taken in a container and
 2  (c) W = 0 (d) all the above are true
expanded reversibly and adiabatically from 1 litre to 4
litre starting from initial temperature of 320 K. E or U 20. What is the change in molar entropy of helium in the
for the process is : following process ?
(a) –240 R (b) 240 R 1 He (298 K, 1 bar)  1 He (100 K, 10 bar)
(c) 480 R (d) –960 R (a) 41.8 J K–1 mol–1 (b) 4.18 J K–1 mol–1
14. 2 mole of an ideal monoatomic gas undergoes a (c) – 41.8 J K–1 mol–1 (d) – 4.18 J K–1 mol–1
2
reversible process for which PV = C. The gas is expnaded
from initial volume of 1 L to final volume of 3L starting H
21. S  holds good for
from initial temperature of 300 K. Find H for the process: T
(a) –600R (b) –1000R (a) an adiabatic process
(c) –3000R (d) None of these (b) an isothermal reversible-phase change
15. A certain gas in expanded from (lL, 10 atm) to (4L, 5 atm) (c) a process at constant pressure
against a constant external pressure of 1 atm. If the
(d) a process under any condition
initial temperature of gas is 300 K and heat capacity for
the process is 50 J/ºC, the enthalpy change during the 22. rH0 for solid-to-liquid transition for proteins A and B
process is : (Use : 1L atm 100 J) are 2.73 kcal mol–1 and 3.03 kcal mol–1. The two melting
(a) 15 kJ (b) 15.7 kJ points are 0ºC and 30ºC respectively. The entropy
changes SA and SB at two transition temperatures
(c) 14.3 kJ (d) 14.7 kJ
are related as :
16. The molar heat capacities at constant pressure (assumed
(a) SA = SB (b) SA < SB
constant with respect to temperature) for A, B and C are
in ratio of 3 : 1.5 : 2.0. The enthalpy change for the 303SA
(c) SB > SA (d) SB =
exothermic A + 2B  3C at 300 K and 310 K is H300 and 273
H310 (magnitudes) respectively then : 23. For the real gases reaction
(a) H300 > H310 2CO (g) + O2(g) 

 2CO2 (g) H = –560 kJ.
(b) H300 < H310
In 10 litre rigid vessel at 500 K the initial pressure is
(c) H300 = H310 70 bar and after the reaction it becomes 40 bar. The
(d) if T2 > T1 then H310 > H300 and if T2 < T1 change in internal energy is :
then H310 < H300 (a) –557 kJ (b) –530 kJ
17. The specific heat of a gas at constant volume is 0.075 cal/g. (c) –563 kJ (d) None of these
Predict the atomicity of the gas. Molar mass of gas is 24. At 5 × 105 bar pressure, density of diamond and graphite
–1
40 g mol . are 3 g/cc and 2 g/cc respectively, at certain temperature
(a) 1 (b) 2 ‘T’. Find the value of U–H for the conversion of
(c) 3 (d) None of these 1 mole of graphite to 1 mole of diamond at temperature
‘T’ :
18. 10 mole of an ideal gas is heated at constant pressure of
o
one atmosphere from 27 C to 127 C.
o (a) 100 kJ/mol (b) 50 kJ/mol
(c) – 100 kJ/mol (d) None of these

25. The enthalpy of formation of NH3(g) at constant pressure 30. Given that,
and 3500C temperature is –50.0 kJ mol–1. What will be the H0f (CO2, g) = – 393.509 kJ mol–1,
enthalpy of formation of NH3(g) at constant volume at
the same temperature ? H0f (H2O, l ) = – 285.830 kJ mol–1,
(a) – 50.0 kJ mol–1 (b) – 45 kJ mol–1 H0f (C2H5OH, l) = – 277.800 kJ mol–1.
(c) – 60.4kJ mol–1 (d) – 54 kJ mol–1 Calculate the Hº (combustion) of liquid ethanol. The
26. Mg(s) + 2HCl(aq.) MgCl2(aq) + H2(g); following is the required reaction.
rH0 = – 467 kJ/mol C2H5OH (l ) + 3O2 (g) 2CO2 (g) + 3H2O (l )
MgO (s) + 2HCl (aq) MgCl2 (aq) + H2O (l ) ; (a) – 1366.82 kJ mol–1 (b) – 278.82 kJ mol–1
rH0 = – 151 kJ/mol (c) – 2264.66 kJ mol–1 (d) – 1155.78 kJ mol–1
According to the information, and given the fact that 31. The enthalpy of neutralization of a strong acid by a
for water, fH0 = – 286 kJ/mol, what is the fH0 for strong base is –57.32 kJ mol–1. The enthalpy of formation
MgO(s) ? of water is –285.84 kJ mol–1. The enthalpy of formation
of the hydroxyl ion is
(a) – 904 kJ/mol (b) – 602 kJ/mol
(a) + 228.52 kJ mol–1 (b) – 114.26 kJ mol–1
(c) – 334 kJ/mol (d) – 30 kJ/mol
(c) – 228.52 kJ mol–1 (d) + 114.26 kJ mol–1
1
27. The enthalpy of reaction CH4(g) + O2(g) CH3OH(L ) 32. Heat of neutralisation of NaOH and HCl is –57.46 kJ/
2 equivalent. The heat of ionisation of water will be :
is negative. If enthalpy of combustion of CH4 and (a) – 57.46 kJ/mol (b) 57.46 kJ/mol
CH3OH are x and y respectively then which of the
(c) – 114.92 kJ/mol (d) 114.92 kJ/mol
following relations is correct?
33. In which case of mixing of a strong acid and strong
(a) x > y (b) x < y
base, each of 1N concentration, temperature increase is
(c) x = y (d) x  y
the highest ?
28. For the allotropic change represented by the equation
C (diamond)  (graphite) the enthalpy change is (a) 20 ml acid and 30 ml alkali
H = – 1.89 kJ (b) 10 ml acid and 40 ml alkali
If 6g of diamond and 6 g of graphite are separately burnt
(c) 25 ml acid and 25 ml alkali
to yield carbon dioxide, the heat, liberated in the first
case is (d) 35 ml acid and 15 ml alkali
(a) less than in the second case by 1.89 kJ
34. Heat of neutralization of a strong dibasic acid in dilute
(b) more than in the second case by 1.89 kJ
solution by NaOH is nearly
(c) less than in the second case by 11.34 kJ
(a) – 27.4 kcal/eq (b) 13.7 kcal/mol
(d) more than in the second case by 0.945 kJ
29. The enthalpy of combustion for octane (a major (c) – 13.7 kcal/eq (d) – 13.7 kcal/mol
component of gasoline) is – 47.8 kJ/g. How much energy 35. Heat released in neutralization of strong acid and strong
is released by burning 1.0 L of octane (density
0.740 g/mL) ? base is 13.4 kcal/mol. The heat released on neutralization
(a) – 35400 kJ (b) – 64600 kJ of NaOH with HCN is 2.9 kcal/mol, then H° of
(c) – 47800 kJ (d) – 57200 kJ ionization of HCN in water is
(a) 10.5 kcal (b) 16.3 kcal
(c) 9.5 kcal (d) 11.5 kcal

36. Calculate the enthalpy change when 1.0 g of water is (c) rG0 is + 50.8 kJ and the reaction is driven by both
frozen at 00C ( H0f = 1.435 kcal mol–1) enthalpy and entropy.
(d) rG0 is – 50.8 kJ and the reaction is driven by both
(a) – 1.435 cal g–1 (b) – 80.0 cal g–1
enthalpy and entropy.
(c) 80.0 cal g–1 (d) – 55.6 cal g–1
41. Given fH0 (kJ/mol) S0m (J/k/mol)
37. Given are the following entropy values at 298 K and 1
atm: CCl4 (l ) – 135.4 215.4
–1 –1 –1 –1
H2 (g) = 130.6 J K mol ; Cl2 (g) = 223.0 J K mol ; CCl4 (g) – 103.0 308.7
HCl (g) = 186.7 J K–1 mol–1 What is the boiling point of carbon tetrachloride ?
The entropy change for the reaction (a) 8.25ºC (b) 74.3ºC
H2 (g) + Cl2 (g)  2HCl (g) would be (c) 92.3ºC (d) 45.8ºC
(a) +540.3 J K–1 mol–1 (b) +727 J K–1 mol–1 42. Calculate  f G o for (NH4Cl, s) at 310 K.
(c) –166.9 J K–1 mol–1 (d) +19.8 J K–1 mol–1
Given :  f H o (NH4Cl, s)= –314.5 kJ/mol;  r C p =0
38. The free-energy change for the conversion of maleate
into fumarate is 3.0 kJ. In metabolism, this reaction is SoN2 (g) =192 JK–1 mol–1; SoH2 (g) =130.5JK–1 mol–1
coupled with the conversion fumarate to asparate,
SoCl2 (g) =233 JK–1 mol–1 SoNH4 Cl(s) = 99.5 JK–1 mol–1
0
which is exergonic by 15.5 kJ. Calculate G for the
overall reaction. (All data given at 300K)
(a) – 18.5 kJ (b) + 18.5 KJ (a) – 198.56 kJ/mol (b) –426.7 KJ/mol
(c) – 12.5 kJ (d) – 25.0 kJ (c) –202.3 KJ/mol (d) None of these
39. The G for the following reactions at 8000C are given as 43. The bond energy of H2 is 104.3 kcal/mol. It means that
S2 (s) + 2O2 (g) 2SO2 (g); G = – 544 kJ (a) 104.3 kcal heat is needed to break one bond to form two
atoms
2Zn (s) + S2 (s) 2ZnS (s) ; G = – 293 kJ
(b) 104.3 kcal is required to break 6.02 × 1023 molecules
2Zn (s) + O2 (g) 2ZnO (s); G = – 480 kJ
into 1.2406 × 1024 atoms of hydrogen
The G for the reaction
(c) 104.3 kcal is required to break 3.015 × 1023 hydrogen
2Zn S + 3O2 (g) 2ZnO (s) + 2SO2 (g) will be molecules to 6.02 × 1023 hydrogen atoms
(a) – 357 kJ (b) – 731 kJ (d) none of these
(c) – 773 kJ (d) – 229 kJ 44. Determine C–C and C–H bond enthalpy (in kJ/mol)
40. Consider the reaction below at 298 K :
Given:  f H o (C2 H 6 , g) = –85 kJ/mol
C (graphite) + 2H2 (g)  CH4 (g) fHº (kJ/mol) = 74.9
 f H o (C3 H8 , g) = –104 kJ/mol
S0m (J/K/mol)
+ 5.6 + 130.7 + 186.3  sub H o (C,s) =718 kJ/mol B.E.(H  H) = 436 kJ/mol
Which statement below is correct ? (a) 414, 345 (b) 345, 414
(a) rG0 is – 50.8 kJ and the reaction is driven by enthalpy (c) 287, 404.5 (d) None of these
only.
(b) rG0 is – 50.8 kJ and the reaction is driven by entropy
only.

45. What is the bond enthalpy of Xe–F bond? 50. A sample containing 1.0 mol of an ideal gas is expanded
isothermally and reversily to ten time of its original
XeF4  Xe  (g)  F (g)  F2 (g)  F(g);
volume, in two separate experiments. The expansion is
 r H  292 kcal / mol carried out 200 K and at 400 K, respectively. Choose the
Given: Ionization energy of Xe = 279 kcal/mol correct option.
B.E. (F–F) = 38 kcal/mol, (a) Work done at 400 K is twice the work done at
200 K.
Electron affinity of F = 85 kcal/mol
(b) Work done at 400 K is twice the work doen at
(a) 24 kcal/mol (b) 34 kcal/mol 200 K.
(c) 8.5 kcal/mol (d) None of these (c) Work done at 400 K is 20 times the work done at
46. The lattice energy of solid NaCl is 180 kcal per mol. The 200 K.
dissolution of the solid in water in the form of ions is
(d) E  0 in both cases.
endothermic to the extent of 1 kcal per mol. If the
solvation energies of Na+ and Cl– ions are in the ratio 51. The normal boiling point of a liquid ‘X’ is 400 K.
6 : 5, what is the enthalpy of hydration of sodium ion ? Which of the following statement is true about the
(a) – 85.6 kcal/mol (b) – 97.5 kcal/mol process X(l)  X(g) ?

(c) 82.6 kcal/mol (d) + 100 kcal/mol (a) at 400 K and 1 atm pressure G  0
 5  (b) at 400 K and 2 atm pressure G   ve

47. 0.5 mole each of two ideal gases A  C v,m  R  and B
 2  (c) at 400 K and 0.1 atm pressure G   ve
(Cv,m = 3R) are taken in a container and expanded (d) at 410 K and 1 atm pressure G   ve
reversibly and adiabatically, during this process
temperature of gaseous mixture decreased from 350 K Numerical Value Type Questions
and 250 K. Find H (in cal/mol) for the process : 52. Assume that the human body is a heat engine. For a
(a) –100 R (b) –137.5 R food intake equivalent to 1.0 × 107 J day-1, a human
(c) –375 R (d) None of these can work for 6 h day-1 at a rate equivalent to 0.0374
HP (1 HP = 746 W). What is the efficiency of the
Objective Questions II
human body?
[One or more than one correct option] 53. Heat of neutralisation of a polybasic acid by a strong
48. Among the following, the state function(s) is/are base is -54.8 k cal mol-1. What is basicity of the acid?
(a) Internal energy 54. Find change in internal energy, when 0.5 mole of Ar
(b) Irreversible expansion work having a specific heat at constant pressure of
(c) Reversible expansion work 20.814 J g-1 deg-1 is heated from 27oC to 31oC at
(d) Molar enthalpy constant volume. (Atomic mass of Ar = 40) (give your
answer in kJ)
49. If enthalpy of hydrogenation of C6H6(l) into C6H12(l)
55. The enthalpy of neturalizaton of 0.4 M H2SO4 will be
is –205 kJ and resonance energy of C6H6(l) is –152 kJ/
how many times the enthalpy of neutralization of
0.1 M HCl?
mol then enthalpy of hydrogenation of is
Assume Hvap of C6H6(l), C6H8(l), C6H12(l) all are equal:
(a) – 535.5 kJ/mol (b) – 238 kJ/mol
(c) – 357 kJ/mol (d) – 119 kJ/mol

61. Assertion (A) : Heat of neutralization of HF is more
Assertion Reason
than that of HCl by NaOH.
(A) If both Assertion and Reason are correct
Reason (R) : HCl is stronger acid than HF.
and Reason is the correct explanation of
(a) A (b) B
Assertion.
(B) If both Assertion and Reason are true but (c) C (d) D
Reason is not the correct explanation of 62. Assertion (A) : Enthalpy of neutralization of
CH3COOH by NaOH is less than that of HCl by NaOH.
Assertion.
(C) If Assertion is true but Reason is false. Reason (R) : Enthalpy of neutralization of CH3COOH
is less because of the absorption of heat in the
(D) If Assertion is false but Reason is true. ionization process.
56. Assertion (A) : The extensive properties of a single (a) A (b) B
pure substance will not only depend upon the number (c) C (d) D
of moles of the substance present but also on any
two of the three variables. 63. Assertion (A) : When a salt dissolves in water, the
temperature of solution decreases.
Reason (R) : Any extensive property if expressed as
per mole or per gram becomes an intensive property. Reason (R) : Energy equal to lattice energy is required
to ionize the salt in solution.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
57. Assertion (A) : There is no change in internal energy
for an ideal gas at constant temperature. Match the following
Reason (R) : Internal energy of an ideal gas is a Each questions has two columns. Four options are
function of temperature only.
given representing matching elements from
(a) A (b) B
Column-I and Column-II. Only one of these four
(c) C (d) D
options corresponds to a correct matching for each
58. Assertion (A) : A reversible process produces more
questions.
work than the same process if it is carried out
irreversibly for the same increase in volume. 64. Match the Column-I with Column-II
Reason (R) : A reversible process is exothermic while Column - I Column - II
irreversible process is endothermic A. H 2 O(l)  H 2 O(g) p. G  0
(a) A (b) B
B. C(s)  O 2 (g)  CO 2 (g) q. H  0
(c) C (d) D
C. H 2 O(s)  H 2 O(l) r. S  0
59. Assertion (A) : Entropy change in reversible
adiabatic expansion of an ideal gas is zero. 1
D. C(s)  O 2 (g)  CO(g) s. H  0
Reason (R) : The increase in entropy due to volume 2
increase just componsate the decrease in entropy 65. Match the Column-I with Column-II
due to fall in temperature.
Column I Column II
(a) A (b) B
(A) O2 (p)   1.4
(c) C (d) D
60. Assertion (A) : When internal energy of reactants (B) N2 7
(q) CP  R
becomes greater than that of products the energy is 2
given out to the surrounding.
(C) CO2, CH4 23
Reason (R) : All exothermic reactions take place at (r) C P  R
6
constant temperature, E will be positive.
(a) A (b) B (D) 1 mol O2 + 2 mol O3 (s)   1.33
(c) C (d) D

Paragraph Type Questions Use the following passage, to solve Q. 69 to Q. 70

Use the following passage, to solve Q. 66 to Q. 68 Passage
Passage Standard Gibb’s energy of reaction (  r G o ) at a certain
Observe the following graphic representation of four
temperature can be computed as  r G o   r H o  T. r So
basic thermodynamic processes.
and the change in the value of  r H o and  r So for a
reaction with temperature can be computed as follow:
Isobaric
Pressure  r H oT2   r H oT1   r Cop (T2  T1 )
Isochoric
Isothermal
Adiabatic T 
 r SoT2   r SoT1   r Cop ln  2 
 T1 
 r G o   r H o  T. r So
Volume and by  r G o  RT ln K eq .
66. Which of the following is true for isochoric process ? Consider the following reaction:
(a) V = 0 (b) U = q + PV  CH3OH(g)
CO(g)  2H 2 (g) 
(c) U = qv (d) All of these
Given:  f H o (CH3OH, g) = –201 kJ/mol;
67. Which of the following is not true for isothermal process ?
 f H (CO, g) = –144 kJ/mol
o
V2 o o –1 –1
(a) wexp = –2.303 nRT log V S (CH3OH, g) = 240 J/K-mol; S (H2, g) = 29 JK mol
1 o
S (CO, g) = 198 J/mol-K; Cop, m (H 2 ) =28.8 J/mol-K
P1
(b) wexp = –2.303 nRT log P Cop, m (CO) =29.4 J/mol-K; Cop, m (CH3 OH) = 44 J/mol-K
2
(c) T = 0  320 
and ln    0.06 , all data at 300 K
(d) T1V11  T2V21  300 
CP 69.  r So at 300 K for the reaction is :

68. If the ratio  1.30 , the atomicity of gas is
CV (a) 152.6 J/K-mol (b) 181.6 J/K-mol
(a) 1 (b) 2 (c) –16 J/K-mol (d) None of these
(c) 3 (d) 4 70.  r H o at 300 K for the reaction is :
(a) –87 kJ/mol (b) 87 kJ/mol
(c) –315 kJ/mol (d) –288 kJ/mol

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Objective Questions I [Only One Correct Option] (d) not defined, because pressure is not constant
1. The difference between heats of reaction at constant 7. Which of the following reactions defines Hºf ? (2003)
pressure and constant volume for the reaction (a) C(diamond) + O2(g)  CO2 (g)
2C6H6 (l ) + 15O2(g)  12CO2(g) + 6H2O (l ) 1 1
(b) H 2 (g)  F2 (g)  HF(g)
at 25º C in kJ is (1991) 2 2
(a) – 7.43 (b) + 3.72 (c) N2 (g) + 3H2 (g)  2NH3(g)
1
(c) – 3.72 (d) + 7.43 (d) CO(g)  O2 (g)  CO2 (g)
2
2. For an endothermic reaction, where H represents the
8. Spontaneous adsorption of a gas on solid surface is an
enthalpy of the reaction in kJ/mol, the minimum value for
exothermic process because (2004)
the energy of activation will be (1992)
(a) H increases for system (b) S increases for gas
(a) less than H (b) zero
(c) S decreases for gas (d) G increases for gas
(c) more than H (d) equal to H
9. H vap = 30 kJ/mol and S vap = 75 Jmol –1 K–1 . Find
3. The Hºf for CO2(g), CO(g) and H2O (g) are – 393.5, – 110.5
temperature of vapour, at one atmosphere. (2004)
and – 241.8 kJ mol–1 respectively. The standard enthalpy
(a) 400 K (b) 350 K
change (in kJ mol–1) for the reaction
(c) 298 K (d) 250 K
CO2 (g) + H2(g)  CO(g) + H2O(g) is. (2000)
10. 2 moles of an ideal gas expanded isothermally and reversibly
(a) 524.1 (b) + 41.2
from 1 L to 10 L at 300 K. What is the enthalpy change ?
(c) – 262.5 (d) – 41.2
4. In thermodynamics, a process is called reversible when (2004)
(2001) (a) 4.98 kJ (b) 11.47 kJ
(a) surroundings and system change into each other
(c) – 11.47 kJ (d) 0 kJ
(b) there is no boundary between system and surroundings
(c) the surroundings are always in equilibrium with the 11. When one mole of monoatomic ideal gas at TK undergoes
system adiabatic change under a constant external pressure of
(d) t he s ys t em c ha nges in t o t he su rr ound i ngs 1 atm changes volume from 1 L to 2 L. The final temperature
spontaneously
in kelvin would be (2005)
5. Which of the following statements is false ? (2001)
(a) Work is a state function T 2
(a) (b) T 
22/3 3  0.0821
(b) Temperature is a state function
2
(c) Change in the state is completely defined when the (c) T (d) T 
initial and final states are specified 3  0.0821
(d) Work appears at the boundary of the system 12. A monoatomic ideal gas undergoes a process in which the
6. One mole of a non-ideal gas undergoes a change of state ratio of p to V at any instant is constant and equals to 1.
(2.0 atm, 3.0 L, 95 K)  (4.0 atm, 5.0 L, 245 K) with a change What is the molar heat capacity of the gas ? (2006)
in internal energy, E = 30.0L-atm. The change in enthalpy
(H) of the process in L-atm is (2002) 4R 3R
(a) (b)
2 2
(a) 40.0 (b) 42.10
5R
(c) 44.0 (c) (d) 0
2

13. The direct conversion of A to B is difficult, hence it is  f G o [C(diamond)] = 2.9 kJ mol–1
carried out by the following shown path The standard state means that the pressure should be 1
C D bar, and substance should be pure at a given temperature.
The conversion of graphite [C(graphite)] to diamond
A B [C(diamond)] reduces its volume by 2 × 10–6 m3 mol–1. If
Given S(AC) = 50 eu C(graphite) is converted to C(diamond) isothermally at
T = 298 K, the pressure at which C(graphite) is in equilibrium
S(CD) = 30 eu
with C(diamond), is
S(DB) = 20 eu [Useful information : 1 J = 1 kg m2s–2,
where eu is entropy unit, then S(AB) is (2006) 1 Pa = 1 kg m–1 s–2; 1 bar = 105 Pa] (2017)
(a) 58001 bar (b) 1450 bar
(a) + 100 eu (b) + 60 eu
(c) 14501 bar (d) 29001 bar
(c) – 100 eu (d) – 60 eu Objective Questions II
14. For the process H2O (l ) (1 bar, 273 K)  H2O(g) (1 bar, 373 [One or more than one correct option]
K), the correct set of themodynamic parameters is(2007) 19. Identify the intensive quantities from the following (1993)
(a) G = 0, S = +ve (b) G = 0, S = –ve (a) enthalpy (b) temperature
(c) volume (d) refractive index
(c) G = + ve, S = 0 (d) G = – ve, S = +ve
20. The following is (are) endothermic reaction (s) (1999)
15. The value of log10 K for a reaction A  B is (a) combustion of methane
(Given : rHº298K = – 54.07 kJ mol , –1 (b) decomposition of water
–1 –1
rSº298 K = 10 JK mol and R = 8.314 JK–1 mol ; –1 (c) dehydrogenation of ethane to ethylene
(d) conversion of graphite to diamond
2.303 × 8.314 × 298 = 5705 (2010)
(a) 5 (b) 10 21. Among the following, the state function(s) is (are) (2009)
(c) 95 (d) 100 (a) internal energy
16. For the pocess (b) irreversible expansion work

(c) reversible expansion work
H2O     H2O  g  (d) molar enthalpy
at T = 100°C and 1 atmosphere pressure, the correct choice 22. An ideal gas in a thermally insulated vessel at internal
is (2014) pressure=P1, volume = V1, and absolute temperature =T1
(a) Ssystem > 0 and Ssurroundings > 0 expands irreversibly against zero external pressure as
(b) Ssystem > 0 and Ssurroundings < 0 shown in the diagram. The final internal pressure, volume
and absolute temperature of the gas are P2, V2 and T2,
(c) Ssystem < 0 and Ssurroundings > 0
respectively. For this expansion, (2014)
(d) Ssystem < 0 and Ssurroundings < 0
17. One mode of an ideal gas at 300 K in thermal contact with
surroundings expands isothermally from 1.0 L to 2.0 L
against a constant pressure of 3.0 atm. In this process, the
change in entropy of surroundings (Ssurr) in JK–1 is
(1L atm = 101.3 J) (2016)
(a) 5.763 (b) 1.013
(c) –1.013 (d) –5.763
18. The standard state Gibbs free energies of formation of
C(graphite) and C(diamond) at T = 298 K are (a) q = 0 (b) T2 = T1
 f G o [C(graphite)] = 0 kJ mol–1 (c) P2V2 = P1V1 (d) P2 V2   P1V1

23. An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) 26. In thermodynamics the P-V work done is given by
under different conditions. The correct statement(s) among
w    dVPext.
the following is (are) (2017)
(a) The work done by the gas is less when it is expanded For a system undergoing a particular process, the work
done is,
reversibly from V1 to V2 under adiabatic conditions as
 RT a 
compared to that when expanded reversibly from V1 to V2 w    dV   2 .
under isothermal conditions. Vb V 
(b) The change in internal energy of the gas is (i) zero, if it The equation is applicable to a (2020)
is expanded reversibly with T1 = T2, and (ii) positive, if it is (a) System that satisfies the van der Waals equation of
expanded reversibly under adiabatic conditions with state.
T 1  T 2. (b) Process that is reversible and isothermal
(c) If the expansion is carried out freely, it is simultaneously (c) Process that is reversible and adiabatic
both isothermal as well as adiabatic (d) Process that is irreverisble and at constant isothermal.
(d) The work done on the gas is maximum when it is 27. An ideal gas undergoes a reversible isothermal expansion
compressed irrversibly from (p2, V2) to (p1, V1) against from state I to stable II followed by a reversible adiabatic
constant pressure p1. expansion from state II to state III. The correct plot(s)
24. A reversible cyclic process for an ideal gas is shown below, representing the changes from state I to state III is(are)
Here, P, V, and T are pressure, volume and temperature, (p : pressure, V : volume, T : tempeature, H : enthalpy,
respectively. The thermodynamic parameters q, w, H and S : entropy) (2021)
U are heat, work, enthalpy and internal energy, respectively.
(a) (b)
(c) (d)
The correct option(s) is (are) (2018)

(a) qAC = U BC and wAB = P2 (V2 – V1)
(b) w BC  P2 (V2  V1 ) and q BC  H AC
28. The enthalpy for the following reactions (Hº) at 25ºC are
(c) H CA  U CA and q BC  H AC given below
(d) q BC  H AC and H CA  U CA 1 1
(i) H2(g) + O2(g)  OH(g) Hº = –10.06 kcal
25. Choose the reaction(s) from the following options, for which 2 2
the standard enthalpy of reaction is equal to the standard (ii) H2(g)  2H(g) Hº = 104.18 kcal
enthalpy of formation (2019) (iii) O2 (g)  2O(g) Hº = 118.32 kcal
1 Calculate the O — H bond energy in the hydroxyl radical.
(a) S8 (s)  O 2 (g)SO 2 (g)
8 (1981)
(b) 2H 2 (g)  O 2 (g)  2H 2 O(l) 29. The standard heats of formation of CCl4(g), H2O(g), CO2(g)
3 and HCl(g) at 298 K are –25.5, –57.8, – 94.1 and –22.1
(c) O 2 (g)  O3 (g) kcal/mol respectively. Calculate Hº (298 K) for the reaction
2
(d) 2C(g)  3H 2 (g)  C2 H 6 (g) CCl4(g) + 2H2O(g)  CO2(g) + 4HCl(g) (1982)

30. The molar heats of combustion of C2H2(g), C (graphite) Compound : H2(g) CH4(g) C2H6(g) C(graphite)
and H2(g) are 310.62 kcal, 94.05 kcal and 68.32 kcal Hº (kJ/mol) : –285.8 –890.0 –1560.0 –393.0
The standard heat of formation of C3H8(g) is –103 kJ/mol.
respectively. Calculate the standard heat of formation of
C2H2(g). (1983) (1992)
38. The polymerization of ethylene to linear polyethylene is
31. Given the following standard heats of reactions
represented by the reaction,
(i) heat of formation of water = – 68.3 kcal
n [CH2  [ CH 2 – CH 2 ]n
CH2] 
(ii) heat of combustion of acetylene = – 310.6 kcal
where, n has large integral value. Given that the average
(iii) heat of combustion of ethylene = – 337.2 kcal
enthalpies of bond dissociation for C C and C—C at
Calculate the heat of reaction for the hydrogenation of 298 K are + 590 and +311 kJ/mol respectively, calculate the
acetylene at constant volume (25º C). (1984) enthalpy of polymerization per mole of ethylene at 298 K.
32. The bond dissociation energies of gaseous H2, Cl2 and (1994)
HCl are 104, 58 and 103 kcal/mol respectively. Calculate the 39. From the following data, calculate the enthalpy change
enthalpy of formation of HCl gas. (1985) for the combustion of cyclopropane at 298 K. The enthalpy
33. The standard molar heat of formation of ethane, carbon of formation of CO2(g), H2O (l) and propane (g) are –393.5,
dioxide and liquid water are –21.1, –94.1, and –68.3 kcal –285.8 and 20.42 kJ mol–1 respectively. The enthalpy
respectively. Calculate the standard molar heat of of isomerization of cyclopropane to propene is
combustion of ethane. (1986) –33.0 kJ mol–1. (1998)
34. An intimate mixture of ferric oxide, Fe2O3, and aluminium, 40. Estimate the average S–F bond energy in SF6. The values
Al, is used in solid fuel rockets. Calculate the fuel value of standard enthalpy of formation of SF6(g), S(g) and F(g)
per gram and fuel value per cc of the mixture. Heats of are :
formation and densities are as follows :
– 1100, 275 and 80 kJ mol–1 respectively. (1999)
Hf (Al2O3) = – 399 kcal/mol
41. A sample of argon gas at 1 atm pressure and 27ºC expands
Hf (Fe2O3) = – 199 kcal/mol reversibly and adiabatically from 1.25 dm3 to 2.50 dm3.
Density of Fe2O3 = 5.2 g/cc, Calculate the enthalpy change in this process C Vm for
Density of Al = 2.7 g/cc (1989)
argon is 12.49 JK–1 mol–1. (2000)
35. An athlete is given 100g of glucose (C6H12O6) of energy
42. Diborane is a potential rocket fuel which undergoes
equivalent to 1560 kJ. He utilizes 50 percent of this gained
combustion according to the reaction
energy in the event. In order to avoid storage of energy in
the body, calculate the weight of water the would need to B2 H6 (g) + 3O2 (g) 
 B2O3 (s) + 3H 2O(g)
perspire. The enthalpy of evaporation of water is 44 kJ/mol.
From the following data, calculate the enthalpy change for
(1989)
the combustion of diborane. (2000)
36. The standard enthalpy of combustion at 25ºC of hydrogen,
3
cyclohexene (C6H10) and cyclohexane (C6H12) are –241, 2B(s) + O2 (g)  B2O3 (s), H  1273 kJ mol 1
2
– 3800 and –3920 kJ/mol respectively. Calculate the heat of
1
hydrogenation of cyclohexene. (1989) H 2 (g) + O2 (g) 
 H 2 O(l ), H  286 kJ mol1
2
37. Determine the enthalpy of the reaction,
H 2 O(l ) 
 H 2 O(g), H  44 kJ mol1
C3H8(g) + H2(g)  C2H6(g) + CH4(g), at 25ºC, using the
2B (s) + 3H 2 (g) 
 B2 H6 (g), H = 36 kJ mol –1
given heat of combustion values under standard conditions.

43. In a constant volume calorimeter, 3.5g of a gas with

molecular weight 28 was burnt in excess oxygen at 298.0 K.
The temperature of the calorimeter was found to increases
from 298.0 K to 298.45 K due to the combustion process.
Given that the heat capacity of the calorimeter is 2.5 kJ K–1,
the numerical value for the enthalpy of combustion of the
gas in kJ mol–1 is (2009) (U : Internal energy, S : entropy, p : pressure, V : volume,
44. The surface of copper gets tarnished by the formation of R : gas constant)
copper oxide. N2 gas was passed to prevent the oxide (Given : molar heat capacity at constant volume, CV.m of
formation during heating of copper at 1250 K. However, 5
the gas is R)
2
the N2 gas contains 1 mole % of water vapour as impurity.
Assertion Reason
The water vapour oxidises copper as per the reaction given
below : (2018) (A) If both Assertion and Reason are correct and
Reason is the correct explanation of Assertion.
2Cu(s) + H2O(g)  Cu2O(s) + H2(g)
(B) If both Assertion and Reason are true but
p H 2 is the minimum partial pressure of H2 (in bar) needed Reason is not the correct explanation of
Assertion.
to prevent the oxidation at 1250 K. The value of ln (p H2 ) is
(C) If Assertion is true but Reason is false.
......... .
(D) If Assertion is false but Reason is true.
(Given : total pressure = 1 bar, R (universal gas constant)
47. Assertion (A) : The heat absorbed during the isothermal
= 8J K–1 mol–1, ln (10) = 2.3. Cu(s) and Cu2O(s) are mutually
expansion of an ideal gas against vacuum is zero.
immiscible.
Reason (R) : The volume occupied by the molecules of an
45. Tin is obtained from cassiterite by reduction with coke. ideal gas is zero. (2000)
Use the data given below to determine the minimum (a) A (b) B
tempeature (in K) at which the reduction of cassiterite by
(c) C (d) D
coke would take place. (2020)
48. Assertion (A) : For every chemical reaction at equilibrium
At 298 K :  f H 0 (SnO 2 (s))  581.0kJmol1 , standard Gibbs’ energy of reaction is zero.
Reason (R) : At constant temperature and pressure,
 f H 0 (CO 2 (g))  394.0 kJ mol 1 chemical reactions are spontaneous in the direction of
decreasing Gibbs’ energy. (2008)
S0 (SnO 2 (s))  56.0JK 1mol 1 ,S0 (Sn(s))  52.0 JK 1mol1
(a) A (b) B
1 1 1 1
S (C(s))  6.0JK mol ,S (CO 2 (g))  210.0 J K mol
0 0
(c) C (d) D
Assume that the enthalpies and the entropies are 49. Assertion (A) : There is a natural asymmetry between
temeprature independent. converting work to heat and converting heat to work.
46. One mole of an ideal gas at 900 K, undergoes two reversible Reason (R) : No process is possible in which the sole
processes, I followed by II, as shown below. If the work result is the absorption of heat from a reservoir and its
done by the gas in the two processes are same, the value complete conversion into work. (2008)
v3 (a) A (b) B
of ln v is _________. (2021)
2 (c) C (d) D

Subjective Type Questions 55. Two moles of a perfect gas undergo the following
50. Following statement is true only under some specific processes :
conditions. Write the conditions for that in not more than (a) a reversible isobaric expansion from (1.0 atm, 20.0L) to
two sentences (1.0 atm, 40.0 L)
“The heat energy q, absorbed by a gas is H.” (1984) (b) a reversible isochoric change of state from (1.0 atm,
51. In order to get maximum calorific output, a burner should 40.0 L) to (0.5 atm, 40.0 L)
have an optimum fuel to oxygen ratio which corresponds (c) a reversible isothermal compression from (0.5 atm, 40.0L)
to 3 times as much oxygen as is required theoretically for to (1.0 atm, 20.0 L)
complete combustion of the fuel. A burner which has been (i) Sketch with labels each of the processes on the same
adjusted for methane as fuel (with x litre/hour of CH4 and p-V diagram.
6x litre/hour of O2) is to be readjusted for butane, C4H10. In
(ii) Calculate the total work (W) and the total heat change
order to get the same calorific output, what should be the (Q) involved in the above processes.
rate of supply of butane and oxygen ? Assume that losses
due to incomplete combustion etc., are the same for both (iii) What will be the values of U, H and S for the
fuels and that the gases behave ideally. Heats of overall process ? (2002)
combustions : 3R 3R
56. CV value of He is always but CV value of H2 is at
CH4 = – 809 kJ/mol, C4H10 = – 2878 kJ/mol (1993) 2 2
5R
52. The standard enthalpies of formation of cyclohexane (l) low temperature and at moderate temperature and more
2
and benzene (l) at 25ºC are –156 and +49 kJ mol–1
5R
respectively. The standard enthalpy of hydrogenation of than at higher temperature. Explain in two or three
2
cyclohexene (l) at 25ºC is –119 kJ mol–1. Use these data to lines. (2003)
estimate the magnitude of the resonance energy of 57. 100 mL of a liquid contained in an isolated container at a
benzene. (1996) pressure of 1 bar. The pressure is steeply increased to 100
53. Show that the reaction, bar. The volume of the liquid is decreased by 1 mL at this
constant pressure. Find the H and U. (2004)
1
CO(g) + O 2 (g)   CO 2 (g) at 300 K, is spontaneous Fill in the Blanks
2
and exothermic, when the standard entropy change is 58. The total energy of one mole of an ideal monatomic gas at
27ºC is ..................... cal. (1984)
–0.094 kJ mol–1 K–1. The standard Gibbs’ free energies of
formation for CO2 and CO are –394.4 and –137.2 kJ mol–1, 59. Cp – CV for an ideal gas is .................. (1984)
respectively. (2000) 60. A system is said to be ............. if it can neither exchange
54. When 1-pentyne (A) is treated with 4 N alcoholic KOH at matter nor energy with the surroundings. (1993)
175ºC, it is converted slowly into an equilibrium mixture of 61. The heat content of the products is more than that of the
1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of 1, reactants in an ................. reaction. (1993)
2-pentadiene (C). The equilibrium was maintained at 175ºC. 62. When Fe(s) is dissolved in aqueous hydrochloric acid in a
Calculate Gº for the following equilibria. closed vessel, the work done is .................. . (1997)
 A,
B  G o  ?
1 63. Enthalpy is an ............... property. (1997)
 C,
B  G o2  ?
True / False
From the calculated value of G and G indicate the
o
1
o
2 64. First law of thermodynamics is not adequate in predicting
order of stability of (A), (B) and (C). Write a reasonable the direction of a process. (1982)
reaction mechanism showing all intermediates leading to 65. Heat capacity of a diatomic gas is higher than that of a
(A), (B) and (C) (2001) monatomic gas. (1985)

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71
Chapter 11
1. INTRODUCTION
Equilibrium represents the state of a process in which the proprties Rate of sublimation of solid = rate of desublimation of vapours.
like temperature, pressure, concentration of the system do not 2.1.4 Equilibrium Involving Saturated Solutions:
show any change with the passage of time.
In a saturated solution, an equilibrium exits between the solute
If the opposing processes involve only physical changes, the molecules in the solid state and in the solution:
equilibrium is called physical equilibrium. If the opposing
processes involve chemical changes, i.e., the opposing processes Sugar (solution)  Sugar (solid)
are chemical reactions, the equilibrium is called chemical Rate of dissolution of sugar = rate of crystallisation of sugar.
equilibrium.
Same type of equilibrium exists when a gas dissolves in of liquid.
2. TYPES OF EQUILIBRIUM 2.1.5 Characteristics of Physical Equilibrium:

(i) Physical equilibrium is possible only in a closed system and
Equilibrium is classified into 4 types: at constant temperature.
(i) Physical Equilibrium (ii) Both forward and reverse processes occur at the same rate
(ii) Chemical Equilibrium and there is a dynamic but stable condition.
(iii) Thermal Equilibrium (iii) All measurable properties of the system remain constant.
(iv) Mechanical Equilibrium (iv) The magnitude of physical quantities like concentration,
melting point etc. at any stage indicates the extent to which
Here we will study about physical and chemical equilibrium.
the physical process has proceeded before reaching
2.1 Physical Equilibrium equilibrium.
The equilibrium estabilised during physical state transformation 3. TYPES OF REACTIONS
is called physical equilibrium.
2.1.1 Solid - Liquid Equilibrium: 3.1 Reversible Reactions
For any substance the equilibrium estabilised at 1 atm pressure A reaction in which not only the reactants react to form the
and its normal melting or freezing point is called solid-liquid products under certain conditions but also the products react to
equilibrium. form reactants under the same conditions is called a reversible
reaction.
Rate of melting of soild = rate of freezing of liquid.
In other words a reaction which takes place not only in the forward
For example equilibrium estabilised between ice and water at 1
direction but also in the backward direction under the same
atm pressure and 0o C temperature. conditions is called a reversible reaction.
2.1.2 Liquid -Vapour Equilibrium Example :
For any substance the equilibrium estabilised at 1 atm pressure N 2  3H 2  2NH 3
and its normal boiling point is called liquid-vapour equilibrium.
3.2 Irreversible Reactions
Rate of evaporation of liquid = rate of condensation of vapours.
If a reaction cannot take place in the reverse direction, i.e., the
For example equilibrium estabilised between water and steam at 1
products formed do not react to give back the reactants under
atm pressure and 100o C temperature. the same conditions, it is called an irreversible reaction.
2.1.3 Soild -Vapour Equilibrium
A + B 
 C+D
The equilibrium estabilised when a solid is converted into its
vapours directly, for example when dry ice changes into CO2 gas.
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CHEMICAL EQUILIBRIUM 72
exactly similar conditions as before, equilibrium is attained
Types of Reactions
containing D2 and ND3 in place of H2 and NH3 but in the same
Irreversible reaction Reversible reaction amounts. Now, if the two reaction mixtures are mixed, then after
Reaction which proceeds Reaction which proceeds some time, it is found that the concentrations of ammonia and
in forward direction only in forward as well as hydrogen are same except that now all forms of ammonia (i.e.,
backward direction NH3, NH2D, NHD2, ND3) and all forms of hydrogen (i.e., H2, HD,
Reactants are nearly Reactants are never
D2) are present. This shows that at equilibrium, the reaction is
completely converted in completely converted in to
still going on, i.e., equilibrium is dynamic in nature.
to products products
Do not attain equilibrium Attain the equilibrium state
state and never go to completion
4. CHEMICAL EQUILIBRIUM
Just like physical equilibrium in physical processes, we have
chemical equilibrium in reversible chemical reactions.
When the rates of the forward and reverse reactions become
equal and the concentrations of the reactants and the products
become constant, this state is called chemical equilibrium.
Chemical equilibrium is dynamic in nature because it consists of
a forward reaction in which the reactants give product(s) and
reverse reaction in which product(s) gives the original reactants.
Equilibrium in manufacture of NH3

4.1 Characteristics of Chemical Equilibrium
(i) At equilibrium, the concentration of each of the reactants

and the products becomes constant.
(ii) At equilibrium, the rate of forward reaction becomes equal

to the rate of backward reaction and hence the equilibrium is
dynamic in nature.
(iii) A chemical equlibrium can be established only if none of the

products is allowed to escape out or separate out as a solid.
e.g. if CO2 gas escapes out in case of decomposition of

Attainment of chemical equilibrium CaCO3, the reaction will no longer remain reversible.
 Rate of forward reaction = Rate of backward reaction Similarly, the reaction is irreversible if one of the products
 This equilibrium is dynamic and stable in nature separates out as solid,
Example of Chemical Equilibrium
 AgCl  + KNO3
AgNO3 + KCl 
In the Haber’s process, starting with definite amounts of N2 and
H2 and carrying out the reaction at a particular temperature, when (iv) Chemical equilibrium can be attained from either direction,
equilibrium is attained, the concentrations of N2, H2 and NH3 i.e., from the direction of the reactants as well as from the
direction of the products.
become constant. If the experiment is repeated by taking
deuterium (D2) in place of H2 but with the same amounts and
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5. HOMOGENEOUS AND HETEROGENEOUS At constant temperature, as kf and kb are constant, therefore,

EQUILIBRIA kf
5.1 Homogeneous Equilibria k b = K is also constant at constant temperature and is called
Equilibrium estabilish in reactions with all reactants and products
‘equilibrium constant’.
in the same phase is called homogenous equilibrium.
The product of the molar concentrations of the products, each
For example: 2NO2 (g)  N2O4 (g) raised to the power equal to its stoichiometric coefficient divided
Here, reactant and product both are gases. by the product of the molar concentrations of the reactants, each
raised to the power equal to its stoichiometric coefficient is
5.2 Heterogeneous Equilibria
constant at constant temperature and is called equilibrium
Equilibrium established in reaction where various phases/states constant.
exist is termed as heterogeneous equilibrium.
6.2 Equilibrium Constant in Gaseous Systems
Example CaCO3(s)  CaO(s) + CO2(g)
Equilibrium constant of the reactions are expressed in terms of
This example there is the gas as well as solid phase. molar concentration of the reactants and products, and
In heterogeneous equilibria involving a pure liquid or pure solid, represented as Kc. For reactions involving gases, however, it is
the molar concentration of pure solid or liquid is taken as usually more convenient to express the equilibrium constant in
constant. terms of partial pressures.
On the other end molar concentration of gaseous and solutes in From ideal gas equation, we know that
aqueous solution varies during the reaction.
pV  nRT
6. LAW OF MASS ACTION n
p RT
V
“The rate of a reaction is proportional to the product of the active
masses of the reactants, each raised to the power equal to its
stoichiometric coefficient as represented by the balanced chemical n
Here, is molar concentration of the reactant or product.
equation”. This is called law of mass action. V
For a gaseous reaction
aA + bB + cC + ...... 
 Products
aA  bB  cC  dD
Rate of reaction  [A]a [B]b [C]c .....
Equilibrium constant can be given as
Law of chemical equilibrium is a result obtained by applying the
law of mass action to a reversible reaction in equilibrium.
 C  D 
c d
 pcC  pdD 
 C + D Kc  ; Kp 
A + B 
 A a  Bb  paA  pBb 
Rate of the forward reaction  [A] [B] = kf [A] [B]
6.3 Relationship between Kp and Kc
Rate of the backward reaction  [C] [D] = kb [C] [D]
Kp and Kc of a gaseous reactions can be related as follows:
6.1 Equilibrium Constant
At equilibrium, aA  bB  cC  dD
Rate of forward reaction = Rate of backward reaction p  C.RT
[C] [D] k f
k f [A] [B]  k b [C] [D] or 
[A] [B] k b
K
Kp 
 pcC  pdD   C c  D d  RT  c  d 

 paA  pbB   Aa  Bb  RT a b 
 Cc  D d RT n n
Kp     K c  RT 
 A a Bb
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where n = (number of moles of gaseous products) – (number of For the reactions, H 2  g   I 2  g   2HI, Kp and Kc have no
moles of gaseous reactants) in the balanced chemical equation.
unit. N 2 O4  g   2NO 2  g  , Kc has unit mol/L and Kp has unit
Gaseous reaction can be of three types based on change in
bar. Equilibrium constants can also be expressed as dimension-
number of gaseous mode.
less quantities if the standard state of reactants and products are
(i) Those reactions where gaseous moles increase specified.
(n = +ve)
7.CHARACTERISTICS OF EQUILIBRIUM CONSTANT
PCl5 (g)  PCl3 (g) + Cl2 (g)
(ii) Those reactions where gaseous moles remain the same (i) The value of the equilibrium constant for a particular reaction
is always constant depending only upon the temperature of
(n = 0), In this case Kp =Kc
the reaction and is independent of the concentrations of the
H2 (g) + I2 (g)  2HI (g) reactants with which we start or the direction from which the
(iii) Those reactions where gaseous moles decrease equilibrium is approached.
(n = – ve) (ii) If the reaction is reversed, the value of the equilibrium
constant in inversed.
2NO2 (g)  N2O4 (g)
for the reaction
6.4 Equilibrium Constant in Terms of Mole Fractions (K )
Just like molar concentration mole fraction can also be used to H2(g) + I2(g)  2HI(g) as, K c 
 HI2  x
represent equilibrium constant.
 H 2  I 2 
Considering a simple reaction; The equilibrium constant for the reverse reaction,
aA  cC 2HI(g) H2(g) + I2(g), at the same temperature is,
The equilibrium constant for the reaction is as

K 'c 
 H 2  I 2   1
 HI
2
x
 cC
K 
 aA
Thus, K 'c = 1 / Kc
K  can be related to Kp as follows: (iii) If the equation (having equilibrium constant K) is divided
by 2, the equilibrium constant for the new equation is the
PCc  cC  cC
 a   PT 
ba
Kp  square root of K (i.e., K ).
PA  A  A
a a
For example, if the reaction is written as,

K p  K    PT 
ba
½ H2(g) + ½ I2(g)  HI(g)

K   K p   PT 
ba
the equilibrium constant for the above reaction is given by

K   K p  PT 
n
K ''c 
 HI  K c1/ 2
Here, K  and Kp are the equilibrium constant in terms of molar  H 2   I2 
1/ 2 1/ 2
fraction and pressure respectively and PT represents the partial

pressure of the reactants and products and n represents the (iv) If the equation (having equilibrium constant K) is multiplied
by 2, the equilibrium constant for the new equation is the
no. of moles of the reactants minus the no.of moles of the
products. square of K (i.e., K2)
6.5 Units of Equilibrium Constant For example, if the reaction is written as,
The value of equilibrium constant Kc can be calculated by sub- 2 H2(g) + 2 I2(g)  4HI(g)
stituting the concentration terms in mol/L and for Kp partial pres- the equilibrium constant for the above reaction is given by
sure is substituted in Pa, kPa, bar or atm. This results in units of
 HI 
4
equilibrium constant based on molarity or pressure, unless the
K ''c   K c2
H 2  I2 
2 2
exponents of both the numerator and denominator are same.
SCAN CODE

8. APPLICATIONS OF EQUIIBRIUM CONSTANTS NOTE

Q is a variable which always approaches K which is a
8.1 Predicting the Extent of a Reaction constant.
High value of Kc (Kc > 103)  At equilibrium reaction is forward

dominant 8.3 Calculating Equilibrium Concentrations
Low value of Kc (Kc < 10–3)  At equilibrium reaction is backward Suppose we are given the following data :
dominant 1. The balanced reaction and value of Kc
Moderate value of Kc (between 103 and 10–3)  At equilibrium 2. The initial concentration of the reactants, or the initial moles
neither direction dominates 3. Volume of the container
We need to find the final equilibrium concentration of the reactants
and products. Then we can follow the following steps :
Step-1: Write down the balanced chemical equation for the
reaction.
Step-2: Under every reactant and product, write down the initial
moles/concentration.
Step-3: Subtract the amount reacting and add the amount
Dependence of extent of reaction on Kc produced in terms of a variable x and note down the
8.2 Predicting the Direction of a Reaction equilibrium concentration in terms of x. If we are dealing
The equilibrium constant helps in predicting the direction of a in moles then we will need to divide the moles by volume
reaction in which it will proceed at any stage. For this purpose, to obtain concentrations.
we calculate the reaction quotient Q. Step-4: Substitute the equilibrium concentration in the
The reaction quotient, Q is defined in the same way as the expression of Kc and equate it to the value of Kc.
equilibrium constant K except that the concentrations in Q are Step-5: Solve the above equation and calculate the value of x
not necessarily equilibrium values. and in case of multiple solutions select the value which
aA + bB  cC + dD is sensible from reaction point of view. Then back
substitute the value of x in the equilibrium concentration
expression and obtain the actual value of the same.
Q
Cc  Dd
Example: 3.00 mol of PCl5 kept in 1L closed reaction vessel was
 A   B
a b
allowed to attain equilibrium at 380K. Calculate

Q > K : Reaction will tend towards backward direction composition of the mixture at equilibrium. Kc = 1.80
Q < K : Reaction will tend towards forward direction Sol.
Q = K : Reaction will be at equilibrium
PCl5  PCl3  Cl2
Initial conc. 3.0 0 0
At equilibrium: (3  x) x x
Kc 
 PCl3 Cl2 
 PCl5 
x2
1.8 
3  x 
x 2  1.8x  5.4  0
Predicting the direction of the reaction
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On solving quadratic equation 9.2 Observed Molar Mass at Equilibrium

x = 1.59 For a dissociating substance, at equilibrium, both the substance
and the dissociated products are present. Thus, the molar mass
[PCl5] = 3.0 – x = 3 –1.59 = 1.41 M
of the equilibrium mixture will be the average of the molar mass of
[PCl3] = [Cl2] = x = 1.59 M all the substances present in the equilibrium mixture. It is also
known as observed molar mass.
9. DEGREE OF DISSOCIATION (
If the dissociation of a substance is a reversible reaction, then An  g   nA  g 
some amount of the substance will remain undissociated at the Initial 1 0
equilibrium. At equilibrium 1   n
Degree of dissociation is basically the amount of reactant Total moles at equilibrium  1  (n  1)
dissociated at equilibrium, if we start with one mole of the reactant.
Mass
Degree of dissociation    We know that, moles  Molar Mass
Number of moles dissociated at equilibriumm

Initial number of moles taken Thus, molar mass of equilibrium mixture
Percentage dissociation =  × 100 Mass of the equilibrium mixture


Example - Suppose 5 moles of PCl5 is taken and if 2 moles of PCl5 Total moles at equilibrium
dissociated then- Since mass remains conserved during a chemical process,
PCl5 (g)  PCl3 (g)  Cl2 (g) mass of equilibrium mixture = initial mass
Initial 5mole 0 0 = 1 × Molar mass of An = Mactual
At equilibrium 5  2  3mole 2mole 2mole
M actual
2 Thus, molar mass of equilibrium mixture  1   n  1 
   0.4
5
Observed molar mass of a dissociating substance can be thus
9.1 Equilibrium Constant in Terms of 
calculated using the formula -
Since equilibrium constant is independent of the amount of
substance taken initially, we can assume that we are starting with M actual
M Observed 
one mole of the substance. (if the initial amount is not given) 1   n  1 
PCl5  g   PCl3  g   Cl 2  g  9.3 Vapour Density of an Equilibrium Mixture

Initial 1 0 0
at equilibrium 1    Vapour density is the ratio of density of the gas divided by density
of hydrogen under same temperature & pressure.
Total moles at equilibrium = 1 + 
Molar Mass
Partial pressures of reaction components can be given as Vapour density 
2
1      If the vapour density of a substance without dissociation
PPCl5  P; PPCl3  P; PCl2  P
1    1    1    M actual
D
2
 2 .P
KP 
1   2
And, the vapour density of equilibrium mixture  d 
M observed
2
2D
Then, 2d  1   n  1 
SCAN CODE

For example to get more ammonia from Haber’s process, constant
D
 1   n  1  addition of nitrogen and hydrogen gases and constant removal
d
of ammonia is requred.
D
 1   n  1  N 2  g   3H 2  g   2NH3  g 
d
10.3 Effect of Change of Pressure
D  d Low pressure favours those reactions which are accompanied
On rearranging, we get   n  1  d
  by increase in total number of moles of gases and high pressure
favours those reactions which take place with decrease in total
number of moles of gases.
10. FACTORS AFFECTING EQUILIBRIA-
LE CHATELIER’S PRINCIPLE N 2  g   3H 2  g   2NH3  g 
If a distrubance is introduced in any factor determining equilibrium High pressure favours the formation of ammonia while low
condition of the system, then equilibrium mixture behave so as pressure favours decomposition of ammonia.
to undo the distrubance and re-establish the equilibrium. However, pressure has no effect on an equilibrium of a reaction
10.1 Effect of Change in Temperature which proceeds with no change in total number of moles of gases.
Exothermic reactions are favoured by low temperature whereas For example H 2  g   I2  g   2HI  g  .
endothermic reations are favoured by high temperature.
Reactants and products have 2 moles each of gases therefore on
This can be explained by Van’t Hoff equation.
changing pressure of reaction equilibrium remains unchanged.
 K   H   1 1  10.4 Effect of Change in Volume
ln  2    
 K   R   T T  or The effect of decrease of volume is equivalent to the effect of
 1  1 2
increase of pressure.
Hence the effect of decrease in volume will be to shift the
 K   H   1 1 
log  2     equilibrium in the direction in which the number of gaseous moles
 K   2.303R   T T 
 1  1 2  decreases.
An increase in volume will shift the equilibrium in the direction in
For exothermic reactions, H is negative.
which the number of gaseous moles also increases.
On increasing the temperature the equilibrium constant will
decrease i.e. The reaction will become more backward dominant. For example 2SO2  g   O2  g   2SO3  g  .
For endothermic reactions, H is positive. If volume of the reaction container is increased to double of
On increasing the temperature the equilibrium constant will increase. original volume then the reaction will shift in backward direction
The reaction will become more forward dominant. and more decomposition of SO3 will take place.
For example dimerisation of NO2 gas to give N2O4 is an exothermic 10.5 Effect of Addition of Catalyst
reaction. A catalyst increases the rate of the chemical reaction by making
available a new low energy pathway for the conversion of
2NO 2  g   N 2 O 4  g  ; H  57.2 kJ mol 1 reactants to products. It increases the rate of forward and reverse
This reaction moves in forward direction on decreasing the reactions that pass through the same transition state and does
temperature while on increasing the temperature it proceeds in not affect equilibrium. Catalyst does not affect the equilibrium
reverse direction. composition of a reaction mixture. It does not appear in the
balanced chemical equation or in the equilibrium constant
10.2 Effect of Change of Concentration expression.
If in a reaction in equilibrium, the concentration of any reactant is In Haber’s process iron is used as catalyst, which means it
increased, the equilibrium shifts in the forward direction. On the significantly increases the rate of formation of ammonia at
other hand, if the concentration of any product is increased, the optimum temperature and pressure but it can also increase the
equilibrium shifts in the backward direction. The reverse happens rate of decomposition ammonia if temperature and pressure
if the concentrations are decreased. favours the backward reaction.
SCAN CODE

10.6 Effect of Adding an Inert Gas 11. RELATIONSHIP OF Keq AND G

10.6.1 At Constant Volume
For any reaction :
If the reaction takes place at constant volume addition of an inert
G = Gº + RT lnQ Where Q is the reaction quotient.
gas will not change the molar concentrations of the reactants
and products. Hence, the state of equilibrium will remain At equilibrium G = 0 and Q = Keq
unaffected. Addition of any inert gas in any gaseous reaction
Gº = –RT lnKeq = – 2.303RT log Keq
like
where Keq is generally taken as Kp. It depends on the definition
H 2  g   I2  g   2HI  g  of standard values to define Gº.
will not cause any change in equilibrium state. If the standard active masses are taken as 1 M each then we will
10.6.2 At Constant Pressure take Keq = Kc and if they are taken as 1 atm each then we will take
If the reaction takes place at constant pressure, addition of inert Keq = Kp.
gas must accompany in increase in the total volume to keep o /RT
pressure constant. Thus, reaction shifts towards larger number If Gº < 0, then –Gº/RT is positive, and e G  1 , making
of gaseous moles. K >1, which indicates a spontaneous reaction.
2NO2  g   N 2 O4  g  o
If Gº > 0, then –Gº/RT is negative, and e G /RT  1 , that is ,
On adding an inert gas this reaction will shift it backward. K < 1, which indicates a non-spontaneous reaction.
2. CARBOHYDRATES
SCAN CODE

SUMMARY
SCAN CODE

SOLVED EXAMPLES
Example - 1 PH2  PI2 0.08atm  0.08atm

The following reaction has attained equilibrium  KP  P2

(0.04atm) 2
 4.0.
HI
CO(g)  2H 2 (g) CH 3 OH(g), H o  92.0kJ mol1 Example - 3
What will happen if (i) volume of the reaction vessel is One mole of H2O and one mole of CO are taken in a 10
suddenly reduced to half? (ii) the partial pressure of litre vessel and heated at 725 K. At equilibrium, 40% of
hydrogen is suddenly doubled? (iii) an inert gas is added water (by mass) reacts with CO according to the
to the system? equation:
Kc 
 CH3 OH  , K  PCH OH 3
H 2 O(g)  CO(g)  H 2 (g)  CO 2 (g)
Sol.
 CO  H 2 
p
2
PCO  PH2 2
Calculate the equilibrium constant for the reaction.
(i) When volume of the vessel is reduced to half, the
concentration of each reactant or product becomes double. Sol. H 2 O  g   CO  g   H 2  g   CO2  g 
Thus,
1 1
Initial conc. M M 0 0
2  CH 3 OH  1 10 10
Qc   K c As Q  K , equilibrium
2[CO]  (2[H 2 ]) 2 4 c c
1  0.4 1  0.4 0.4 0.4
will shift in the forward direction, producing more of At equilibrium M M M M
10 10 10 10
CH 3OH to make Q c  K c .
= 0.06 M = 0.06 M = 0.04 M = 0.04 M
PCH3OH 1 1
(ii) Q P  P   Kp 1  0.40
(2P ) 2
4 At equilibrium,  H 2 O   mol L1 = 0.06 mol L–1,
CO H2 10
[CO]= 0.06 mol L–1.
Again Qp < Kp, equilibrium will shift in the forward direction
to make Qp= Kp.
0.4
(iii) As volume remains constant, molar concentration will H2   mol L1  0.04 mol L1 ,
10
not change. Hence there is no effect on the state of
equilibrium. [CO2] = 0.04 mol L–1,
Example - 2
A sample of HI (g) is placed in a flask at a pressure of 0.2 KC 
 H2 CO2   0.04  0.04  0.444
atm. At equilibrium, the partial pressure of HI (g) is 0.04  H2O CO 0.06  0.06
atm. What is Kp for the given equilibrium?
Example - 4
Sol. 2HI(g) H 2 (g)  I 2 (g)
At 700 K, equilibrium constant for the reaction
Initial pressure 0.2 atm 0 0
H 2 (g)  I2 (g) 2HI(g)is 54.8. If 0.5 mol L–1 of HI (g)
At equilibrium 0.2 - 2x x x is present at equilibrium at 700K, what are the
0.2 – 2x = 0.04 concentrations of H2(g) and I2(g) assuming that we
initially started with HI (g) and allowed it to reach
x = 0.08 atm
equilibrium at 700 K.
(Decrease in the pressure of HI = 0.2–0.04=0.16 atm.)

Sol. H 2  g   I 2  g   2HI  g  , K  54.8 Example - 6
Ethyl acetate is formed by the reaction between ethanol

1 and acetic acid and the equilibrium represented as:
2HI(g) H2 (g)  I2 (g), K ' 
54.8 CH 3 COOH(l )  C2 H 5 OH(l )
CH3COOC 2 H 5 (l )  H 2 O(l )
At equilibrium [HI]= 0.5 mol L–1, (i) Write the concentration ratio (reaction quotient),
Qc for this reaction (Note: water is not in excess and
 H2   [I2 ]  x mol L1 is not a solvent in this reaction)
(ii) At 293 K, if one starts with 1.00 mol of acetic acid
K 
 H 2  I 2   x  x 
1 and 0.18 mol of ethanol, there is 0.171 mol of ethyl
 HI 
2
(0.5) 2 54.8 acetate in the final equilibrium mixture. Calculate
the equilibrium constant.
This gives x  0.068. i.e., [H2]= [I2] = 0.068 mol L–1 (iii) Starting with 0.5 mol of ethanol and 1.0 mol of acetic
acid and maintaining it at 293 K, 0.214 mol of ethyl
Example - 5 acetate is found after some time. Has equilibrium
What is the equilibrium concentration of each of been reached?
substances in the equilibrium when the initial
concentration of ICl was 0.78 M? CH3COOC2 H5 H 2O
Sol. (i) Q c  CH COOH C H OH
 3  2 5 
2ICl(g) I 2 (g)+Cl 2 (g),K c =0.14
(ii) CH3COOH  C2H5OH CH3COOC2 H5  H2O

Sol. Suppose at equilibrium,  I2  =  Cl2  = x mol L-1 . Then
Initial moles 1.00 mol 0.180 mol
2ICl I 2 (g) + Cl 2 (g)
Initial conc. 0.78 M 0 0 At eqm. 1–0.171 0.180–0.171 0.171 mol 0.171 mol
At equilibrium 0.78 - 2x x x
= 0.829 mol = 0.009 mol
Kc =
 I2  Cl2   0.14 
x x
Molar concs 0.829/V 0.009/V 0.171/V 0.171/V
 ICl  (0.78  2 x) 2
2
Kc 
 CH3COOC2 H5  H 2 O   0.171/ V  0.171/ V   3.92
x CH3COOH C2 H5 OH   0.829 / V  0.009 / V 
or x  0.14(0.78  2x) or  0.14  0.374
2 2
0.78  2 x
(iii) CH3COOH  C2H5OH CH3COOC2 H5  H2O
or x  0.292  0.748 x or 1.748 x  0.292 or x  0.167
Hence, at equilibrium, Initial moles 1.0 mol 0.5 mol
 I2  = Cl2  = 0.167M,  ICl After time t = 1–0.214 0.500–0.214 0.214 mol 0.214 mol
= 0.786 mol = 0.286 mol
= 0.78 - 2 × 0.167M = 0.446M
 0.214 / V  (0.214 / V)  0.204
Reaction quotient (Qc) =
(0.786 / V)(0.286 / V)
As Q c  K c , equilibrium has not been attained

Example - 7
1
Sol. 2HBr  g   H 2 (g)  Br2 (g). K 
A sample of pure PCl5 was introduced into an evacuated (1.6  105 )
vessel at 473 K. After equilibrium was attained,
Initial 10 bar 0 0
concentration of PCl5 was found to be 0.5×10–1 mol L–1.
At eqm. 10–p p/2 p/2
If value of Kc is 8.3 × 10–3, what are the concentrations of
PCl3 and Cl2 at equilibrium? (p / 2)(p / 2) 1 p2 1
Kp    
(10  p) 2
1.6 105
4(10  p)2 1.6 105
Sol. PCl5 (g) PCl3 (g)  Cl2(g) Taking square root of both sides, we get
At eqm 0.5× 10–1 M xM x M (suppose) p 1


2(10  p) 4  102 or 
4  10 2  p  2(10  p)
 Kc 
 PCl3  Cl2   x 2  8.3 103 (Given) 20
 PCl5  0.5  101 or 402p  20 or p   4.98  10 2 bar
402
Hence, at equilibrium, p H2  p Br2

or x 2  (8.3  10 3 )(0.5  10 1 )  4.15  10 4
= p/2 = 2.5×10–2 bar, p HBr  10  p  10 bar
or x  4.15 104  2.04 102 M  0.02M
Example - 10
Hence,  PCl3 eq   Cl 2 eq  0.02M Dihydrogen gas used in Haber’s process is produced
by reacting methane from natural gas with high
Example - 8 temperature steam. The first stage of two stage reaction
Equilibrium constant, K c for the reaction, involves the formation of CO and H2. In second stage,
CO formed in first stage is reacted with more steam in
N 2 (g)  3H 2 (g) 2NH3 (g) at 500 K is 0.061. At a
water gas shift reaction,
particular time, the analysis shows that composition of
the reaction mixture is 3.0 mol L–1 N2, 2.0 mol L–1 H2 and CO(g)  H2 O(g) CO2 (g)  H2 (g) . If a reaction
0.5 mol L–1 NH3. Is the reaction at equilibrium? If not, in vessel at 400ºC is charged with an equimolar mixture of
which direction does the reaction tend to proceed to CO and steam such that pCO  pH2O = 4.0 bar, what will
reach equilibrium?
be the partial pressure of H2 at equilibrium? Kp = 0.1 at
400ºC.
 NH3    0.5
2 2
Sol. Qc   0.0104
 N 2  H 2 3  3.0  2.0 3 Sol. Suppose the partial pressure of H2 at equilibrium= p bar
As Q c  K c , reaction is not in equilibrium CO(g)  H 2 O(g) CO2(g) + H2 (g)
Initial pressure 4.0 bar 4.0 bar

As Q c  K c , reaction will proceed in the forward direction.
At eqm (4–p) (4–p) p p
Example - 9
p2 p
The equilibrium constant for the reaction Kp   0.1(given)   0.1  0.316
(4  p)2 4p
H 2 (g)  Br2 (g) 2HBr(g) at 1024 K is 1.6 ×105. Find
the equilibrium pressure of all gases if 10.0 bar of HBr is p = 1.264 – 0.316p or 1.316p = 1.264 or p = 0.96 bar.
introduced into a sealed container at 1024 K.
Hence, (pH2 )eq = 0.96 bar

Predict which of the following reaction will have At temperature T, a compound AB 2(g) dissociates
appreciable concentration of reactants and products: according to the reaction
(a) Cl 2 (g) 2Cl(g), K c  5  10 39 2AB2  2AB  g   B2  g 
with a degree of dissociation, x, which is small compared

(b) Cl2 (g)  2NO(g) 2NOCl(g),Kc  3.7108
with unity. Deduce the expression for x in terms of the
equilibrium constant Kp and the total pressure, P.
(c) Cl2 (g)  2NO2 (g) 2NO2 Cl(g),K c  1.8
Sol. 2AB 2 2AB(g)  B2 (g)
Sol. For reaction (c), as Kc is neither very high nor very low, Initial moles 1 mole 0 0
reactants and products will be present in comparable At equilibrium 1 – x 2x x
amounts. Total number of moles at equilibrium = 1 – x + 2x + x
Example - 12 = 1 + 2x
Partial pressure = mole fraction × PTotal
The value of Kc for reaction, 3O2(g) 2O3 (g), is
2.0 × 10–50 at 25ºC. If the equilibrium concentration of O2 in 1 x 2x x
air at 25ºC is 1.6 × 10–2, what is the concentration of O3? p AB2   P, p AB   P, p B2  P
1 2 x 1  2x 1  2x
 O3   2.0  1050   O3 
2 2 2
p 2AB  p B 2  2x  P   x  P   1  2x 
2
Kc   Kp      
Sol.  O2  1.6 102   1  2x   1  2x   1  x  p 
3 3
p 2AB 2
or [O3]2 = (2.0 × 10–50) (1.6×10–2)3 = 8.192×10–56 4x 3 P

or K p 
or [O3]= 2.86×10–28 M 1  x 1  2x 
Example - 13 Neglecting x in comparison to unity,
The reaction, CO(g)+3H2(g) CH4(g) + H2O (g), is at 1/ 3
equilibrium at 1300 K in a 1 L flask. It also contains 0.30  Kp 
K p  4x 3 P or x   
mol of CO, 0.10 mol of H2 and 0.02 mol of H2O and an  4P 
unknown amount of CH4 in the flask. Determine the
concentration of CH4 in the mixture. The equilibrium Example - 15
constant KC, for the reaction at the given temperature is
Prove that the pressure necessary to obtain 50%
3.90.
dissociation of PCl5 at 500 K is numerically equal to three
times the value of the equilibrium constant, Kp.
Kc 
 CH 4  H 2 O
Sol.
CO H 2 
3
Sol. PCl5 PCl3  Cl2
Initial moles 1 0 0
 3.90 
 CH 4   0.02 
Moles at eqm. 1–0.5=0.5 0.5 0.5
 0.30  0.10 
3
Total=1.5 moles
(molar conc= No. of moles because volume of flask = 1L)
If P is the total required pressure, then
or [CH4]= 0.0585 M=5.85×10–2 M
0.5 P 0.5 P
p PCl5   P  , p PCl3  P 
1.5 3 1.5 3

0.5 P Example - 18
p Cl2  P 
1.5 3 At 540 K, 0.10 mol of PCl5 are heated in a 8.0 L flask. The
p PCl3  p Cl2 (P / 3)(P / 3) P pressure of the equilibrium mixture is found to be 1.0
 Kp    or P  3K p. atm. Calculate Kp and Kc for the reaction.
p PCl5 (P / 3) 3
Sol. PCl5 PCl3  Cl2
Example - 16
Initial 0.1 mol
What is the effect of reducing the volume on the system At eqm. 0.1 – x x x
described below? Total no. of moles at eqm. = 0.1 + x
2C(s)  O 2 (g) 2CO(g) PV 1 8

PV  nRT, i.e., n    0.18
RT 0.0821 540
Sol. On reducing the volume, the pressure will increase. By Le
 0.1  x  0.18 or x  0.08
Chatelier’s principle, equilibrium will shift to the side
accompanied by decrease of pressure, i.e., decrease in the (0.08 / 8)(0.08 / 8)
number of gaseous moles, i.e., backward direction.  Kc   0.04
(0.02 / 8)
Example - 17
K p  K c (RT)n  0.04(0.0821 540)1  1.77
The degree of dissociation is 0.4 at 400 K and 1.0 atm for Example - 19
the gaseous reaction
An equilibrium mixture,
PCl5 PCl3 + Cl2
CO(g)  H 2 O(g) CO 2 (g)  H 2 (g), present in a
Assuming ideal behaviour of all the gases, calculate the vessel of one litre capacity at 1000 K was found to
density of the equilibrium mixture at 400 K and 1.0 contain 0.4 mole of CO, 0.3 mole of H2O, 0.2 mole of CO2
atmosphere. (Atomic mass of P = 31.0 and Cl = 35.5) and 0.6 mole of H2. If it is desired to increase the
concentration of CO to 0.6 mole by adding CO2 into the
Sol. PCl5 PCl3 + Cl2 vessel, how many moles of it must be added into
Initial 1 mole 0 0 equilibrium mixture at constant temperature in order to
get this change.
At eqm. 0.6 0.4 0.4 moles
Sol. Step 1. To calculate Kc of the reaction.
Average molecular mass of mixture
Kc 
CO2 (g) H2 (g)  0.2  0.6  1
0.6(31  5  35.5)  0.4(31  3 35.5)  0.4(2  35.5)  CO(g) H2 O(g) 0.4  0.3

0.6  0.4  0.4 Step 2. To calculate extra CO2 to be added
Suppose extra CO2 to be added = x mole. Then writing the
125.1  55  28.4
  148.92 reverse reaction, we have
1.4
CO2 + H2 CO + H2O
For ideal gases, initial moles
after addition 0.2 + x 0.6 0.4 0.3
w w Moles (Molar
PV  nRT  RT or PM  RT  d RT
M V Conc.)at new (0.2+x –0.2) (0.6–0.2) 0.6 (0.3+0.2)
equilibrium =x = 0.4 = 0.5
PM 1  148.92 (V=1L) (given)
d   = 4.540g L–1
RT 0.082  400
1 0.6  0.5
Kc '    1 or x  0.75 moles
Kc x  0.4

The degree of dissociation of N2O4 into NO2 at one When   D glucose is dissolved in water, it undergoes
atmospheric pressure and 313 K is 0.310. Calculate Kp of mutarotation to form an equilibrium mixture of
the dissociation reaction at this temperature. What will
be the degree of dissociation at 10 atmospheric pressure   D glucose and   D glucose containing 63.6% of
at the same temperature? the latter. Calculate Kc for the mutarotation.
Sol. For the dissociation reaction Sol. α-D glucose   - D glucose

At equilibrium 36.4% 63.6%
N 2 O 4 (g) 2NO2 (g)
KC 
  D glucose   63.6  1.747
Initial moles 1 0    D glucose  36.4
Moles at eqm. 1 – 0.310 2 × 0.310 (  0.310, Given) Example - 22
= 0.69 = 0.62
At 77ºC and one atmoshpheric pressure, N2O4 is 70%
Total = 0.69 + 0.62 = 1.31 moles
dissociated into NO2. What will be the volume occupied
At one atmospheric pressure, by the mixture under these conditions if we start with
10g of N2O4?
0.69 0.62
p N 2 O4   1 atm, p NO 2   1atm
1.31 1.31 Sol. N 2 O4  2NO2
10
2 Initial moles 0
p NO2 (0.62 /1.31atm) 2 92
Kp    0.425atm
p N 2O4 (0.69 /1.31atm) 10 70 10
After dissociation   2 × 0.076
92 100 92
At 10 atmoshperic pressure, suppose degree of = 0.109 – 0.076 = 0.152
dissociation =  . Then = 0.033
Molar mass of N2O4
N 2 O4 2NO 2 = 28 + 64 = 92g mol–1
Total moles after dissociation = 0.033 + 0.152 = 0.185
Initial moles 1 0
T = 77°C = 77 + 273 K = 350 K
Moles at eqm 1  2 , Total = 1+ 
nRT
PV = nRT or V =
P
1  2
p N 2 O4   10atm, p NO2   10atm
1  1  0.185 mole  0.0821L atm K –1 mol –1  350K
V=
1 atm
[20 /(1   )]2 40 2 40 2 V = 5.32 L
Kp   
[10(1   ) /(1  )] 1   (1  ) 1   2
40 2
  0.425
1  2
Neglecting 2 in comparison to 1, 40 2 = 0.425
or  = 0.103 = 10.3 %

Example - 23 Example -24

0.1 mole of N 2O4 (g) was sealed in a tube under What is K c for the following equilibrium when the
atmospheric condition at 25ºC. Calculate the number of equilibrium concentration of each substance is: [SO2]=
moles of NO2(g) present if the equilibrium N2O4(g) is 0.60 M, [O2] = 0.82 M and [SO3] = 1.90 M ?
reached after some time (Kp = 0.14).
2SO 2 (g)  O2 (g)  2SO3 (g)
Sol. N 2 O 4 (g) 2NO2(g) Sol. Equilibrium constant (K c ) which is the ratio of
Initial amount 0.1 mole 0 concentration of product to reactant when each raise to
At equilibrium (0.1–x) 2x the power of its stoichiometric constant.It can be
Total = 0.1 + x moles expressed as:
SO3 
2
0.1  x 2x Kc =
As P=1 atm, p N 2 O4  , p NO2  atm
SO 2  O 2 
2
0.1  x 0.1  x
1.90  M 2
2
p 2NO2 (2x /(0.1  x)) 2 =

Kp    0.60  (0.82)M 3
2
p N2O4 (0.1  x) /(0.1  x)

=12.23M -1
4x 2 4x 2 Hence, the value of equilibrium constant is 12.23 M–1.
 
(0.1  x)(0.1  x) 0.01  x 2 Example - 25
For the following equilibrium, K c  6.3  1014 at 1000 K
4x2
  0 .1 4 NO(g)  O3 (g)  NO2 (g)  O 2 (g)
0 .0 1  x 2
Both the forward and reverse reactions in the equilibrium
or 4.14 x2 = 0.0014 or x = 0.018 are elementary bimolecular reactions. What is Kc, for the
 No. of moles of NO2 at equilibrium reverse reaction?
= 2x = 2 × 0.018= 0.036 mole Sol. K c  6.3  1014 at 1000 K
1
K’c for the reverse reaction will be  K
c


Introduction to Equilibrium & Law of Mass Action 6. For the system A(g) + 2B(g) C(g),the equilibrium
concentrations are A = 0.06 mol/litre, B = 0.12 mol/litre,
1. In chemical reaction A B, the system will be known in C = 0.216 mole/litre. The Keq for the reaction is
equilibrium when
(a) 250 (b) 416
(a) A completely changes to B
(c) 4 × 10–3 (d) 125
(b) 50% of A changes to B
7. For the reaction A + 2B C, the expression for
(c) The rate of change of A to B and B to A on both the sides equilibrium constant is
are same
(d) Only 10% of A changes to B [ A ] [ B] 2 [A] [B]
(a) (b)
2. According to law of mass action, rate of a chemical reaction [C ] [C]
is proportional to
[C ] [C ]
(a) Concentration of reactants (c) (d) 2 [B] [A ]
[A ] [B]2
(b) Molar concentration of reactants
8. Unit of equilibrium constant for the reversible reaction
(c) Concentration of products
H 2 + I2 2HI is
(d) Molar concentration of products
(a) mol–1 litre (b) mol–2 litre
3. The rate constant for forward and backward reactions of
hydrolysis of ester are 1.1 × 10–2 and 1.5 × 10–3 per minute (c) mol litre–1 (d) None of these
respectively. Equilibrium constant for the reaction is 9. In a reaction A + B C + D, the concentrations of A, B,
CH3COOC2H5 + H2O CH3COOH + C2H5OH C and D (in moles/litre) are 0.5, 0.8, 0.4 and 1.0 respectively.
The equilibrium constant is
(a) 4.33 (b) 5.33
(a) 0.1 (b) 1.0
(c) 6.33 (d) 7.33
(c) 10 (d) 
Equilibrium Constants (K p and K c) and Their 10. The suitable expression for the equilibrium constant of the
Properties reaction 2NO (g) + Cl2(g) 2NOCl (g) is
4. For the system 3A + 2B C, the expression for
equilibrium constant is [2 NOCl] [ NOCl]2
(a) K c  [2 NO] [Cl ] (b) K c 
2 [ NO]2 [Cl 2 ]
[3A][2B] [C]
(a) (b) [3A][2B]
C [ NOCl]2 [ NOCl]2
(c) K c  (d) K c 
[ NO] [Cl 2 ]2 [ NO]2 [Cl 2 ]2
[A]3[B]2 [C]
(c) (d) [A]3[B]2
[C] 11. For the reaction 2SO2 + O2 2SO3, the units of Kc are
5. On a given condition, the equilibrium concentration of HI, (a) litre/mol (b) mol/litre
H2 and I2 are 0.80, 0.10 and 0.10 mole/litre. The equilibrium
constant for the reaction H2 + I2 2HI will be (c) (mol litre ) –1 2
(d) (litre mol–1)2
12. The equilibrium concentration of X, Y and YX2 are 4, 2 and
(a) 64 (b) 12
2 moles respectively for the equilibrium
(c) 8 (d) 0.8
2X + Y YX2. The value of Kc is
(a) 0.625 (b) 0.0625
(c) 6.25 (d) 0.00625

13. In a 500 ml capacity vessel, CO and Cl2 are mixed to form 19. At a given temperature, the equilibrium constant for reaction
COCl2. At equilibrium, it contains 0.2 moles of COCl2 and PCl5(g) PCl3(g) + Cl2(g) is 2.4 × 10–3. At the same
0.1 mole of each of CO and Cl2. The equilibrium constant Kc temperature, the equilibrium constant for reaction.
for the reaction CO + Cl2 COCl2 is
PCl3(g) + Cl2(g) PCl5(g) is
(a) 5 (b) 10
(a) 2.4 × 10–3 (b) – 2.4 × 10–3
(c) 15 (d) 20
(c) 4.2 × 102 (d) 4.8 ×10-2
14. An equilibrium mixture of the reaction
20. In which of the following reaction, the value of K p will be
2H2S(g) 2H2 (g) + S2(g)
equal to K c ?
had 0.5 mole H2S, 0.10 mole H2 and 0.4 mole S2 in one litre
vessel. The value of equilibrium constant (K) in mole litre-1 is (a) H2 + I2 2HI (b) PCl5 PCl3 + Cl2
(a) 0.004 (b) 0.008
(c) 2NH3 N2 + 3H2 (d) 2SO2 + O2 2SO3
(c) 0.016 (d) 0.160
21. For N2 + 3H2 2NH3 + heat
15. For the reaction equilibrium N2O4(g) 2NO2(g), the
concentrations of N 2O 4 and NO 2 at equilibrium are (a) Kp = Kc (RT) (b) Kc = Kp (RT)
4.8 × 10–2 and 1.2 × 10–2 mol litre–1 respectively. The value of (c) Kp = Kc (RT)–2 (d) Kp = Kc (RT)–1
Kc for the reaction is
22. In which of the following equilibria, the value of Kp is less
(a) 3.3 × 102 mole litre–1 (b) 3 × 101 mol litre–1 than Kc?
(c) 3 × 10–3 mol litre–1 (d) 3 × 103 mol litre–1
(a) H2 + I2 2HI (b) N2 + 3H2 2 NH3
16. In the reaction, H2 + I2 2HI. In a 2 litre flask, 0.4 moles of
(c) N2 + O2 2NO (d) CO + H2O CO2 + H2
each H2 and I2 are taken. At equilibrium 0.5 moles of HI are
formed. What will be the value of equilibrium constant, Kc? 23. For the reaction H2(g) + I2(g) 2HI(g) at 721K the value
(a) 20.2 (b) 25.4 of equilibrium constant (Kc) is 50. When the equilibrium
concentration of both is 0.5M, the value of Kp under the
(c) 0.284 (d) 11.1 same conditions will be?
17. Equilibrium constants K1 and K 2 for the following equilibria (a) 0.002 (b) 0.2
1 (c) 50.0 (d) 50 / RT
NO(g) + O NO2(g) and
2 2
24. 4 moles of A are mixed with 4 moles of B. At equilibrium for
2NO2(g) 2NO(g) + O2(g) are related as the reaction A + B C + D, 2 moles of C and D are
formed. The equilibrium constant for the reaction will be
1
(a) K 2  K (b) K 2  K12 1 1
1 (a) (b)
4 2
K1 1 (c) 1 (d) 4
(c) K 2  (d) K 2 
2 K12 25. For which of the following reactions does the equilibrium
constant depend on the units of concentration?
18. Two gaseous equilibria
1 1
1 (a) NO(g) N 2 (g)  O2 (g)
SO 2 (g)  O 2 (g) SO3(g) and 2 2
2
2SO3(g) 2SO2(g) + O2(g) have equilibrium constants (b) Zn (s)  Cu 2 (aq) Cu (s)  Zn 2 (aq)
K1 and K2 respectively at 298 K. Which of the following
(c) C2H5OH (l) + CH3COOH CH3COOC2H5(l) + H2O (l)
relationships between K1 and K2 is correct?
(Reaction carried in an inert solvent)
(a) K1 = K2 (b) K2 = K12
(d) COCl2(g) CO(g) + Cl2(g)
(c) K2 = 1/K12 (d) K2 = 1/K1

26. A + B C + D. If initially the concentration of A and B 33. For the reversible reaction,
are both equal but at equilibrium, concentration of D will be
N2(g) + 3H2(g) 2NH3(g)
twice of that of A then what will be the equilibrium constant
of reaction? at 500°C, the value of Kp is 1.44 × 10–5 when partial pressure
(a) 4 / 9 (b) 9 / 4 is measured in atmospheres. The corresponding value of Kc
with concentration in mole litre-1, is
(c) 1 / 9 (d) 4
(a) 1.44 × 10–5/(0.082 × 500)–2 (b) 1.44 × 10–5/(8.314 × 773)–2
27. 4.5 moles each of hydrogen and iodine heated in a sealed
ten litre vessel. At equilibrium, 3 moles of HI were found. (c) 1.44 × 10–5/(0.082 × 773)2 (d) 1.44 × 10–5/(0.082 × 773)–2
The equilibrium constant for H2(g) + I2(g) 2 HI(g) is 34. A mixture of 0.3 mole of H2 and 0.3 mole of I2 is allowed to
(a) 1 (b) 10 react in a 10 litre evacuated flask at 500ºC. The reaction is
H2+ I2 2HI, the K is found to be 64. The amount of
(c) 5 (d) 0.33 unreacted I2 at equilibrium is
28. For the equilibrium N2 + 3H2 2NH3, Kc at 1000K is (a) 0.15 mole (b) 0.06 mole
2.37 × 10–3 If at equilibrium [N2] = 2M, [H2] = 3M, the
concentration of NH3 is (c) 0.03 mole (d) 0.2 mole
(a) 0.00358 M (b) 0.0358 M 35. XY2 dissociates as :
(c) 0.358 M (d) 3.58 M XY2  XY  Y

29. Two moles of NH3 when put into a previously evacuated Initial pressure of XY2 is 600 mm Hg. The total pressure at
vessel (one litre), partially dissociate into N2 and H2. If at equilibrium is 800 mm Hg. Assuming volume of system to
equilibrium one mole of NH3 is present, the equilibrium remain constant, the value of Kp is
constant is
(a) 50 (b) 100
(a) 3/4 mol2 litre–2 (b) 27/64 mol2 litre–2
(c) 200 (d) 400
(c) 27/32 mol2 litre–2 (d) 27/16 mol2 litre–2
36. 15 mol of H2 and 5.2 moles of I2 are mixed and allowed to
30. The equilibrium constant for the reaction attain equilibrium at 500ºC. At equilibrium, the concentration
of HI is found to be 10 mol. The equilibrium constant for the
N2(g) + O2(g) 2NO (g) at temperature T is 4 × 10–4. The
formation of HI is.
value of Kc for the reaction
(a) 50 (b) 25
1 1
NO (g) N 2 (g )  O 2 (g) at the same temperature (c) 200 (d) 15
2 2
is 37. For the equilibrium AB (g) A(g) + B(g). Kp is equal to
(a) 4 × 10–4 (b) 50 four times the total pressure. Calculate the number moles of
A formed if one mol of AB is taken initially.
(c) 2.5 × 10 2
(d) 0.02
(a) 0.45 (b) 0.30
31. 2 mol of N2 is mixed with 6 mol of H2 in a closed vessel of one
litre capacity. If 50% of N2 is converted into NH3 at (c) 0.60 (d) 0.90
equilibrium, the value of Kc for the reaction .
38. I 2  I   I3
N2(g) + 3H2(g) 2NH3(g) is
This reaction is set-up in aqueous medium. We start with
(a) 4/27 (b) 27/4 1 mol of I2 and 0.5 mol of I– in 1L flask. After equilibrium is
(c) 1/27 (d) 24 reached, excess of AgNO3 gave 0.25 mol of yellow precipitate.
Equilibrium constant is
32. The reaction between N2 and H2 to form ammonia has
Kc = 6 × 10–2 at the temperature 500°C. The numerical value (a) 1.33 (b) 2.66
of Kp for this reaction is
(c) 2.00 (d) 3.00
(a) 1.5 × 10–5 (b) 1.5 × 105
(c) 1.5 × 10–6 (d) 1.5 × 106

39. At a certain temp. 2HI H2 + I2 Only 50% HI is 45. A 1 M solution of glucose reaches dissociation equilibrium
dissociated at equilibrium. The equilibrium constant is according to equation given below 6HCHO C6H12O6 .
What is the concentration of HCHO at equilibrium if
(a) 0.25 (b) 1.0 equilibrium constant is 6 × 1022?
(c) 3.0 (d) 0.50 (a) 1.6 × 10–8 M (b) 3.2 × 10–6 M
40. An amount of solid NH4HS is placed in a flask already (c) 3.2 × 10–4 M (d) 1.6 × 10–4 M
containing ammonia gas at a certain temperature and 0.50
atm. pressure. Ammonium hydrogen sulphide decomposes 46. 0.6 mole of NH3 in a reaction vessel of 2dm3 capacity was
to yield NH 3 and H 2S gases in the flask. When the brought to equilibrium. The vessel was then found to
decomposition reaction reaches equilibrium, the total contain 0.15 mole of H2 formed by the reaction.
pressure in the flask rises to 0.84 atm. The equilibrium
constant for NH4HS decomposition at this temperature is 2NH3 (g) N2 (g) + 3H2 (g)
(a) 0.30 (b) 0.18 which of the following statements is true?

(c) 0.17 (d) 0.11
(a) 0.15 mole of the original NH3 had dissociated at
Applications of Equilibrium Constant equilibrium.
41. In which of the following, the reaction proceeds towards (b) 0.55 mole of ammonia is left the vessel
completion?
(a) K = 103 (b) K = 10–2 (c) At equilibrium the vessel contained 0.45 mole of N2
(c) K = 10 (d) K = 1 (d) The concentration of NH3 at equilibrium is 0.25 mole

per dm3
42.  G º (HI; g)   1.7 kJ. What is the equilibrium constant at
25ºC for 2HI(g) H2(g) + I2(g)? 47. 5 moles of SO2 and 5 moles of O2 are allowed to react to form
SO3 in a closed vessel. At the equilibrium stage 60% of SO2
(a) 24.0 (b) 3.9 is used up. The total number of moles of SO2, O2 and SO3 in
(c) 2.0 (d) 0.5 the vessel now is
43. Calculate Gº for conversion of oxygen to ozone (a) 10.0 (b) 8.5
(c) 10.5 (d) 3.9
3
O (g)  O3(g) at 298 K, if Kp for this conversion is 2.47
2 2  4 PCl3(g) is attained
48. The equilibrium P4 (s) + 6 Cl2 (g) 
× 10–29 by mixing equal moles of P4 and Cl2 in an evacuated vessel.
(a) 163 kJ mol–1 (b) 2.4 × 102 kJ mol–1 Then at equilibrium
(c) 1.63 kJ mol–1 (d) 2.38 × 106 kJ mol–1 (a) [Cl2] > [PCl3] (b) [Cl2] > [P4]
(c) [P4] > [Cl2] (d) [PCl3] > [P4]
44. In Haber process, 30 litres of dihydrogen and 30 litres of
dinitrogen were taken for reaction which yielded only 50% 49. 40% of a mixture of 0.2 mol of N2 and 0.6 mol of H2 reacts to
of the expected product. What will be the composition of give NH3 according to the equation :
gaseous mixture under the a foresaid condition in the end?
N 2  3H 2  2NH 3
(a) 20 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
at constant temperature and pressure. Then the ratio of the
(b) 20 litres ammonia, 20 litres nitrogen, 20 litres hydrogen final volume to the initial volume of gases are
(c) 10 litres ammonia, 25 litres nitrogen, 15 litres hydrogen (a) 4 : 5 (b) 5 : 4

(c) 7 : 10 (d) 8 : 5
(d) 20 litres ammonia, 10 litres nitrogen, 30 litres hydrogen

50. Calculate the partial pressure of carbon monoxide from the 55. At the equilibrium of the reaction,
following
N2O4 (g)  2 NO2 (g),
CaCO3 (s) CaO(s) + CO2 ; Kp = 8 × 10–2
the observed molecular weight of N2O4 is 80 g mol–1 at 350 K.
CO2(g) + C (s)  2CO (g) ; Kp = 2 The percentage of dissociation of N2O4 (g) at 350 K is
(a) 0.2 (b) 0.4 (a) 10% (b) 15%
(c) 1.6 (d) 4 (c) 20% (d) 18%
Degree of Dissociation Le Chatelier’s Principle

51. 3.2 moles of hydrogen iodide were heated in a sealed bulb at 56. Pure ammonia is placed in a vessel at temperature where its
444°C till the equilibrium state was reached. Its degree of dissociation (  ) is appreciable. At equilibrium
dissociation at this temperature was found to be 22%. The (a) Kp does not change significantly with pressure
number of moles of hydrogen iodide present at equilibrium
are (b)  does not change with pressure
(a) 2.496 (b) 1.87 (c) Concentration of NH3 does not change with pressure
(c) 2 (d) 4 (d) Concentration of H2 is less than that of N2
52. One mole of N2O4(g) at 100 K is kept in a closed container at 57. Change in volume of the system does not alter the number
1.0 atm pressure. It is heated to 400 K, where 30% by mass of moles in which of the following equilibrium
of N2O4(g) decomposes of NO2(g). The resultant pressure
will be (a) N2(g)+ O2(g) 2NO (g)
(a) 4.2 (b) 5.2 (b) PCl5 (g) PCl3 (g) + Cl2(g)
(c) 3.2 (d) 6.2
(c) N2(g) + 3H2(g) 2NH3(g)
53. The vapour density of completely dissociated NH4Cl is
(d) SO2Cl2(g) SO2(g) + Cl2(g)
(a) Double than that of NH4Cl 58. The equilibrium constant (Kp) for the reaction.
(b) Half than that of NH4Cl 
PCl5(g)   PCl3(g) + Cl2(g) is 16. If the volume of the
(c) Same as that of NH4Cl container is reduced to one half its original volume, the
value of Kp for the reaction at the same temperature will be
(d) Determined by the amount of solid NH4Cl taken (a) 32 (b) 64
54. The equilibrium constant (Kp) for the decomposition of (c) 16 (d) 4
gaseous H2O
59. Consider the following equilibrium in a closed container :
1 N2O4 (g) 2 NO2(g). At a fixed temperature, the volume
H2O (g)  H2 (g) + O2(g) of the reaction container is halved. For this change, which
2
of the followinng statement held true regarding the equilib-
is related to degree of dissociation () at a total pressure p,
given by rium constant  K p  and degree of dissociation    :-
(a) neither Kp nor  changes

 3 p1/ 2 3 p3 / 2
(a) K p  (b) K p  (b) both Kp and  change
(1  ) (2   )1/ 2 (1   ) (2  )1/ 2
(c) Kp changes but  does not change
3 / 2 p2  3 / 2 p1/ 2
(c) K p  (d) K p  (d) Kp does not change but  changes
(1   ) (2  )1/ 2 (1   ) (2  )1/ 2

60. What is the effect of halving the pressure by doubling the 66. The reaction A + B C + D +Heat has reached
volume on the following system at 500°C? equilibrium. The reaction may be made to proceed
forward by
 2HI(g)
H2(g) + I2(g) 
(a) Adding more C
(a) Shift to product side
(b) Adding more D
(b) Shift to product formation
(c) Decreasing the temperature
(c) Liquefaction of HI
(d) Increasing the temperature
(d) No effect
67. According to Le-chatelier principle, if heat is given to solid-
 CH3COO– + H+
61. In equilibrium CH3COOH + H2O  liquid system, then
(a) Quantity of solid will reduce
The equilibrium constant may change when
(b) Quantity of liquid will reduce
(a) CH3COO– are added (b) CH3COOH is added
(c) Increase in temperature
(c) Catalyst is added (d) Mixture is heated
(d) Decrease in temperature
62. Which of the following statements regarding a chemical
equilibrium is wrong? 68. Following gaseous reaction is undergoing in a vessel
(a) An equilibrium can be shifted by altering the temperature C2H4 + H2 C2H6; H = – 32.7 Kcal
or pressure Which will increase the equilibrium concentration of C2H6?
(b) An equilibrium is dynamic (a) Increase of temperature
(c) The same state of equilibrium is reached whether one (b) By reducing temperature
starts with the reactants or the products
(c) By removing some hydrogen
(d) The forward reaction is favoured by the addition of a
catalyst (d) By adding some C2H6
63. The formation of SO3 takes place according to the following 69. The effect of increasing the pressure on the equilibrium
reaction,
2A(g) + 3B(g) 3A(g) + 2B(g) is
2SO2 + O2 2SO3 ; H = – 45.2 kcal
(a) Forward reaction is favoured
The formation of SO3 is favoured by
(b) Backward reaction is favoured
(a) Increasing in temperature
(c) No effect
(b) Removal of oxygen
(d) None of the above
(c) Increase of volume
70. The exothermic formation of ClF3 is represented by the
(d) Increasing of pressure equation
64. N2 + O2 2NO - Q cals Cl2(g) + 3F2(g) 2ClF3(g); H = – 329 kJ
In the above reaction which is the essential condition for Which of the following will increase the quantity of ClF3 in
the higher production of NO? an equilibrium mixture of Cl2, F2 and ClF3?
(a) High temperature (b) High pressure (a) Increasing the temperature
(c) Low temperature (d) Low pressure (b) Removing Cl2
65. Which of the following reactions proceed at low pressure? (c) Increasing the volume of the container
(a) N2 + 3H2 2NH3 (b) H2 + I2 2HI (d) Adding F2
(c) PCl5 PCl3 + Cl2 (d) N2 + O2 2NO

71. In which of the following system, doubling the volume of If some CO is added into the vessel, then after the equilibrium
the container cause a shift to the right? is attained again, concentration of
(a) H2(g) + Cl2(g) 2HCl(g) (a) PCl5 will increase

(b) PCl5 will decrease
(b) 2CO(g) + O2(g) 2CO2(g)
(c) PCl5 will remain unaffected
(c) N2(g) + 3H2(g) 2NH3(g)
(d) Cl2 will increase
(d) PCl5(g) PCl3(g) + Cl2(g)
77. In the reaction, A2(g) + 4 B2(g) 2AB4(g)
72. Which of the following information can be obtained on the
basis of Le-chatelier’s principle? H  0 the formation of AB4 is will be favoured at
(a) Entropy change in a reaction (a) Low temperature, high pressure
(b) Dissociation constant of a weak acid (b) High temperature, low pressure
(c) Equilibrium constant of a chemical reaction (c) Low temperature, low pressure
(d) Shift in equilibrium position on changing value of a (d) High temperature, high pressure
constant
78. In the following reversible reaction
73. The equilibrium SO2Cl2 (g) SO2(g) + Cl2(g) is attained
at 25°C in a closed container and an inert gas helium is 2SO2 + O2 2SO3 + Q Cal
introduced which of the following statement is correct? Most suitable condition for the higher production of SO3 is
(a) More chlorine is formed (a) High temperature and high pressure
(b) Concentration of SO2 is reduced (b) High temperature and low pressure
(c) More SO2Cl2 is formed (c) Low temperature and high pressure
(d) Concentration of SO2Cl2, SO2 and Cl2 does not change (d) Low temperature and low pressure
74. H2(g) + I2(g) 2HI(g) H = + q cal, then formation of HI 79. In the reaction A(g) + 2B(g) C(g) + Q kJ, greater product
(a) Is favoured by lowering the temperature will be obtained or the forward reaction is favoured by
(b) Is favoured by increasing the pressure (a) At high temperature and high pressure
(c) Is unaffected by change in pressure (b) At high temperature and low pressure
(d) Is unaffected by change in temperature (c) At low temperature and high pressure
75. The formation of nitric oxide by contact process (d) At low temperature and low pressure
N2 + O2 2NO, H = 43.200 kcal is favoured by 80. The yield of product in the reaction
(a) Low temperature and low pressure A2(g)+ 2B(g) C(g) – Q.kJ. would be high at
(b) Low temperature and high pressure (a) High temperature and high pressure
(c) High temperature and high pressure (b) High temperature and low pressure
(d) High temperature and excess reactants concentration (c) Low temperature and high pressure
76. The following two equilibria exist simultaneously in a (d) Low temperature and low pressure
closed vessel :
PCl5(g)  PCl3(g) + Cl2 (g)
COCl2 (g)  CO (g) + Cl2 (g)


Objective Questions I [Only one correct option]
1. For the reaction (2002) 6. For the reaction (2004)
1 Kp
CO (g) + O (g) CO2 (g), Kp/Kc is CO(g) + Cl2 (g) COCl2 (g), the is equal to
2 2 Kc
(a) RT (b) (RT)–1

1
(c) (RT)–1/2 (d) (RT)1/2 (a) (b) 1.0
RT
2. In which of the following reactions, increase in the pressure
(c) RT (d) RT
at constant temperature does not affect the moles at
equilibrium? (2002) 7. The equilibrium constant for the reaction
(a) 2NH3(g) N2(g) + 3H2(g) N2(g) + O2(g) 2NO(g)
(b) C(g) + 1/2O2(g) CO(g) at temperature, T is 4 × 10–4. The value of Kc for the reaction
(c) H2(g) + 1/2O2(g) H2O(g) 1 1
NO2(g) N2(g) + O2(g)
(d) H2(g) + I2(g) 2HI(g) 2 2
3. For the reaction equilibrium at the same temperature is (2004)
N2O4 (g) 2NO2 (g) (a) 2.5 × 10 2
(b) 0.02
–4
the concentrations of N2O4 and NO2 at equilibrium are (c) 4 × 10 (d) 50
4.8 × 10–2 and 1.2 × 10–2 mol L–1 respectively. The value of Kc 8. A small amount of NH4HS is placed in a flask already
for the reaction is (2003) containing ammonia gas at a certain temperature and 0.50
atm pressure. Ammonium hydrogen sulphide decomposes
(a) 3 × 103 mol L–1 (b) 3.3 × 102 mol L–1
to yield NH 3 and H 2 S gases in the flask. When the
(c) 3 × 10–1 mol L–1 (d) 3 × 10–3 mol L–1 decomposition reaction reaches equilibrium, the total
4. The conditions favourable for the reaction pressure in the flask rises to 0.84 atm. The equilibrium
constant for NH4HS decomposition at this temperature is
2SO2(g) + O2(g) 2SO3(g); Hº = – 198 kJ (2005)
are (2003) (a) 0.30 (b) 0.18
(a) Low temperature, high pressure (c) 0.17 (d) 0.11
(b) Any value of T and P 9. For the reaction
(c) Low temperature and low pressure 2NO2(g) 2NO (g) + O2(g)
(d) High temperature and high pressure
(Kc = 1.8 × 10–6 at 184ºC) [R = 0.0831 kJ/(mol.K)]
5. What is the equilibrium expression for the reaction
When Kp and Kc are compared at 184ºC it is found that
(2004)
(2005)
P4 (s) + 5O2 (g) P4O10 (s) ?
(a) Whether Kp is greater than, less than or equal to Kc
[ P4 O10 ] 1 depends upon the total gas pressure
(a) K c  (b) K c 
[ P4 ] [O 2 ]5 [O 2 ]5 (b) Kp = Kc
(c) Kp is greater than Kc
[P4 O10 ]
(c) Kc = [O2] 5
(d) K c  (d) Kp is greater than Kc
5 [P4 ] [O 2 ]

10. Phosphorus pentachloride dissociates as follows, in a closed (a) 1.8 atm (b) 3 atm
reaction vessel, (c) 0.3 atm (d) 0.18 atm
PCl5 (g) PCl3(g) + Cl2(g)
1
If total pressure at equilibrium of the reaction mixture is P 15. For the reaction SO2(g) + O SO3(g) ,if
2 2(g)
and degree of dissociation of PCl5 is x, the partial pressure of
Kp = Kc(RT)x where the symbols have usual meaning then
PCl3 will be (2006)
the value of x is : (assuming ideality) (2014)
 x   2x  (a) -1/2 (b) 1/2
(a)  P (b)  P
 x 1 1 x  (c) 1 (d) –1
16. At a certain temperature, only 50% HI is dissociated into H2
 x   x  and I2 at equilibrium. The equilibrium constant is:
(c)  P (d)  P
 x 1 1 x  (Online 2014 Set-1 )
11. The equilibrium constant for the reaction (a) 1.0 (b) 3.0
(c) 0.5 (d) 0.25
1
SO3(g) SO2(g) + O2(g) 17. What happens when an inert gas is added to an equilibrium
2
keeping volume unchanged? (Online 2014 Set-3)
is Kc = 4.9 × 10–2. The value of Kc for the reaction (a) More reactant will form
2SO2 + O2(g) 2SO3(g) will be (2006) (b) More product will form
(a) 416 (b) 2.40 × 10–3 (c) Equilibrium will remain unchanged
(d) Less product will form
(c) 9.8 × 10–2 (d) 4.9 × 10–2
18. For the decomposition of the compound represented as
12. The equilibrium constants K p and K p for the reactions
1 2
NH2COONH4(s) 2 NH3(g) + CO2(g)
X 2Y and Z P + Q, respectively are in the ratio of
1 : 9. If the degree of dissociation of X and Z be equal then The Kp = 2.9 × 10 atm .
–5 3
the ratio of total pressure at these equilibria is (2008) If the reaction is started with 1 mol of the compound, the
(a) 1 : 36 (b) 1 : 1 total pressure at equilibrium would be :
(c) 1 : 3 (d) 1 : 9 (Online 2014 Set-4)
13. For the following three reactions 1, 2 and 3 equilibrium (a) 5.82 × 10 atm
–2
(b) 7.66 × 10–2 atm
constants are given (c) 38.8 × 10–2 atm (d) 1.94 × 10–2 atm
(1) CO(g) + H2O(g) CO2(g) + H2(g); K1 19. The standard Gibbs energy change at 300 K for the reaction
2A B + C is 2494.2 J. At a given time, the composition
(2) CH4(g) + H2O(g) CO(g) + 3H2(g); K2
1 1
(3) CH4(g) + 2H2O(g) CO2(g) + 4H2(g); K3 of the reaction mixture is [A] = , [B] = 2 and [C]= . The
2 2
Which of the following relations is correct ? (2008)
reaction proceeds in the : (2015)
(a) K 1 K 2  K 3 (b) K 2 K 3  K1 [R = 8.314 J/K/mol, e = 2.718]
(a) forward direction because Q < KC
(c) K3 = K1K2 (d) K3 . K 32 K12
(b) reverse direction because Q < KC
14. A vessel at 1000 K contains CO with a pressure of 0.5 atm. (c) forward direction because Q > KC
Some of the CO2 is converted into CO on the addition of
(d) reverse direction because Q > KC
graphite. If the total pressure at equilibrium is 0.8 atm, the
value of Kp is (2011)

20. The increase of pressure on ice water system at (c) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(l)
constant temperature will lead to : (Online 2015 Set-1)
(d) 3O2(g) 2O2(g)
(a) a decrease in the entropy of the system
26. At a certain temperature in a 5L vessel, 2 moles of carbon
(b) an increase in the Gibbs energy of the system monoxide and 3 moles of chlorine were allowed to reach
(c) no effects on the equilibrium equilibrium according to the reaction,
(d) a shift of the equilibrium in the forward direction CO + Cl2  COCl2
21. For the equilibrium, A(g) B(g), H is 40 kJ/mol. If the At equilibrium, if one mole of CO is present then equilibrium
ratio of the activation energies of the forward (Ef) and reverse constant (Kc) for the reaction is : (Online 2018 Set-2)
2 (a) 2 (b) 2.5
(Eb) reactions is then : (Online 2015 Set- 1)
3 (c) 3 (d) 4
(a) Ef = 80 kJ/mol; Eb = 120 kJ/mol  N 2O 4(g) is an
27. The gas phase reaction 2NO 2(g) 
(b) Ef = 60 kJ/mol; Eb = 100 kJ/mol exothermic reaction. The decomposition of N 2O 4, in
(c) Ef = 30 kJ/mol; Eb = 70 kJ/mol equilibrium mixture of NO2(g) and N2O4(g), can be increased
by : (Online 2018 Set-3)
(d) Ef = 70 kJ/mol; Eb = 30 kJ/mol
(a) lowering the temperature.
22. The equilibrium constant at 298 K for reaction
A+B C + D is 100. If the initial concentration of all (b) increasing the pressure.
the four species were 1M each, then equilibrium (c) addition of an inert gas at constant volume.
concentration of D (in mol L–1) will be: (2016) (d) addition of an inert gas at constant pressure.
(a) 0.818 (b) 1.818 28. Consider the following reversible chemical reactions
(c) 1.182 (d) 0.182

A 2  g   B2  g  
K 1

 2AB  g  .....(1)
23. A solid XY kept in an evacuated sealed container undergoes
decomposition to form a mixture of gases X and Y at
temperature T. The equilibrium pressure is 10 bar in this 
6AB  g  
2

 3A 2  g   3B 2  g 
K
....(2)
vessel. Kp for this reaction is : (Online 2016 Set-2)
The relation between K1 and K2 is: (09-01-2019 Shift-2)
(a) 5 (b) 10
(c) 25 (d) 100 1
(a) K1K 2  (b) K 2  K13
3
24. The following reaction occurs in the Blast Furnace where
iron ore is reduced to iron metal : (c) K 2  K13 (d) K1 K 2  3
Fe2O3(s) + 3CO(g)  2Fe(l) + 3CO2(g)
29. The value of Kp/Kc for the following reactions at 300 K are,
Using the Le Chatelier’s principle, predict which one of the
respectively: (At 300 K, RT = 24.62 dm3 atm mol-1)
following will not disturb the equilibrium ?
(Online 2017 Set-2) N 2  g   O 2  g   2NO  g 
(a) Removal of CO (b) Removal of CO2 N 2 O 4  g   2NO 2  g 
(c) Addition of CO2 (d) Addition of Fe2O3 N 2  g   3H 2  g   2NH3  g  (10-01-2019 Shift-1)
25. In which of the following reactions, an increase in the volume
of the container will favour the formation of products ? (a) 1, 24.62 dm3 atm2 mol, 606.0 dm6 atm2 mol
(Online 2018 Set-1) (b) 1, 24.62 dm3 atm mol–1, 1.65 x 10–3 dm–6 atm–3 mol2
(a) 2NO2(g) 2NO(g) + O2(g) (c) 1, 4.1 × 10–2 dm atm mol, 606 dm6 atm2 mol
(d) 24.62 dm3 atm mol, 606 dm6 atm2 mol, 1.65 × 10–3 dm atm
mol2
(b) H2(g) + I2(g) 2HI(g)

30. 5.1g NH4SH is introduced in 3.0 L evacuated flask at 327oC, 34. For the following reactions, equilibrium constants are given,
30% of the solid NH4SH decomposed to NH3 and H2S as
gases. The Kp of the reaction at 327oC is (R = 0.082 L atm S  s   O2  g   SO 2  g  ; K1  1052
mol–1 K–1, molar mass of S = 32 g mol–1, molar mass of N = 14 2S  s   3O2  g   2SO3  g  ; K 2  10129
g mol–1) (10-01-2019 Shift-2)
The equilibrium constant for the reaction, is
(a) 0.242 × 10–4 atm2 (b) 1 × 10–4 atm2
(c) 4.9 × 10–3 atm2 (d) 0.242 atm2 2SO2  g   O2  g   2SO3  g  (08-04-2019 Shift-2)
31. Consider the reaction N 2  g   3H 2  g   2NH3  g  (a) 10154 (b) 10181

(c) 1025 (d) 1077
The equilibrium constant of the above reaction is Kp. If pure
35. For the reaction,
ammonia is left to dissociate, the partial pressure of ammonia
at equilibrium is given by (Assume that PNH3  PTotal at 2SO 2  g   O 2  g   2SO3  g 
equilibrium) (11-01-2019 Shift-1) H  57.2 kJ mol1 and K c  1.7  1016
3 1 1 Which of the following statement is INCORRECT?

3 2 K p2 P 2 K p2 P 2
(a) (b) (10-04-2019 Shift-2)
16 16
(a) The equilibrium constant is large suggestive of
1 3 1
reaction going to completion and so no catalyst is
K p2 P 2 3 2 K p2 P 2 required.
(c) (d)
4 4 (b) The equilibrium will shift in forward direction as the
pressure increases.
32. Two solids dissociate as follows
(c) The equilibrium constant decreases as the
A  s   B  g   C  g  ; K P1  zatm , D  s  
2
temperature increases.
(d) The addition of inert gas at constant volume will
C  g   E  g  ; K P2  yatm 2 not affect the equilibrium constant.
The total pressure when both the solids dissociate 36. In which one of the following equilibria, K P  K C ?
simultaneously is. (12-01-2019 Shift-1)
(12-04-2019 Shift-2)
(a) x  yatm (b) 2  
x  y atm (a) 2C(s) + O2(g)  2CO(g)
(b) 2HI(g)  H2(g) + I2(g)

(c)  x  y  atm (d) x 2  y 2 atm
(c) NO2(g) + SO2(g)  NO(g) + SO3(g)

33. In a chemical reaction, A  2B  K
 2C  D , the initial (d) 2NO(g)  N2(g) + O2(g)
concentration of B was 1.5 times of the concentration of A,
but the equilibrium concentrations of A and B were found 37. For the reaction,
to be equal. The equilibrium constant (K) for the aforesaid 2H2(g) + 2NO(g)  N2(g) + 2H2O(g)
chemical reaction is: (12-01-2019 Shift-1)
The observed rate expression is, rate  k f  NO   H 2  .
2
(a) 4 (b) 16
The rate expression for the reverse reaction is:
1
(c) (d) 1 (07-01-2020 Shift-2)
4
(a) k b  N 2  H 2 O  (b) k b  N 2  H 2 O
2
(c) k b  N 2  H 2 O  /  H 2  (d) k b  N 2  H 2 O  /  H 2 
2 2

38. In the figure shown below reactant A (represented by the
40. If the equilibrium constant for A  B + C is K eq and that
1
square) is in equilibrium with product B (represented by

circle). The equilibrium constant is:  
of B + C  P is K eq , the equilibrium constant for A 
2
(09-01-2020 Shift-2) P is: (04-09-2020 Shift-2)
(a) K eq K eq (b) K eq  K eq

1 2 2 1
(c) K eq  K eq (d) K eq / K eq

1 2 1 2
41. Consider the following reaction:

N2O4(g)  2NO2(g); = + 58 kJ
(a) 1 (b) 2
For each of the following cases (A, B), the direction in which
(c) 8 (d) 4
the equilibrium shifts is:
39. For the equilibrium A  B the variation of the rate of the (A) Temperature is decreased
forward (a) and reverse (b) reaction with time is given by:
(B) Pressure is increased by adding N2 at constant T.
(09-01-2020 Shift-1)
(05-09-2020 Shift-1)
(a) (A) towards reactant, (B) towards product
(b) (A) towards reactant, (B) no change
(a) (c) (A) towards product, (B) towards reactant
(d) (A) towards product, (B) no change
42. For the reaction (06-09-2020 Shift-1)
3
Fe 2 N  s   H 2  g   2Fe  s   NH 3  g 
2
(b) (a) K c  K p  RT 
1/ 2
(b) K c  K p  RT 
1/ 2
3
(c) K c  K p  RT  2 (d) K c  K p  RT 
43. The variation of equilibrium constant with temperature is

given below:
(c) Temp., Equilibrium Constant

T1  25C, K1  10
T2  100C, K 2  100
The value of H, G at T1 and H, G at T2(in kJmol–1)

respectively, are close to
[use R = 8.314 JK–1 mol–1] (06-09-2020 Shift-1)
(d)
(a) 28.4, –7.14 and –5.71 (b) 0.64. –7.41 and –5.71
(c) 28.4, –5.71 and –14.29 (d) 0.64, –5.71 and –14.29

44. The value of KC is 64 at 800 K for the reaction 49. A homogeneous ideal gaseous reaction
N2(g) + 3H2(g)  2NH3(g) The value of KC for the following AB2 g   A g   2B g  is carried out in a 25 litre flask at 27oC.
reaction is: The initial amount of AB2 was 1 mole an the equilibrium
1 3 pressure was 1.9 atm. The value of KP is x 102 . The value
NH 3  g   N 2  g   H2  g  (06-09-2020 Shift-2)
2 2 of x is ___. (Integer answer) (26-02-2021 Shift-1)
(a) 1/4 (b) 8
50. For the reaction A  g   B  g  at 495 K,  r G = –9.478 kJ
(c) 1/8 (d) 1/64
mol–1. If we start the reaction in a closed container at 495 K
Numerical Value Type Questions with 22 millimoles of A, the amount of B in the equilibrium
45. For a reaction X + Y  2Z, 1.0 mol of X, 1.5 mol of Y and 0.5 mixture is_____ millimole. [Round off to the Nearest integer).
[R = 8.314J mol–1K–1; ln 10 = 2.303] (16-03-2021 Shift-1)
mol of Z were taken in a 1 L vessel and allowed to react. The
equilibrium, the concentration of Z was 1.0 mol L–1. The 51. Consider the reaction N 2 O4  g   2NO 2  g  . The
x temperature at which KC = 20.4 and KP = 600.1, is ….. K.
equilibrium constant of reaction is…… . The value of x
15 (Round off to the Nearest integer). [Assume all gases are
is. (05-09-2020 Shift-2) ideal and R = 0.0831 L bar K–1 mol–1]
(17-03-2021 Shift-2)
46. For the reaction A g   B g  , the value of the equilibrium
constant at 300 K and 1 atm is equal to 100.0. The value of 52. The gas phase reaction 2A  g   A 2  g 
 r G for the reaction at 300 K and 1 atm in J mol–1 is -xR,
at 400 K has G   25.2 kJ mol 1
where x is_____. (Rounded off to the nearest integer)
the equilibrium constant KC for this reaction is … x 10–2.
[R = 8.31] mol–1 K–1 and ln 10 = 2.3)
(Round off to the Nearest integer).
(24-02-2021 Shift-1)
[Use: R = 8.3J mol–1 K–1, ln 10 = 2.3, log102 = 0.30,
47. At 1990 K and 1 atm pressure, there are equal number of 1 atm = 1 bar] [antilog (–0.3) = 0.501](18-03-2021 Shift-2)
Cl2 molecules and Cl atoms in the reaction mixture. The
53. 2SO2  g   O2  g   2SO3  g 
value of KP for the reaction Cl 2 g   2Cl g  under the
above conditions is x  101 . The value of x is _____. In an equilibrium mixture, the partial pressures are
(Rounded off to the nearest integer) PSO3  43kPa; PO2  530Pa and PSO2  45 kPa . The
(24-02-2021 Shift-1) equilibrium constant K P  _____102  kPa 
1
(nearest
48. Assuming ideal behaviour, the magnitude of log K for the
integer) (20-07-2021 Shift-1)
following reaction at 25oC is x 101 . The value of x is _____ 54. Value of Kp for the equilibrium reaction
(integer answer)
N 2 O4 g   2NO 2  g  at 288 K is 47.9. The Kc for this
3HC  CH g   C6 H6 l 
reaction at same temperature is _____. (Nearest integer). (R
= 0.083 L bar K–1 mol–1) (20-07-2021 Shift-2)
[Given:  f G  HC  CH   2.04  105 Jmol 1 ;
55. For the reaction A  B  2C the value of equilibrium
 f G  C6 H 6   1.24  10 Jmol ; R  8.314JK mol ]
5 1 1 1
constant is 100 at 298 K. If the initial concentration of all the
three species is 1 M each, then the equilibrium concentration
(24-02-2021 Shift-2)
of C is x  101 M . The value of x is _____. (Nearest integer)
(25-07-2021 Shift-1)

56. Equilibrium constant for the reaction 59. The reaction rate for the reaction
 PtCl4 

 H 2 O   Pt  H 2 O  Cl3   Cl 
2
1
A s   M  s   O2  g 
2
was measured as a function of concentrations of different
is KP = 4. At equilibrium, the partial pressure of O2 is _____ species, it was observed that
atm. (Round off to the nearest integer)
d  PtCl4  
2
 
 4.8 105  PtCl 4    2.4  103
2
(27-07-2021 Shift-2)
dt  
57. PCl5  PCl3  Cl2 ; K c  1.844
  Pt  H O  Cl     Cl 
3.0 moles of PCl5 is introduced in a 1 L vessel. The number  2 3
 
of moles of PCl5 at equilibrium is _____ x 10–3. (Round off to where square brackets are used to denote molar
the Nearest integer) (27-07-2021 Shift-1)
concentrations. The equilibrium constant, K c  _____
58. The equilibrium constant Kc at 298 K for the reaction
(26-08-2021 Shift-2)
A + B  C + D is 100. Starting with an equimolar solution
60. When 5.1 g of solid NH4HS is introduced into a two litre
with concentrations of A, B, C and D all equal to 1 M, the
evacuated flask at 27oC, 20% of the solid decomposes into
equilibrium concentration of D is….. x 10–2 M. (Nearest
gaseous ammonia and hydrogen sulphide. The Kp for the
integer) (26-08-2021 Shift-2)
reaction at 27oC is x  102 . The value of x is _____.
(integer answer)[Given R = 0.082 L atm K–1 mol–1]
(26-08-2021 Shift-1)


1. A vessel at 1000 K contains CO 2 with a pressure of 5. N2O4 2NO2, Kc = 4. This reversible reaction is studied
0.5 atm. Some of the CO2 is converted to CO on addition of graphically as shown in the given figure. Select the correct
graphite. If the total pressure at equilibrium is 0.8 atm, the statement out of I, II and III.
value of K is :
I : Reaction quotient has maximum value at point A
(a) 0.18 atm (b) 1.8 atm
II : Reaction proceeds left to right at a point when
(c) 3 atm (d) 0.3 atm [N2O4] = [NO2] = 0.1 M
2. The equilibrium reaction : 2AB(aq)  2A(aq) + B2 (g) has III : Kc = Q when point D or F is reached.
an equilibrium constant equal to 1.28. If the concentrations
of AB and A are 5 mol/L and 4 mol/L respectively, what is
[B2] ? A
D E
(a) 0.50 M (b) 1.60 M
NO2
(c) 2.00 M (d) 2.84 M
Concentration
3. For a reversible reaction : A + B C C
N2O4
 dx  F G
  = 2.0 × 103 L mol–1 s–1 [A] [B] – 1.0 × 102 s–1 [C]
 dt 
where x is the amount of ‘A’ dissociated. The value of B Time
equilibrium constant (Keq) is :
(a) 10 (b) 0.05 (a) I, II (b) II, III
(c) 20 (d) Can’t be calculated (c) II (d) I, II, III
4. Equilibrium constant Kc for the following reaction at 800K
6. I 2 + I– I3
is, 4.
This reaction is set-up in aqueous medium. We start with 1
1 3
NH3  N2  H2 ; mol of I2 and 0.5 mol of I– in 1L flask. After equilibrium is
2 2 reached, excess of AgNO3 gave 0.25 mol of yellow ppt.
The value of KP for the following reaction will be : Equilibrium constant is : [Given : AgNO3 gives yellow ppt
with I–]
N 2  3H 2  2NH 3
(a) 1.33 (b) 2.66
2 (c) 2.00 (d) 3.00
 800R 
(a)   (b) 16 × (800R)2 7. Equilibrium constant for two complexes are :
 4  37
A : K4 [Fe(CN)6] K=2.6 × 10 (for dissociation)
2 17
 1  B : K3 [Fe(CN)6] K=1.9 × 10 (for dissociation)
(c)   (d) (800R)1/2 4 (a) A and B are equally stable
 4  800R 
(b) A is more stable than B
(c) B is more stable than A
(d) the predictable stability

8. Consider the reaction 13. During thermal dissociation, the observed vapour density
of N2O4 (g) is 26.0. The extent of dissociation of N2O4 (g)
NaBr(aq)+H 2SO 4 (aq)  NaHSO 4 (aq)+HBr(aq) .
is :
–2
The equilibrium constant is 8.3 × 10 . If the equilibrium (a) 50% (b) 87%
concentrations of NaBr, H2SO4 and NaHSO4 are 6.0 M,
(c) 77% (d) 23%
9.0 M and 3.0 M respectively, what is the molarity of HBr ?
(a) 1.8 × 10 M
–2
(b) 6.7 × 10 M
–1 14. For the reaction N2O4 (g)  2NO2 (g), the value of Kp is 1.7
0 1 × 103 at 500 K and 1.78 × 104 at 600 K. Which of the following
(c) 1.5 × 10 M (d) 3.6 × 10 M
is correct ?
9. For the all gas reaction at 1000 K : 2HI  H 2 + I2, I. The proportion of NO2 in the equilibrium mixture is
K = 0.0344. If you were to begin with 8.0 M of HI in a fixed increased by decreasing the pressure
volume container, what would be the equilibrium
II. The standard enthalpy change for the forward reaction
concentration of H2 ?
is negative
(a) 1.10 M (b) 0.48 M
III. units of Kp are atm
(c) 5.8 M (d) 2.92 M
IV. At 500 K, the degree of dissociation N2O4 decreases by
10. If for the heterogeneous equilibrium 50% by increasing the pressure by 100%.
CaCO3(s)  CaO(s) + CO2 (g) ; K = 1 at 1 atm, The correct choice is :
the temperature is given by : (a) I, III (b) I
(c) II, IV (d) III
Sº Hº
(a) T  (b) T 
Hº Sº 1
15. Consider the equilibrium, CO 2  CO  O2
2
Gº Gº
(c) T  (d) T  The equilibrium constant K is given by (when  <<< 1) :
R Hº
–1
11. The free energy of formation of NO is 78 kJ mol at the 3/ 2 3
temperature of an automobile engine (1000 K). What is the (a) K  (b) K 
2 2
equilibrium constant for this reaction at this reaction at 1000
K?
 3/ 2 3/ 2
(c) K  (d) K 
1 1 2 3
N 2  g   O 2  g   NO  g 
2 2
–5 –9
16. For the reaction, N 2O 4(g)  2NO 2(g) ; if percentage
(a) 8.4 × 10 (b) 7.1 × 10
–10 –19
dissociation of N2O4 are 25%, 50%, 75% and 100%, then the
(c) 4.2 × 10 (d) 1.7 × 10 sequence of observed vapour densities will be :
12. Volume of the flask in which the following equilibria are (a) d1 > d2 > d3 > d4 (b) d4 > d3 > d2 > d1
separately established are transferred to a flask that is double
(c) d1 = d2 = d3 = d4 (d) (d1 = d2) > (d3 = d4)
the size of the earlier flask. In which of the following cases,
equilibrium constants are affected ? 17. In the preparation of CaO from CaCO3 using the equilibrium,
CaCO3 (s)  CaO(s)  CO2 (g), (At 1 atm)
(a) N 2(g)  H 2 g   2NH3 g  , exothermic
8500
(b) N 2 g   O 2 g   2NO g  , endothermic Kp is expressed as log Kp = 7.282  .
T
(c) PCl5 g   PCl3 g  Cl2 g  , endothermic For complete decomposition of CaCO3 the temperature in
celsius to be used is :
(d) none of these
(a) 1167 (b) 894
(c) 8500 (d) 850

18. To the system H2 (g) + I2 (g)  2HI (g)
     
1/ 2 1/ 2 1/ 2
(c) K c  K c  K c (d) K c3  K c1  K c2
in equilibrium, some N2 gas was added at constant volume. 3 1 2
Then, 23. In the reaction : A + B  2C + D. The initial concentration

8
(a) Kp will remain constant and Kc will change of A and B are 1M each. The value of Kc is 10 . What is the
(b) Kc will remain constant and Kp will change equilibrium concentration of A ?
–4 4
(c) Both Kp and Kc will remain constant (a) 2 × 10 M (b) 2 × 10 M
(d) Both Kp and Kc will change (c) 0.005 M (d) 0.0025 M
24. For the reaction, [Ag(CN)2]  Ag + 2CN , the equilibrium
– + –
19. Some quantity of water is contained in a container as shown
–19 +
in figure below. As neon is added to this system at constant constant Kc at 25ºC is 4 × 10 ; then Ag concentration in
pressure, the amount of liquid water in the vessel: a solution which has 0.1 M KCN and 0.03M AgNO3 is :
18 –18
(a) 7.5 × 10 (b) 7.5 × 10
19 –19
(c) 7.5 × 10 (d) 7.5 × 10
25. In reversible reaction A  B , the initial concentration of
Vapour A and B are a and b in moles per litre and the equilibrium
concentration are (a – x) and (b – x) respectively ; express x
Water
in terms of k1, k2, a and b.
(a) increases (b) decrease k1a  k 2 b k1a  k 2 b

(a) (b)
(c) remains same (d) change unpredictably k1  k 2 k1  k 2
20. Solubility of a substance which dissolves with a decrease
in volume and absorption of heat will be favoured by k1a  k 2 b k1a  k 2 b
(c) (d)
(a) high p and high T (b) low p and low T k1k 2 k1  k 2
(c) high p and Low T (d) low p and high T 26. In each of the following, total pressure set-up at equilibrium
21. When a liquid in equilibrium with its vapour is heated is assumed to be equal and is one atm with equilibrium
constants KP given :
(a) the rate of the reaction, vapour  liquid, is increased
I : CaCO3 (s)  CaO (s) + CO2 (g), K1
(b) the same equilibrium mixture is re-established
(c) a new equilibrium mixture with a higher vapour pressure II : NH4HS (s)  NH3 (g) + H2S (g), K2
is established III : NH2COONH4 (s)  2NH3 (g) + CO2 (g), K3
(d) a new equilibrium mixture is established in which the rate
In the increasing order :
of evaporation is greater than the rate of condensation
(a) K1 = K2 = K3 (b) K1 < K2 < K3
22. Given the following reactions and associated equilibrium
constants, select the correct expression for the third (c) K3 < K2 < K1 (d) None of these
equilibrium constant in terms of the first two. 27. The equilibrium constant for the decomposition of water,
(A) 2CO(g)  O 2 (g)  2CO 2 (g); K c  1 

 H 2 O  g   H 2  g   2 O 2  g 
1
 
1
(B) H 2 (g)  O 2 (g)  H 2 O(g); K c is given by :
2 2
(C) CO(g)  H 2 O(g)  CO 2 (g)  H 2 (g); K c  3 p1/ 2  3/ 2 p1/ 2

3 (a) K  (b) K 
(1   )(2   )1/ 2 (1   )(2   )1/ 2
K 
1/ 2
K c1 c1
(a) K c3  (b) K c3  3 p1/ 2  3 p 3/ 2
K c2 K c2 (c) K  (d) K 
2 (1   )(2   )1/ 2

28. In a 1.0 L aqueous solution when the reaction 30. For the following reaction through stages I, II and III
2 Ag (aq )  Cu (s )  Cu (2aq

)  2 Ag ( s ) AI
 II
B  III
C  D
reaches equilibrium, [Cu2+] = x M and [Ag+] = y M. quantity of the product formed (x) varies with temperature
If the volume of solution is doubled by adding water, then (T) as given. Select correct statement :
at equilibrium :
B
x y A I II D
2
(a) [Cu ]  M, [Ag  ]  M III
2 2
X C
x
2  y
(b) [Cu ]  M, [Ag ]  M
2 2
T
x
2  y
(c) [Cu ]  M, [Ag ]  M (a) Stages I and III are endothermic but II is exothermic
2 2
(b) Stages I and III are exothermic but II is endothermic
x
2  y
(d) [Cu ]  M, [Ag ]  M (c) Stages II and III are exothermic but I is endothermic
2 2
(d) Stage I is exothermic but stages II and III are
29. For the reaction PCl5 (g)  PCl3 (g) + Cl2 (g) endothermic
Which of the following sketch may represent above 31. Densities of diamond and graphite are 3.5 and 2.3 g/mL
equilibrium ? Assume equilibrium can be achieved from respectively. Increase of pressure on the equilibrium
either side and by taking any one or more components
C (diamond)  C (graphite)
initially. (Given KC for the reaction < 2) ?
(a) favours backward reaction
6 Cl2 (b) favours forward reaction
4 PCl3 (c) has no effect
(a) Concentration
Mol/litre 2 PCl5 (d) increase the reaction rate
32. A solution is transferred to a 1 L flask, some pure ice is
0
Total added and a stopper is inserted to close the flask. After the
system has reached constant temperature, there are still a
6 few cubes of ice left in the flask, but no other solid. Which
4 of the following statements is false relative to this system at
(b) Concentration 3 PCl5
Mol/litre PCl3 equilibrium ?
2
Cl2 (a) The system is a heterogeneous one.
(b) There are four phases present in the system, not
Total
including the container and stopper.
6 PCl5 (c) The vapour pressure is constant.
4 PCl3 (d) The temperature of the system is below 0ºC.
(c) Concentration 33. On heating a mixture of SO2Cl2 and CO, two equilibria are
Mol/litre 2 Cl2
simultaneously established :
0
Total SO 2 Cl 2 (g)  SO 2 (g)  Cl 2 (g)
6 PCl5 CO(g)  Cl 2 (g)  COCl 2 (g)
4 Cl2 On adding more SO2 at equilibrium what will happen ?

(d) Concentration (a) Amount of CO will decrease
Mol/litre 2 PCl3
(b) Amount of SO2Cl2 and COCl2 will increase
0
Total (c) Amount of CO will remain unaffected
(d) Amount of SO2Cl2 and CO will increase

Objective Questions II RT
(c) loge K = Constant 
[One or more than one correct option] H
34. Which of the following statements about the reaction
quotient, Q are correct ? H
(d) loge K = Constant 
(a) the reaction quotient, Q and the equilibrium constant RT
always have the same numerical value 38. An industrial fuel, ‘water gas’ which consists of a mixture of
(b) Q may be lesser than, equal to or greater than Keq H2 and CO can be made by passing steam over red-hot
(c) Q (numerical value) varies as reaction proceeds carbon. The reaction is
(d) Q = 1 at equilibrium C(s)  H2O(g)  CO(g)  H2 (g);ΔH  131kJ

35. Variation of equilibrium constant K for the reaction The yield of CO and H2 at equilibrium would be shifted to
the product side by
2A  s   B  g   C  g   2D  g 
(a) raising the relative pressure of steam
is plotted against absolute temperature T in figure as : ln K
(b) adding hot carbon
vs (1/T)
(c) raising the temperature
(d) reducing the volume of the system
39. Yield of NH3 in Haber’s process
ln K
N 2(g )  3H 2(g )  2NH3(g), H = – 22 kcal;
can be increased by
1/T
(a) compressing the reaction system
(a) the forward reaction is exothermic
(b) raising the temperature
(b) the forward reaction is endothermic
(c) decreasing the temperature
(c) the slope of line is proportional to H
(d) using the catalyst to lower down the activation energy
(d) adding ‘A’ favours forward reaction
40. The volume of the reaction flask is reduced to half of its
36. Which is/are correct ?
initial value, temperature being constant. In which of the
Hº Sº following cases the position of the equilibrium would shift?
(a) 2.303 log K   
RT R (a) NH4HS(s)  NH3(g) + H2S(s)
(b) Gº = – 2.303 RT log K
(b) 2NOCl(g)  2NO(g) + Cl2(g)
Hº Sº
(c) –2.303 log K    (c) CO(g) + H2O(g)  CO2(g) + H2(g)
RT 2 R
1 (d) I2(g)  2I(g)
(d) 2.303 log K  (Hº Sº )
RT 41. KNO3(s) dissociates on heating as :
37. The variation of equilibrium constant K with temperature is
represented by : 1
KNO3(s)  KNO2(s) + O 2 (g )
2
H T2  1 
R T1  T 
At equilibrium in a closed container
(a) log e K 2  log e K1     dT
(a) addition of NaNO3(s) favours forward reaction
(b) addition of KNO2(s) favours reverse reaction
 d log e K  H
(b)    (c) increasing temperature favours forward reaction
 dT P RT
(d) decreasing pressure favours forward reaction

42. The dissociation of phosgene, which occurs according to 47. For the reaction : PCl5 (g)  PCl3 (g) + Cl2 (g) , The forward
the reaction : reaction at constant temperature is favoured by
COCl2(g)  CO(g) + Cl2(g) (a) introducing an inert gas at constant volume
is an endothermic process. Which of the following factors (b) introducing chlorine gas at constant volume
will increase the degree of dissociation of COCl2 ? (c) introducing an inert gas at constant pressure
(a) Adding Cl2 to the system (d) increasing the volume of the container
(b) Adding helium to the system at constant pressure 48. The dissociation of ammonium carbamate may be
(c) Decreasing the temperature of the system represented by the equation
(d) Reducing the total pressure NH4CO2NH2(s)  2NH3(g) + CO2(g)
43. For the following endothermic equilibrium established by H° for the forward reaction is negative. The equilibrium
dissociation of NH4HS to its components, will shift from right to left if there is
NH4HS(s)  NH3(g) + H2S(g) (a) a decrease in pressure
partial pressure of NH3 will increase (b) an increase in temperature
(a) if NH3 is added after equilibrium is established (c) an increase in the concentration of ammonia
(b) if H2S is added after equilibrium is established (d) an increase in the concentration of carbon dioxide
(c) temperature is increased 49. Which of the following factors will increase solubility of a
(d) volume of the flask is decreased well known weak base, NH3(g), in H2O ?
44. Volume of the flask in which the following equilibria are NH3(g) + H2O(aq)  NH4OH(aq)
separately established are transferred to a flask that is double (a) increase in pressure (b) addition of water
the size of the earlier flask. In which of the following cases,
(c) addition of an acid to water
equilibrium concentrations are affected ?
(d) addition of a base to water
(a) N 2 (g)  3H 2 (g)  2NH3 (g)
50. For the gas phase reaction,
(b) N 2 (g)  O 2 (g)  2NO(g) C2H4(g) + H2(g)  C2H6(g) ; Hº = –136.8 kJ mol
–1
(c) PCl5 (g)  PCl3 (g)  Cl2 (g) carried out in a vessel, the equilibrium concentration of C2H4
can be increased by :
(d) 2NO(g)  N 2 (g)  O 2 (g) (a) increase in temperature(b) decrease in pressure
45. For the reaction : PCl5(g)  PCl3(g) + Cl2(g), (c) removing some H2 (d) adding some C2H6
The forward reaction at constant temperature is favoured Numerical Value Type Questions
by 51. Given the hypothetical reaction :
(a) introducing an inert gas at constant volume
2A(s) + nB(g)  3C(g) Kp = 0.0105
(b) introducing chlorine gas at constant volume
and Kc = 0.45 at 250ºC. What is the value of coefficient
(c) introducing an inert gas at constant pressure ‘n’ ?
(d) increasing the volume of the container
52. For the equilibrium AB(g)  A(g) + B(g), at a given
46. Which of the following factors will favour the backward
reaction ? 1 P
temperature rd of AB is dissociated, then will be
3 Kp
Cl2(g) + 3F2(g)  2ClF3 (g) ; H = –ve
numerically equal to _____.
(a) Addition of inert gas at constant pressure
(b) Addition of Cl2 gas
(c) Increase in the temperature of reaction
(d) Increasing the volume of the container

53. SO2Cl2 and Cl2 are introduced into a 3L vessel. Partial pressure 58. Assertion (A) : The reaction quotient, Q has the same form
of SO2Cl2 and Cl2 at equilibrium are 1 atm and 2 atm as the equilibrium constant Keq and is evaluated using any
respectively. The value of Kp for the following reaction given concentrations of the species involved in the reaction,
SO2Cl2(g)  SO2(g) + Cl2(g) is 10. and not necessarily equilibrium concentrations.
Reason (R) : If the numerical value of Q is not the same as
The total pressure in atm at equilibrium would be ____.
the value of equilibrium constant, a reaction will proceed.
54. What weight of solid ammonium carbamate (NH2COONH4)
(a) A (b) B
when vaporised at 200ºC will have a volume of 8.96 litre at
(c) C (d) D
1 atm ? Assume that solid completely decomposes into CO2
and NH3 at 200ºC and 1 atm. 59. Assertion (A) : The active mass of pure solids and pure
liquids is taken unity.
55. Two equilibria are simultaneously existing in a vessel at
25ºC Reason (R) : The active mass of pure solids and liquids
depends on density and molecular mass. The density and
NO(g) + NO2(g)  N2O3(g); K p (say) molecular mass of pure liquids and solids are constant.
1
(a) A (b) B
2NO2(g)  N2O4(g); K p = 8 atm–1
2 (c) C (d) D
If initially only NO and NO2 are present in a 3 : 5 mole ratio 60. Assertion (A) : For a reaction at equilibrium, the free energy
and the total pressure at equilibrium is 5.5 atm with the for the reaction is minimum.
pressure of NO2 is 0.5 atm, calculate K p (in 10–1) Reason (R) : The free energy for both reactants and products
1
decreases and become equal.
56. Two solids A and C dissociate into gas products as (a) A (b) B
follows.
(c) C (d) D
A(s)  B(g) + D(g); K p = 400 61. Assertion (A) : If some PCl 5(g) containing labelled
1
C(s)  E(g) + D(g); K p = 900 phosphorus 31P is added to a system with following
2 equilibrium, after sometime the system was found to contain
At 25ºC, the pressure over excess solid A only is 40 atm, radioactive PCl3.
and that over solid C only is 60 atm. Find the pressure PCl5(g) PCl3(g) + Cl2(g)
over the solid mixture.
Reason (R) : Chemical equilibrium is dynamic in nature.
Assertion Reason (a) A (b) B
(A) If both Assertion and Reason are correct and (c) C (d) D
Reason is the correct explanation of Assertion. 62. Assertion (A) : As a reversible system approaches
equilibrium, entropy of the system increases.
Reason (R) : The state of equilibrium is the most disordered
Reason is not the correct explanation of
state of a reversible system.
Assertion.
(a) A (b) B
(C) If Assertion is true but Reason is false. (c) C (d) D
(D) If Assertion is false but Reason is true. 63. Assertion (A) : The dissociation of CaCO3 can be represented
57. Assertion (A) : Chemical equilibrium represents a state of a as, CaCO3(s)  CaO(s) + CO2(g). Some solid CaCO3 is
reversible reaction in which measurable properties of the placed in an evacuated vessel enclosed by a piston and
system (pressure, concentration, colour etc.) become heated so that a portion of it is decomposed. If the piston is
constant under the given set of conditions. moved so that the volume of the vessel is doubled, while
Reason (R) : The chemical equilibrium is an apparent state the temperature is held constant, the number of moles of
of rest in which two opposing reactions are proceeding at CO2 in the vessel increases.
the same rate. Reason (R) : The pressure of CO2 in the vessel will remain
the same.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D

64. Assertion (A) : For the reaction 68. Match the Column-I with Column-II :
Column-I Column-II
A(g)  B(g)  2AB(g)
(Reaction) (Effect on equilibrium)
at the given temperature, there will be no effect by addition
(A) N2(g) +3H2(g)  2NH3 (p) Forward shift by
of inert gas either at constant pressure or at constant volume.
Reason (R) : For the reaction where n = 0, there is no H = –ve lowering of
effect of inert gas either at constant volume or at constant temperature
pressure because Kp becomes purely a number. (B) N2(g) + O2(g)  2NO(g) (q) Forward shift by rise
(a) A (b) B H = +ve in temperature
(c) C (d) D (C) PCl5(g)  PCl3(g)+Cl2(g) (r) No effect of pressure
65. Assertion (A) : Addition of an inert gas at constant pressure H = +ve change
equilibrium will support the dissociation of PCl5 at the same
(D) 2SO2(g)+O2(g)  2SO3(g) (s) Forward shift by rise
temperature.
H = –ve in pressure
Reason (R) : The addition of an inert gas will tend to increase
(a) A- p,s B- q,r C- q D- p,s (b) A- p,r B- q,r C- s D- p,s
the total pressure.
(c) A- p,s B- q,r C- r D- p,s (d) A- p,r B- q,r C- r D- p,s
(a) A (b) B
69. Match the conditions on the left column with states on the
(c) C (d) D right column.
66. Assertion (A) : The addition of an inert gas under constant Column–I Column–II
volume condition cause the total pressure of the system to Equilibrium types Kp/Kc
increase. This would thus lower the degree of dissociation relationship
of PCl5.
(A) A2(g)  2A(g); Kc = 1. (p) System is at
Reason (R) : Addition of inert gas at equilibrium increase
the kinetic energy of molecules. Mixture of 1.0 mole of
each equilibrium
(a) A (b) B
is prepared in a 1.0 L
(c) C (d) D
flask.
Match the Following (B) A(g) + 2B(g)  AB2(g) (q) Goes to right
Each question has two columns. Four options are Kc= 2. A mixture of 2.0
moles
given representing matching of elements from
of each A, B and AB2
Column-I and Column-II. Only one of these four is prepared in a 1.0 L
options corresponds to a correct matching. For flask.
each question, choose the option corresponding (C) A2(g)  2A(g) ; Kp = 2. At (r) n(A) > n(A2) at
to the correct matching. equilibrium the total
pressure equilibrium
67. Match the Column-I with Column-II :
is 2.0 atm.
Column-I Column-II
(D) 2A(g)  A2(g)Kp = 2. A (s) n(A) < n(A2) at
(Equations) (Type of process)
mixture, initially
(A) Kp > Q (p) Non spontaneous containing equilibrium
(B) Gº < RT loge Q (q) Equilibrium both A and A2 at 1.0 atm
(C) Kp = Q (r) Spontaneous and partial pressure is
endothermic prepared.
(a) A-p, r; B-p,q; C-p,q,r; D-p,q,b
H
(D) T  (s) Spontaneous (b) A-p, s; B-p,q; C-p,q,s; D-p,q,b
S
(a) A -s, B - p, C - q, D - r (b) A -p, B - q, C - s, D - r (c) A-p, r; B-p,q; C-p,q,r; D-p,r,b
(d) A-p, r; B-p,q; C-p,s,r; D-p,r,b
(c) A -r, B - q, C - p, D - r (d) A -q, B - r, C - s, D - p

70. Match the Column–I with Column–II
Hº Sº
Column–I Column–II  log K1   
2.303RT1 2.303R
(A) N2(g) + 3H2(g)  2NH3(g) (p) No effect of inert
gas addition at Hº Sº
 log K 2   
constant volume 2.303RT2 2.303R
(B) N2(g) + O2(g)  2NO(g) (q) Homogenous Substracting (iv) from (v) we get.
equilibria
K2 Hº  1 1 
(C) CaCO3(s)  CaO(s)+CO2(g) (r) Kp > Kc  log    
K1 2.303R  T1 T2 
(D) NH2COONH4(s)  2NH3(g) (s) Kp depends on
+ CO2(g) partial pressures From the above relation we can conclude that the value of
equilibrium constant increases with increase in temperature
of products only.
for an endothermic reaction and the same decreases with
(a) A - q; B - q, p; C - r, s; D - s, r the increase in temperature for an exothermic reaction.
(b) A - r; B - q, s; C - s; D - s, r Answer the following three questions based on the above
(c) A - q; B - q, p; C - r; D - s, r information.
(d) A - q; B - r, p; C - s; D - s, r 71. If standard heat of dissociation of PCl5 is 230 cal, then slope
Paragraph Type Questions 1

of the graph of log K vs is
T
Use the following passage, to solve Q. 71 to Q. 73
Passage
(a) +50 (b) –50
Effect of temperature on the equilibrium process is analyzed
by using the thermodynamics. From the thermodynamics (c) 10 (d) None of these
relation. 72. For exothermic reaction if Sº < 0, then the sketch of log K
Gº = – 2.303 RT logK ...(i) vs 1/T may be
Gº : Standard free energy change

Gº = Hº – TSº ...(ii)
Hº : Standard heat of the reaction (a) (b)
From (i) and (ii)
–2.303 RT log K = Hº – Sº
Sº : Standard entropy change
Hº Sº
 log K    ...(iii) (c) (d)
2.303RT 2.303R
73. If for a particular reversible reaction : Kc = 57 at 355ºC and

If a plot of log K vs 1/T is made then it is a straight line
K 'c = 69 at 450º, then
 Hº  Sº
having slope  and Y intercept  (a) H < 0
2.303R 2.303R
(b) H > 0
If at temperature T 1, equilibrium constant be K1 and at
temperature T2, equilibrium constant be K2 then the above (c) H = 0
equation reduces to : (d) Sign of H can’t be determined

Use the following passage, to solve Q. 74 to Q. 76 Experiments show this colour becomes deeper upon
addition of more Fe(NO3)3 or KSCN. The colour disappears
Passage when Na 2 HPO 4 is added. Use one or more of the
These 3 questions deal with the following chemical reaction: interpretations below.
(a) Unreacted Fe3+ (aq) is present in the original
2
Ni  aq   6NH 3  aq    Ni  NH 3 6 
2
 aq  equilibrium mixture.
 green solution   BlueSolution  (b) Unreacted SCN– (aq) is present in the original
When H+(aq) is added, the colour green is favoured. Use equilibrium mixture.
one or more of the following interpretations to answer the (c) Colour change indicates a new equilibrium ;
questions. [Fe(SCN)2+ (aq)] has been reduced.
I. Some unreacted Ni2+ (aq) is present in the solution at (d) Colour change indicates a new equilibrium ;
equilibrium. [Fe(SCN)2+ (aq)] has been increased.
II. Some unreacted NH3 (aq) is present in the solution at 77. The deepening of colour on addition of more Fe(NO3)3
equilibrium. supports
III. The colour change indicates new equilibrium conditions (a) A only (b) A and D only
with reduced [Ni(NH3)6]2+(aq). (c) A and B only (d) B and D only
IV. The colour change indicates new equilibrium conditions 78. The disappearance of colour on addition of Na2HPO4
with increased [Ni(NH3)6]2+(aq). supports
74. The deepening colour on dissolving more Ni(NO3)2 supports (a) A only (b) A and D only
interpretation(s)
(c) A and B only (d) C only
(a) I only (b) I and IV only
(c) II and IV only (d) I and II only
75. The deepening colour on addition of more NH3(aq) supports Passage
intepretation(s) Le-Chatelier’s principle : If a system at equilbrium is
(a) I only (b) I and IV only subjected to a change of any one of the factors such as
(c) I and II only (d) II and IV only concentration, pressure or temperature, the system adjusts
76. The disappearance of colour on addition of H (aq). + itself in such a way as to “Nullify” the effect of that change.
supports interpretation(s) If a system in equilibrium consists of gases, then the
(a) I only (b) II and IV only concentrations of all components can be altered by changing
(c) I and II only (d) III only the pressure. When the pressure on the system is increased,
the volume decreases proportionly. The total number of
moles per unit volume will now be more and the equilibrium
Passage will shift in that direction in which there is decrease in number
These 3 questions refer to the following experiment. Some of moles i.e, towards the direction in which there is decrease
Fe(NO3)3 solution is added to KSCN solution and a dark red in volume.
colour appears. This colour is caused by [Fe(SCN)]2+, which
is formed by the reaction :
Fe3+ (aq) + SCN– (aq)  [Fe(SCN)]2+

Solids whose volume decreases on melting e.g., ice, 1 1
diamond, carborundum, magnesium nitride and quartz. 80. For the reaction : N 2 (g)  O 2 (g)  NO(g)
2 2
Solid (higher volume)  liquid (lower volume) If pressure is increased by reducing the volume of the
The process of melting is facilitated at higher pressure, container, then
thus the melting point is lowered. (a) total pressure at equilibrium will remain same
Solids whose volume increase on melting e.g. Fe, Cu, (b) concentration of all the components at equilibrium will
Ag, Au, etc. change
Solid (lower volume)  liquid (higher volume) (c) concentration of all the components at equilibrium will
remain same
In this case, the process of melting becomes difficult at
high pressure ; thus melting point becomes high. (d) equilibrium will shift in the forward direction
Answer the following two questions based on the
above information.
79. Au(s)  Au(l)
Above equilibrium is favoured at
(a) high pressure, low temperature
(b) high pressure, high temperature
(c) low pressure, high temperature
(d) low pressure, low temperature


1. Pure ammonia is placed in a vessel at a temperature where
5. For the reversible reaction, N2(g) + 3H2(g)  2NH3(g) at
its dissociation constant () is appreciable. At equilibrium
500ºC, the value of Kp is 1.44 × 10–5 when partial pressure is
N2 + 3H2  2NH3 (1984) measured in atmospheres. The corresponding value of Kc,
(a) Kp does not change significantly with pressure with concentration in mole litre–1 is (2000)
(b)  does not change with pressure
1.44  10 5 1.44 10 5
(c) concentration of NH3 does not change with pressure (a) (b)
(0.082  500)  2 (8.314  773)  2
(d) concentration of hydrogen is less than that of nitrogen
2. The equilibrium SO2Cl2(g) SO2 (g) + Cl2(g) is attained 1.44  10 5 1.44 10 5
at 25ºC in a closed container and an inert gas, helium is (c) (d)
(0.082  773) 2 (0.082  773)  2
introduced. Which of the following statements are correct?
(1989) 6. When two reactants, A and B are mixed to give products C
(a) Concentration of SO2, Cl2 and SO2Cl2 change and D, the reaction quotient Q, at the initial stages of the
reaction (2000)
(b) More chlorine is formed
(a) is zero (b) decreases with time
(c) Concentration of SO2 is reduced
(c) is independent of time (d) increases with time
(d) All the above are incorrect
7. At constant temperature, the equilibrium constant (Kp) for
3. For the reaction ;
the decomposition reaction N2O4  2NO2 is expressed by
CO (g) + H2O(g)  CO2 (g) + H2 (g),
Kp = (4x2P) / (1 – x2), where P = presssure, x = extent of
at a given temperature, the equilibrium amount of CO2(g) decomposition. Which one of the following statements is
can be increased by (1998) true ? (2001)
(a) adding a suitable catalyst (a) Kp increases with increase of P
(b) adding an inert gas (b) Kp increases with increase of x
(c) decreasing the volume of the container (c) Kp increases with decrease of x
(d) increasing the amount of CO(g) (d) Kp remains constant with change in P and x
4. For the chemical reaction 8. Consider the following equilibrium in a closed container
3X (g) + Y (g)  X3Y (g) N2O4 (g) 2NO2(g)
the amount of X3Y at equilibrium is affected by (1999) At a fixed temperature, the volume of the reaction container
is halved. For this change, which of the following statements
(a) temperature and pressure
hold true regarding the equilibrium constant (Kp) and degree
(b) temperature only of dissociation () ? (2008)
(c) pressure only (a) Neither Kp nor  changes
(d) temperature, pressure and catalyst (b) Both Kp and  changes
(c) Kp changes but  does not change
(d) Kp does not change but  changes

9. N2 + 3H3  2NH3 13. For a reaction, A  P, the plots of [A] and [P] with time at
Which is correct statement if N2 is added at equilibrium temperatures T1 and T2 are given below. (2018)
condition ? (2006)
(a) The equilibrium will shift to forward direction because
according to IInd law of thermodynamics the entropy must
increase in the direction of spontaneous reaction
(b) The condition for equilibrium is G N 2  3G H 2  2G NH3

where G is Gibbs free energy per mole of the gaseous
species measured at that partial pressure. The condition
of equilibrium is unaffected by the use of catalyst, which
increases the rate of both the forward and backward
If T2 > T1, the correct statement(s) is (are)
directions to the same extent
(c) The catalyst will increase the rate of forward reaction by (Assume H o and So are independent of temperature

and ratio of lnK at T1 to lnK at T2 is greater than T2/T1. Here
(d) Catalyst will not alter the rate of either of the reaction.
H, S, G and K are enthalpy, entropy, Gibbs energy and
equilibrium constant, respectively.)
[One or more than one correct option] (a) H o  0, So  0
10. For the gas phase reaction
C2H4 + H2 C2H6 (H = – 32.7 kcal)carried out in a vessel, (b) G o  0, H o  0
the equilibrium concentration of C2H4 can be increased by
(1984) (c) G o  0, So  0
(a) increasing the temperature
(d) G o  0, So  0
(b) decreasing the pressure
(c) removing some H2
(d) adding some C2H6 Numerical Value Type Questions
11. When NaNO3 is heated in a closed vessel, oxygen is liberated 14. For the following reaction, equilibrium constant KC at 298
and NaNO2 is left behind. At equilibrium (1986) is 1.6  1017
(a) addition of NaNO2 favours reverse reaction
Fe2+(aq) + S2–(aq)  FeS(s)
(b) addition of NaNO3 favours forward reaction
(c) increasing temperature favours forward reaction When equal volume of 0.06 M Fe+2(aq) and 0.2 M S–2(aq)
(d) increasing pressure favours reverse reaction solution are mixed, then equilibrium concentration of
12. For the reaction, PCl5 (g) PCl3(g) + Cl2(g) Fe+2(aq) is found to be Y  10-17 M. The value of Y
is_____. (2019)
The forward reaction at constant temperature is favoured
by (1991)
(a) introducing chlorine gas at constant volume
(b) introducing an inert gas at constant pressure
(c) increasing the volume of the container
(d) introducing PCl5 at constant volume

15. For the reaction, X(s)  Y(s) + Z(g), the plot of ln d  ln K  H
(Given  , where the equilibrium
pz 10 4 1 R
d 
p versus T is given below (in solid line), where p z is T
the pressure (in bar) of the gas Z at temperature T and
pz
p = 1 bar. constant, K  p and the gas constant,
R = 8.314 J K–1 mol–1)
The value of S° (in J K–1 mol–1) for the given reaction, at
1000 K is_______. (2021)
Paragraph Type Questions

Passage
d  ln K  H Thermal decomposition of gaseous X2 to gaseous X at 298
(Given  , where the equilibrium constant,
1 R K takes place according to the following equation :
d 
T X2(g)  2X(g)
The standard reaction Gibbs energy, rG°, of this reaction
pz
K is positive. At the start of the reaction, there is one mole of
p and the gas constant, R = 8.314 J K mol )
–1 –1
X2 and no X. As the reaction proceeds, the number of moles

of X formed is given by . Thus,  equilibrium is the number of
The value of standard enthalpy, H (in kJ mol–1) for the
moles of X formed at equilibrium. The reaction is carried
given reaction is_____. (2021)
out at a constant total pressure of 2 bar. Consider the gases
pz to behave ideally. (Given : R = 0.083 L bar K–1 mol–1)
16. For the reaction, X(s)  Y(s) + Z(g), the plot of ln p 17. The equilibrium constant Kp for this reaction at 298 K,
in terms of  equilibrium, is (2016)
104
versus is given below (in solid line), where pz is the 2
T 2
8equilibrium 8equilibrium
pressure (in bar) of the gas Z at temperature T and p°= 1 (a) 2   (b) 2
equilibrium 4  equilibrium
bar.
2 2
4equilibrium 4equilibrium
(c) (d) 2
2  equilibrium 4  equilibrium
18. The INCORRECT statement among the following, for this

reaction, is (2016)
(a) Decrease in the total pressure will result in formation of
more moles of gaseous X
(b) At the start of the reaction, dissociation of gaseous X2
takes place spontaneously
(c)  equilibrium = 0.7
(d) KC < 1

Subjective Type Questions 26. 0.15 mole of CO taken in a 2.5 L flask is maintained at 750 K
19. One mole of nitrogen is mixed with three moles of hydrogen along with a catalyst so that the following reaction can take
in a four litre container. If 0.25 per cent of nitrogen is place
converted to ammonia by the following reaction CO(g) + 2H2 ( g) CH3OH(g)
N2(g) + 3H2 (g)  2NH3 (g), then calculate the equilibrium Hydrogen is introduced until the total pressure of the
constant, Kc in concentration units. What will be the value system is 8.5 atm at equilibrium and 0.08 mole of methanol is
of Kc for the following equilibrium ? formed. Calculate (i) Kp and Kc and (ii) the final pressure if
the same amount of CO and H2 as before are used, but with
1 3
N 2 (g) + H 2 (g)  NH3 (g) (1981) no catalyst so that the reaction does not take place.
2 2
(1993)
20. One mole of Cl2 and 3 moles of PCl5 are placed in a 100 litre 27. The degree of dissociation is 0.4 at 400 K and 1.0 atm
vessel heated at 227oC. The equilibrium pressure is 2.05 at-
mosphere. Assuming ideal behaviour, calculate the de- for the gaseous reaction, PCl5  PCl3  Cl2
gree of dissociation for PCl5 and Kp for the reaction Assuming ideal behaviour of all the gases, calculate the
density of equilibrium mixture at 400 K and 1.0 atm (relative
PCl5 (g)  PCl3 (g)  Cl2 (g) (1984)
atomic mass of P = 31.0 and Cl = 35.5) (1998)
21. Equilibrium constant of the reaction 28. When 3.06 g of solid NH4SH is introduced into a two litre
evacuated flask at 27°C , 30% of the solid decomposes into
A 2 (g)  B2 (g)  2AB(g)
gaseous ammonia and hydrogen sulphide. (i) Calculate Kc
at 100°C is 50. If a one litre flask containing one mole of and Kp for the reaction at 27°C. (ii) What would happen to
A2 is connected to a two litre flask containing two moles the equilibrium when more solid NH4SH is introduced into
of B2, how many mole of AB will be formed at 373°C ? the flask ? (1999)
(1985)
22. At a certain temperature, equilibrium constant Kc is 16 Fill in the Blanks
29. For a given reversible reaction at a fixed temperature,
for the reaction
equilibrium constant Kp and Kc are are related by ..............
SO 2 (g)+NO 2 (g)  SO3 (g)+NO(g) (1994)
If we take one mole of each of all the four gases in a one litre 30. A ten-fold increase in pressure on the reaction, N2(g) + 3H2
container, what would be the equilibrium concentration of (g)  2NH3 (g) at equilibrium, results in ................ in Kp.
NO and NO2 ? (1987) (1996)
23. N 2 O 4  2NO 2 is 25% dissociated at 37 C ° and one atmo- 31. For a gaseous reaction 2B  A, the equilibrium constant
sphere pressure. Calculate (i) Kp and (ii) the percentage dis- Kp is ........... to/than Kc. (1998)
sociation at 0.1 atmosphere and 37oC ? (1988)
24. The equilibrium constant Kp of the reaction,
True / False
32. When a liquid and its vapour are at equilibrium and the
2 SO3 ( g )  2SO2 ( g )  O2 ( g ) pressure is suddenly decreased, cooling occurs. (1984)
is 900 atm at 800 K. A mixture containing SO3 and O2 having 33. If equilibrium constant for the reaction, A2 + B2  2AB, is
initial pressure of 1 and 2 atm respectively is heated at con-
stant volume to equilibrate. Calculate the partial pressure of 1 1
K, then for the backward reaction AB  A 2  B2 ,
each gas at 800 K. (1989) 2 2
25. For the reaction, CO(g)  2H 2 ( g)  CH 3 OH(g) 1

the equilibrium constant is . (1984)
K
hydrogen gas is introduced into a five litre flask at 327oC
containing 0.2 mole of CO(g) and a catalyst, until the pres- 34. Catalyst makes a reaction more exothermic. (1987)
sure is 4.92 atm. At this point 0.1 mole of CH3OH(g) is formed. 35. The rate of an exothermic reaction increases with increasing
Calculate the equilibrium constant, Kp and Kc. temperature. (1993)
(1990)

Note:


IONIC EQUILIBRIUM

Chapter 12 118
IONIC EQUILIBRIUM
Ionic equilibrium is the study of equilibrium in the reactions where 2.1.3 Neutralization
the formation of ions takes place in an aqueous solution. According to Arrhenius’s theory, neutralization is a process in
which H+ ions and OH– ions combine to form a water molecule.
1. ELECTROLYTES
H   aq   OH –  aq   H2 O
Electrolytes are those compounds which on dissolving in polar
solvents like water break into ions. When acids and bases are mixed in an aqueous solution, salts
1.1 Classification of Electrolytes and water are formed and the properties of acids and bases are
destroyed.
Electrolytes can be classified based on their strength into two
categories: NaOH  HCl  NaCl  H 2 O
Strong electrolytes: Those electrolytes that easily break into ions 2.1.4 Limitations of Arrhenius Concept
and give almost complete dissociation. E.g. HCl, NaOH, NaCl,
Arrhenius’s concept does not explain the acidic and basic
HNO3, HClO4, H2SO4 etc.
behaviour of the substances in solvents other than water such as
Weak electrolytes: Those electrolytes which dissociate partially. alcohol, liquid ammonia, etc.
E.g. CH3COOH, NH4OH, HCN, H2C2O4, and all organic acids and
It could not explain the acidic and basic behaviour of certain
bases, etc. Electrolytes can be further classified based on the
substances: CO2, SO2, SO3, etc. are acids but do not contain
kind of compound they are- Acids, Bases, and Salts
H atom. They produce H+ ions in the solution
2. CONCEPT OF ACIDS AND BASES
 CO32–  aq   2H   aq 
CO 2  H 2 O 
Different concepts have been put forward to explain acids and
bases. Similarly, NH3, CaO, MgO, etc. are bases that do not contain the
OH– group but produce OH– ions in solution.
1. Arrhenius Concept
2. Bronsted-Lowry Concept  NH 4  aq   OH  aq 
NH3  H 2 O 
3. Lewis Concept
 Ca 2   aq   2OH –  aq 
CaO  H 2 O 
2.1 Arrhenius Concept
This theory defines acids and bases from the perspective of wa- 2.2 Bronsted-Lowry Concept
ter as a solvent. 2.2.1 Acid and Base
2.1.1 Arrhenius Acids Acid is a substance that tends to give a proton (H+) and a base is
Those compounds which will increase H ion concentration in
+ a substance that tends to accept a proton (H+).
water.
 NH 4  aq   OH  aq 
NH3  aq   H 2 O 
HA  H+ + A–
HCl, HNO3, H2SO4 are acids because they dissociate in water and In the above examples, H2O is donating proton hence acting as
give H+ ions. acid. NH3 is accepting the proton hence acting as base.
HNO3(aq)  H+(aq) + NO–3 (aq) 2.2.2 Amphiprotic Species
H2SO4 (aq)  2H+ (aq) + SO2–4(aq) In the following examples, H2O acts as a base whereas SH– and
NH+4 ions, etc. act as acids.
2.1.2 Arrhenius Base
A base is a substance that given hydroxyl ions in water.  H3O  S2 
SH –  H2 O 
NaOH  aq   Na   aq   OH –  aq   H3O  NH 4 OH

NH 4  2H 2 O 
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IONIC EQUILIBRIUM 119
Water may act as an acid as well as a base and is called amphiprotic. (iv) Molecules whose central atom is linked with more
Amphiprotic species may be an ion or neutral molecule, for ex- electronegative atom by double bond:
ample, H2O, SH-, HCO–3, etc. Example: CO2, SO2, SO3
 H3O  CO32–
HCO3–  H2O  2.3.3 Types of Lewis Bases
(i) Molecules Having Lone Pair of Electrons :
 H2 CO3  OH
HCO3–  H2 O  
    
2.2.3 Conjugate Acid-Base Pairs Alcohols  R — O— H  , amines  R N H2  ,
 
  
Acids and bases which differ by a proton (H+) only are called     
conjugate acid-base. N H3 , P H3 , P Cl3 , R — O— R, H 2 O etc.

 
The pair having one H+ less is a conjugate base whereas the pair (ii) Molecules Containing Multiple Bonds:
having one H+ more is conjugate acid.
CH2 = CH2, Cyclopentadienyl anion etc.
HCl  H 2 O  H 3 O 
 Cl  2.3.4 Limitations of Lewis Concept
Acid 1 Base 1 Acid  2 Base  2 It does not explain the behaviour of protonic acids such as HCl,
H2SO4, HNO3, etc. which do not accept electron pairs.
2.2.4 Limitations of Bronsted Lowry Concept
It does not predict the relative strength of acids and bases.
This concept cannot explain the reaction between acidic oxides
such as CO2, SO2, SO3, etc., and basic oxides such as CaO, MgO, According to this concept, neutralization is treated as a coordina-
etc. because there is no proton transfer. tion reaction. But coordination reaction are slow, but neutraliza-
tion reaction are extremely fast.
CaO  CO 2  CaCO 3
3. DISSOCIATION OF WEAK ACIDS AND BASES
BF3, AlCl3, FeCl3 etc. behave like acids but they do not contain H-
atom. Their acidic character cannot be explained by the Bronsted- Unlike strong acids and bases, weak acids and bases dissociate
Lowry concept. partially and their comparative dissociation is expressed in terms
of the degree of dissociation(a).
2.3 Lewis Concept
3.1 Degree of Dissociation
2.3.1 Acid and Base
It is a measure to express the extent of dissociation of an electro-
According to Lewis’s concept, acid is a species that can accept a
lyte in solution.
pair of electrons and base is a species that can donate a pair of
electrons. Strong electrolytes have a high value of the degree of dissocia-
tion while for weak electrolytes its value is low. It is calculated as
 H3 N  BF3
E.g. BF3  NH3 
Moles of electrolyte dissociated at time

In the above reaction, BF3 is a Lewis acid and NH3 is a Lewis base. Moles of electrolyte added initially
2.3.2 Types of Lewis Acids 3.2 Factors Affecting the Degree of Dissociation
(i) Molecules with a Central Atom Having Incomplete Octet: 3.2.1 Nature of Electrolyte
All the electron-deficient molecules act as Lewis’s acids e.g., BF3, For weak electrolytes  ranges between 1-10% normally and for
BCl3, BI3, AlCl3, GaCl3, BeF2, etc. strong electrolytes  ranges between 90-100%.
(ii) Molecules with Central Atom Having Empty d-Orbitals 3.2.2 Nature of the Solvent
Molecules with central atom having empty d-orbitals : e.g., SiX4, The greater the value of the dielectric constant of the solvent, the
PX3, PX5, SF4, AlF3, SnCl3, AsF5 etc. greater is the degree of dissociation of the electrolyte.
(iii) Cations: 3.2.3 Dilution or Concentrations
Cations with noble gas configuration (e.g., Na , Mg , Al , etc.)
+ 2+ 3+
With the dilution of solution of a weak electrolyte  increases
have little affinity for an electron while ions like H+, Ag+, Cu2+, and at infinite dilution, dissociation is 100% (or  = 1).
Fe3+, etc. have more affinity.
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3.2.4 Temperature
NOTE
Since dissociation is an endothermic process, hence, increase in
temperature favours the dissociation. Greater the value of  or H+ ions produced at a given
temperature and concentration, the greater is the acid strength.
3.2.5 Presence of Other Substances
The larger the value of Ka at a given temperature, the stronger
The degree of dissociation of a weak electrolyte is suppressed by is the acid.
the presence of common ion furnished by a strong electrolyte
4.1.2 Ionization Constants of a Weak Base
(common ion effect).
 B  aq  OH –  aq 
Similarly, for a weak base : BOH  aq 
4. OSTWALD’S DILUTION LAW
 B   OH – 
For a weak electrolyte at a constant temperature, the degree of Kb    
ionization is directly proportional to the square root of the vol-  BOH 
ume containing one mole of the electrolyte or inversely propor- Kb is called the ionization or dissociation constant of the weak
tional to the square root of molar concentration. base.
When a weak electrolyte (AB) is dissolved in water, there exists OH –   C
an equilibrium between the un-ionized molecules and ions formed.
or

 AB  A  B 
 –
  OH –   K b  C
A  B–  C.C
Kc        C2 NOTE
 AB C 1–  
Greater the value of  or OH– ions produced at a given
Kc 1 temperature and concentration, the greater is the basic strength.
or   
C C The larger the value of Kb at a given temperature, the stronger
If V is the volume in litre containing one mole of the weak electro- is the base.
1
lyte, then C  5. SELF-IONIZATION OF WATER
V
5.1 Dissociation Constant of Water
  Kc  V    V
In pure water, one H2O molecule donates a proton and another
Thus the degree of ionization (a) increases with dilution, or de-
water molecule accepts a proton.
crease in the molar concentration (C) of the weak electrolyte.
4.1 Ionization Constants of Weak Acid and Base  H3 O   aq   OH –  aq 
H 2 O  H 2 O 
4.1.1 Ionization Constants of a Weak Acid  H   aq   OH –  aq 
or H 2 O 
Let us consider the dissociation of a weak acid (HA). This ionization is called the self-ionization of water.
 A  aq   H 3 O  aq 
HA  aq   H 2 O  – 
Applying the law of chemical equilibrium,
Applying law of chemical equilibrium  H3 O  OH – 
K ...(1)
 A –   H3 O   H 2 O
K   
 HA  H 2 O  H   OH – 
Or K     ...(2)
As H2O is solvent and its concentration remains almost constant  H 2 O
(55.5 mol/L), let K[H2O] = Ka.
K is called the ionization or dissociation constant of water.
 A   H 3O 
– 
5.2 Ionic Product of Water
Ka    
 HA  Water is pure liquid and its concentration remains constant,
i.e.,[H2O] = constant.
Ka is called the ionization or dissociation constant of the weak
Equation (1) or (2) may be written as,
acid.
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K  H 2 O    H    OH –  – log K a – log K b  – log K w
K w   H    OH –  pK a  pK b  pK w  14  at 25C 
Or
( pK a  – log K a and  pK b  – log K b 
Or K w   H 3 O   OH – 
Kw is called the ionic product of water. 6. pH SCALE
The product of the molar concentration of H and OH ions in an + –
Sorensen (1909) suggested a convenient method to express H+
aqueous solution is constant at constant temperature and it is ion concentration in terms of pH. This word is derived from a
called the ionic product of water (Kw). Value of Kw at 25°C (298 K) Danish word potenz meaning power.
is 1.0 × 10–14.
“pH is defined as the negative logarithm of the molar concentra-
In pure water H   OH  ,
 – tion of hydrogen ion.”
pH  – log  H  
Therefore,  H   OH   1.0  10
 – –7
mol/L
Similarly, pOH is equal to negative logarithm of OH- ion concen-
On increasing the temperature, more water molecules ionize to tration.
give H+ and OH– ions.
pOH  – log  OH – 
Therefore, Kw increases with an increase in temperature.
Relation Between pH and pOH
But at all temperatures  H   OH  .
 –
K w   H    OH –   1  10 –14
Acidic, basic or neutral aqueous solutions always contain H+ and (at 298 K or 25°C)
OH– ions and the product of their molar concentrations at 25°C is
Taking logarithm and multiplying both the sides with negative:
always 1 × 10–14, i.e.,
 – log K w  – log  H  – log  OH   14
 –
H  OH   110

 – –14
or pK w  pH  pOH
Acidic solution :  H   OH  ,  H   10
 –  –7
pH and pOH of an Acidic, Basic or Neutral Solution

Neutral solution :  H    OH   1  10
 – –7
Acidic solution :
Basic solution :  H   OH  ,  H   10

 –  –7
pH  7, pOH  7,  H    10 –7 ,  OH –   10 –7
5.3 Relation Between Ka & Kb of Conjugate Acid-Base Pair Basic solution :
Let us consider a weak acid HA and its conjugate base is A . –
pH  7, pOH  7,  H    10 –7 ,  OH –   10 –7
 H   A –
HA  Neutral solution :
H  A 
 –
pH  pOH  7,  H    OH –   1 10 –7
Ka      ...(i)
 HA 
 HA  OH –
and A –  H 2 O 
 HA  OH – 
Kb  ...(ii)
 A – 
Multiplying the above two equations (i) and (ii)
K a  K b   H    OH –  ...(iii)
Or K a  K b  K w  1 10 –14
By taking logarithm and multiplying both the sides with negative
pH of daily used items
sign :
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7. pH CALCULATION OF ACIDS AND BASES obtained from water are not negligible in comparison to the ions
obtained from acids or bases.
7.1 Calculation of pH for Strong Acids and Bases
7.6 pH of Polyprotic Acids
1. For a strong acid : [H+] = Normality of the acid
A polyprotic acid is that which furnishes more than one proton
2. For a strong base : [OH–] = Normality of the base per molecule in its solutions, e.g., H2SO4, H3PO4, H2CO3 etc.
3. If the strength of the acid or base is given in molarity, it should For almost all the polyprotic acid value of Ka1 is much larger than
be converted into normality subsequent dissociation constants. So [H+] conc, is mainly de-
Normality = n × Molarity, n = 1,2,3,... termined by the first deprotonation constant (i.e., Ka1 ) except
only for H2SO4 in which Ka2 is also significant.
4. For monobasic acid or monoacid base :
Normality = Molarity 8. COMMON ION EFFECT
7.2 Calculation of pH of Weak Acids and Weak Bases Weak electrolytes such as weak acids and weak bases dissociate
1. For a weak acid :  H   C  K a  C
 to a small extent in an aqueous solution.
The dissociation of the weak electrolyte is further decreased in
2. For a weak base :  OH   C  K b  C
–
the presence of an ion common with the weak electrolyte.
Ka Kb “Suppression of dissociation of a weak electrolyte due to the
3.  and   presence of a strong electrolyte having a common ion is called
C C
common ion effect.”
4. K b  K a  K w   H    OH –   1 10 –14
Let us consider the dissociation of CH3COOH to which a small
pH  pOH  14 (at 25°C) amount of CH3COONa has been added.
7.3 pH of Mixtures of Strong Acids and Strong Bases  CH3COO –  H 

CH3COOH 
Equivalents (or milli-equivalents) of strong acids and strong bases CH 3 COONa  CH 3 COO –  Na 
are calculated. Acids and bases neutralize each other. One equiva-
According to Le Chatelier’s principle, on increasing the concen-
lent of acid is neutralized by one equivalent of a base. The equiva-
tration of CH3COO– ion, the equilibrium shifts in the backward
lent of acid or base left is calculated. Now knowing the normality
direction. That is the dissociation of CH3COOH is suppressed.
of the strong acid or strong base left, pH can be calculated.
The dissociation of CH3COOH is also suppressed in presence of
Equivalents = Normality × Volume (in litres) and
HCl having H+ common ion.
Milli-equivalent(s) = Normality × Volume (in mL).
CH3COOH is a weak acid, it dissociates partially to give CH3COO–
7.4 pH of Mixtures of Weak Acids or Weak Bases and H+ ions.
 H    K a1 .C1  K a 2 .C 2  CH 3COO –  H  ;
CH3COOH 
Ka and C represent the dissociation constant and concentration
CH3 COO –   H  
of acid 1 and 2 respectively. Ka  
CH3COOH or
1 1 1 1
pH  – log  H    pK a1  pK a 2 – log C1 – log C2 K a  CH 3 COOH 
2 2 2 2  H   
CH 3 COO – 
For a mixture of weak bases, we use pK b1 and pK b2 in place of
The value of the dissociation constant (Ka) is constant at a con-
pK a1 and pK a 2 to calculate pOH. stant temperature.
7.5 pH of Very Dilute Acids and Bases In the presence of CH3COONa, the concentration of CH3COO–
When the solutions of acids or bases are concentrated, the H+ or ion increases. Therefore, the concentration of H+ ion decreases,
OH– ions obtained from water are not considered. i.e., dissociation of CH3COOH decreases.
It is because the ions obtained from water are negligible in com-

parison to ions obtained from acids or bases.
But in the case of very dilute solutions of acids or bases, ions
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9. BUFFER SOLUTIONS On adding a small amount of strong base such as NaOH, KOH,
etc., the OH– ions combine with NH4+ ions forming a weak base
“A buffer solution is defined as a solution that resists change in NH4OH.
pH when a small amount of an acid or base is added or when the
solution is diluted.”  NH 4 OH
NH 4  OH – 
9.1 Types of Buffer Solutions The pH of the buffer solution does not change.
Based on composition, buffer solutions are of three types: Thus a buffer solution has reserve acidity and reserve basicity.
(i) Acidic buffer: It is a mixture of a weak acid and its salt with a 9.2.3 Buffer Action of Salt Buffer
strong base, e. g., CH3COONa + CH3COOH, etc. An aqueous solution of CH3COONH4 is a buffer solution. It dis-
(ii) Basic buffer: It is a mixture of a weak base and its salt with a sociates in water to produce CH3COO– and NH4+ ions.
strong acid, e. g., NH4Cl + NH4OH, etc.
CH 3 COONH 4  CH 3 COO –  NH 4
(iii) Salt buffer: It is a solution of a salt of a weak acid and a weak
base, e. g., NH4CN, CH3COONH4, etc. On adding a small amount of strong acid, it is converted into weak
9.2 Buffer Action CH3COOH acid. Similarly, on adding a strong base, it is converted
into a weak base NH4OH. Therefore, the pH of the buffer solution
9.2.1 Buffer Action of Acidic Buffer
does not change.
Suppose, a buffer solution contains CH3COOH and CH3COONa.
9.3 Calculation of pH of a Buffer Solution
CH 3 COOH and CH3COONa . 9.3.1 pH of an Acidic Buffer Solution
 CH3COO –  H  pH of an acidic buffer solution is calculated from the Henderson

CH3COOH 
equation.
CH 3 COONa  CH 3 COO –  Na 
K a  Acid 
On adding an acid such as HCl, H2SO4, etc., the H+ ions combine  H    ...(1)
with CH3COO– ions forming weak acetic acid.
Salt 
pH may be derived by taking the logarithm of equation (1) and
CH 3 COO –  H   CH 3 COOH multiplying both sides by a minus (–).
On adding a base such as NaOH, KOH, etc., the OH– ions are
– log  H    – log K a – log  Acid   log Salt 
neutralized by the H+ ions produced by the weak acid CH3COOH.
H   OH –  H 2 O Salt 
Or pH  pK a  log Acid ...(2)
 
Since H ions are removed from equilibrium, CH3COOH dissoci-
+
ates to give more H+ ions. The concentration of H+ ions remains 9.3.2 pH of a Basic Buffer Solution
the same. the pH of the basic buffer solution is also calculated from the
Thus the addition of strong acid or strong base does not change Henderson equation.
the pH of the buffer solution. K b  Base 
OH –   ...(3)
9.2.2 Buffer Action of Basic Buffer Salt 
Suppose, a buffer solution contains NH4OH and NH4Cl. pOH may be derived by taking the logarithm of equation (3) and
 NH  OH
NH 4 OH  
4
– multiplying both sides by a minus (–).
NH 4 Cl  NH 4  Cl – pOH  pK b  log
Salt 
On adding a small amount of strong acid such as HCl, the H+ ions
 Base
are neutralized by OH– ions produced by the weak base NH4OH. pH  pK w – pOH

H  OH  H 2 O
–
9.4 Buffer Capacity of a Buffer Solution
Since OH– ions are removed from equilibrium, NH4OH dissociates The capacity of a buffer solution to keep its pH constant is called
to give more OH– ions. The concentration of OH– remains the its buffer capacity.
same.
The buffer capacity of a buffer solution is equal to the number of
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moles of an acid or base required to change the pH of one liter  CH3 COOH   OH –  Ch  Ch Ch 2
buffer solution by one unit. Kh   
CH 3 COO –  C 1 – h  1 – h 
Moles of acid or base added in one litre of buffer
Buffercapacity 
Change in pH Kh
K h  Ch 2 and h  ...(2)
C
The buffer capacity of an acidic buffer solution is maximum when
[Acid] = [Salt]. For basic buffer solution: [Base] = [Salt]. The weak acid (CH3COOH) ionizes in solution,
9.5 Buffer Range of a Buffer Solution CH 3 COOH  CH 3 COO –  H  ,
For acidic buffer, buffer range is given by pK a  1 CH3 COO –   H  
Ka  ...(3)
For basic buffer, buffer range is given by pK b  1 CH3COOH
We know, ionic product of water
10. SALT HYDROLYSIS
K w   H    O H  ...(4)
“The interaction of cations/anions or both with water making the
solution acidic or basic is called salt hydrolysis.” Kw
Kh 
10.1 Salts of Strong Acids and Strong Bases K a and from equation (2)
Salts of this type are not hydrolyzed, e.g., NaCl, KBr, NaNO3,
Kw
KNO3, Na2SO4, KClO4, etc. Ch 2  K h 
Ka
It is because the cations on interaction with water produce strong
bases such as NaOH, KOH, etc. and the anions on interaction Kw
 h ...(5)
with water produce strong acids (such as HCl, HNO3, H2SO4, etc.) Ka  C
which are completely ionized in aqueous solution.
10.2 Salts of Weak Acids and Strong Bases CH 3 COO –  H 2 O  CH 3 COOH  OH –
Salts of this type are hydrolyzed and the solution is alkaline due Initial C 0 0
to the formation of OH– ions. Hence, the pH of the solutions is At eq. C(1 – h) Ch Ch
more than 7.
Kw
 OH –   Ch, But  H    OH – 

Examples are CH3COONa, KCN, Na2CO3, Na3PO4, K2CO3 etc.
 
CH 3 COONa  CH 3 COO –  Na 
Kw
  H  

 CH3 COOH  OH –
CH3COO –  H 2 O  Ch
In the salts of a weak acid and strong base, it is the anion that is Substituting the value of h from equation (5)
hydrolyzed and produces weak acid. It is called anionic hydroly-
sis.
K Ka C K w Ka
 H    w  ...(6)
C Kw C
Suppose, the molar concentration of CH3COONa solution is C
and the salt is completely dissociated. The concentration of Taking the logarithm of eq. (6) and multiplying both the sides
CH3COO– ion will be C mol/lit in solution. CH3COO– ion under- by –1,
goes hydrolysis.
K w Ka
Suppose ‘h’ is the degree of hydrolysis. – log  H    – log
C
CH 3 COO –  H 2 O  CH 3 COOH  OH –
1
Initial C 0 0 Or pH   pK w  pK a  log C 
2
At eq. C(1 – h) Ch Ch
At 298 K, pKw = 14, therefore, at 298 K
Applying law of equilibrium, the hydrolysis (Kh) is given by :
1 1
pH  7  pK a  log C
2 2
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10.3 Salts of Strong Acids and Weak Bases Kw Kw  C
 H    C  ...(6)
Salts of this type are hydrolyzed and the solution is acidic due to Kb  C Kb
the formation of H+ ions. Therefore, the pH of the solution is less
Taking the logarithm of eq. (6) and multiplying both the sides
than 7. Examples are NH4Cl, (NH4)2SO4, CuSO4, FeCl3, AlCl3 etc.
by –1,
NH 4 Cl  NH 4  Cl –
1
NH  H 2 O  NH 4 OH  H
  – log  H    – log K w – log K b  log C
4 2
In the salts of strong acid and weak base, it is the cation that is 1
hydrolyzed and produces a weak base. It is called cationic hy- or pH   pK w – pK b – log C
2
drolysis.
1 1
Suppose, the concentration of NH4+ ion will be C mol/lit in solu- pH  7 – pK b – log C
2 2
tion. NH4+ ion undergoes hydrolysis. Suppose, degree of hy- 10.4 Salts of Weak Acids and Weak Bases
drolysis is ‘h’.
Salts of this type are hydrolyzed. Weak acid and weak base are
NH 4  H 2 O  NH 4 OH H produced due to hydrolysis. Both cations and anions are hydro-
Initial C 0 0 lyzed. The solution may be slightly acidic, basic, or neutral de-
pending upon the relative strength of weak acid and weak base.
At eq. C(1 – h) Ch Ch
Ka > Kb Solution is acidic pH < 7
Applying law of equilibrium:
Kb > Ka Solution is basic pH > 7
 NH 4 OH   H   Ch  Ch
Ka = Kb Solution is neutral pH = 7
Kh    Ch 2 ...(1)
 NH 4  C 1 – h 
Examples are CH3COONH4, NH4CN, (NH4)2CO3, (NH4)2S, AlPO4
Kh etc.
h ...(2)
C Let us take the example of CH3COONH4. Suppose, the molar con-
The weak base (NH4OH) ionizes in solution. centration of CH3COONH4 is C and the salt is completely dissoci-
ated in solution. The concentration of CH3COO- and NH4+ will be
NH 4 OH  NH 4  OH – C. Suppose degree of hydrolysis is h.
 NH 4  OH –  CH 3 COO – + NH 4 + H 2 O  CH 3 COOH + NH 4 OH

Kb   ...(3)
 NH 4 OH  Initial C C 0 0
Eq. C(1 – h) C(1– h) Ch Ch
K w   H    OH –  ...(4)
Kh 
CH3 COOH  NH 4 OH 
Kw ...(1)
From equation (1), (3) and (4) K h  K  CH3 COO –   NH 4 
b
C2 h 2 h2
Kw Kh   ...(2)
and from equation (2), Ch  K h  K  C 1 – h    C 1 – h   1 – h 
2
b
If h is very small (1 – h) may be taken equal to 1.
Kw
Or h  Kb  C ...(5) Kh  h2 or
NH 4  H 2 O  NH 4 OH H h  Kh ...(3)
Initial C 0 0 Both CH3COOH and NH4OH ionize in solution.

At eq. C(1 – h) Ch Ch CH 3 COOH  CH 3 COO –  H  ,
  H    Ch, Substitute the value of h from equation (5). CH3 COO –   H  

Ka   ...(4)
CH3COOH
NH 4 OH  NH 4  OH – ,
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IONIC EQUILIBRIUM

 NH 4  OH –  11.2 Solubility Product (Ksp)
Kb   ...(5)
 NH 4 OH  In a saturated solution of a sparingly soluble salt, there exists an
equilibrium between the undissolved solid salt and the ions in the
Ionic product of water K w   H   OH  .
 –
..(6) solution. Let us take the example of sparingly soluble salt BaSO4.
From equation (1), (4), (5) and (6) BaSO4  s   Ba 2  aq   SO2–
4  aq 
Kw Applying law of equilibrium,

Kh 
Ka  Kb
 Ba 2   SO 2–
4 

K
Kw
and from eq. (3) K h  h  K  K
2  BaSO 4 
a b
Or K  BaSO 4    Ba  SO 4 
2 2–
Kw
Or h ...(7) For a pure solid substance, the concentration remains constant.
Ka  Kb
K sp   Ba 2   SO 2–
4 

CH 3 COOH  CH 3 COO –  H  ,
Here Ksp is called the solubility product.
CH3 COO –   H  
Ka  At a given temperature, Ksp is equal to the product of the molar
CH3COOH concentration of the ions in its saturated solution, each concen-
K a  CH 3 COOH  K a Ch K h tration raised to the power equal to the number of ions produced
 
Or  H    CH 3 COO  –
  a
C 1 – h  1 – h ...(8) by the dissociation of one molecule of the electrolyte.
In general, for a sparingly soluble electrolyte AxBy,
From the equation of the hydrolysis of CH3COO– and NH 4 ions,
A x By  s   XA y   yBx – ,
 CH 3 COOH   Ch, CH 3COO –   C 1 – h  x
K sp   A y    Bx – 
y
h
But from equation (2),  Kh 11.3 Relation Between Solubility (S) and
1– h Solubility Product (Ksp)
Putting the value of [H+] from equation (8),
Type of salt Expression of Ksp Example
 H    K a  K h AB type Ksp = S 2
AgCl, AgBr, BaSO4
Kw Kw  Ka AB2 type Ksp = 4S 2
CaCl2,PbI2,Ag2CO3
Or  H    K a   ...(9)
Ka  Kb Kb AB3 type Ksp = 27S 4
AlCl3,FeCl3,Na3PO4
Taking the logarithm of eq. (9) and multiplying both the sides A2B3 type Ksp =108S5 Al2(SO4)3,La2(CO3)3
by –1,
11.4 Ionic Product
1
– log  H   –  log K w  log K a – log K b 

At a given temperature, the ionic product of an electrolyte in a
2 solution is equal to the product of the molar concentration of the
1 1 ions, each concentration raised to the power equal to the number
pH  7  pK a – pK b
2 2 of ions produced by the dissociation of one molecule of it.
11. SOLUBILITY AND SOLUBILITY PRODUCT Ksp applies to saturated solutions only whereas ionic product
applies to all solutions.
11.1 Solubility Predition of Precipitation in solution
The amount (or moles) of a substance dissolved in 1 litre of solu- Condition Result
tion at a given temperature is termed solubility.
IP > Ksp Precipitation occurs
Based on solubility, salts are classified into three types:
IP > Ksp Solution is fomed
I) Soluble Solubility > 0.1 M
IP > Ksp Saturated solution is formed
II) Slightly soluble 0.01 M < solubility < 0.1 M
III) Sparingly soluble Solubility < 0.01 M
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IONIC EQUILIBRIUM

12. INDICATORS
12.1 Acid Base Indicators
An indicator is a substance, which is used to indicate the comple-
tion (endpoint or equivalence point) of a chemical reaction by a
Benzenoid and quinonoid forms
change in its colour.
Benzenoid form of phenolphthalein is colourless and stable in an
In general, indicators are either weak acids or weak bases with a
acidic medium. When medium changes from acidic to basic ben-
characteristic colour of unionized and ionized form.
zenoid form is converted into a quinonoid form which provides
The change in colour of an acid-base indicator occurs in a pH pink colour to the solution.
range. This range is different for different indicators.
pH range of indicators
Indicator pH Acidic Basic
range medium medium
(i) Methyl orange 3.2-4.5 Red Yellow
(ii) Methyl red 4.2-6.5 Red Yellow
(iii) Litmus 5.5-7.5 Red Blue
(iv) Phenol red 6.8-8.4 Yellow Red
(v) Phenolphthalein 8.3-10.5 Colourless Pink
12.2 Theories of Acid-Base Indicators
12.2.1 Ostwald’s Theory
According to this theory, the colour change is due to the ioniza- Benzenoid and quinonoid forms of phenolphthalein
tion of the acid-base indicator.
13. ACID-BASE TITRATIONS
The colours of the unionized indicator and ion obtained from it,
are different. An acidic indicator yields a coloured anion while a An acid-base titration is a method used to find the amount of an
basic indicator gives coloured cation. unknown acidic or basic substance through acid-base reactions.
For example, Phenolphthalein The analyte is the solution with unknown molarity while the ti-
It can be represented as HPh, it ionizes as – trant is the solution with known molarity that is made to react with
the analyte.
HPh  H   Ph –
A suitable indicator is used to detect the endpoint of the titration
 H   Ph 
 –
 Ph 
 reaction.
K in      pH  pK in  log 
 HPh   HPh  At the endpoint of the reaction, the gram equivalents of the acid
consumed are always equal to the gram equivalents of the base
where Kin is the ionization constant of the indicator. consumed.
In presence of an acid, the ionization of HPh is practically negli-
For example: NaOH  HCl  NaCl  H 2 O
gible. Thus the solution remains colourless.
On addition of alkali, hydrogen ions are neutralized and equilib- Gram equivalents of HCl = Gram equivalents of NaOH
rium shifts in the forward direction and the solution becomes N1V1  HCl   N 2 V2  NaOH 
pink.
12.2.2 Quinonoid Theory n1M1V1  Acid   n 2 M 2 V2  Base 
(i) All the acid-base indicators contain aromatic rings and exist For example, if we have to calculate the volume of 1N HCl required
in two tautomeric forms, benzenoid and quinonoid, which to neutralize 0.5 N 100 ml KOH,
remain in equilibrium with each other. Then N1 = 1N, N2 = 0.5 N and V2 = 100 ml
(ii) The colour of the quinonoid form is usually darker than the According to N1V1 = N2V2
benzenoid form. Between two forms, one is more stable in V1 = 0.5 × 100 = 50 ml
acid medium while the other is in basic medium.
So. 50 ml HCl is required to neutralize the given KOH.
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IONIC EQUILIBRIUM

SUMMARY
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IONIC EQUILIBRIUM

IONIC EQUILIBRIUM
129
SOLVED EXAMPLES
Example - 1  M2 = 1.36 × 10–2 M
Calculate the pH of the following solutions:  H     HCl  1.36  10 2 M.
(a) 2g of TlOH dissolved in water to give 2 litre of the solution
(b) 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of the pH   log(1.36  102 )  2  0.1335  1.87
solution Example - 2
(c) 0.3 g of NaOH dissolved in water to give 200 mL of the The degree of ionization of a 0.1 M bromoacetic acid solution
solution is 0.132. Calculate the pH of the solution and the pKa
(d) 1 mL of 13.6 M HCl is diluted with water to give 1 litre of bromoacetic acid.
the solution.
Sol. CH 2 (Br)COOH CH 2 (Br)COO   H 
Sol.
(a) Molar conc. of TlOH Intial Conc C 0 0
Conc at eqm C – C C C
2g 1
= (204 16 1)gmol1  2L = 4.52 ×10–3 M
C.C C2
Ka  
C(1  ) 1    C  0.1 (0.132)  1.74 10
2 2 3
  OH     TlOH   4.52  10 3 M
pK a   log(1.74  10 3 )  3  0.2405  2.76
 H   10
 14 3
/(4.52  10 )  2.21 10 12
M
 H    C   0.1 0.132  1.32  10 2 M
pH   log(2.21 10 12 )  12  (0.3424)  11.66
pH   log(1.32  102 )  2  0.1206  1.88
0.3g 1 3
(b) Molar conc. of Ca(OH)2 =  40  34 gmol1  0.5L  8.1110 M Example - 3
The pH of 0.005 M codeine (C18H21NO3) solution is 9.95.
Ca(OH) 2  Ca 2   2 OH  Calculate the ionization constant and pKb.
  OH    2  Ca(OH) 2   2  (8.11  10 3 ) M Sol. Cod  H 2 O CodH   OH
= 16.22×10–3 M pH  9.95  pOH  14  9.95  4.05i.e.
pOH   log(16.22  103 )  3  1.2101  1.79  log  OH    4.05
pH  14  1.79  12.21 or log  OH   4.05  5.95


or
(c) Molar conc. of NaOH
 OH    8.913  10 5 M
0.3g 1
   3.75  102 M
CodH  OH  OH  8.91105 
1
40g mol 0.2L 2 2
Kb   
Cod Cod 5 103
 OH    3.75  10 2 M
= 1.588 × 10–6
pOH   log(3.75  10 2 )  2  0.0574  1.43
pK b   log 1.588  10 6   6  0.1987  5.8
 pH  14  1.43  12.57
(d) M1V1  M 2 V2 13.6M  1mL  M 2  1000mL

IONIC EQUILIBRIUM
130
Calculate the hydrogen ion concentration in the following The pH of 0.1M solution of cyanic acid (HCNO) is 2.34.
biological fluids whose pH are given: Calculate the ionization constant of the acid and its degree
(a) Human muscle–fluid, 6.83 of ionization in the solution.
(b) Human stomach fluid, 1.2 Sol. HCNO H   CNO

(c) Human blood, 7.38
pH = 2.34 means –log[H+] = 2.34 or log [H+] = –2.34 = 3.66
(d) Human saliva, 6.4
or  H   Anti log 3.66  4.57  10 M
 3
Sol. (a) log[H  ]   pH  6.83  7.17
[H  ]  Antilog 7.17  1.479  107 M  CNO     H    4.57  10 3 M
(b) log[H  ]   pH  1.2  2.8 (4.57  103 )(4.57  103 )
Ka   2.09  104
 [H  ]  Antilog 2.8  6.31 102 M 0.1
(c) log[H  ]   pH  7.38  8.62   K a / C  2.09 104 / 0.1  0.0457

[H  ]  Antilog 8.62  4.169  10 8 M Example - 8
(d) log[H  ]   pH  6.4  7.60 The ionic product of water at 310 K is 2.7 ×10–14. What is the
pH of neutral water at this temperature?
[H  ]  Antilog 7.60  3.981  10 7 M
Example - 5 Sol.  H    K w  2.7 1014  1.643 107 M
If 0.561 g KOH is dissolved in water to give 200 mL of solution pH   log  H     log(1.643  107 )
at 298 K. Calculate the concentration of potassium hydrogen  7  0.2156  6.78
and hydroxyl ions. What is its pH?
Example - 9
0.561 1000
Sol.  KOH    M  0.050M On the basis of the equation pH = – log[H+],the pH of
56 200
10–8 mol dm–3 solution of HCl should be 8. However, it is
As KOH  K   OH  ,  K     OH    0.05M observed to be less than 7.0. Explain the reason.
Sol. pH of 10–8 M HCl solution is not 8 because this concentration
 H    K w /  OH    10 14 / 0.05  10 14 /(5  102 )
is so low that H+ ion produced from H2O in the solution (viz.
= 2.0×10–13 M. 10 –7 M) cannot be neglected. Total [H + ]
pH =–log [H+]=– log (2.0×10–13)= 13–0.3010= 12.699 = 10–8 + 10–7 M. Solving and calculating pH, we get the value
Example - 6 close to 7 but less than 7 as the solution is acidic.
Example - 10
The solubility of Sr(OH)2 at 298 K is 19.23 g/L of solution.
Calculate the concentration of strontium and hydroxyl ions pH of a solution of a strong acid is 5.0. What will be the pH
and the pH of the solution. (Atomic mass of Sr = 87.6) of the solution obtained after diluting the given solution
Sol. Molar mass of Sr(OH)2= 87.6+34=121.6g mol–1 100 times?
Sol. pH = 5 means [H+]= 10 –5 M. On diluting 100 times,
19.23gL1
Solubility of Sr(OH)2 in moles L =
–1  0.1581M 105
121.6gmol1  H     107 M
100
Assuming complete dissociation,
This should give pH =7 but it cannot be so because solution
Sr(OH)2  Sr2+ + 2 OH– is acidic and pH should be less than 7. The reason is that
 [Sr 2  ]  0.1581M.[OH  ]  2  0.1581  0.3162M [H+] from H2O cannot be neglected. Thus, total [H+] = 10–7 M
(from HCl) + 10–7 M (from H2O) = 2 × 10–7 M
pOH   log 0.3162  0.5,  pH  14  0.5  13.5 7
 pH   log(2  10 )  7  0.3010  6.699.

IONIC EQUILIBRIUM
131
pH of 0.08 mol dm–3 HOCl solution is 2.85. Calculate its Arrange the given compounds in the decreasing order of
Ionisation constant. basicity on the basis of Bronsted–Lowry concept: BaO,
Sol. pH of HOCl=2.85 i.e., –log [ H+] = – 2.85 CO2, SO3, B2O3, Cl2O7.
or log [H+] = – 2.85 = 3.15 Sol. BaO + H2O Ba(OH)2 (Basic)
or [H+] = antilog 3.15 = 1.413 × 10–3 M CO 2  H 2 O H 2 CO3 (weakly acidic)

For weak monobasic acid HA H+ + A–
SO3  H 2 O H 2SO 4 (Strongly acidic)
1.413 10 
2 3 2
H  
Ka     = 2.4957 × 10–5. B2 O3  3H 2 O 2H3 BO3 (Very weaky acidic)

 HA  0.08
Example - 12 Cl 2 O7  H 2 O 2HClO4 (Very strongly acidic)
Prove that the degree of dissociation of a weak monoprotic Hence, in the decreasing order of basicity, we gave
acid is given by BaO  B2 O3  CO 2  SO3  Cl2 O7 .
1 Example - 14
 (pK a  pH) where Ka is the dissociation constant of
1  10 What are the conjugate bases of the following?
the acid.
Sol. Suppose we start with C mol L–1 of the weak monoprotic CH3OH, HN3, [Al(H2O)6]3+.
acid HA. Then
Sol. CH3O  N3 [Al(H 2 O)5 OH]2 (H+ ion has been removed
HA H +
+A – methoxideion, azideion
Initial molar conc. C 0 0 from one H2O molecule).
Molar conc C – C C C Example - 15
after dissociation= C(1–  ) Glycine is an  –amino acid which exists in the form of Zwitter
+
C.C C2 K (1  ) ion as N H 3 CH 2 COO - . Write the formula of its conjugate
Thus, Ka   or C  a 2 ..(i)
C(1  ) 1    base.
Also,  H   C

Sol. Conjugate acid =
Substituting the value of C from eqn. (i), we get  
N H3 CH 2 COO  H   N H3 CH 2 COOH
K a (1  ) K (1   )
 H      a Conjugate base =
 2


  log H   [log Ka  log(1  )  log ] N H3 CH 2 COO   H   NH 2 CH 2 COO 
Example - 16
or pH  pK a  log(1   )  log 
1  1  Write reaction for autoprotolysis of water. How is ionic
or log  pK a  pH or  10pKa pH product of water related to ionization constant of water?
 
Derive the relationship.
1
or  1  10 pKa pH Sol. Autoprotolysis of H2O takes place as:

1 1 H2O  H2O H 3 O   OH 
or  1  10pK a pH or  
 1  10pKa pH For ionization of H2O, H 2 O H   OH 
[H  ][OH  ] Kw Kw
Ki    or
[H 2 O] [H 2 O] 55.55 mol L1
K w  K i  55.55.

IONIC EQUILIBRIUM
132
Example - 17 Sol. K2 < < K1. Hence H+ ions are mainly from 1st dissociation,
i.e. H2S H+ +HS–
Why PO 43- ion is not amphiprotic? 2
 H    HS   H  
Sol. An amphiprotic ion is one which can donate proton as well K1      or  H    K1[H 2S]
 H 2S  H 2S  
as accept proton. PO 34 ion can accept proton(s) but cannot
 [H  ]  10 7  101  10 4
donate any proton. Hence, PO34 is not amphiprotic.
Hence, pH=4
Example - 18
Example - 23
In the reaction between BF3 and C2H5OC2H5 which one of
them will act as an acid? Justify your anwer. Calculate the pH at equivalence point when a solution of
0.10 M acetic acid is titrated with a solution of 0.10 M NaOH
Sol. The reaction between BF3 and C2H5OC2H5 is solution, Ka for acetic acid = 1.9×10–5
Sol. At the equivalence point, CH3COONa is formed and its
0.1
concentration = M  0.05M . It is a salt of weak acid
2
As BF3 accepts a pair of electrons, hence BF3 is the Lewis and strong base. The formula for finding the pH of such a
acid. salt is
Example - 19 1
pH   [log K w  log K a  log c]
2
Which is a stronger base in each of the following pairs and
why? 1
 pH   [log1014  log(1.9105 ) –log (5×10–2)]
2
(i) H2O, Cl– (ii) CH3COO–, OH–
1
Sol (i) H2O (ii) OH–   [14  (5  0.2788)  (2  0.6990)]
2
According to Bronsted-Lowry concept H2O and OH– are 1
stronger base.  (14  5  0.2788  2  0.6990)
2
Example - 20 17.42
  8.71
Classify the following species as Lewis acids and Lewis 2
bases Example - 24
NH3, BF3, SnCl4, C5H5N, CO, Ni2+ A certain weak acid has Ka = 1.0×10–4. Calculate the
Sol. Lewis acids: BF3, SnCl4, Ni 2+ equilibrium constant for its reaction with a strong base.
Lewis bases: NH3, C5H5N, CO.  BOH
Sol. HA
weak strong BA + H2O
Example - 21
or HA + B+ + OH– B+ + A–+H2 O or
Explain why pH of 0.1 molar solution of acetic acid will be
HA + OH –
A + H2O
–
higher than that of 0.1 molar solution of HCl?
Sol. Acetic acid is a weak electrolyte. It is not completely ionized [A  ]
K .......(i)
and hence gives less H+ ion concentration. HCl is a strong [HA][OH  ]
acid. It is completely ionized giving more H + ion Further, for the weak acid, HA H+ + A–,
concentration. As pH =–log [H+]; less the [H+], greater will
[H  ][A  ]
be the pH. Ka  ......(ii)
[HA]
Example - 22 Also Kw = [H+] [ OH–] .....(iii)
Calculate the approximate pH of a 0.100 M aqueous H2S From eqns. (i), (ii) and (iii),
solution. K 1 and K 2 for H 2 S are 1.00 ×10 –7 and K a 10 4
1.30 ×10–13 respectively at 25ºC, K   1010
K w 10 14

IONIC EQUILIBRIUM
133
Example - 25 Sol. NH +4  H 2 O NH4OH+H+, Ka = 5.6 ×10–10
The pH of 0.05 M aqueous solution of diethylamine is 12.0. kf
Calculate its Kb NH3 + H2O kb
NH 4  OH  , k b  3.4  1010
Sol. (C2 H 5 ) 2 NH  H 2 O (C2 H 5 ) 2 NH 2  OH  Aim. To find kf

We know that for a conjugate acid–base pair
As pH = 12,  [H  ]  1012 M or [OH – ] = 10 –2 M,
K acid  K base  K w , i.e., K a  K b  K w
[(C 2 H 5 ) 2 NH]  0.05  0.01  0.04M
Kw 10 14
 
[(C 2 H 5 ) 2 N H ][O H ] 10  10 2 2  Kb  
Kb  2
  2.5  10  3 K a 5.6  10 10
[(C 2 H 5 ) 2 N H ] 0.04
kf
  But K b  k f  K b  k b
[(C 2 H5 ) 2 NH ]  [OH ]
2 kb
Example - 26 10 14
 3.4 1010  0.607 106  6.07 105
An aqueous solution contains 10% ammonia by mass and 5.6  10 10
has a densityof 0.99 g cm–3. Calculate hydroxyl and Example - 28
hydrogen ion concentration in this solution. K a for What will be the resultant pH when 200 ml of an aqueous
NH +4 = 5.0 ×10 -10 M solution of HCl (pH=2.0) is mixed with 300 ml of an aqueous
solution of NaOH (pH=12.0)?
Sol. 10% ammonia by mass means 10g NH3 are present in 100g of
the solution. Sol. pH = 2 means [H+] = 10–2M
 Molarity of the solution pH = 12 means [H+]= 10–12or [OH–]= 10–2 M
10 1 Thus, 200 ml of 10–2 M HCl are mixed with 300 ml of 10–2 M

   1000 = 5.82 M NaOH.
17 100 / 0.99
After neutralization NaOH left = 100 ml of 10–2 M
NH 3  H 2  NH 4 OH  NH 4  OH 
Total volume after mixing = 500 ml
Initial conc. C mol L–1
 In the final solution, after mixing , [OH – ]=
After dissociation C – C  C C
102 1014
= C (1 –)  2  103 M or[H  ]   5 1012
5 2  103
Kh  pH   log[H  ]   log(5  10 12 )  12  0.69  11.31
[OH  ]  C   C  KhC
C Example - 29
14
Kw 10 Calculate the degree of dissociation of 0.5 M NH3 at 25ºC in
 C   5.82 = 1.079 × 10–2 M
Ka 5.0  10 10 a solution of pH=12.
Kw 1014 Sol. NH 4 OH NH 4  OH 
[H  ]  
[OH ] 1.079  102

Initial conc. C mol L–1 0 0

= 0.9268 × 10–12 M = 9.268 × 10–13 M
After disso. C  C C C
Example - 27
+
pH  12 means [H  ]  10 12 or[OH  ]  10 2
The ionization constant of NH in water is
4
102
5.6 × 10–10 at 25ºC. The rate constant for reaction of NH +4  [OH  ]  C  102 or  
C
and OH– to form NH3 and H2O at 25ºC is 3.4×1010
litre mol–1 sec–1. Calculate the rate constant for prton transfer 102
  2  102 or 2%.
from water of NH3. 0.5

IONIC EQUILIBRIUM
134
Example - 30 x
or log  0.0996  1.004  0.1
Calculate the amount of (NH4)2 SO4 in g which must be added 100
to 500 mL of 0.2 M NH 3 to yield a solution of or log x = 2.1 or x = 125.9
pH = 9.35. Kb for NH3 = 1.78×10–5.
125.9
Sol. As it is a basic buffer, pOH  Millimoles of (NH4)2SO4 to be added =  62.95
2
[Salt] [NH 4 ]
= pKb + log   log K b  log ( 1 millimole of (NH 4 ) 2 SO 4  2 millimoles of NH 4+ )
[Base] [NH 4 OH]
As pH = 9.35, pOH  14  9.35  4.65  Mass of (NH4)2SO4 to be added = (62.95 × 10–3 moles)
(132 g mol–1) = 8.3094 g.
Millimoles of NH4OH is solution = 0.2×500 = 100
Suppose millimoles of NH 4 to be added = x
5 x / 500
 4.65   log(1.78  10 )  log
100 / 500
x
 (5  0.2504)  log
100


Theory of Electrolytes and Theory of Acids and 11. Review the equilibrium and choose the correct statement
Bases 
HClO4 + H2O  H3O + ClO4
+ –
1. Which shows weak ionisation in water (a) HClO4 is the conjugate acid of H2O
(a) H2SO4 (b) NaCl (b) H3O+ is the conjugate base of H2O
(c) HNO3 (d) NH3 (c) H2O is the conjugate acid of H3O+
2. Which one of the following substance has the highest (d) ClO4– is the conjugate base of HClO4
proton affinity 12. Which of the following is the weakest acid
(a) H2O (b) H2S (a) HF (b) HCl
(c) NH3 (d) PH3 (c) HBr (d) HI
3. Which of the following is not a Lewis acid 13. Among the following, the weakest Lewis base is
(a) BF3 (b) FeCl3 (a) H– (b) OH–
(c) SiF4 (d) C2H4 (c) Cl– (d) HCO3–
4. The conjugate base of NH2 is
–
14. Which one is the weakest acid

(a) NH3 (b) NH2– (a) HNO3 (b) HClO4
(c) NH4+ (d) N3– (c) H2SO4 (d) HBr
5. Cl– is the conjugate base of 15. The correct order of acid strength is
(a) HClO4 (b) HCl (a) HClO < HClO2 < HClO3 < HClO4
(c) HOCl (d) HClO3 (b) HClO4 < HClO < HClO2 < HClO3
6. Which one is lewis acid (c) HClO2 < HClO3 < HClO4 < HClO
(a) Cl– (b) Ag+ (d) HClO4 < HClO3 < HClO2 < HClO
(c) C2H5OH (d) S2– 16. Ammonium ion is
7. Which of the following is the weakest base (a) Neither an acid nor base
(a) NaOH (b) Ca(OH)2 (b) Both an acid and a base
(c) NH4OH (d) KOH (c) A conjugate acid
8. Conjugate base of NH3 is (d) A conjugate base
 
(a) NH 4
(b) NH 2 Dissociation of Weak Acids and Bases
(c) NH2 (d) N2 17. Degree of dissociation of 0.1 N CH3COOH is
(Dissociation constant = 1 × 10–5)
9. According to Bronsted principle, an aqueous solution of
HNO3 will contain (a) 10–5 (b) 10–4
(a) NO2– (b) NO3– (c) 10–3 (d) 10–2
(c) NO2+ (d) NO+ 18. The values of dissociation constants of some acids (at 25°C)
are as follows. Indicate which is the strongest acid in water
10. The conjugate acid of HPO4 is 2–
(a) 1.4 × 10–2 (b) 1.6 × 10–4

(a) H2PO4– (b) PO43–
(c) 4.4 × 10–10 (d) 4.3 × 10–7
(c) H3PO4 (d) H3PO3

19. The following equilibrium exists in aqueous solution, C
Ka
(b)  
2
(a)  
2
CH3COOH  CH3COO– + H+ if dil HCl is added, without Ka
C
change in temperature, the
Ka C
(a) Concentration of CH3COO– will increase (c)   (d)   Ka
C
(b) Concentration of CH3COO– will decrease
27. The degree of dissociation of 0.1 M HCN solution is 0.01%.
(c) The equilibrium constant will increase
Its ionisation constant would be
(d) The equilibrium constant will decrease
(a) 10–3 (b) 10–5
20. The hydrogen ion concentration in weak acid of
(c) 10–7 (d) 10–9
dissociation constant Ka and concentration c is nearly equal
to 28. For a weak acid HA, Ostwald’s dilution law is represented
by the equation
(a) Ka / c (b) c/Ka c  2c
(a) K a  2 (b) K a 
(c) Kac (d) Kac 1  1 
21. 0.2 molar solution of formic acid is ionized 3.2%. Its Kac  2c
(c)   (d) K a 
ionization constant is 1 c 1 2
(a) 9.6 × 10–3 (b) 2.1 × 10–4 29. Concentration CN in 0.1 M HCN is [Ka = 4 × 10–10]
–
(a) 2.5 × 10–6 M (b) 4.5 × 10–6 M

(c) 1.25 × 10–6 (d) 4.8 × 10–5
(c) 6.3 × 10–6 M (d) 9.2 × 10–6 M
22. For a “c molar” concentrated solution of a weak electrolyte
AxBy, the degree of dissociation is given as Self-ionization of Water
(a)   K eq / c ( x  y) 30. In the reaction 2H2O H3O+ + OH–, water is

(a) A weak base
(b)   K eq c /( xy)
(b) A weak acid

(c)   K eq / c x  y 1x x y 
y 1 /( x  y ) (c) Both a weak acid and a weak base
(d) Neither an acid nor a base
(d) K eq / xyc
31. The unit of ionic product of water Kw are
23. The pH of a 0.1 M aqueous solution of a weak acid (HA) is (a) Mol–1L–1 (b) Mol–2L–2
3. What is its degree of dissociation ?
(c) Mol–2L–1 (d) Mol2L–2
(a) 1% (b) 10%
32. Autoprotolysis constant of NH3 is
(c) 50% (d) 25%
(a) [NH 4 ] [NH 3 ] (b) [NH 2 ] [NH 3 ]
24. In which of the following dissociation of NH4OH will be
minimum (c) [NH 4 ] [NH 2 ] (d) [NH 4 ] /[NH 2 ]
(a) NaOH (b) H2O 33. Ionic product of water increases, if
(c) NH4Cl (d) NaCl (a) Pressure is reduced (b) H+ is added
Ostwald's Dilution Law (c) OH– is added (d) Temperature increases

34. At 90ºC, pure water has [H3O ] = 10–6 mole litre–1. What is the
+
25. A monoprotic acid in 1.00 M solution is 0.01% ionised. The

value of Kw at 90º C ?
dissociation constant of this acid is
(a) 10–6 (b) 10–12
(a) 1 × 10–8 (b) 1 × 10–4
(c) 10–14 (d) 10–8
(c) 1 × 10–6 (d) 10–5
35. 2H2O  H3O+ + OH–, Kw = 1 × 10–14 at 25ºC hence Ka is:
26. If  is the degree of ionization, C the concentration of a
weak electrolyte and Ka the acid ionization constant, then (a) 1 × 10–14 (b) 5.55 × 10–3
the correct relationship between , C and Ka is (c) 18 × 10–17 (d) 1.00 × 10–7

Calculation of pH (a) 8 (b) – 8
36. At a certain temperature the value of pKw is 13.4 and the (c) Between 7 and 8 (d) Between 6 and 7
measured pH of soln is 7. The solution is 45. A is an aqueous acid; B is an aqueous base. They are diluted
(a) Acidic (b) Basic separately, then
(c) Neutral (d) Unpredictable (a)pH of A increases and pH of B decreases
37. For a pure water, (b)pH of A increases and pH of B decreases till pH in each
case is 7
(a)pH increases and pOH decreases with increase in
temperature (c)pH of A and B increase
(d) pH of B and A decrease
(b)pH decreases and pOH increases with increase in
temperature 46. An acid solution of pH = 6 is diluted hundred times. The
pH the solution becomes :
(c)both pH and pOH increase with increase in temperature
(a) 6.95 (b) 6
(d)both pH and pOH decrease with increase in temperature
(c) 4 (d) 8
38. What is the pH value of N/1000 KOH solution
47. The number of H ions present in 1 mL of a solution having
+
(a) 10–11 (b) 3

pH = 13 is :
(c) 2 (d) 11
(a) 1013 (b) 6.023 × 1013
39. Pure water is kept in a vessel and it remains exposed to
(c) 6.023 × 107 (d) 6.023 × 1010
atmospheric CO2 which is absorbed, then its pH will be
48. The dissociation constants of monobasic acids A, B, C and
(a) Greater than 7
D are 6 × 10–4, 5 × 10–5, 3.6 × 10–6 and 7 × 10–10 respectively.
(b) Less than 7 The pH values of their 0.1 molar aqueous solutions are in
(c) 7 the order :
(d) Depends on ionic product of water (a) A < B < C < D (b) A > B > C > D
40. The pH of a solution is increased from 3 to 6; its H+ ion (c) A = B = C = D (d) None of these
concentration will be : 49. What is the pH of a 0.015 M Ba(OH)2 solution ?
(a) reduced to half (b) doubled (a) 1.82 (b) 1.52
(c) reduced by 1000 times (d) increased by 1000 times (c) 12.48 (d) 12.18
41. A patient is said to suffer from acidosis when the pH of his 50. Equal volumes of two solutions of hydrochloric acid are
blood mixed. One solution has a pH 1 while the other has a pH 5.
(a) falls below 7.35 The pH of the resulting solution is :
(b) rises above 7.35 (a) less than 1 (b) Between 1 and 2
(c) Shows sudden fall and rise (c) 3 (d) Between 4 and 5
(d) has strong basic character 51. Aspirin (acetyl salicyclic acid, molar mass = 180 g mol–1)
used as analgesic has pKa value of 2. Two tablets of aspirin
42. The pH of a dilute solution of acetic acid was found to be
each weighing 90 mg are dissolved in 100 mL of water. The
4.3. The addition of a small crystal of sodium acetate will
pH of the solution is
cause pH to
(a) 0.5 (b) 1.0
(a) Become less than 4.3 (b) Become more than 4.3
(c) 2.0 (d) 4.0
(c) Remain equal to 4.3 (d) Unpredictable
52. In a mixture of a weak acid and its salt, the ratio of
43. The pH of a 0.001 M NaOH will be
concentration of acid to salt is increased ten-fold. The pH
(a) 3 (b) 2 of the solution
(c) 11 (d) 12 (a) Decreases by one (b) Increases by one-tenth
44. The pH of a 10 M solution of HCl in water is
–9
(c) Increases by one (d) Increases ten-fold

53. The dissociation constant of HCN is 5 × 10–10. The pH of the 61. 100 mL of a buffer solution contains 0.1 M each of weak
solution prepared by mixing 1.5 mole of HCN and 0.15 moles acid HA and salt NaA. How many gram of NaOH should be
of KCN in water and making up the total volume to 0.5 dm3 added to the buffer so that its pH will be 6 ?
is (Ka of HA = 10–5).
(a) 7.302 (b) 9.302 (a) 0.328 (b) 0458
(c) 8.302 (d) 10.302 (c) 4.19 (d) None
Buffer Solutions and Relationship Between Ka 62. Two buffer solutions, A and B, each made with acetic acid
and sodium acetate differ in their pH by one unit, A has salt
and Kb for a Conjugate Pair
: acid = x : y, B has salt : acid = y : x. If x > y, then the value
54. Calculate the pH of a buffer prepared by mixing 0.10 mol of of x : y is
sodium formate and 0.05 mole of formic acid in 1.0 L of (a) 10,000 (b) 3.17
solution. [HCO2H : Ka =1.8 × 10–4]
(c) 6.61 (d) 2.10
(a) 1.8 × 10–4 (b) 3.44
63. Ka for HF is 3.5 × 10 . Calculate Kb for the fluoride ion.
–4
(c) 4.05 (d) 5.31

(a) 3.5 × 10–4 (b) 1.0 × 10–7
55. 0.1 mole of CH3NH2 (Kb = 5 × 10–4) is mixed with 0.08 mole of
(c) 2.9 × 10–11 (d) 1.0 × 10–14
HCl and the solution diluted to one litre. The H+ ion
concentration in the solution will be Salt Hydrolysis
(a) 1.6 × 10 –11
(b) 8 × 10 –11
64. A certain buffer solution contains equal concentration of

(c) 5 × 10 –5
(d) 8 × 10–2
X and HX. The Kb for X is 10–10. The pH of the buffer is
56. The pKa of weak acid (HA) is 4.5. The pOH of an aqueous
(a) 4 (b) 7
buffered solution of HA in which 50% of the acid is ionized
is (c) 10 (d) 14
(a) 7.0 (b) 4.5 65. Aq. solution of sodium cyanide is
(c) 2.5 (d) 9.5 (a) Acidic (b) Amphoteric

(c) Basic (d) Netural
57. Buffer solutions can be prepared from mixtures of
66. The solution of strong acid and weak base (FeCl3) is
(a) HCl and NaCl (b) NaH2PO4 and Na2HPO4
(a) Acidic (b) Basic
(c) CH3COOH + NaCl (d) NH4OH + NH3
(c) Neutral (d) none of these
58. For preparing a buffer solution of pH 6 by mixing sodium
acetate and acetic acid, the ratio of the concentration of 67. Which one of the following salts gives an acidic solution
salt and acid should be (Ka = 10–5) in water
(a) CH3COONa (b) NH4Cl
(a) 1 : 10 (b) 10 : 1
(c) NaCl (d) CH3COONH4
(c) 100 : 1 (d) 1 : 100
68. An aqueous solution of aluminium sulphate would show
59. How many moles of HCOONa must be added to 1L of 0.1 M
HCOOH to prepare a buffer solution with a pH of 3.4 ? (a) An acidic reaction
(Given : Ka for HCOOH = 2 × 10 )–4 (b) A neutral reaction

(c) A basic reaction
(a) 0.01 (b) 0.05
(d) Both acidic and basic reaction
(c) 0.1 (d) 0.2
69. An aqueous solution of sodium carbonate is alkaline
60. What is the pH of a buffer solution which is 0.250 M in
because sodium carbonate is a salt of
benzoic acid, C6H5COOH, and 0.150 M in sodium benzoate,
C6H5COONa, if Ka for benzoic acid is 6.5 ×10–5 ? (a) Weak acid and weak base
(a) 3.40 (b) 3.97 (b) Strong acid and weak base
(c) Weak acid and strong base
(c) 4.19 (d) 4.41
(d) Strong acid and strong base

70. The aqueous solution of ammonium chloride is
79. The pK a1 and pK a 2 of an amino acid are 2.3 and 9.7
(a) Neutral (b) Basic
respectively. The isoelectric point of amino acid is :
(c) Acidic (d) Amphoteric
(a) 12 (b) 7.4
71. The aqueous solution of FeCl3 is acidic due to
(c) 6.0 (d) 3.7
(a) Acidic impurities (b) Ionisation
80. HCN is a weak acid (Ka = 6.2 × 10–10). NH4OH is a weak base
(c) Hydrolysis (d) Dissociation
(Kb = 1.8 × 10–5). A 1.0 M solutionk of NH4CN would be :
72. Which is the correct alternate for hydrolysis constant of
(a) strongly acidic (b) weakly acidic
NH4CN
(c) neutral (d) weakly basic
Kw Kw
(a) (b) K  K 81. Ka for hydrofluoric acid is 6.9 × 10–4. What is the equilibrium
Ka a b constant K for the following reaction ?
Kb Ka F (aq.)  H 2 O(l )  HF(aq.)  OH  (aq.)
(c) (d) K
c b
(a) 6.9 × 10–11 (b) 1.4 × 10–11
73. Which of the following salt is basic ?
(c) 2.6 × 10–9 (d) 8.3 × 10–6
(a) HOCl (b) NaOCl
82. To 1.0 L solution containing 0.1 mol each of NH3 and NH4Cl,
(c) NaHSO4 (d) NH4NO3
0.05 mol NaOH is added. The change in pH will be (pKa for
74. The pKb of CN  is 4.7. The pH of solution prepared by CH3COOH = 4.74)
mixing 2.5 mol of KCN of 2.5 mol of HCN in water and making (a) 0.30 (b) –0.30
the total volume upto 500 mL is (c) 0.48 (d) –0.48
(a) 10.3 (b) 9.3 83. Fixed volume of 0.1 M benzoic acid (pKa = 4.2) solution is
(c) 8.3 (d) 4.7 added into 0.2 M sodium benzoate solution and formed a
75. The pH of blood is maintained by the balance between 300 mL, resulting acidic buffer solution. If pH of the resulting
H2CO3 and NaHCO3. If the amount of CO2 in the blood is solution is 3.9, then added volume of benzoic acid is
increased, how will it effect the pH of blood ? (a) 240 mL (b) 150 mL
(a) pH will remain same (b) pH will be 7 (c) 100 mL (d) None
(c) pH will increase (d) pH will decrease 84. In a saturated solution of H2S,decreasing the pH of the
76. Calculate the carbonate ion concentration in a 0.10 M solution will cause
solution of the weak acid, carbonic acid are (H2CO3). The (a) the S2– concentration to decrease
dissociation constants of carbonic acid are (b) the H2S concentration to decrease
Ka1 = 4.5 × 10–7 and Ka2 = 4.7 × 10–11.
(c) the S2– concentration to increase
(a) 4.7 × 10–11 M (b) 1.0 × 10–7 M
(d) no change in either the H2S or S2– concentration
(c) 4.5 × 10–7 M (d) 2.1 × 10–4 M
85. What is the pH of 0.01 M glycine solution ? For glycine
77. Which one of the following statements is true with regard
to a 0.10 M H2SO4 solution ? K a1  4.5 × 10–3 and K a2  1.7 × 10–10 at 298 K
(a) [H2SO4] > [H+] (b) [H+] = [SO 24  ] (a) 3.0 (b) 10.0
2  
(c) [SO ] > [HSO ]
4 4
(d) [H ] > [HSO ]
+
4
(c) 6.1 (d) 7.2
78. The pH 0.1 M solution of the following salts increases in 86. The equilibrium constant for this reaction is 3.6×10–7.
the order :
OCl (aq.)  H 2 O(l )  HOCl(aq.)  OH  (aq.)
(a) NaCl < NH4Cl < NaCN < HCl
(b) HCl < NH4Cl < NaCl < NaCN What is Ka for HOCl ?
(c) NaCN < NH4Cl < NaCl < HCl (a) 2.8 × 10–8 (b) 3.6 × 10–7
(d) HCl < NaCl < NaCN < NH4Cl. (c) 6 × 10–4 (d) 2.8 × 10–6

Solubility and Solubility Product 97. Ksp for Ca(OH)2 is 5.5 × 10–6. What is the maximum pH that
can be attained in a sewage tank treated with slaked lime ?
87. Let the solubility of an aqueous solution of Mg(OH)2 be x
then its ksp is (a) 9.35 (b) 10.35
(a) 4x3 (b) 108x5 (c) 11.35 (d) 12.35
(c) 27x4 (d) 9x 98. For a sparingly soluble salt Ap Bq, the relationship of its
solubility product (LS) with its solubility (S) is :
88. The solubility of CaF2 is a moles/litre. Then its solubility
product is........ (a) LS = Sp+q . pp. qq (b) LS = Sp+q . pq . qp
(a) s2 (b) 4s3 (c) 3s2 (c) LS = Spq . pp . qq (d) LS = Spq (pq)p+q
(d) s3 99. The solubility product of different sparingly soluble salts
89. Which is the correct representation of the solubility product are :
constant of Ag2CrO4 1. XY = 4 × 10–20 2. X2Y = 3.2 × 10–11
(a) [Ag+]2 [CrO4–2] (b) [Ag+] [CrO4–2] 3. XY3 = 2.7 × 10–31
(c) [2Ag+] [CrO4–2] (d) [2Ag+]2 [CrO4–2] The increasing order of solubility is :
90. The correct representation for solubility product of SnS2 is (a) 1, 3, 2 (b) 2, 1, 3
(a) [Sn ] [S ]
4+ 2– 2
(b) [Sn ] [S ]
2+ 2– 2
(c) 1, 2, 3 (d) 3, 1, 2
(c) [Sn2+] [2S2–] (d) [Sn4+] [2S2–]2 100. Solubility of AgCN is maximum in :
91. Ksp of Mg(OH)2 is 4.0 × 10 . At what minimum pH, Mg
–6 2+ (a) acidic buffer solution (b) basic buffer solution
ions starts precipitating 0.01 MgCl2 (c) in pure water (d) equal in all solution
(a) 2 + log 2 (b) 2 – log 2 101. The pH of an aqueous solution of Ba(OH)2 is 10. If the Ksp
(c) 12 + log 2 (d) 12 – log 2 of Ba(OH)2 is 1 × 10–9, then the concentration of Ba2+ ions
92. The solubility product of a salt having general formula MX2, in the solution in mol L–1 is
in water is : 4 × 10–12. The concentration of M2+ ions in the (a) 1 × 10–2 (b) 1 × 10–4
aqueous solution of the salt is (c) 1 × 10–1 (d) 1 × 10–5
(a) 2.0 × 10 M –6
(b) 1.0 × 10 M –4
102. CaCO 3 and BaCO 3 have solubility product values
(c) 1.6 × 10 M –4
(d) 4.0 × 10–10 M 1 × 10–8 and 5 × 10–9, respectively. If water is shaken up with
93. The solubility in water of a sparingly soluble salt AB2 is 1.0 both solids till equilibrium is reached, the concentration of
× 10–5 mol l–1. Its solubility product number will be CO32 ion is
(a) 4 × 10–15 (b) 4 × 10–10 (a) 1.5 × 10–8 (b) 1.225 × 10–4
(c) 1 × 10 –15
(d) 1 × 10 –10
(c) 2.25 × 10–9 (d) None of these

94. Solubility product of BaCl2 is 4 × 10–9. Its solubility in moles/ 103. A precipitate of AgCl is formed when equal volumes of the
litre would be following are mixed. [Ksp for AgCl = 10–10]
(a) 1 × 10–3 (b) 1 × 10–9 (a) 10–4 M AgNO3 and 10–7 M HCl
(c) 4 × 10 –27
(d) 1 × 10 –27
(b) 10–5 M AgNO3 and 10–6 M HCl

95. Solubility of AgCl will be minimum in (c) 10–5 M AgNO3 and 10–4 M HCl
(a) 0.001 M AgNO3 (b) Pure water (d) 10–6 M AgNO3 and 10–6 M HCl
(c) 0.01 M CaCl2 (d) 0.01 M NaCl 104. The solubility of CH3COOAg in a buffer solution with
96. At 298 K, the solubility product of PbCl2 is 1.0 × 10–6.
What will be the solubility of PbCl2 in moles/litre 104
pH = 4, whose Ksp = 10–12 and Ka = is
3
(a) 6.3 × 10–3 (b) 1.0 × 10–3
(c) 3.0 × 10–3 (d) 4.6 × 10–14 (a) 10–6 (b) 0.5 × 10–6
(c) 5 × 10–6 (d) 2 × 10–6

Preferential Precipitation of Salts and Theory of (a) (i)  A, (ii)  B, (iii)  C
Indicators (b) (i)  A, (ii)  C, (iii)  B
105. When equal volumes of the following solutions are mixed, (c) (i)  B, (ii)  C, (iii)  A
precipitation of AgCl (Ksp = 1.8 × 10–10) will occur only with: (d) (i)  C, (ii)  A, (iii)  B
(a) 10 M (Ag ) and 10 M (Cl )
–4 + –4 –
Acid Base Titration
(b) 10–5 M (Ag+) and 10–5 M (Cl–)
(c) 10–6 M (Ag+) and 10–6 M (Cl–) 112. At equivalence point, which of the following acid base
(d) 10 –10
M (Ag ) and 10
+ –10
M (Cl )– reaction pH will be greater than 8 ?
106. The pH indicators are : (a) Acetic acid versus ammonia
(a) salts of strong acids and strong bases (b) Acetic acid versus sodium hydroxide
(b) salts of weak acids and weak bases (c) Hydrochloric acid versus ammonia
(c) either weak acids or weak bases (d) Hydrochloric and versus sodium hydroxide
(d) either strong acids or strong bases 113. Why are strong acids generally used as standard solutions
107. Phenolphthalein does not act as an indicator for the titration in acid-base titrations ?
between
(a)The pH at the equivalent point will always be 7
(a) HCl and NH4OH (b) Ca(OH)2 and HCl
(b)They can be used to titrate both strong and weak bases
(c) NaOH and H2SO4 (d) KOH and CH3COOH
(c)Strong acids form more stable solutions than weak acids
108. Methyl orange gives red colour in
(d)The salts of strong acid do not hydrolyze
(a) KOH solution (b) HCl solution
(c) Na2CO3 solution (d) NaCl solution 114. In which of the following acid-base titration, pH is greater
than 8 at the equivalence point ?
109. Which acid-base indicator should be used in an aqueous
solution titration which is complete at about (a) Acetic acid vs ammonia
0.001 M H+ (aq)? The transition range in pH is given in (b) Acetic acid vs sodium ammonia
parenthesis. (c) Hydrochloric acid vs ammonia
(a) Methyl violet (0.5 – 1.5)
(d) Hydrochloric acid vs sodium hydroxide
(b) Methyl red (4.2 – 6.3)
115. What will be the pH of a solution formed by mixing 40 ml of
(c) Methyl yellow (2.9 – 4.0)
0.10 M HCl with 10 ml of 0.45 M NaOH
(d) Phenol red (6.4 – 8.0)
(a) 12 (b) 10
110. The best indicator for detection of end point in titration of
a weak acid and a strong base is : (c) 8 (d) 6
(a) methyl orange (3 to 4) 116. The rapid change of pH near the stoichiometric point of an
acid-base titration is the basis of indicator detection. pH of
(b) methyl red (5 to 6)
the solution is related to ratio of the concentrations of the
(c) bromothymol blue (6 to 7.5)
conjugate acid (HIn) and base (In–) forms of the indicator
(d) phenolphthalein (8 to 9.6) by the expression
111. Which indicator is suitable for the titrations :
[HIn]
Titration Indicator (a) log  pH  pK In
[In  ]
(i) HCOOH/NaOH (A) Bromothymol blue or
phenolphthalein or methyl [In  ]
(b) log  pH  pK In
[HIn]
orange or thymolphthalein
(ii) HBr/KOH (B) Methyl orange or methyl [ In  ]
(c) log  pK In  pH
red or bromocresol green [ HIn]
(iii) NH4OH/HNO3 (C) Phenolphthalein or [HIn]
(d) log  pK In  pH
thymolphthalein [In  ]

117. Which of the following mixture will have the pH close to 1? 119. 20 cm3 of x M solution of HCl is exactly neutralised by 40
(a) 100 ml of M/10 HCl + 100 ml of M/10 NaOH cm3 of 0.05 M NaOH solution, the pH of HCl solution is
(b) 55 ml of M/10 HCl + 45ml of M/10 NaOH (a) 1.0 (b) 2
(c) 10 ml of M/10 HCl + 90 ml of M/10 NaOH (c) 1.5 (d) 2.5
(d) 75 ml of M/5 HCl + 25 ml of M/5 NaOH 120. A sample of 50.0 mL of 0.10 M NH3 (Kb = 1.8 × 10–5) is
titrated with 0.10 M HCl. Calculate the pH at the equivalence
118. Consider the titratiokns listed below. In which is the pH at
point.
the equivalence point described incorrectly ?
(a) 6.98 (b) 2.87
Acid Base pH at equiv.pt.
(c) 7.78 (d) 5.28
(a) CH3COOH NaOH > 7.00
(b) HNO3 Ca(OH)2 = 7.00
(c) HCl NH3 < 7.00
(d) HF NaOH < 7.00


1. The molar solubility (in mol L–1) of a sparingly soluble salt Which of the following is the correct sequence of their acid
MX4 is ‘s’. The corresponding solubility product is Ksp ‘s’ strength ? (2008)
is given in terms of Ksp by the relation (2004) (a) iv < ii < iii < i (b) ii < iii < i < iv
1/ 4 1/ 5
 K sp   K sp  (c) i < iii < ii < iv (d) iii < i < iv < ii
(a) s   
 (b) s   

 128   256  9. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base,
(c) s = (256 Ksp)1/5 (d) s = (128 Ksp)1/4 BOH, is 4.78. The pH of an aqueous solution of the
corresponding salt, BA, will be (2008)
2. The conjugate base of H 2 PO 4 (2004)
(a) 8.58 (b) 4.79
(a) PO34 (b) HPO 24
(c) 7.01 (d) 9.22
(c) H3PO4 (d) P2O5
10. Solid Ba (NO3)2 is gradually dissolved in a 1.0 × 10–4 M
3. The solubility product of a salt having general formula MX2; Na2CO 3 solution. At what concentration of Ba+2 will a
in water is 4 × 10–12. The concentration of M2+ ions in the precipitate being to form ? (Ksp for BaCO3 = 5.1 × 10–9);
aqueous solution of the salt is (2005)
(2009)
(a) 4.0 × 10–10 M (b) 1.6 × 10–4 M
(a) 4.1 × 10–5 M (b) 5.1 × 10–5 M
(c) 1.0 × 10–4 M (d) 2.0 × 10–6 M
(c) 8.1 × 10–8 M (d) 8.1 × 10–7 M
4. What is the conjugate base of OH– ? (2005)
(a) O2– (b) O– 11. At 25ºC, the solubility product of Mg(OH)2 is 1.0 × 10–11. At
which pH, will Mg2+ ions start precipitating in the form of
(c) H2O (d) O2
Mg(OH)2 from a solution of 0.001 M Mg2+ ions ? (2010)
5. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous
buffered solution of HA in which 50% of the acid is ionized (a) 9 (b) 10
is (2007) (c) 11 (d) 8
(a) 4.5 (b) 2.5 12. Solubility product of silver bromide is 5.0 × 10–13. The
(c) 9.5 (d) 7.0 quantity of potassium bromide (molar mass taken as
6. In a saturated solution of the sparingly soluble strong 120 g mol–1) to be added to 1L of 0.05 M solution of silver
electrolyte AgIO3 (molecular mass = 283) the equilibrium nitrate to start the precipitation of AgBr is (2010)
which sets in is (a) 1.2 × 10–10 g (b) 1.2 × 10–9 g
AgIO3(s ) Ag (aq .) + IO 3( aq .) (c) 6.2 × 10–5 g (d) 5.0 × 10–8 g
If the solubility product constant Ksp of AgIO3 at a given 13. In aqueous solution, the ionisation constants for carbonic
temperature is 1.0 × 10–8, what is the mass of AgIO3 acid are K1 = 4.2 × 10–7 and K2 = 4.8 × 10–11 (2010)
contained in 100 mL of its saturated solution ? (2007) Select the correct statement for a saturated 0.034 M solution
(a) 28.3 × 10 g –2
(b) 2.83 × 10 g –3 of the carbonic acid.
(c) 1.0 × 10 g –7
(d) 1.0 × 10–4g (a) The concentration of CO32 is 0.034 M
7. The first and second dissociation constant of an acid H2A
are 1.0 × 10–5 and 5.0 × 10–10 respectively. The overall (b) The concentration of CO32 is greater than that of
dissociation constant of the acid will be (2007) HCO3
(a) 5.0 × 10–5 (b) 5.0 × 1015
(c) The concentration of H+ and HCO3 are approximately
(c) 5.0 × 10 –15
(d) 0.2 × 10 15
equal
8. Four species are listed below
(d) The concentration of H+ is double that of CO32
(i) HCO3 (ii) H 3O 
(iii) HSO 4 (iv) HSO 3 F

Base Acid End Point
14. Three reactions involving H 2 PO 4 are given below :
(a) Strong Strong Pink to colourless
I. H3PO4 + H2O  H3O+ + H 2 PO 4 (b) Weak Strong Colourless to pink
 2 
II. H 2 PO  H 2 O  HPO  H3O
4 4
(c) Strong Strong Pinkish red to yellow
III. H 2 PO4  OH  H3 PO4  O2 (d) Weak Strong Yellow to pinkish red
22. Assuming that the degree of hydrolysis is small, the pH of
In which of the above does H 2 PO 4 act as an acid ?(2010) 0.1 M solution of sodium acetate (Ka = 1.0 × 10–5) will be:
(a) II only (b) I and II
(a) 8.0 (b) 6.0
(c) III only (d) I only (c) 9.0 (d) 5.0
15. The Ksp for Cr(OH)3 is 1.6 × 10–30. The molar solubility of 23. In some solutions, the concentration of H3O+ remains
this compound in water is (2011) constant even when small amounts of strong acid or strong
base are added to them. These solutions are known as:
(a) 2 1.6 1030 (b) 4 1.6 1030
(c) 4 1.6 1030 / 27 (d) 1.6 1030 / 27 (a) Buffer solutions (b) True solutions
16. An acid HA ionises as (c) Ideal solutions (d) Colloidal solutions
24. The conjugate base of hydrazoic acid is:
 H   A 
HA 
The pH of 1.0 M solution is 5. Its dissociation constant
would be (2011) (a) N2 (b) N3
(a) 1 × 10–10 (b) 5 (c) N–3 (d) HN3

(c) 5 × 10–8 (d) 1 × 10–5 25. Zirconium phosphate [Zr3 (PO4)4] dissociates into three
17. Among the following oxoacids, the correct decreasing order zirconium cations of charge +4 and four phosphate anions
of acid strength is : (2014) of charge –3. If molar solubility of zirconium phosphate is
denoted by S and its solubility product by Ksp then which
(a) HClO4 > HOCl > HClO2 > HClO3
of the following relationship between S and Ksp is correct ?
(b) HClO4 > HClO3 > HClO2 > HOCl (Online 2014 Set - 4)
(c) HClO2 > HClO4 > HClO3 > HOCl (a) S = {Ksp/(6912) }
1/7
(b) S = (Ksp/6912)1/7
(d) HOCl > HClO2 > HClO3 > HClO4 (c) S = {Ksp/144}1/7 (d) S = {Ksp/6912}7
18. Which has the highest pH ? (2015) 26. Addition of sodium hydroxide solution to a weak acid (HA)
results in a buffer of pH 6. If ionisation constant of HA is
(a) CH3COONH4 (b) Na2CO3
10+5, the ratio of salt to acid concentration in the buffer
(c) NH4Cl (d) NaNO3 solution will be : (Online 2017 Set - 1)
19. pK a of a weak acid (HA) and pK b of a weak base (BOH) (a) 4 : 5 (b) 1 : 10
(c) 10 : 1 (d) 5 : 4
are 3.2 and 3.4, respectively. The pH of their salt (AB)
solution is : (2017) 27. 50 mL of 0.2 M ammonia solution is treated with 25 mL of
0.2 M HCl. If pKb of ammonia solution is 4.75, the pH of the
(a) 6.9 (b) 7.0 mixture will be : (Online 2017 Set - 2)
(c) 1.0 (d) 7.2 (a) 3.75 (b) 4.75
20. Which of the following salts is the most basic in aqueous (c) 8.25 (d) 9.25
solution? (2018) 28. The minimum volume of water required to dissolve 0.1 g
(a) Pb(CH3COO)2 (b) Al(CN)3 lead(II) chloride to get a saturated solution
(c) CH3COOK (d) FeCl3 (Ksp of PbCl 2 = 3.2 × 10-8 ; atomic mass of Pb =207u)
21. An alkali is titrated against an acid with methyl orange as is : (Online 2018 Set - 1)
indicator, which of the following is a correct combination (a) 0.36 L (b) 17.98 L
(2018) (c) 0.18 L (d) 1.798 L

29. Which of the following is a Lewis acid ? 34 Consider the following statements
(I) The pH of a mixture containing 400 mL of 0.1 M H2SO4
(a) PH3 (b) B(CH3)3 and 400 mL of 0.1 M NaOH will be approximately 1.3.
(c) NaH (d) NF3 (II) Ionic product of water is temperature dependent.
30. Following four solutions are prepared by mixing different (III) A monobasic acid with K a = 10–5 has a pH = 5. The
volumes of NaOH and HCl of different concentrations, pH
degree of dissociation of this acid is 50%
of which one of them will be equal to 1 ?
(Online 2018 Set - 2) (IV) The Le Chatelier’s principle is not applicable to
common-ion effect.
M M
(1) 100 mL HCl + 100 mL NaOH The correct statements are: (2019-04-10/Shift-1)
10 10
M M (a) I, II, III (b) I, II, IV
(2) 75 mL HCl + 25 mL NaOH
5 5 (c) II, III (d) I, II
M M 35. The pH of a 0.02 M NH 4 Cl solution will be [given
10 10 Kb(NH4OH) = 10–5 and log 2 = 0.301](2019-04-10/Shift-2)
M M (a) 2.65 (b) 4.35
10 10 (c) 4.65 (d) 5.32
31. The pH of rain water, is approximately: 36 What is the molar solubility of Al(OH)3 in 0.2 M NaOH
(2019-01-09/Shift-2) solution? Given that, solubility product of
(a) 5.6 (b) 7.5 Al(OH)3 = 2.4 x 10–24: (2019-04-12/Shift-1)
(a) 3 x 10–19 (b) 12 x 10–21
(c) 7.0 (d) 6.5
(c) 3 x 10–22 (d) 12 x 10–23
32. If Ksp of Ag2CO3 is 8 x 10–12, the molar solubility of Ag2CO3
in 0.1 M AgNO3 is: (2019-01-12/Shift-2) 37 The molar solubility of Cd(OH)2 is 1.84 x 10–5 M in water.
The expected solubility of Cd(OH)2 in a buffer solution of
(a) 8 x 10–12 M (b) 8 x 10–11 M
pH = 12 is: (2019-04-12/Shift-2)
(c) 8 x 10–10 M (d) 8 x 10–13 M
33. In an acid base titration, 0.1 M HCl solution was added to 2.49
(a) 1.84  109 M (b)  10 9 M
the NaOH solution of unknown strength. Which of the 1.84
following correctly shows the change of pH of the titration
mixture in this experiment? (2019-04-09/Shift-2) (c) 6.23 1011 M (d) 2.49 1010 M
38. The stoichiometry and solubility product of a salt with the

solubility curve given below is, respectively:
(2020-01-08/Shift-1)
(a) (B) (b) (A)

(c) (C) (d) (D) (a) X 2 Y, 2  10 9 M 3 (b) XY2 ,1  109 M 3
(c) XY2 , 4  10 9 M 3 (d) XY, 2  106 M 3

39. The Ksp for the following dissociation is = 1.6 x 10–5. (a) (A) > (C) > (D) > (B) (b) (B) > (D) > (C) > (A)
(c) (B) > (C) > (D) > (A) (d) (A) > (D) > (C) > (B)
PbCl2  s   Pb 2   aq   2Cl  aq 
44. The solubility of AgCN in a buffer solution of pH = 3 is x.
Which of the following choices is correct for a mixture of The value of x is:
300 mL 0.134 M Pb(NO3)2 and 100 mL 0.4 M NaCl?
[Assume: No cyno complex is formed;
(2020-01-09/Shift-1)
Ksp[AgCN] = 22 x 10–16 and Ka(HCN) = 6.2 x 10–10]
(a) Q  K sp (b) Q  K sp (2021-02-25/Shift-1)
(c) Q  K sp (d) Not enough data provided (a) 1.9 x 10–5 (b) 2.2 x 10–16
40. The solubility product of Cr(OH)3 at 298 K is 6 x 10–31. The (c) 1.6 x 10–6 (d) 0.625 x 10–6
concentration of hydroxide ions in a saturated solution of 45. The solubility of Ca(OH)2 in water is:
Cr(OH)3 will be: (2020-01-09/Shift-2) [Given: The solubility product of Ca(OH)2 in water
(a) 18  10 
31 1/ 4
(b) 18  10 
31 1/ 2 = 5.5 x 10–6] (2021-02-25/Shift-2)
(a) 1.11 x 10 –6
(b) 1.77 x 10–6
(c)  2.22  10 
31 1/ 4
(d)  4.86  10 
29 1/ 4
(c) 1.77 x 10–2 (d) 1.11 x 10–2
41. An acidic buffer is obtained on mixing: 46. A solution is 0.1 M in Cl and 0.001 M in CrO 24  . Solid
(2020-09-03/Shift-1)
AgNO3 is gradually added to it. Assuming that the addition
(a) 100 mL of 0.1 M HCl and 200 mL of 0.1 M CH3COONa
does not change in volume and
(b) 100 mL of 0.1 M HCl and 200 mL of 0.1 M NaCl
K sp  AgCl   1.7  1018 M 2 and
(c) 100 mL of 0.1 M CH3COOH and 100 mL of 0.1 M NaOH
(d) 100 mL of 0.1 M CH3COOH and 200 mL of 0.1 M NaOH
K sp  Ag 2 CrO4   1.9 1012 M 3
42. 100 mL of 0.1 M HCl is taken in a beaker and to it 100 mL of
0.1 M NaOH is added in steps of 2 mL and the pH is Select correct statement form the following:
continuously measured. Which of the following graphs (2021-07-20/Shift-2)
correctly depicts the change in pH? (a) AgCl precipitates first because its Ksp is high
(2020-09-03/Shift-2)
(b) Ag2CrO4 precipitates first as its Ksp is low
(c) Ag2CrO4 precipitates first because the amount of Ag+
needed is low
(a) (b) (d) AgCl will precipitates first at the amount of Ag+ needed
to precipitate is low

47. Two solutions A and B each of 100 L was made by dissolving
4g of NaOH and 9.8g of H2SO4 in water, respectively. The
(c) (d)
pH of the resulting solution obtained from mixing 40 L of
solution A and 10 L of solution B is:(2020-01-07/Shift-1)
43. Arrange the following solutions in the decreasing order of 48. 3 grams of acetic acid is added to 250 mL of 0.1 M HCl and
pOH: (2020-09-06/Shift-1) the solution is made up to 500 mL. To 20 mL of this solution
(A) 0.01 M HCl, (B) 0.01 M NaOH mL of 5 M NaOH is added. The pH of this solution is____.
(C) 0.01 M CH3COONa, (D) 0.01 M NaCl (Giving: log 3 = 0.4771, pKa of acetic acid = 4.74, molar mass
of acetic acid = 60 g/mole). (2020-01-07/Shift-2)

49. The photoelectric current from Na (Work function, 56. 0.01 moles of a weak acid HA (Ka = 2.0 x 10–6) is dissolved in
w0 = 2.3 eV) is stopped by the output voltage of the cell 1.0 L of 0.1 M HCl solution. The degree of dissociation of
Pt(s) H2 (g, 1 Bar) HCl (aq. pH = 1) | AgCl(s) | Ag(s). HA is ….. x 10–5 (Round off to the Nearest integer). [Neglect
The pH of aq. HCl required to stop the photoelectric current volume change on adding HA. (2021-03-17/Shift-1)
from K(w0 = 2.25 eV), all other conditions remaining the Assume degree of dissociation << 1]
same, is ……. x 10–2 (to the nearest integer). 57. In order to prepare a buffer solution of pH 5.74, sodium
acetate is added to acetic acid. If the concentration of acetic
RT
Given, 2.303  0.06V; E oAgCl|Ag|Cl  0.22V acid in the buffer is 1.0 M, the concentration of sodium
F
acetate in the buffer is…… M. (Round off to the Nearest
(2020-09-03/Shift-1)
integer).
50. A soft drink was bottled with a partial pressure of CO2 of 3
[Given: pKa (acetic acid) = 4.74] (2021-03-18/Shift-1)
bar over the liquid at room temperature. The partial pressure
of CO2 over the solution approaches a value of 30 bar when 58. The solubility of CdSO4 in water is 8.0 x 10–4 mol L–1. Its
44g of CO2 is dissolved in 1 kg of water at room temperature. solubility in 0.01 M H2SO4 solution is …… x 10–6 mol L–1.
The approximate pH of the soft drink is ….. x 10–1. (Round off to the Nearest integer).
(First dissociation constant of (Assume that solubility is much less than 0.01 M)
(2021-03-18/Shift-2)
H2CO3 = 4.0 x 10–7; log 2 = 0.3;
59. The OH– concentration in a mixture of 5.0 mL of 0.0504 M
density of the soft drink = 1 g mL–1)(2020-09-07/Shift-1)
NH4Cl and 2 mL of 0.0210 M NH3 solution is X x 10–6 M. The
51. If the solubility product of AB2 is 3.20 x 10–11 M3, then the value of x is _____. (Nearest integer)
solubility of AB2 in pure water is….. x 10–4 mol L–1 [Assuming
[Given Kw = 1 x 10–14 and Kb = 1.8 x 10–5]
that neither kind of ion reacts with water].
(2021-08-26/Shift-1)
(2020-09-06/Shift-2)
60. A3B2 is a sparingly soluble salt of molar mass M (g mol–1)
52. The solubility product of Pbl2 is 8.0 x 10–9. The solubility of
and solubility x gL–1. The solubility product satisfies
lead iodide in 0.1 molar solution of lead nitrate is
5
x 106 mol/L. The value of x is ____. (Rounded off to the  x 
K sp  a   . The value of a is _____. (Integer Answer)
M
nearest integer) [Given 2  1.41 ]
(2021-08-31/Shift-1)
(2021-02-24/Shift-2)
61. The pH of a solution obtained by mixing 50 mL of 1 M HCl
53. The pH ammonium phosphate solution, if pK a of
phosphoric acid and pKb of ammonium hydroxide are 5.23 and 30 mL of 1 M NaOH is x 104 . The value of x is _____.
and 4.75 respectively, is_____. (2021-02-26/Shift-2) (Nearest integer) [log 2.5 = 0.3979]
Given 4.99 (2021-08-31/Shift-2)
54. Two salts A2X and MX have the same value of solubility 62. The molar solubility of Zn(OH)2 in 0.1 M NaOH solution is
product of 4.0 x 10–12. The ratio of their molar solubilities i.e. x 1018 M. The value of x is ….. (Nearest integer)
S  A 2 X  _____. (Round off to the Nearest integer).
 (Given: The solubility product of Zn(OH)2 is 2 1020 )
S  MX 
(2021-09-01/Shift-2)
(2021-03-16/Shift-1)
55. Sulphurous acid (H 2 SO 3 ) has Ka1  1.7  102 and
Ka 2  6.4  108 . The pH of 0.588 M H2SO3 is ___. (Round

off to the Nearest integer). (2021-03-16/Shift-2)

Assertion Reason 64 For the following Assertion and Reason, the correct option
(A) If both Assertion and Reason are correct is (2020-01-08/Shift-2)
and Reason is the correct explanation of Assertion (A): When Cu (II) and sulphide ions are mixed,
Assertion. they react together extremely quickly to give a solid.
(B) If both Assertion and Reason are true but Reason (R): The equilibrium constant of Cu2+(aq) + S2–(aq)
Reason is not the correct explanation of  CuS(s) is high because the solubility product is low..
Assertion. (a) (A) is false and (R) is true.
(b) Both (A) and (R) are false
(c) Both (A) and (R) are true but (R) is not the explanation
63. For the following assertion and reason, the correct option for (A).
is: (2020-01-08/Shift-2)
(d) Both (A) and (R) are true but (R) is the explanation for
Assertion (A) : The pH of water increases with increase in (A)
temperature.
65. Given below are two statements. (2021-08-26/Shift-1)
Reason (R) : The dissociation of water into H+ and OH– an
Statement I: In the titration between strong acid and weak
exothermic reaction.
base methyl orange is suitable as an indicator.
(a) Both assertion and reason are false.
Statement II: For titration of acetic acid with NaOH
(b) Assertion is not true, but reason is true. phenolphthalein is not a suitable indicator.
(c) Both assertion and reason are true and the reason is the In the light of the above statements, choose the most
correct explanation for the assertion. appropriate answer from the options given below.
(d) Both assertion and reason are true, but the reason is (a) Statement I is false, but Statement II is true
not the correct explanation for the assertion.
(b) Statement I is true, but Statement II is false
(c) Both Statement I and Statement II are true
(d) Both Statement I and Statement II are false


Objective Questions I [Only one correct option] (b) The strongest acid that can exist in ammonia solution is
1. In the following reaction : H3O+ (am).
(c) The strongest base, which can exist in ammonia
HCO3  H 2 O  CO32   H3O
solution, is NH 4 (am).
Which two substances are Bronsted bases ?
(d) The addition of an acid to an ammonia solution will
(a) CO32 and H3O  (b) HCO3 and H3O+ increase the concentration of NH2– (am).
7. The concentration of NaOH solution is 10–8 M. Find out the
(c) HCO3 and CO32 (d) CO32 and H2O (OH–) concentration
2. The equilibrium constant for this reaction is approximately (a) 10–8 (b) Greater than 10–6
10–3. (c) 10–6
(d) Lies between 10–6 and 10–7
HPO24 (aq.)  HCO3 (aq.)  H2 PO4 (aq.)  CO32 (aq.) 8. The charge balance equation of species in 0.1 M CH3COOH
solution is given by :
Which is the strongest conjugate base in this reaction ? +
(a) [H ] = [OH ]
–
+ –
(a) HPO24  (aq.) (b) HCO3 (aq.) (b) [H ] = [CH3COO ]
+ – –
(c) [H ] = [OH ] + [CH3COO ]
(c) H 2 PO4 (aq.) (d) CO32  (aq.) + – –
(d) 2[H ] = [OH ] + [CH3COO ]
3. Arrange the following acids in increasing order of their 9. A solution of 2M formic acid (HCOOH) is 0.95% ionized.
acid strength : What is the Ka of formic acid ?
I. HClO4 II. H2SO4 III. H3PO4 (a) 1.9 × 10
–2
(b) 1.8 × 10
–4
(a) III < II < I (b) I < II < III (c) 9 × 10

–5
(d) 4.5 × 10
–5
(c) II < III < I (d) III < I < II 10. What is the Kb of a weak base that produces one OH per
–
4. Consider the following reaction which proceeds molecule if a 0.05 M solution is 2.5% ionized ?
–8 –6
predominantly from (a) 7.8 × 10 (b) 1.6 × 10
–5 –3
(c) 3.2 × 10 (d) 1.2 × 10
HSO4  NH3  NH4  SO42
11. The pKa of acetylsalicylic acid (aspirin) is 3.5. The pH of
From the information given it is clear that gastric juice in human stomach is about 2-3 and the pH in
the small intestine is about 8. Aspirin will be :
(a) HSO4 is a stronger acid than NH 4 .
(a) unionised in the small intestine and in the stomach
(b) NH3 is a weaker base than SO24  (b) completely ionized in the small intestine and in the
stomach
(c) HSO4 is a stronger base than NH 4 (c) ionised in the stomach and almost unionised in the
small intestine
(d) NH3 is a weaker base than NH 4
(d) ionised in the small intestine and almost unionised in
5. A mixture of weak acid is 0.1 M in HCOOH the stomach
–4 –4
(Ka = 1.8 × 10 ) and 0.1 M in HOCN (Ka = 3.1 × 10 ). Hence, 12. In our body, carbon dioxide (CO2) combines with water (H2O)
[H3O ] is to form carbonic acid.
–3 –4
(a) 7.0 × 10 M (b) 4.1 × 10 M H2O + CO2   H2CO3
–3
(c) 0.20 M (d) 4.1 × 10 M Carbonic acid undergoes dissociation as,
6. Like water, ammonia (NH3) is an amphoteric substance that
can be used as a solvent for acid base reactions. The phase H 2 CO3  H   HCO3
label (am) means solvated by ammonia (ammoniated). During the physical and mental stress, the rate of respiration
Which statement is correct, extrapolating from your increses, which results in the decrease in concentration of
knowledge of acid base reactions in water ? CO2 in the blood. What will be the effect on pH of human
(a) Auto-ionization of ammonia is described by blood during the stress ?
(a) Decreases (b) Remains same
2NH3 (l )  NH 4 (am)  NH2 (am)
(c) Increases (d) Cannot be predicted

13. What is the pH of a solution at 25ºC that is 0.010 M in HCl 2. A solution that is 0.1 M NaH 2 PO 4 and 0.1 M
and 0.025 M in HNO3 ? Na2HPO4.
(a) 1.49 (b) 1.60 3. A solution made by mixing 10 mL of 0.1 M HF and
(c) 1.82 (d) 3.60 5.0 mL of 0.1 M NaOH.
14. If 112 mL of HCl(g) at S.T.P. conditions become the solute 4. A solution made by mixing 10 mL of 0.1 M KOH
in 500 mL of water solution, what will be the pH of this and 20 mL of 0.1 M HCl.
mixture ? (a) 1 and 2 (b) 2 and 3
(a) 0.5 (b) 1.0 (c) 3 and 4 (d) 1 and 4
(c) 1.5 (d) 2.0 22. A solution was prepared by mixing 10.0 mL of 0.50 M NaOH
15. Why is it necessary to take the acid-base properties of with 10.0 mL of 1.00 M acetic acid, Ka=1.8 ×10–5. Find the
water into account when computing the hydronium ion pH of solution.
concentration of very dilute solutions of strong acids ? (a) 2.45 (b) 1.67
(a) The hydroxide ion produced from the dissociation of (c) 2.37 (d) 4.74
+
water reacts with most of the H ion produced from the 23. What volume of 0.40 M NH3 solution must be added to
acid. 1.0 L of 0.10 M NH4Cl solution to give a buffer having pH of
(b) The dissociation constant for water is larger in dilute 10.00 ? For NH3, Kb = 1.8 × 10–5
rather than in concentrated solutions of acids. (a) 1.4 L (b) 1.1 L
+
(c) The amount of H ion produced by the dissociation of (c) 0.97 L (d) 0.61 L
water is significant compared to that produced by the acid.
24. For the overall reaction
(d) The conjugate base of the strong acid reacts with the
hydroxide ion produced from the dissociation of water. H 2S(aq)  2H  (aq)  S2  (aq) , the value of K a is
16. When one drop of a concentrated HCl is added to 1×10–22. The Ksp for ZnS is 1.2 × 10–23. What would be the
1 L of pure water at 25ºC, the pH drops suddenly from maximum concentration of Zn+2(aq) ion in a 0.01 M solution
7 to 4. When the second drop of the same acid is added, the of H2S that has its pH adjusted to 5 by mixing a strong acid
pH of the solution further drops to about with the H2S ?
(a) 0 (b) 1.0 (a) 1.2 × 10–9 M (b) 2.4 × 10–6 M
(c) 2.0 (d) 3.7 (c) 3.8 × 10–4 M (d) 1.8 × 10–1 M
–5
17. The pH of 10 M HCl solution if 1 ml of it is diluted to 1000 25. For the overall reaction H2S(aq)  2H+(aq) + S2– (aq), the
ml is : value of Ka is 1 × 10–22. The Ksp for FeS is 4 × 10–19. What
(a) 5 (b) 8 would be the maximum concentration of Fe+2 (aq) ion in a
(c) 7.02 (d) 6.98 0.1 M solution of H2S that has has its pH adjusted to 2 by
mixing a strong acid with the H2S ?
18. On diluting a buffer solution, its pH :
(a) 4 × 10–38 M (b) 6 × 10–10 M
(a) increases (b) decreases
(c) 6 × 10–6 M (d) 4.0 M
(c) remains same (d) can’t say
19. Calculate the [NH3]/[NH4 ] ratio in an ammonia-ammonium
+ 26. H3 PO 4  H 2 O  H3O  H2 PO4 ; pK1 = 2.15
chloride buffer with a pH of 9.00. H 2 PO4  H 2 O  H3 O  HPO24  pK2 = 7.20
(Kb = 1.8 × 10–5 for ammonia)
Hence pH of 0.01 M NaH2PO4 is :
(a) 0.56 : 1.00 (b) 0.74 : 1.00
(a) 9.35 (b) 4.675
(c) 0.86 : 1.00 (d) 1.12 : 1.00
(c) 2.675 (d) 7.350
20. A buffer solution of pH = 9.00 is made by dissolving
ammonium chloride and ammonia in water. How many moles 27. Calculate the molar concentrations of H3O+, HSO4–, and
of ammonium chloride must be added to 1.0 L of 0.25 M SO42– in a 0.250 M solution of H2SO4. Assume K a1 is very
ammonia to prepare this buffer ?
large ; K a 2 = 1.20 × 10–2.
NH3 (aq)  H 2 O  NH 4 (aq)  OH  (aq); Kb=1.8 × 10–5
(a) 0.25 mol (b) 0.45 mol [H3O+], M [HSO4–], M [SO 24  ], M
(c) 0.65 mol (d) 2.2 mol (a) 0.250 0.250 0.000
21. Which of these aqueous solutions are buffers ? (b) 0.250 0.250 0.0120
1. A solution that is 0.1 M HNO3 and 0.1 M HCl. (c) 0.500 0.000 0.500
(d) 0.261 0.239 0.0110

28. What is the equilibrium [OH–] in 0.1413 M H2CO3 ? 35. Which of the following are Lewis acids?
H 2 CO3  H 2 O  H3 O  HCO3 (Ka = 4.30 ×10–7) (a) PH3 and BCl3 (b) AlCl3 and SiCl4
(a) 7.07 × 10–14 M (b) 2.46 × 10–4 M (c) PH3 and SiCl4 (d) BCl3 and AlCl3
(c) 4.16 × 10–11 M (d) 6.84 × 10–6 M 36. A solution of 0.1 M NaZ has pH = 8.90. The Ka of HZ is
–11 –10
29. A 100 mL portion of water is added to each of the following (a) 6.3 × 10 (b) 6.3 × 10
–5 –6
two solutions. (c) 1.6 × 10 (d) 1.6 × 10
(i) 100 mL of 0.02 M KCl (ii) 100 mL of 0.02 M HCl 37. If pKb for fluoride ion at 25ºC is 10.83, the ionisation constant
Which of the following statements is correct ? of hydrofluoric acid in water at this temperature is
–5 –3
(a) There will be no change in pH of solution (i) and (ii) (a) 1.74 × 10 (b) 3.52 × 10
–4 –2
(b) The pH of solution (i) will remain the same but pH of (c) 6.75 × 10 (d) 5.38 × 10
solution (ii) will increase 38. The solubility of silver benzoate (C6H5COOAg) in H2O and
(c) The pH of solution (i) will remain same but of solution in a buffer solution of pH = 2, 3, and 4 are S1, S2, S3 and S4
(ii) will decrease respectively. The decreasing order of solubility is
(d) The pH of solution (ii) will remain same but of solution (a) S1 > S2 > S3 > S4 (b) S4 > S3 > S2 > S1
(i) will increase (c) S2 > S3 > S4 > S1 (d) S3 > S2 > S4 > S1
30. The correct order of increasing [H3O+] in the following 39. Ksp of Mg (OH)2 is 1 × 10 –12. 0.01 M MgCl2 will be
aqueous solution is : precipitating at the limiting pH :
(a) 0.01 M H2S < 0.01 M H2SO4 < 0.01 M NaCl < 0.01 M (a) 8 (b) 9
NaNO3
(c) 10 (d) 12
(b) 0.01 M NaCl < 0.01 M NaNO3 < 0.01 M H2S < 0.01 M
40. The solubility products of MA, MB, MC and MD are
H2SO4
1.8 × 10–10, 4 × 10–3, 4 × 10–8 and 6 × 10–5 respectively. If a
(c) 0.01 M H2S < 0.01 M NaNO3 = 0.01 M NaCl < 0.01 M 0.01 M solution of MX is added dropwise to a mixture
H2SO4 containing A–, B –, C– and D– ions then the one to be
(d) 0.01 M H2S < 0.01 M NaNO3 < 0.01 M NaCl < 0.01 M precipitated first will be :
H2SO4 (a) MA (b) MB
31. pH of water is 7. When a substance Y is dissolved in water, (c) MC (d) MD
the pH becomes 11. The substances Y is a salt of :
41. Solubility of calcium phosphate (molecular mass, M) in water
(a) weak acid and weak base is W g per 100 mL at 25ºC. Its solubility product at 25ºC will
(b) strong acid and strong base be approximately :
(c) strong acid and weak base 5 5
9W 7W
(d) weak acid and strong base (a) 10   (b) 10  
M M
32. Calcium lactate is a salt of weak acid i.e., lactic acid having
5 5
general formula Ca(Lac)2. Aqueous solution of salt has 5W W
3
0.3 M concentration. pOH of solution is 5.60. If 90% of the (c) 10   (d) 10  
salt is dissociated then what will be the value of pKa ? M M
–10
(a) 2.8 – log (0.54) (b) 2.8 + log (0.54) 42. How many grams of AgCl (Ksp = 1.8 × 10 ) will dissolve in
–5
1.0 L of 6.0 M NH3 (Kb = 1.8 × 10 ). The Kformation for
(c) 2.8 + log (0.27) (d) None of these + 7
Ag(NH3)2 is 1.7 × 10 .
33. If 0.1 mol of salt is added to 1L water, which of these salts is (a) 0.0013 g (b) 43 g
expected to produce the most acidic solution ?
(c) 1.3 g (d) 12 g
(a) NaC2H3O2 (b) NH4NO3 –12
43. For Ag 2 CO 3 , K sp = 6.2 × 10 , For AgCl, K sp
(c) CuSO4 (d) AlCl3 –10
= 2.8 ×10 . Solid Ag2CO3 and solid AgCl are added to a
34. Hydrolysis constants of two salts KA and KB of weak acids beaker containing 1.00 M Na 2CO 3(aq). Under these
–8 –6 2– –
HA and HB are 10 and 10 . If the dissociation constant of conditions the [CO3 ] = 1.00 M. Calculate the [Cl ] in
–2
third acid HC is 10 . The order of acidic strengths of three solution when equilibrium is established.
acids will be : (a) 1.1 × 10
–4
(b) 1.26 × 10
–6
(a) HA > HB > HC (b) HB > HA > HC (c) 0.15 (d) 2.8 × 10
–6
(c) HC > HA > HB (d) HA = HB = HC

44. Given the following K sp values : for M(OH) 4 , (c) The dissociation constant for the acid represented by
–19 –14 –4 –4
Ksp(M) = 4.0 × 10 ; for Z(OH)2, Ksp(Z) = 1.0 × 10 . One curve 3 is about 1 × 10 (i.e., Ka = 1 × 10 ).
mole of each of the above solids is placed in a beaker (d) All the responses above are correct.
containing 1 (one) litre of pure water. These solids go into
equilibrium with their ions. Calculate the pH required for
4+ 2+
the metal ion concentrations to be equal, [M ] = [Z ].
[One or more than one correct option]
(a) 12.6 (b) 9.6
(c) 6.7 (d) 11.8 49. Which among the following represent the conjugate
acid/base pairs ?
45. During the titration of weak diprotic acid H2A against strong
base NaOH, the pH of the solution half-way to the first (a) H3O+/H2O
equivalence point and that at first equivalence point are (b) H2SO4/ SO24 
given respectively by :
(a) pK a1 and pK a 2 (c) HCO3 / CO32
pK a1  pK a 2 (d) All are conjugate acid/base pairs

(b) pK a1 and 50. At 25ºC, pH of a 0.01 M solution of a monobasic acid (HA)
2
is 4. The correct statement(s) regarding HA and its given
(c) pKa and (pK a1  pK a 2 ) solution is (are)
pK a1  pK a 2 (a) HA is a weak acid
(d) CK a1 and (b) The ionization constant (Ka) of acid is approximately
2 –6
46. 0.2 g sample of benzoic acid, C6H5COOH is titrated with 10 at 25ºC
0.12 M Ba (OH)2 solution. What volume of Ba(OH)2 solution (c) Increasing the temperature of solution would cause the
is required to reach the equivalence point ? pH to decrease
–1
Molar mass of benzoic acid is 122 g mol (d) Addition of 0.1 M HCl solution would lower pH by
(a) 6.82 mL (b) 13.6 mL increasing degree of ionization.
(c) 17.6 mL (d) 35.2 mL 51. Choose the correct statement :
47. How many milliliters (mL) of a 0.0500 M NaOH (a strong (a) pH of acidic buffer solution decreases if more salt is
base) solution should be added to 1.00 L of 0.100 M H3PO4, added
solution to produce a buffer of pH = 2.00 ? For H3PO4, (b) pH of acidic buffer solution increases if more salt is
K a1 = 6.67 × 10–3 added
(c) pH of basic buffer decreases if more salt is added
Given : H3PO4 + OH– (from NaOH)  H2PO4– + H2O
(d) pH of basic buffer increases if more salt is added
(a) 200 (b) 400
52. Which of the following will function as buffer ?
(c) 600 (d) 800
(a) NaCl + NaOH (b) Borax + Boric acid
48. Following figure represents simulated titration curves for
solutions of four acids titrated with the same standard base (c) NaH2PO4 + NaHPO4 (d) NH4Cl + NH4OH
solution. Based on these titration curves, we can accurately 53. Which of the following mixtures is (are) buffer ?
predict that (a) 10 mL 0.1 M NH4Cl + 10 mL 0.08 M NaOH
12 (b) 20 mL 0.22 M CH3COOH + 30 mL 0.15 M NaOH
10 (c) A 0.10 M NaHCO3 solution
8 (d) 15 mL 0.12 M CH3NH2 + 10 mL 0.07 M HCl
pH 4
6 54. Degree of hydrolysis for a salt of strong acid and weak
3
4
2
base is :
2 1 (a) independent of dilution
0 0 10 20 30 40 (b) increase with dilution
(c) increase with decrease in Kb of the bases
(a) Curve 4 represents the smallest concentration and the
weakest acid. (d) decreases with decrease in temperature
(b) Curve 1 represents the largest concentration and the
strongest acid.

55. A 0.1 M sodium acetate solution was prepared. The 60. The percentage ionization of a weak base is given by
–10
Kh = 5.6 × 10
–5  Ka   1 
(a) The degree of hydrolysis is 7.48 × 10
(a)  c  100 (b)  pK b  pOH   100
–
(b) The [OH ] concentration is 7.48 × 10 M
–3
   1  10 
– –6
(c) The [OH ] concentration is 7.48 × 10 M  Kb 
 
(d) The pH is approximately 8.88 (c)  c   100
 
56. Which among the following salts will give basic solution
on hydrolysis ?  Kw 
 
(d)  c  K of conjugate acid   100
(a) NaH2PO4 (b) NH4Cl  a 
(c) NaCl (d) K2CO3 61. Which of the following statements is/are correct about the
57. A solution containing a mixture of 0.05 M NaCl and 0.05 M ionic product of water ?
Nal is taken. (K sp of AgCl = 10 –10 and K sp of (a) Ka (equilibrium constant of water) < Kw (ionic product
AgI = 4 × 10–16). When AgNO3 is added to such a solution: of water)
(a) the concentration of Ag+ required to precipitate Cl– is
(b) pKa > pKw
2 × 10–9 mol/L –12
(c) At 100ºC, Kw of water becomes 10
(b) the concentration of Ag+ required to precipitate I– is
–14
8 × 10–15 mol/L (d) Ionic product of water at 25ºC is 10
(c) AgCl and AgI will be precipitate together 62. A solution is prepared by mixing 100 mL 0.50 M hydrazoic
–4
(d) first AgI will be precipitated acid (HN3), whose Ka = 3.6 × 10 , with 400 mL of 0.10M
–4
58. Which of the following is (are) correct when 0.1 L of 0.0015 cyanic acid (HOCN), whose Ka = 8 × 10 . Which of the
M MgCl2 and 0.1L of 0.025 M NaF are mixed together ? following is (are) true regarding
(Ksp of MgF2 = 3.7 × 10–8) + –2 –3
(a) [H ] = 10 M (b) [N3 ] = 3.6 × 10
(a) MgF2 remains in solution
– –3 – –13
(b) MgF2 precipitates out (c) [OCN ] = 4.57 × 10 (d) [OH ] = 7.14 × 10
(c) MgCl2 precipitates out 63. Which of the following is (are) correct for buffer solution ?
(d) Cl– ions remain in solution (a) Acidic buffer will be effective within in the pH range
59. The titration curve given below involves 1.0 M solutions (pK a  1)
of an acid and a base.
(b) Basic buffer will be effective within the pH range
14 (pK w  pK b  1)
12 (c) H3PO4 + NaH2PO4 is not a buffer solution
10 (d) Buffer behaves most effectively when the [Salt]/[Acid]
8 ratio equal to one
pH
6 64. The equilibrium constant (Kc) for the reaction of a weak
9
acid HA with strong base NaOH is 10 at 25ºC. Which of the
4
following are correct deduction ?
2 –5
(a) The ionization constant (Ka) at 25ºC is 10 for HA.
0
Volume of titrant (b) pH of a 0.01 M aqueous solution of HA at 25ºC will be
Which of the following is/are correct for the given curve ? 3.5
(a) The solution being titrated is a base and the titrant is an (c) pH of a 0.10 M aqueous solution of NaA at 25ºC will be
acid 9.
–4
(d) If Kb of a weak base BOH is 10 at 25ºC, equilibrium
(b) The pH at the equivalence point must be less than 7
constant for neutralization of HA with BOH at 25ºC will
(c) The titrated solution is strong acid be 10
–5
(d) The titrated solution is strong base

65. Titration curve for a weak acid with a strong base is Given : The dissociation constant for
Ag( NH 3 ) 2
+
14.0 Ag + 2NH3;
–8 –13
12.0 Colour change
Kd = 6.0 × 10 and Ksp (AgBr) = 5.0 × 10 .
Phenolphthalein 73. When a 40 mL of a 0.1 M weak base, BOH is titrated with
10.0 Equivalence
point
8.0
0.10 M HCl, the pH of the solution at the end point is 5.5.
What will be the pH if 10 mL of 0.10 M NaOH is added to
6.0 the resulting solution ?
pH
4.0 Colour change
Bromophenol blue Assertion Reason
2.0
0 (A) If both Assertion and Reason are correct

5.0 10.0 15.0 20.0 25.0 30.0 and Reason is the correct explanation of
Volume of 0.5 M NaOH in ml
Assertion.
Which of the following s/are correct for the above curve ?
(a) At the half-neutralization point pH = pKa
Reason is not the correct explanation of
(b) The pH is greater than 7 at the equivalence point
Assertion.
(c) The colour change in basic medium
(d) The solution at the half neutralization is buffer solution
Numerical Value Type Questions 74. Assertion (A) : [Al(H 2O) 6 ]3+ is a stronger acid than
66. A buffer solution is formed by mixing 100 mL 0.01 M [Mg(H2O)6]2+.
CH3COOH with 200 mL 0.02 M CH3COONa. If this buffer Reason (R) : Size of [Al(H2O)6]3+ smaller than [Mg(H2O)6]2+
solution is made to 1.0 L by adding 700 mL of water, pH will and possesses more effective nuclear charge.
change by a factor of (a) A (b) B
67. If the equilibrium constant of the reaction of a weak acid (c) C (d) D
9
HA with a strong base is 10 , then pH of a 0.10 M NaA 75. Assertion (A) : Water acts as leveling solvent for various
solution is acids.
–9 –3
68. M(OH)x has Ksp of 4 × 10 and its solubility of 10 M. The Reason (R) : Leveling effect of water is due to high dielectric
value of x is ______ . constant and strong proton accepting tendency.
69. Solubility product constant of a springly soluble salt MCl2 (a) A (b) B
–12
is 4 × 10 at 25ºC. Also, at 25ºC, solubility of MCl2 is an (c) C (d) D
8
aqueous solution of CaCl2 is 4 × 10 times less compared to 76. Assertion (A) : Addition of HCl(aq.) to HCOOH(aq.)
its solubility in pure water. Hence, concentration (molarity) decreases the ionization of HCOOH.
of CaCl2 solution is +
Reason (R) : Common ion effect of H ion, reduces the
70. The solubility product constant of a metal carbonate MCO3 ionization of HCOOH.
–12
is 2 × 10 at 25ºC. A solution is 0.1 M in M(NO3)2 and it is (a) A (b) B
saturated with 0.01 M CO2. Also the ionization constant of
(c) C (d) D
–7 –11
CO2 are K a1 = 4 × 10 and K a 2 = 5 × 10 at 25ºC. The 77. Assertion (A) : pH of HCl solution is less than that of
minimum pH that must be maintained to start any acetic acid of the same concentration.
precipitation is Reason (R) : In equimolar solutions, the number of titrable
71. The equivalence point in a titration of 40.0 mL of a solution protons present in HCl in less than that present in acetic
of a weak monoprotic acid occurs when 35.0 mL of a 0.10 M acid.
NaOH solution has been added. The pH of the solution is (a) A (b) B
5.5 after the addition of 20.0 mL of NaOH solution. What is (c) C (d) D
–6
the dissociation constant of the acid ? (in 10 ) 78. Assertion (A) : pH of water increases with an increase in
72. How much AgBr could dissolve in 1.0 L of 0.4 M NH3 ? temperature.
Assume that Ag ( NH 3 ) 2 is the only complex formed . Reason(R): K w of water increases with increase in
temperature.
(a) A (b) B
(c) C (d) D

–8
79. Assertion (A) : pH of 10 M HCl lies between 6 and 7. 87. Assertion (A) : If HA and HB are two weak non-basic acids
Reason (R) : For very dilute solutions of acids, H ion
+ with Ka(HA) < Kb(HB), then, the aqueous solution of NaA
contribution from water is also taken into consideration. will have higher pH than pH of aqueous solution of NaB of
same concentration.
(a) A (b) B
Reason (R) : Conjugate base of a weaker acid is stronger
(c) C (d) D than the same of stronger acid.
–3 –4
80. Assertion (A) : If Ka of HA is 10 and Ka of HB is 10 at (a) A (b) B
25ºC, pH of an aqueous solution of HB will be one unit
greater than pH of equimolar solution of HA. (c) C (d) D
–6 2+
Reason (R) : For weak acids, both concentration and 88. Assertion (A) : On mixing 500 mL of 10 M Ca ion and
–6 –
ionization constant affects the pH. 500 mL of 10 M F ion, the precipitate of CaF2 will be
–18
(a) A (b) B obtained Ksp (CaF2) = 10 .
(c) C (d) D Reason (R) : If Ksp is less than ionic product, precipitate
will be obtained.
81. Assertion (A) : Increasing the temperature of an aqueous
acetic acid solution decreases pH. (a) A (b) B
Reason (R) : Ionization of acetic acid is endothermic in (c) C (d) D
nature. 89. Assertion (A) : The pH of the solution at the mid point of
(a) A (b) B the weak acid strong base titration becomes equal to the
pKa of the acid.
(c) C (d) D
Reason (R) : The molar concentrations of proton acceptor
82. Assertion (A) : pH value of HCN solution decreases when and proton donor become equal at mid point of a weak
NaCN is added to it acid.
Reason (R) : NaCN provides a common ion CN– to HCN. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D
83. Assertion (A) : An aqueous solution of ammonium acetate Match the Following
can act as a buffer. Each question has two columns. Four options are
Reason (R) : Acetic acid is a weak acid and NH4OH is a given representing matching of elements from
weak base.
Column-I and Column-II.
(a) A (b) B
(c) C (d) D 90. Match the Column-I with Column-II :
84. Assertion (A) : Aqueous solution of ammonium carbonate Column - I Column - II
is basic. (A) Degree of hydrolysis (p) the hydrolysis of anion
Reason (R) : Acidic or Basic nature of a salt solution of a for salts of strong which is irreversible.
salt of weak acid and weak base depends on Ka and Kb of acid and weak base
the acid and base forming it.
(B) Hydrolysis constant (q) is not possible because
(a) A (b) B
of the reaction of strong
(c) C (d) D base with strong acid.
85. Assertion (A) : H3BO3 is aprotic acid. (C) Na2O in water is basic (r) is affected when
Reason (R) : Borax is salt of H3BO3 and NaOH ; its aqueous due to temperature is changed
solution is alkaline in nature. and concentration is
(a) A (b) B changed.
+
(c) C (d) D (D) Na + H2O (s) is independent of volume
86. Assertion (A) : When aqueous, solution of CH3COONH4 is NaOH + H
+
of solution taken but
diluted, then its degree of hydrolysis increases. depends
Reason (R) : Ammonium acetate is the salt of weak acid upon temperature
and weak base, its degree of hydrolysis does not depend
on the concentration.
(a) A (b) B
(c) C (d) D

91. Match the Column-I with Column-II : 95. Match the Column-I with Column-II :
Column - I Column - II Column-I Column-II
(A) NH4Cl (p) No hydrolysis
(Salt) (Nature of hydrolysis)
(A) NH4CN (p) Only cation hydrolysis (B) NaCl (q) h  K h / C
(B) CH3COONa (q) Only anion hydrolysis Kw

(C) CH3COONa (r) h  CK
(C) NaClO4 (r) Both cation and anion b
hydrolysis (D) CH3COONH4 (s) h  K h

(D)Fe(NO3)2 (s) No hydrolysis where, C = Concentration of Salt ; Kh = hydrolysis constant
92. Match the Column-I with Column-II : Kw = Ionic product of water ; Kb = Dissociation constant of
Column - I Column - II weak base
+Y X –X Y
(A) [A ] [B ] > Ksp (p) Precipitation just starts Paragraph Type Questions
+Y X –X Y
(B) [A ] [B ] < Ksp (q) Buffer capacity Use the following passage, to solve Q. 96 to Q. 97
+Y X –X Y
(C) [A ] [B ] = Ksp (r) The solid AXB4 will Passage
precipitate out
The concentration of hydrogen ion is a measure of acidity
(D) d(n)/dpH (s) No precipitation or alkalinity of a solution.
93. Match the Column-I with Column-II : For mono basic acids :
Column - I Column - II CH3 COOH  CH3COO  H 
(A) has highest pH at end (p) CH3COOH
–5 Ka
point when titrated against Ka = 1.8 × 10 
C
standard NaOH
where, Ka = Dissociation constant of acid
(B) has lowest pH at the end (q) HCN
C = molarity of acid
–10
point when titrated against Ka = 5 × 10
Ka
standard NaOH [H  ]  C,[H  ]  , [H  ]  CK a

(C) release maximum heat (r) HF pH of a weak acid can be calculated using [H+] by any of
–4
when neutralized with Ka = 5 × 10 above methods.
NaOH [H  ]Total  C1K a1  C 2 K a 2 (When two weak acids are
(D) release equal amount (s) NH4OH mixed)
–5
of heat when neutralized Kb = 1.8 × 10 [H+] of polyprotic acid (weak, H3A) (has dissociation
with strong acid or base constants K a1  K a 2  K a 3 ); will be contributed by first
94. Match the Column-I with Column-II : dissociation at the most.
Column - I Column - II + –6
96. What will be the value of [H ] of 10 M CH3COOH ?
(Titration) (Indicator used) (Ka = 1.8 × 10 )
–5
–6 –6
(A) Strong acid versus (p) Methyl orange (3 – 4.4) (a) 4.24 × 10 M (b) 10 M
–7 –8
strong base (c) 9.5 × 10 M (d) 10 M
(B) Weak acid versus (q) Methyl red (4.3 – 6.3) 97. What will be sulphide ion concentration of a dilute solution
that has been saturated with 0.1 M H2S if the pH of the
strong base solution is 3 ?
(C) Strong acid versus (r) Phenolphthalein (8 – 10)
K a1  1 107 ; K a 2  1.3  1013
weak base –11 –13
(a) 1.25 × 10 (b) 1.3 × 10
(D) Weak acid versus (s) No suitable indicator –9 –15
(c) 1.45 × 10 (d) 1.30 × 10
weak base

Use the following passage, to solve Q. 98 to 101. [PO34 ] ion in the soil with pH = 7, is
Q. 100 (a) 10–3 M (b) 1.2 × 10–4 M
Passage (c) 2.2 × 10–4 M (d) 1.1 × 10–10 M
Hydrogen carbonate and phosphate buffers in the blood 102. [Zn2+] ion in the soil is
+
prevent excess hydrogen ions [H ] produced by metabolic (a) 2.9 × 10–11 M (b) 4.0 × 10–10 M
activity, from decreasing the pH of the blood. Carbon
(c) 3.0 × 10–6 M (d) 9.1 × 10–5 M
dioxide released into the blood during respiration is
regulated by this system and prevented from causing Use the following passage, to solve Q. 103 to
changes in plasma pH prior to its excretion from the lungs.
Excessive change in blood chemistry which would change Q. 105
the plasma pH from its normal level 7.4. This excretes Passage
hydrogen ions and retains hydrogen carbonate ions and
retains hydrogen ions if the pH rises. This may produce Solubility of a salt is defined as the maximum amount of a
change in the pH of the urine from 4.5 to 8.5. A fall in pH salt which can be dissolved in a given amount of solvent at
also stimulates the kidney cells to produce the base ion
a particular temperature. Unit of solubility is mole per litre
ammonia (NH4 ) which combines with acids brought to of solution. The solubility of a salt of weak acid with strong
the kidney and is then excreted as ammonium salts. base (CH3COOAg) in acidic buffer can be calculated as

– +
CH3COOAg  CH3COO (aq) + Ag (aq)
98. The normal pH of blood is
(a) 4.5 (b) 8.5 S–X S
(c) 7.32 (d) 7.4 S = Solubility of salt

– +
99. Which of the following buffer present in the blood ? CH3COO (aq) + H   CH3COOH
(a) HCO3  H 2 CO3 and PO34  HPO 24 (b) (S – X) (from acidic buffer) X
+ –
Ksp = [Ag ] [CH3COO ] = S (S – X)
HCO3  CO32 and HPO 24  H 2 PO 4
Dissociation constant of weak acid
(c) HCO 3  H 2 CO 3 and PO 34  H 3 PO 4 (d) None of these
(S  X) [H  ]
(K a ) 
100. Assuming that the buffer in blood is CO 2  HCO3 . X
Calculate the ratio of conjugate base to acid necessary to
maintain blood at its proper pH. 103. The solubility of LiOH in a solution with pH = 8 is
–7 –12
(K1 of H2CO3 = 4.2 × 10 ) (Ksp = 1.8 × 10 )
–18 –6
(a) 15 (b) 16 (a) 1.8 × 10 (b) 1.8 × 10
–6 –4
(c) 14 (d) 11 (c) 10 (d) 1.8 × 10
104. The solubility of AgCl is maximum in
Use the following passage, to solve Q. 101 to
(a) 0.1 M NaCl (b) 0.1 M CaCl2
Q. 102
(c) 55.5 M H2O (d) None of these
Passage
105. The solubility of CaCO3 is 7 mg/L. Calculate the solubility
H3PO4 is a tribasic acid with pKa1 , pK a 2 and pK a 3 2.12, product of BaCO3 from this information and from the fact
7.21, and 12.32, respectively. It is used in fertiliser that when Na2CO3 is added slowly to a solution containing
productions and its various salts are used in food, detergent, 2+ 2+
equimolar concentration of Ca and Ba , no precipitate is
toothpaste, and in metal treatment. 2+
formed until 90% of Ba has been precipitated as BaCO3.
Small quantities of H3PO4 are used in imparting the sour or –10 –5
(a) 4.9 × 10 (b) 5.9 × 10
tart taste to soft drinkes, such as Coca Cola, and beers, in –10 –5
which H3PO4 in present 0.05% by weight (density = 1.0 g (c) 6.9 × 10 (d) 8.3 × 10
mL–1).
10–3 M H3PO4 (pH = 7) is used in fertilisers as an aqueous
soil digesting. Plants can absorb zinc in water soluble form
only. Zinc phosphate is the source of zinc and PO34 ions
in the soil. Ksp of zinc phosphate = 9.1 × 10–33.

–1
Use the following passage, to solve Q. 106 to 110. The solubility of AgCN (mol-L ) in the above solution is
1/2
Q. 108 (a) S (b) S
2 3
(c) S (d) S
Passage
111. The factor by which the solubility of AgCN is increased in
The product of the concentrations of the ions of an the above solution as compared to its solubility in pure
electrolyte raised to power of their coefficients in the water is
balanced chemical equation in the solution at any (a) 10 (b) 100
concentration. Its value is not constant and varies with
change in concentration. Ionic product of the saturated (c) 1250 (d) 5000
solution is called solubility product Ksp.
Use the following passage, to solve Q. 112 to
(i) When Kip = Ksp, the solution is just saturated and no
precipitation takes place. Q. 115
(ii) When K ip < K sp, the solution is unsaturated and Passage
precipitation will not take place.
100 mL of a solution of X is titrated with a 0.1 M solution of
(iii) When Kip > Ksp, the solution is supersaturated and Y giving the following titration curve :
precipitation takes place.
10
106. Which of the following is most soluble ?
8
(a) Bi2S3 (Ksp = 1× 10–70) (b) MnS (Ksp = 7 × 10–16) pH
6
(c) CuS (Ksp = 8 × 10–37) (d) Ag2S (Ksp = 6 × 10–51)
4
107. The concentration of Ag ions in a given saturated solution
+
2
of AgCl at 25ºC is 1.06 × 10–5 g ion per litre. The solubility
product of AgCl is : 0 10 20 30 40 50 60 70 80
(a) 0.353 × 10–10 (b) 0.530 × 10–10 mL of Y
(c) 1.12 × 10 –10

(d) 2.12 × 10–10 Answer the following four questions based on the
108. If the solubility of Li3Na3 (AlF6)2 is x mol L–1, then its information provided.
solubility product is equal to : 112. Y is a
(a) 12x3 (b) 18x3 (a) strong acid (b) strong base
(c) x8 (d) 2916x8 (c) weak base (d) weak acid
Use the following passage, to solve Q. 109 to 113. X is a
Q. 111 (a) strong acid (b) strong base
(c) weak base (d) weak acid
Passage
114. The initial concentration of X is
The solubility product constant of AgCN is 2.5×10–16. The (a) 0.10 M (b) 0.02 M
acid dissociation constant of HCN is 6.2 × 10–10. Now solid
(c) 0.05 M (d) 0.01 M
AgCN is dissolved in a buffer solution of pH 3.
115. The approximate value of ionization constant (Ka/Kb) of X
Answer the following questions :
–
is
109. The concentration ratio of HCN to CN in the solution is –9 –6
–7 6
(a) 5 × 10 (b) 5 × 10
(a) 6.25 × 10 (b) 1.6 × 10 –4 –5
9 –10
(c) 2 × 10 (d) 3 × 10
(c) 1.6 × 10 (d) 6.2 × 10


Objective Questions I [Only one correct option] 8. An example of a reversible reaction is (1985)
1. The pH of 10–8 M solution of HCl in water is (1981) (a) Pb(NO3)2 (aq) + 2NaI (aq) = PbI2 (s) + 2NaNO3 (aq)
(a) 8 (b) –8 (b) AgNO3 (aq) + HCl (aq) = AgCl (s) + HNO3 (aq)
(c) between 7 and 8 (d) between 6 and 7 (c) 2Na (s) + 2H2O(l) = 2 NaOH (aq) + H2(g)
+ –6 –1
2. At 90ºC, pure water has [H3O ] as 10 mol L . What is the (d) KNO3 (aq) + NaCl (aq) = KCl (aq) + NaNO3 (aq)
value of Kw at 90ºC ? (1981)
9. The best indicator for detection of end point in titration of a
(a) 10–6 (b) 10–12 weak acid and a strong base is (1985)
(c) 10–14 (d) 10–8 (a) methyl orange (3 to 4)
3. Of the given anions, the strongest base is (1981) (b) methyl red (5 to 6)
(c) bromothymol blue (6 to 7.5)
(a) ClO– (b) ClO2
(d) phenophthalein (8 to 9.6)
(c) ClO 
3
(d) ClO 
4
10. The compound that is not a Lewis acid is (1985)
4. An acidic buffer solution can be prepared by mixing the (a) BF3 (b) AlCl3
solution of (1981) (c) BeCl2 (d) SnCl4
(a) solution of acetate and acetic acid
11. The conjugate acid of NH 2 is (1985)
(b) ammonium chloride and ammonium hydroxide
(a) NH3 (b) NH2OH
(c) sulphuric acid and sodium sulphate
(d) sodium chloride and sodium hydroxide (c) NH 4 (d) N2H4
5. The precipitate of CaF2 (Ksp = 1.7 × 10–10) is obtained, when 12. The pKa of acetyl salicylic acid (aspirin) is 3.5. The pH of
equal volumes of the following are mixed (1982) gastric juice in human stomach is about 2–3 and the pH in
(a) 10–4 M Ca2+ + 10–4 M F– the small intestine is about 8. Aspirin will be (1988)
(a) unionised in the small intestine and in the stomach
(b) 10–2 M Ca2+ + 10–3 M F–
(b) completely ionised in the small intestine in the small
(c) 10–5 M Ca2+ + 10–3 M F– intestine
(d) 10–3 M Ca2+ + 10–5 M F– (c) ionised in the stomach and almost unionised in the small
6. A certain buffer solution contains equal concentration of intestine
X– and HX. The Kb for X– is 10–10. The pH of the buffer is (d) ionised in the small intestine and almost unionised in
the stomach
(1984)
(a) 4 (b) 7 13. When equal volumes of the following solutions are mixed,
precipitation of AgCl (Ksp = 1.8 × 10–10) will occur only with
(c) 10 (d) 14
(1988)
7. A certain weak acid has a dissociation constant of
(a) 10–4 M (Ag+) and 10–4 M (Cl–)
1.0 × 10–4. The equilibrium constant for its reaction with a
strong base is (1984) (b) 10–5 M (Ag+) and 10–5 M (Cl–)
(a) 1.0 × 10–4 (b) 1.0 × 10–10 (c) 10–6 M (Ag+) and 10–6 M (Cl–)
(c) 1.0 × 1010 (d) 1.0 × 10–14 (d) 10–10 M (Ag+) and 10–10 M (Cl–)

14. Which of the following is the strongest acid ? (1989) 21. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and
(a) ClO3 (OH) (b) ClO2 (OH) Hg2+ is treated with 10–16 M sulphide ion. If Ksp of MnS,
(c) SO(OH)2 (d) SO2 (OH)2 FeS, ZnS and HgS are 10 –15, 10 –23, 10 –20 and 10 –54
respectively, which one will precipitate first ? (2003)
15. Amongst the following hydroxides, the one which has the
lowest value of Ksp at ordinary temperature (about 25ºC) is (a) FeS (b) MgS
(1990) (c) HgS (d) ZnS
(a) Mg(OH)2 (b) Ca(OH)2 –5
22. HX is a weak acid (Ka = 10 ). It forms a salt NaX (0.1 M) on
(c) Ba(OH)2 (d) Be(OH)2 reacting with caustic soda. The degree of hydrolysis of NaX
is (2004)
16. Which of the following solutions will have pH close to 1.0 ?
(1992) (a) 0.01% (b) 0.0001%
(a) 100 mL of (M/10) HCl + 100 mL of (M/10) NaOH (c) 0.1% (d) 0.5%
(b) 55 mL of (M/10) HCl + 45 mL of (M/10) NaOH 23. A weak acid HX has the dissociation constant 1 × 10–5M. It
(c) 10 mL of (M/10) HCl + 90 mL of (M/10) NaOH forms a salt NaX on reaction with alkali. The percentage
hydrolysis of 0.1 M solution of NaX ? (2004)
(d) 75 mL of (M/5) HCl + 25 mL of (M/5) NaOH
(a) 0.0001% (b) 0.01%
17. The solubility of A2X3 is y mol dm–3. Its solubility product
(c) 0.1% (d) 0.15%
is (1997)
24. A 0.004 M solution of Na2SO4 is isotonic with 0.010 M
(a) 6y4 (b) 64y4
solution of glucose at same temperature. The percentage
(c) 36y5 (d) 108y5 dissociation of Na2SO4 is (2004)
18. The pH of 0.1 M solution of the following salts increase in (a) 25% (b) 50%
the order (1999) (c) 75% (d) 85%
(a) NaCl < NH4Cl < NaCN < HCl 25. CH3NH2 (0.1 mole, Kb = 5 × 10–4) is added to 0.08 moles of
(b) HCl < NH4Cl < NaCl < NaCN HCl and the solution is diluted to one litre, resulting
hydrogen ion concentration is (2005)
(c) NaCN < NH4Cl < NaCl < HCl
(a) 1.6 × 10–11 (b) 8 × 10–11
(d) HCl < NaCl < NaCN < NH4Cl
19. For a sparingly soluble salt ApBq, the relationship of its (c) 5 × 10–5 (d) 8 × 10–2
solubility product (Ls) with its solubility (S) is (2001) 26. Ag+ + NH3 [Ag(NH3)]+ ; K1 = 3.5 × 10–3
(a) Ls = Sp+q . pp .qq [Ag(NH3)]+ + NH3 [Ag (NH3)2]+ ; K2 = 1.7 × 10–3
(b) Ls = Sp+q . pq.qp then the formation constant of [Ag(NH3)2]+ is (2006)
(c) Ls = Spq . pp.qq (a) 6.08 × 10–6 (b) 6.08 × 106
(d) Ls = Spq. (p.q)(p+q) (c) 6.08 × 10–9 (d) None of these
20. Identify the correct order of solubility of Na2S, CuS and 27. The species present in solution when CO2 is dissolved in
ZnS in aqueous medium (2002) water are (2006)
(a) CuS > ZnS > Na2S (a) CO2, H2CO3, HCO3 , CO32
(b) ZnS > Na2S > CuS
(b) H 2 CO3 , CO32
(c) Na2S > CuS > ZnS
(d) Na2S > ZnS > CuS (c) HCO3 , CO32
(d) CO 2 , H 2 CO3

28. N2 + 3H2 2NH3 and its contents (Expt. 1). Because the enthalpy of
Which is correct statement if N2 is added at equilibrium neutralization of a strong acid with a strong base is a
condition ? (2006) constant (–57.0 kJ mol–1), this experiment could be used to
(a) The equilibrium will shift to forward direction because measure the calorimeter constant. In a second experiment
according to IInd law of thermodynamics the entropy (Expt.2), 100 mL of 2.0 M acetic acid (Ka = 2.0 x 10–5) was
must increase in the direction of spontaneous reaction
mixed with 100 mL of 1.0 M NaOH (under identical conditions
(b) The condition for equilibrium is G N 2  3G H 2  2G NH3 to Expt.1) where a temperature rise of 5.6 oC was measured.
where G is Gibbs free energy per mole of the gaseous (Consider heat capacity of all solutions as 4.2 J g–1 K–1 and
species measured at that partial pressure. The condition
density of all solutions as 1.0 g mL–1)
of equilibrium is unaffected by the use of catalyst, which
increases the rate of both the forward and backward The pH of the solution after Expt.2 is (2015)
directions to the same extent
(a) 2.8 (b) 4.7
(c) The catalyst will increase the rate of forward reaction by
 (c) 5.0 (d) 7.0
(d) Catalyst will not alter the rate of either of the reaction. Objective Questions II
29. Solubility product constant (Ksp) of salts of types MX, MX2 [One or more than one correct option]
and M3X at temperature ‘T’ are 4.0 × 10–8, 3.2 × 10–14 and
34. Which of the following statement (s) is (are) correct ?
2.7 × 10–15, respectively. Solubilities (mol, dm–3) of the salts
(1998)
at temperature ‘T’ are in the order (2008)
(a) MX > MX2 > M3X (b) M3X > MX2 > MX (a) The pH of 1.0 × 10–8 M solution of HCl is 8
(c) MX2 > M3X > MX (d) MX > M3X > MX2 (b) The conjugate base of H 2 PO 4 is HPO24
2 (c) Autoprotolysis constant of water increases with
30. 2.5 mL of M weak monoacidic base (Kb = 1 × 10–12 at 25ºC)
5 temperature
2
is titrated with M HCl in water at 25ºC. The (d) When a solution of a weak monoprotic acid is titrated
15 against a strong base, at half-neutralisation point pH =
concentration of H at equivalence point is (Kw = 1 × 10–14
+
at 25ºC) (2008) 1

(a) 3.7 × 10–13 M (b) 3.2 × 10–7 M   pK a
2
(c) 3.2 × 10–2 M (d) 2.7 × 10–2 M 35. A buffer solution can be prepared from a mixture of
31. Passing H2S gas into a mixture of Mn , Ni , Cu and Hg
2+ 2+ 2+ 2+ (1999)
ions in an acidified aqueous solution precipitates. (2011) (a) sodium acetate and acetic acid in water
(a) CuS and HgS (b) MnS and CuS (b) sodium acetate and HCl in water
(c) ammonia and ammonium chloride in water
(c) MnS and NiS (d) NiS and HgS
(d) ammonia and sodium hydroxide in water
32. The Ksp of Ag2CrO4 is 1.1 x 10–12 at 298 K. The solubility (in
36. Aqueous solutions of HNO 3, KOH, CH 3COOH and
mol/L) of Ag2CrO4 in a 0.1 M AgNO3 solution is (2013)
CH3COONa of identical concentrations are provided. The
(a) 1.1 x 10–11
(b) 1.1 x 10 –10
pair(s) of solutions which form a buffer upon mixing is (are)
(c) 1.1 x 10–12 (d) 1.1 x 10–9 (2010)
33. When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M (a) HNO3 and CH3COOH (b) KOH and CH3COONa
NaOH in an insulated beaker at constant pressure, a (c) HNO3 and CH3COONa (d) CH3COOH and CH3COONa
temperature increase of 5.7 oC was measured for the beaker

Numerical Value type Questions 46. A sample of AgCl was treated with 5.00 mL of 1.5 M Na2CO3
solution to give Ag2CO3. The remaining solution contained
37. The concentration of hydrogen ions in a 0.20 M solution of
0.0026 g of Cl– ions per litre. Calculate the solubility product
formic acid is 6.4 × 10–3 mol/L. To this solution, sodium
of AgCl. (1997)
formate is added so as to adjust the concentration of sodium
formate to one mole per litre. What will be the pH of this [Ksp (Ag2CO3) = 8.2 × 10–12]
solution ? The dissociation constant of formic acid is 47. The average concentration of SO2 in the atmosphere over a
solution ? The dissociation constant of formic acid is
city on a certain day is 10 ppm, when the average temperature
2.4 × 10–4 and the degree of dissociation of sodium formate is 298 K. Given that the solubility of SO2 in water at 298 K is
is 0.75. (1985) 1.36653 mol/L and pKa of H2SO3 is 1.92, Estimate the pH of
38. The solubility of Mg(OH)2 in pure water is 9.57 × 10–3 g/litre. rain on that day. (2000)
Calculate its solubility (in g/litre) in 0.02 M Mg(NO3)2 48. 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at
–6
solution. (1986) end point, Given, Ka (HA) = 5 × 10 and  < < 1. (2004)
39. The solubility product (K sp ) of Ca(OH) 2 at 25ºC is 49. The dissociation constant of a substituted benzoic acid at
–5 –4
4.42 × 10 . A 500 mL of saturated solution of Ca(OH)2 is 25ºC is 1.0 × 10 . The pH of 0.01 M solution of its sodium
mixed with equal volume of 0.4 M NaOH. How much Ca(OH)2 salt is (2009)
in milligrams is precipitated ? (1992)
50. In 1 L saturated solution AgCl [Ksp(AgCl) = 1.6 x 10–10],
40. The pH of blood stream is maintained by a proper balance
0.1 mol of CuCl [Ksp(CuCl) = 1.0 x 10–6] is added. The resultant
of H2CO3 and NaHCO3 concentrations. What volume of
5 M NaHCO3 solution should be mixed with a 10 mL sample concentration of Ag+ in the solution is 1.6 x 10–x. The value
of blood which in 2 M in H2CO3, in order to maintain a pH of of “x” is (2011)
7.4 ? (Ka for H2CO3 in blood is 7.8 × 10–7) (1993) 51. The solubility of a salt of weak acid (AB) at pH = 3 is
41. An aqueous solution of a metal bromide MBr2 (0.05 M) is
Y x 10–3 mol L–1. The value of Y is _____.
saturated with H2S. What is the minimum pH at which MS
will precipitate ? (Given that the value of solubility product of AB
Ksp for MS = 6.0 × 10–21, conc. of saturated H2S = 0.1 M and (Ksp) = 2 x 10–10 and the value of ionization constant of HB
K1 = 10–7 and K2 = 1.3 × 10–13, for H2S. (1993) (Ka) = 1 x 10–8) (2018)
42. For the reaction, 52. A solution of 0.1 M weak base (B) is titrated with 0.1 M of
[Ag(CN)2]– Ag+ + 2CN– a strong acid (HA). The variation of pH of the solution with
–19
The equilibrium constant, at 25ºC, is 4.0 × 10 . Calculate the volume of HA added is shown in the figure below. What
the silver ion concentration in a solution which was originally is the pKb of the base?
0.10 M in KCN and 0.03 M in AgNO3. (1994)
The neutralization reaction is given by
43. Calculate the pH of an aqueous solution of 1.0 M ammonium
formate assuming complete dissciation B + HA  BH+ + A– (2020)
(pKa of formic acid = 3.8 and pKb of ammonia = 4.8)
(1995)
44. What is the pH of a 0.50 M aqueous NaCN solution ?
(pKb of CN– = 4.70) (1996)
45. The ionisation constant of NH 4 in water is 5.6 × 10–10 at
25ºC. The rate constant for the reaction of NH 4 and OH– to

form NH3 and H2O at 25ºC is 3.4 × 1010 L/mol/s. Calculate
the rate constant per proton transfer from water to NH3.
(1996)

53. An acidified solution of 0.05 M Zn 2  is saturated with Match each process given in LIST–I with one or more
0.1 M H 2S . What is the minimum molar concentration (M) effect(s) in LIST–II. The correct option is
of H+ required to prevent the precipitation of ZnS? Use (a) P – 4; Q – 2; R – 3; S – 1 (b) P – 4; Q – 3; R – 2; S – 3
K sp  ZnS  1.25  10 22
and overall dissociation constant (c) P – 1; Q – 4; R – 5; S – 3 (d) P – 1; Q – 5; R – 4; S – 1
of H 2S, K NET  K1K 2  1 10 21 (2020) Paragraph Type Questions

Match the Following Use the following passage,to solve Q. 55 to Q. 56
Each question has two columns. Four options are Passage
given representing matching of elements from When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M
Column-I and Column-II. NaOH in an insulated beaker at constant pressure, a
temperature increase of 5.7°C was measured for the beaker
54. Dilution processes of different aqueous solutions, with and its contents (Expt. 1). Because the enthalpy of
water, are given in LIST–I. The effects of dilution of the neutralization of a strong acid with a strong base is a
solutions on [H+] are given in LIST–II. (Note: Degree of constant (57.0 kJ mol), this experiment could be used to
measure the calorimeter constant. In a
dissociation (a) of weak acid and weak base is << 1: degree
second experiment (Expt. 2), 100 mL of 2.0 M acetic
of hydrolysis of salt << 1: [H+] represents the (Ka = 2.0 × 10) was mixed with 100 mL of 1.0 M NaOH
concentration of H+ ions) (2018) (under identical conditions to Expt. 1) where a temperature
rise of 5.6°C was measured.
LIST– I LIST– II
(Consider heat capacity of all solutions as 4.2J g K and
P. (10 mL of 0.1 M NaOH 1. the value of [H+] density of all solutions as 1.0 g mL)
+ 20 mL of 0.1 M acetic does not change 55. Enthalpy of dissociation (in kJ mol) of acetic acid obtained
acid) diluted to 60 mL on dilution from the Expt. 2 is
Q. (20 mL of 0.1 M NaOH 2. the value of [H+] (a) 1.0 (b) 10.0
+ 20 mL of 0.1 M acetic changes to half of its (c) 24.5 (d) 51.4
acid) diluted to 80 mL initial value on dilution 56. The pH of the solution after Expt. 2 is
R. (20 mL of 0.1 M HCl 3. the value of [H+] (a) 2.8 (b) 4.7
+ 20 mL of 0.1 M changes to two times (c) 5.0 (d) 7.0
ammonia solution) of its initial value on Subjective Type Questions

diluted to 80 mL dilution. 57. How many moles of sodium propionate should be added to
S. 10 mL saturated solution 4. the value of [H+] 1 L of an aqueous solution containing 0.020 moles of
propionic acid to obtain a buffer solution of pH 4.75 ? What
1
of Ni(OH)2 is diluted to changes to will be pH if 0.010 moles of HCl are dissolved in the above
2 buffer solution ? Compare the last pH value with the pH of
20 mL (solid Ni(OH)2 times of its initial 0.010 M HCl solution. Dissociation constant of propionic
is diluted to 20 mL value on dilution acid, Ka at 25ºC is 1.34 × 10–5. (1981)
(solid Ni(OH)2 is still 58. 20 mL of 0.2 M sodium hydroxide is added to 50 mL of 0.2 M
acetic acid solution to give 70 mL of the solution. What is
present after dilution).
the pH of this solution ? Calculate the additional volume of
5. the value of [H+] 0.2 M NaOH required to make the pH of the solution 4.74.
changes to 2 times (Ionisation constant of CH3COOH = 1.8 × 10–5). (1982)
of its initial value 59. Give reason for the statement that “the pH of an aqueous
solution of sodium acetate is more than seven”. (1982)
on dilution

60. The dissociation constant of a weak acid HA is 4.9 × 10–8.  nB with time, is
66. The progress of reaction, A 
After making the necessary approximations, calculate : represented in fig. given below. Determine
(i) pH
(ii) OH– concentration in a decimolar solution of the acid.
Water has a pH of 7. (1983)
61. A solution contains a mixture of Ag+ (0.10 M) and Hg2+ (0.10
M) which are to be separated by selective precipitation.
Calculate the maximum concentration of iodide ion and
which one of them gets precipitated almost completely. What
percentage of that metal ion is precipitated ? (1984)
Ksp : AgI = 8.5 × 10–17, HgI2 = 2.5 × 10–26 (i) the value of n
62. What is the pH of the solution when 0.2 mole of hydrochloric (ii) the equilibrium constant, K and
acid is added to one litre of a solution containing (iii) the initial rate of conversion of A. (1994)
(i) 1 M each of acetic acid and acetate ion ? 67. An acid type indicator, HIn differs in colour from its
(ii) 0.1 M each of acetic acid and acetate ion ? conjugate base (In–). The human eye is sensitive to colour
Assume the total volume is one litre. Ka for acetic acid differences only when the ratio [In–]/[HIn] is greater than 10
= 1.8 × 10–5. (1987) or smaller than 0.1. What should be the minimum change in
the pH of the solution to observe a complete colour change
63. Freshly precipitated aluminium and magnesium hydroxides
are stirred vigorously in a buffer solution containing ? (Ka = 1.0 × 10–5) (1997)
0.25 mol/L of NH4Cl and 0.05 M of ammonium hydroxide. Fill in the Blanks
Calculate the concentration of alminimum and magnesium
ions in solution (1989) 68. The conjugate base of HSO4 in aqueous solution is
–5 –12
Kb[NH4OH] = 1.8 × 10 Ksp[Mg(OH)2] = 8.9 × 10 ................. (1982)
–32
Ksp[Al(OH)3] = 6 × 10 69. An element which can exist as a positive ion in acidic solution
64. What is the pH of 1.0 M solution of acetic acid ? To what and also as a negative ion in basic solution is said to be
volume must one litre of this solution be diluted so that the ............... (1984)
pH of the resulting solution will be twice the original value 70. Silver chloride is sparingly soluble in water because its lattice
? Given : Ka = 1.8 × 10–5. (1990) energy is greater than ................ energy. (1987)
–11
65. The solubility product of Ag2C2O4 at 25ºC is 1.29 × 10 71. In the reaction I– + I2 
 I3 , the Lewis acid is ............
3 –3
mol L . A solution of K2C2O4 containing 0.1520 mole in
(1997)
500 mL water is shaken at 25ºC with excess of Ag2CO3 till
the following equilibrium is reached 72. (CH3OH2)+ is ............... acidic than ( CH3 NH3 ). (1997)
Ag2CO3 + K2C2O4 Ag2C2O4 + K2CO3
True / False
At equilibrium, the solution contains 0.0358 mole of K2CO3.
Assuming the degree of dissociation of K2C2O4 and K2CO3 73. Aluminium chloride (AlCl3) is a Lewis acid because it can
donate electrons. (1982)
to be equal, calculate the solubility product of Ag2CO3.
(1991) 74. Solubility of sodium hydroxide increases with increase in
temperature. (1985)
75. The following species are in increasing order of their acidic
property : ZnO, Na2O2, P2O5, MgO (1985)

Note:
IONIC EQUILIBRIUM


ANSWER KEY 166
Answer Key
CHAPTER -10 THERMODYNAMICS AND THERMOCHEMISTRY
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS
DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.
1. (a) 2. (d) 3. (a) 4. (a) 5. (c) 1. (a) 2. (d) 3. (b) 4. (d) 5. (d)
6. (c) 7. (d) 8. (b) 9. (b) 10. (b) 6. (d) 7. (c) 8. (d) 9. (a) 10. (d)
11. (c) 12. (a) 13. (c) 14. (b) 15. (d) 11. (c) 12. (b) 13. (a) 14. (c) 15. (a)
16. (d) 17. (d) 18. (c) 19. (a) 20. (c) 16. (a) 17. (d) 18. (a) 19. (c) 20. (c)
21. (b) 22. (a) 23. (b) 24. (b) 25. (b) 21. (b) 22. (b) 23. (d) 24. (b) 25. (b)
26. (d) 27. (c) 28. (b) 29. (b) 30. (c) 26. (d) 27. (c) 28. (a) 29. (d) 30. (c)
31. (d) 32. (a) 33. (b) 34. (b) 35. (a) 31. (c) 32. (c) 33. (d) 34. (b) 35. (d)
36. (b) 37. (d) 38. (c) 39. (d) 40. (d)
36. (a) 37. (d) 38. (b) 39. (b) 40. (c)
41. (b) 42. (b) 43. (a) 44. (b) 45. (b)
41. (c) 42. (b) 43. (b) 44. (a) 45. (c) 46. (a) 47. (b) 48. (b) 49. (d) 50. (b)
46. (c) 47. (d) 48. (c) 49. (a) 50. (d)
51. (d) 52. (c) 53. (d) 54. (c) 55. (a)
51. (a) 52. (b) 53. (d) 54. (b) 55. (b)
56. (d) 57. (c) 58. (b) 59. (b) 60. (c)
56. (a) 57. (c) 58. (a) 59. (b) 60. (a)
61. (a) 62. (c) 63. (c) 64. (a) 65. (c)
61. (c) 62. (a) 63. (d) 64. (c) 65. (c)
66. (a) 67. (b) 68. (a) 69. (a) 70. (2.70)
66. (c) 67. (d) 68. (d) 69. (b) 70. (b)
71. (-192.50) 72. (48.00) 73. (6.25)
71. (d) 72. (b) 73. (c) 74. (a) 75. (c)
74. (189494.39) 75. (-326400.00)
76. (a) 77. (d) 78. (a) 79. (a) 80. (b)
81. (b) 82. (a) 83. (b) 84. (c) 85. (c) 76. (-13538.00) 77. (b)
86. (d) 87. (b) 88. (b) 89. (a) 90. (c) 78. (741.00) 79. (15.00)
91. (c) 92. (d) 93. (d) 94. (c) 95. (a) 80. (200.00) 81. (309.00)
96. (d) 97. (c) 98. (c) 99. (d) 100. (a) 82. (2218.00) 83. (230.00)
101. (d) 102. (b) 103. (c) 104. (b) 105. (b) 84. (128.00) 85. (667.00)
106. (a) 107. (d) 108. (b) 109. (b) 110. (b)
86. (336.00) 87. (21.00)
111. (b) 112. (d) 113. (a) 114. (b) 115. (a)
88. (101.00) 89. (50.00)
116. (a) 117. (d) 118. (b) 119. (d) 120. (b)
90. (82.00) 91. (31.00)
92. (38.00) 93. (82.00)
94. 964.00) 95. (5.00)

ANSWER KEY 167
CHAPTER -10 THERMODYNAMICS AND THERMOCHEMISTRY
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

1. (a) 2. (a) 3. (d) 4. (a) 5. (d) 1. (a) 2. (c) 3. (b) 4. (c) 5. (a)
6. (c) 7. (a) 8. (a) 9. (a) 10. (b) 6. (c) 7. (b) 8. (c) 9. (a) 10. (d)
11. (c) 12. (b) 13. (d) 14. (b) 15. (b) 11. (d) 12. (a) 13. (a) 14. (a) 15. (b)
16. (c) 17. (c) 18. (d) 19. (d) 20. (c) 16. (b) 17. (c) 18. (c) 19. (b,d)
21. (b) 22. (a) 23. (b) 24. (a) 25. (b) 20. (b,c,d) 21. (a,c,d)
26. (b) 27. (a) 28. (d) 29. (a) 30. (a) 22. (a,b,c) 23. (a,c,d)
31. (c) 32. (b) 23. (c) 34. (c) 35. (a) 24. (b, c) 25. (a, c)
36. (b) 37. (d) 38. (c) 39. (b) 40. (a) 26. (a, b, c) 27. (a, b, d)
41. (b) 42. (a) 43. (b) 44. (b) 45. (b) 28. (121.31) 29. (-41.4)
30. (-54.2) 31. (41.104)
46. (b) 47. (d) 48. (a, d) 49. (c,d) 50. (b, d)
32. (22.0) 33. (-372.0)
51. (a, b, c) 52. (6.00) 53. (4.00) 54. (1.00)
55. (8.00) 56. (b) 57. (a) 58. (d) 34. (3.94) 35. (319.1)
59. (a) 60. (c) 61. (b) 62. (a) 63. (d) 36. (-121.0) 37. (-55.7)
64. (A  p, q, r) ; (B  p, s); (C  p, q, r); D  (p, r, s)
38. (72.0) 39. (-2091.32)
65. (A  p,q) ; (B  p, q); (C  s); (D  r)
40. (309.16) 41. (-115.41)
66. (d) 67. (c) 68. (c) 69. (c) 70. (a)
42. (-2035.0) 43. (9.00)
44. (-14.6) 45. (935.00)
46. (10.00) 47. (b)
48. (c) 49. (b)
58. (900) 59. (R)
60. (Isolated) 61. (Exothermic rection)
62. (Zero) 63. (Extensive)
64. True 65. True

ANSWER KEY 168
Answer Key
CHAPTER -11 CHEMICAL EQUILIBRIUM

1. (c) 2. (b) 3. (d) 4. (d) 5. (a) 1. (c) 2. (d) 3. (d) 4. (a) 5. (b)
6. (a) 7. (c) 8. (d) 9. (b) 10. (b) 6. (a) 7. (d) 8. (d) 9. (d) 10. (a)
11. (a) 12. (b) 13. (d) 14. (c) 15. (c) 11. (a) 12. (a) 13. (c) 14. (a) 15. (a)
16. (d) 17. (d) 18. (c) 19. (c) 20. (a) 16. (d) 17. (c) 18. (a) 19. (d) 20. (d)
21. (c) 22. (b) 23. (c) 24. (c) 25. (d) 21. (a) 22. (b) 23. (c) 24. (d) 25. (a)
26. (d) 27. (a) 28. (c) 29. (d) 30. (b) 26. (b) 27. (d) 28. (c) 29. (b) 30. (d)
31. (a) 32. (a) 33. (d) 34. (b) 35. (b) 31. (a) 32. (b) 33. (a) 34. (c) 35. (a)
36. (a) 37. (d) 38. (a) 39. (a) 40. (d) 36. (a) 37. (c) 38. (b) 39. (b) 40. (a)
41. (a) 42. (d) 43. (a) 44. (c) 45. (d) 41. (b) 42. (a) 43. (c) 44. (c)
46. (d) 47. (b) 48. (c) 49. (a) 50. (b) 45. (16.00) 46. (1380.00)
51. (a) 52. (b) 53. (b) 54. (d) 55. (b) 47. (5.00) 48. (855.00)
56. (a) 57. (a) 58. (c) 59. (d) 60. (d) 49. (73.00) 50. (20.00)
61. (d) 62. (d) 63. (d) 64. (a) 65. (c) 51. (354.00) 52. (2.00)
66. (c) 67. (a) 68. (b) 69. (c) 70. (d) 53. (172.00) 54. (2.00)
71. (d) 72. (d) 73. (d) 74. (c) 75. (d) 55. (25.00) 56. (16.00)
76. (b) 77. (a) 78. (c) 79. (c) 80. (a) 57. (1396.00) 58. (182.00)
59. (0.02) 60. (6.00)

ANSWER KEY 169
CHAPTER -11 CHEMICAL EQUILIBRIUM

1. (b) 2. (c) 3. (c) 4. (c) 5. (b) 1. (a) 2. (d) 3. (d) 4. (a) 5. (d)
6. (a) 7. (c) 8. (c) 9. (a) 10. (b) 6. (d) 7. (d) 8. (d) 9. (b)
11. (a) 12. (d) 13. (c) 14. (a) 15. (a) 10. (a,b,c,d) 11. (c,d) 12. (b, c,d)
16. (a) 17. (b) 18. (c) 19. (b) 20. (a) 13. (a, c) 14. (8.93)
21. (c) 22. (b) 23. (a) 24. (b) 25. (b) 15. (166.28) 16. (141.34)
26. (c) 27. (b) 28. (c) 29. (c) 30. (a) 17. (b) 18. (c)
31. (a) 32. (b) 33. (d) 34. (b,c) 35. (a,c) 19. (1.48 × 10 L mol , 3.84 × 10–3L mol–1 )
–5 2 –2
36. (a,b) 37. (a,d) 38. (a,c) 20. (0.33 , 0.4) 21. (1.86)
39. (a,c) 40. (a,b,d) 41. (c,d) 22. (1.6 mol L , 0.4 mol L-1)
-1
42. (b,d) 43. (a,c) 44. (a,c) 23. (0.266 atm, 63%)
45. (c,d) 46. (a,c,d) 47. (c,d)
48. (b,c,d) 49. (a,b,c) 24. ( PO2 =2.0118 atm, PSO2  0.0236 atm,
50. (a,b,c,d) 51. (4.00)
52. (8.00) 53. (8.00) P  0.9764 atm )
SO3
54. (6.00) 55. (4.00)
2 2
56. (72.00) 57. (a) 58. (b) 59. (a) 25. ( Kp  0.11atm ,Kc  277.77M )
60. (c) 61. (a) 62. (c) 63. (b) 64. (a) 27. (4.54 g/L)
65. (a) 66. (d) 67. (a) 68. (a) 69. (a)
70. (a) 71. (b) 72. (a) 73. (b) 74. (c) 28. (i) 8.1  105 , 4.9  102 ,(ii) No effect
75. (b) 76. (d) 77. (d) 78. (d) 79. (c)
29. ( Kp = Kc (RT) )
Δn
80. (b)
30. no change 31. smaller 32. True
33. False 34. False 35. False

ANSWER KEY 170
Answer Key
CHAPTER -12 IONIC EQUILIBRIUM

1. (d) 2. (c) 3. (d) 4. (b) 5. (b) 1. (b) 2. (b) 3. (c) 4. (a) 5. (c)
6. (b) 7. (c) 8. (c) 9. (b) 10. (a) 6. (b) 7. (c) 8. (c) 9. (c) 10. (b)
11. (d) 12. (a) 13. (c) 14. (a) 15. (a) 11. (b) 12. (b) 13. (c) 14. (a) 15. (c)
16. (c) 17. (d) 18. (a) 19. (d) 20. (d) 16. (a) 17. (b) 18. (b) 19. (a) 20. (c)
21. (b) 22. (c) 23. (a) 24. (c) 25. (a) 21. (d) 22. (c) 23. (a) 24. (b) 25. (b)
26. (c) 27. (d) 28. (c) 29. (b) 30. (b)
26. (c) 27. (d) 28. (d) 29. (c) 30. (c)
31. (a) 32. (c) 33. (b) 34. (a) 35. (d)
31. (b) 32. (c) 33. (d) 34. (b) 35. (c)
36. (c) 37. (d) 38. (c) 39. (a) 40. (a)
36. (b) 37. (d) 38. (d) 39. (b) 40. (c) 41. (a) 42. (c) 43. (d) 44. (a) 45. (d)
41. (a) 42. (b) 43. (c) 44. (d) 45. (a) 46. (d) 47. (10.6) 48. (5.23)
46. (a) 47. (c) 48. (a) 49. (c) 50. (b) 49. (58.00) 50. (37.00)
51. (c) 52. (a) 53. (c) 54. (c) 55. (b) 51. (2.00) 52. (141.0)
56. (d) 57. (b) 58. (b) 59. (b) 60. (b) 53. (7.00) 54. (50.00)
61. (a) 62. (b) 63. (c) 64. (a) 65. (c) 55. (1.00) 56. (2.00)
66. (a) 67. (b) 68. (a) 69. (c) 70. (c) 57. (10.00) 58. (64.00)
71. (c) 72. (b) 73. (b) 74. (b) 75. (d) 59. (3.00) 60. (108.0)
76. (a) 77. (d) 78. (b) 79. (c) 80. (d) 61. (6021.00) 62. (2.00)
81. (b) 82. (c) 83. (b) 84. (a) 85. (c) 63. (a) 64. (c) 65. (b)
86. (a) 87. (a) 88. (b) 89. (a) 90. (a)
91. (c) 92. (b) 93. (a) 94. (a) 95. (c)
96. (a) 97. (d) 98. (a) 99. (a) 100. (a)
101. (c) 102. (b) 103. (c) 104. (d) 105. (a)
106. (c) 107. (a) 108. (b) 109. (c) 110. (d)
111. (d) 112. (b) 113. (c) 114. (b) 115. (a)
116. (b) 117. (d) 118. (d) 119. (a) 120. (d)

ANSWER KEY 171
CHAPTER -12 IONIC EQUILIBRIUM


1. (d) 2. (d) 3. (a) 4. (a) 5. (a) 1. (d) 2. (b) 3. (a) 4. (a) 5. (b)
6. (a) 7. (d) 8. (c) 9. (b) 10. (c) 6. (a) 7. (c) 8. (d) 9. (d) 10. (c)
11. (d) 12. (c) 13. (a) 14. (d) 15. (c) 11. (a) 12. (d) 13. (a) 14. (a) 15. (d)
16. (d) 17. (d) 18. (c) 19. (a) 20. (b) 16. (d) 17. (d) 18. (b) 19. (a) 20. (d)
21. (a) 22. (d) 23. (a) 24. (a) 25. (d) 21. (c) 22. (a) 23. (b) 24. (c) 25. (b)
26. (b) 27. (d) 28. (c) 29. (b) 30. (b) 26. (a) 27. (a) 28. (b) 29. (d) 30. (d)
31. (d) 32. (a) 33. (b) 34. (c) 35. (d) 31. (a) 32. (b) 33. (b) 34. (b,c)
36. (c) 37. (c) 38. (c) 39. (b) 40. (a) 35. (a,b,c) 36. (c,d) 37. (4.20)
41. (b) 42. (b) 43. (a) 44. (d) 45. (b) 38. (8.7 × 10–4) 39. (747.4)
46. (a) 47. (d) 48. (d) 49. (a,c) 40. (80.00) 41. (1.00)
50. (a,b,c) 51. (b,c) 42. (7.50×10–18) 43. (6.5)
52. (b,c,d) 53. (a,c,d) 44. (11.5) 45. (6.12 × 105)
54. (b,c,d) 55. (a,c,d) 46. (2 × 10–8) 47. (4.86)
56. (a,d) 57. (a,b,d) 48. (9.00) 49. (8.00)
58. (b,d) 59. (a,b,c) 50. (7.00) 51. (4.47)
60. (b,c,d) 61. (a,b,c,d) 52. (3.00) 53. (0.20)
62. (a,b) 63. (a,b,d) 54. (d) 55. (a)
64. (a,b,c,d) 65. (a,b,c,d) 56. (b) 68. ( SO24)
66. (0.00) 67. (9.00)
68. (2.00) 69. (2.00) 70. (4.00) 71. (4.00) 69. (Amphoteric) 70. (Hydration)
72. (0.001) 73. (9.00) 74. (a) 75. (a) 71. (I2) 72. (More)
76. (a) 77. (c) 78. (d) 79. (a) 80. (d) 73. False 74. False 75. False
81. (a) 82. (d) 83. (b) 84. (a) 85. (b)
86. (d) 87. (a) 88. (d) 89. (a)
90 (A  r); (B  s); (C  p); (D  q)
91. (A  r); B  r); (C  s); (D  p)
92 (A  r); (B  s); (C  p); (D  q)
93. (A  q); (B  r); (C  r); (D  p,s)
94. (A  p,q,r); (B  r); (C,p,q); (D  s)
95. (A  q,r); (B  p); (C  q); (D  s)
96. (a) 97. (d) 98. (d) 99. (a)
100. (d) 101. (c) 102. (a) 103. (b)
104.(c) 105. (a) 106. (b) 107. (c)
108. (d) 109. (b) 110. (c) 111. (c)
112. (a) 113. (c) 114. (b) 115. (c)

MASTER INDEX
VOLUME 1:
Structure of an Atom
Periodic Properties
Chemical Bonding
Mole & Equivalent concept
VOLUME 2:
Redox Reactions
Gaseous State
General Organic Chemistry
Hydrocarbons
Hydrogen
VOLUME 3:
Chemical Equilibrium
Ionic Equilibrium
VOLUME 4:
s- Block
p-Block (group 13 and 14)
Environmental Chemistry

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THERMODYNAMICS AND THERMOCHEMISTRY

Exercise - 1 : Basic Objective Questions........................................................................................... 38

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 47

Solved Examples ............................................................................................................................... 80

Exercise - 1 : Basic Objective Questions........................................................................................... 87

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 94

Exercise - 3 : Advanced Objective Questions ................................................................................. 101

Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 112

Answer Key ........................................................................................................................................ 168

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Theory ................................................................................................................................................ 117

Exercise - 1 : Basic Objective Questions........................................................................................... 135

Exercise - 2 : Previous Year JEE MAINS Questions .......................................................................... 143

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THERMODYNAMICS AND THERMOCHEMISTRY

1. INTRODUCTION 2.2.2 Closed System

2.1 System and The Surroundings

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In thermodynamics, state of the system defined by state functions

2.3.1 State Functions

These physical quantities whose value depend only upon the

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3. ZEROTH LAW OF THERMODYNAMICS

This statement just says that, if body 'A' is in thermal equilibrium

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The equation,  U = q + w is a mathematical statement of the first

First law of thermodynamics

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then, volume change    A  V   Vf  Vi 

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Therefore, at constant temperature (isothermal process),

3. For adiabatic change, q = 0,  U = wad

Vf Vf 8.1.1 Isothermal Process

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 P V  P V  nRT 9.1.2 Molar Heat Capacity at Constant Volume

1. Identify the type of curve given, whether it is P-V, V-T or P-T

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Graphical representation of various thermodynamic processes

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Thus, pVB – pVA = nBRT – nART = (nB –nA)RT

Coffee cup calorimeter

We know that H = q p (at constant p) and, therefore, heat

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H vapour G sys  H sys  TSsys  Ssys T

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