Nirav Sir Page 1

CHAPTER 4 EQUILIBRIUM PROCESS

Explain Equilibrium:
If there is no change in the concentration of substances in a reversible reaction at constant
temperature and pressure then such state is called equilibrium
OR
A condition in which opposing forces are balanced then no change in macroscopic property of the
system such a state is called equilibrium.
The state of equilibrium is a state in which the measurable properties of system do not undergo any
noticeable change under a particular set of conditions.
Equilibrium plays an important role in physical processes and chemical changes.
Such transformations never go to completion when carried out at a fixed temperature and pressure
in a closed vessel.
There are only reactants in the closed vessel initially which transform into the products slowly when
reaction takes place. With time, the concentration of the reactants keeps on decreasing while that
of the products keeps on increasing for sometime after which there is no change in the
concentration either of the reactants or products.
A time comes when there will be no change in the on concentration of the reactants or products. At
this stage, the system attains equilibrium.
A state of equilibrium is recognized by constancy of certain observable properties. For example
In case of decomposition of calcium carbonate state of equilibrium can be recognized by constant
pressure of carbon dioxide gas.
While in case of preparation of HI by reaction between H
2
and I
2
state of equilibrium can be
recognize by constancy in the colour of reaction mixture.
Reversible process:
The reactions in which products under suitable conditions react to give back reactants are called
reversible reaction.
OR
If during a chemical reaction the reactants give products and the products so produced undergo
reaction and give the (original) reactants we call such reactions as reversible reactions.
A reversible reaction is represented by putting two arrows in opposite direction between the
formula of reactant and products as shown below.
CaCO
3(s)
CaO
(s)
+ CO
2(g)
In reversible reaction, reaction in which reactants converts into products is called forward reaction.
In reversible reaction, reaction in which products converts into reactants is called reverse reaction.
In a reversible reaction when rate of forward and reverse reaction becomes equal state of
equilibrium is established.
Other examples of reversible reactions are as follows.
Decomposition of ammonium chloride in to ammonia and hydrogen chloride.
Formation of hydrogen iodide by reaction between hydrogen and iodine.
Preparation of ammonia.
Decomposition of phosphorous pentachloride.
Discuss dynamic nature of equilibriumfor heterogeneous equilibrium [3 marks]
If a reversible reaction is performed in a close container it is observed that it appears to stop after
some time although reactants are not completely consumed such state of system is refer as
equilibrium state.
The most important aspects of equilibrium process are that there is always transformation of the
reactants into products and the products into reactants i.e. it is dynamic in nature.
The decomposition reaction of solid calcium carbonate in a closed vessel, at high temperature is as
below.
CaCO
3(s)
CaO
(s)
+ CO
2(g)
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Thus both the forward and reverse reaction takes place simultaneously. In a closed vessel at
equilibrium, both the forward and reversible reactions take place with same velocity.
It is very difficult to determine the dynamic nature of equilibrium, even then with the help of
radioactive isotope.
It can be proved viz.
14
CO
2
gas containing radioactive isotope
14
C and Ca
12
CO
3
are taken in two
different flasks and CO
2
obtained by decomposition of CaCO
3
is connected with vessel containing
14
CO
2
gas, after some time, Ca
14
CO
3
will be formed in the vessel of Ca
12
CO
3
and
12
CO
2
will be obtained
in the vessel containing
14
CO
2
.
Thus, if the equilibrium would have been steady, there must not be exchange of
12
C and
14
C. With the
help of suitable counter, the radioactivity can be measured and the proof for the dynamic nature of
equilibrium can be obtained though the proportions of concentrations of reactants and products
remain constant.
This shows that the reaction is dynamic and not a static one.
Give difference between physical equilibrium and chemical equilibrium
physical equilibrium Chemical equilibrium
Equilibrium between different physical
phases of same chemical species is called
physical equilibrium.
Conversion of ice in to water, water into
vapour are the examples of physical
process
The state of reversible reaction when the
two opposing reactions occurs at the
same rate and the concentrations of
reactant and products do not change with
time then such state is called chemical
equilibrium.
For example, thermal decomposition of
calcium carbonate
How equilibrium reactions can be classify on the basis of extent of the reactions. [2 mark]
i. Reactions which are almost at the extent of completion and concentration of reactants may be
negligible. It is not possible to detect this experimentally.
ii. Reactions in which the products are formed in very less proportions and most part of the reactant
remains unchanged at the equilibrium.
iii. Reactions in which the concentrations of reactants and products are in comparable proportions at
equilibrium.
Explain Physical Equilibrium with suitable example. OR Explain equilibrium between liquid and gaseous
state of substance. [2 mark]
Consider water kept in a closed vessel at a given temperature. Water in the vessel will evaporate
with time and form water vapour. Concentration of water vapour over water surface will increase
gradually.
After some time, the molecules of vapour will be transformed into water due to mutual attraction.
After an interval of time the rate of vapour formation from water and the rate of condensation of
vapour to water will be same. Hence equilibrium is established. Such a type of equilibrium is termed
physical equilibrium.
In such a process, there is no change in the constitution of the molecules concerned but there is
only a change of phases or states of the matter.
In the above process, water is evaporated in the vapour in the forward reaction and water from
vapour in the reverse direction.
2 ( ) 2 ( )
evapouration
l g
Liquefaction
H O H O

The changes in external factors like temperature, pressure and concentration affect the equilibrium
state in the physical processes.
In physical equilibrium, the transformation takes place in solid, liquid or gaseous phases only.

Nirav Sir Page 3

Explain equilibrium between solid-liquid states of substance with example. [2 mark]
Consider a system containing ice and water in a thermos flask at 0 C (273 K) at normal atmospheric
pressure. Close the thermos. There is no exchange of heat between the system and atmosphere as
there is vacuumbetween the walls of the thermos.
After some time, we will notice that the mass of ice and water do not change and the temperature
remains constant. Following equilibrium is established in the system:
H
2
O
(s)
H
2
O
(l )
Experimentally, it is proved that even after establishment of the equilibrium in the flask, some
molecules of ice get converted into water, and at the same time some amount of molecules of
water get converted into ice. Hence, the quantity of ice and water in the thermos flask or the total
number of molecules remain constant.
This is one type of equilibrium, i.e. physical equilibrium between solid and liquid. It is important to
note that there is no chemical change in the substance and therefore, this process is called physical
equilibrium.
Explain equilibrium between liquid-vapour states of substance with example. [2 mark]
Take water in a closed vessel at constant temperature. Water will slowly evaporate into vapour.
The quantity of vapour in the vessel will increase and hence the vapour pressure gradually
increases.
After some time, at a certain stage, there will not be any further increase of vapour pressure. It will
then remain constant. This is a state of equilibrium.
After attaining equilibrium in the closed vessel, some of the water molecules will be transformed
into vapour and at the same time, same number of the molecules of vapour will be transformed
into water. Hence, the number of molecules of water as well as of vapour will be constant. At this
time vapour pressure becomes constant.
This type of equilibrium is called liquid-vapour equilibrium.
H
2
O
(l)
H
2
O
(g)
It is important to note that there is no chemical change in the substance and therefore, this process
is called physical equilibrium.
Explain equilibriuminvolving dissolution of solids or gases in solutions[4 mark]
Solids in solutions:
This can be explained by considering dissolution of sugar in water. At a given temperature, take a
small quantity of water in a container.
Now, slowly add a small quantity of sugar and dissolve it with constant stirring. Initially the sugar
will be dissolved but at a certain stage, no more of the sugar will be dissolved and will remain as
undissolved solid in water.
At this stage, we will have a saturated solution. The equilibrium established can be represented as
Sugar (un dissolved) Sugar (dissolved)
(Rate of dissolution of sugar = Rate of crystallization of sugar)
The equilibrium being dynamic, the number of molecules of sugar dissolving into water will be
same as those crystallizing into solid from the solution.
As a result, at equilibrium, the number of molecules of solid sugar and the number of molecules of
sugar in the solution will remain unaltered.
Gases in solutions:
Consider a closed system which contains water at a given temperature and pressure and we
dissolve gaseous carbon dioxide gas into it.
A definite amount of carbon dioxide will be dissolved into water initially. After a certain stage, no
more carbon dioxide can be dissolved in water remaining gas will remain undissloved. The quantity
of dissolved carbon dioxide will be fixed at that stage. Equilibrium will be established as follows.
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CO
2(Solution)
CO
2(g)
The equilibrium being dynamic, some of the molecules of gaseous carbon dioxide will be dissolved
in water while same number of molecules of dissolved carbon dioxide will be converted into
gaseous state.
Both the reactions take place at the same rate. The number of dissolved and undissolved molecules
of carbon dioxide will be thus constant.
Explain solid - gas process equilibrium with example. [2 mark]
When certain solid substances are heated, they get converted into gaseous state and on cooling are
converted directly into solid from gaseous state. This process is known as sublimation.
For the study of the equilibrium of this let us take example of solid iodine (I
2
). In a closed vessel
(system) some amount of solid iodine is taken and it is heated. At constant temperature, vapour of
iodine is formed from solid iodine, which appears as a violet coloured gas. If the temperature is
constant equilibriumcan be expressed as below :
I
2(s)
I
(g)
Solid Gas
As equilibrium is dynamic at constant temperature, the number of molecules (amount) of iodine that
are changed from solid iodine to vapour of iodine remain the same as the number of molecules
(amount) of iodine vapour to solid iodine. Thus, in the closed vessel, the amount of iodine (solid and
gaseous form) remains constant.
During equilibrium some of the properties of the equilibrium state remain constant by which state of
equilibrium can be identified.
Process Conclusion
Liquid Vapour H
2
O
(l)
H
2
O
(g)
At constant temperature P
H2O
constant
Solid Liquid H
2
O
(s)
H
2
O
(l)
Melting point is fixed at constant pressure
Solute
(s)
Solute
(solution)
Sugar
(s)
Sugar
(solution)
Concentration of solute in solution is constant at a
given temperature
Gas
(g)
Gas
(aq)
CO
2(g)
CO
2(aq)
[gas
(aq)
]/[gas
(g)
] is constant at a given temperature
[CO
2(aq)
]/[CO
2(g)
] is constant at a given temperature
Describe general characteristics of equilibrium involved in physical processes[2 mark]
i. At constant temperature, equilibrium is possible only in closed system.
ii. Both the processes (reactions) opposite to each other that is, the forward and the reverse reactions
occur at the same rates and the equilibrium involved in it remains dynamic but condition remains
steady (static).
iii. All the properties of the system which can be measured remain constant.
iv. For physical process, when equilibrium is obtained then at constant temperature, the value of one
of the factors remains constant. The list of these properties is shown in above table.
v. At any stage magnitude of such quantities show to what extent the physical processhas advanced
before reaching to equilibrium.
Chemical Equilibrium
If during a chemical reaction the reactants give products and the products so produced undergo
reaction and give the (original) reactants we call such reactions as reversible reactions.
At a given temperature and pressure in a closed system, if a reversible reaction takes place, a
state is arrived at when the concentrations of the reactants and products are unchanged ever
after a lapse of time their concentrations are unaltered, a state attained in this way is called
chemical equilibrium.
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Such equilibriumis dynamic in nature. The dynamic equilibrium consists of forward reaction in
which reactants give products and reverse reaction, in which products give the original reactants.
In a reversible reaction, when carried out in a closed vessel, the rate of forward reaction is high and
this rate decreases gradually -with time. As soon as the products are formed, there begins the
reverse reaction with low rate. This rate gradually increases with time. When both the rates
become equal a chemical equilibrium is established. It is shown in the graph below for reaction.
A + B C + D
In above reaction even if reaction is started from C and D then also state of equilibrium can be
achieved.
Explain dynamic nature of chemical equilibrium. [3 mark]
The dynamic nature of chemical equilibrium can be demonstrated in the synthesis of ammonia by
Habers process.
In a series of experiments, Haber started with known amounts of dinitrogen and dihydrogen
maintained at high temperature and pressure and at regular intervals determined the amount of
ammonia present. He was successful in determining also the concentration of unreacted dihydrogen
and dinitrogen.
Experimental result shows that after a certain time the composition of the mixture remains the same
even though some of the reactants are still present. This constancy in composition indicates that
the reaction has reached equilibrium.
In order to understand the dynamic nature of the reaction, synthesis of ammonia is carried out with
exactly the same starting conditions (of partial pressure and temperature) but using D
2
(deuterium)
in place of H
2
. The reaction mixtures starting either with H
2
or D
2
reach equilibrium with the same
composition, except that D
2
and ND
3
are present instead of H
2
and NH
3
.
After equilibrium is attained, these two mixtures (H
2
, N
2
, NH
3
and D
2
, N
2
, ND
3
) are mixed together
and left for a while. Later, when this mixture is analyzed, it is found that the concentration of
ammonia is just the same as before.
However, when this mixture is analyzed by a mass spectrometer, it is found that ammonia and all
deuterium containing forms of ammonia (NH
3
, NH
2
D, NHD
2
and ND
3
) and dihydrogen and its
deutrated forms (H
2
, HD and D
2
) are present.
Thus one can conclude that scrambling of H and D atoms in the molecules must result from a
continuation of the forward and reverse reactions in the mixture. If the reaction had simply stopped
when they reached equilibrium, then there would have been no mixing of isotopes in this way.
Use of isotope (deuterium) in the formation of ammonia clearly indicates that chemical reactions
reach a state of dynamic equilibrium in which the rates of forward and reverse reactions are equal
and there is no net change in composition.
Equilibrium can be attained from both sides, whether we start reaction by taking, H
2(g)
and N
2(g)
and
get NH
3(g)
or by taking NH
3(g)
and decomposing it into N
2(g)
and H
2(g)
.
equilibrium time
c
o
n
c
e
n
t
r
a
t
i
o
n
C or D
A or B
Nirav Sir Page 6
By the use of radioactive isotope, the dynamic nature of equilibrium can be proved viz. For the
reaction, H
2(g)
+ I
2(g)
2HI
(g)
radioactive isotope
131
I of iodine can be used to study the dynamic
nature of chemical equilibrium. As the equilibrium is dynamic, certain properties or factors are found
similar. e.g. Intensity of colour, constant pressure, constant concentration etc.
Mention the types of equilibrium with examples.
There are two types of equilibriums components in chemical reactions. (1) Homogeneous
Equilibrium (2) Heterogeneous Equilibrium.
Homogeneous Equilibrium:
In a homogeneous system, all the reactants, products and catalyst are in the same phase.
In homogeneous mixture all the components are forming uniform mixture hence there is no
separating boundaries between different species involved in equilibrium.
In homogeneous equilibrium properties of system such as colour, concentration, temperature and
pressure are same in all parts of system.
For example,
CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
CH
3
COOC
2
H
5(l)
+ H
2
O
(l)
N
2 (g)
+ 3H
2 (g)
2NH
3 (g)
All the products and reactants are in homogeneous solution phase and hence cannot be separated.
Heterogeneous Equilibrium:
In heterogeneous equilibrium reactants, products and catalyst do not have same physical state.
Equilibrium in such a system has more than one phase.
Reactants and products do not form homogeneous mixture.
In heterogeneous equilibrium properties of system such as colour, concentration, temperature and
pressure are not same in all parts of system i.e the properties of the system are not uniform
throughout.
Examples of heterogeneous equilibrium are as below.
CaO
(s)
+ CO
2(g)
CaCO
3(S)
NH
4
OH
(l)
NH
3(g)
+ H
2
O
(l)
In a system of heterogeneous equilibrium, the components can be separated.
Write difference between homogeneous and heterogeneous equilibrium.(H.W.)
State the requirements for Chemical Equilibrium: [ 2marks]
Reaction must be reversible.
Reaction must be taking place in closed container.
External factors like temperature, pressure and concentrations of the components which can affect
the equilibrium must remain constant.
Characteristics of Chemical Equilibrium: .[additional point]
The properties of a system like colour, temperature, pressure and concentration remain constant
at chemical equilibrium state and they do not undergo change with time. In a homogeneous system
these properties are uniform throughout.
The rates of forward and reverse reactions are equal at the state of dynamic equilibrium.
If the external factors like temperature pressure and concentration change at a stage of chemical
equilibrium, the equilibrium state will also change.
If equilibrium is established, at a given temperature and pressure, with varying concentration of the
reactants then at equilibrium concentration of reactants and products will be different in both sets,
however, the equilibrium constant will be constant. In other words, the value of equilibrium
constant is independent of initial concentration of the reactants.
Even if the initial concentration of the reactants is same, the concentration of the reactants and
products, at equilibrium, will differ if the temperature is varied.
Nirav Sir Page 7
An equilibrium state of a reversible reaction can be attained either by carrying out the reaction in
forward or reverse direction.
A catalyst does not affect the equilibrium state but it increases the rate of both the reactions
(forward and reverse) and allows the reaction to reach an equilibrium position more rapidly.
The system has a tendency to attain highest entropy at equilibrium state.
The system has a tendency to attain minimum enthalpy at equilibrium state.
All the reversible reactions have tendency to attain equilibrium state.
Explain Law of Chemical Equilibrium derive formula for equilibrium constant (Kc). [ 3 marks]
In 1864. the Norwegian scientists, Gouldberg and Waag presented the law as follows.
"At a given temperature and pressure, the rate of a chemical reaction proportional to the product of
the concentration in .moles in proper power of the reactants."
Fromthe experimental studies of many reversible reactions scientists of Norway, Guldberg and
Waage mentioned in 1864 that the concentrations of substances in equilibrium mixture can be
expressed by following equilibrium equation.
For reaction A + B C + D
[ ][ ]
[ ][ ]
C D multiplicationof concentrationof product
Kc
A B multiplicationof concentrationof reactant
= =
where Kc is equilibrium constant and [ ] bracket expresses concentration of reactant or product in
mollit
1
or M. The equilibrium equation is also known as law of active masses because in the yearly
years of chemistry, concentration was said to be 'active mass'.
Consider a following reaction
a A + bB c C + d D
In such a reaction, on the basis of Guldberg and Waages law the rates of forward and reverse
reactions are
V
f
[A]
a
[B]
b
V
r
[C]
c
[D]
d
.
Where V
f
= the rate of forward reaction V
r
= the rate of reverse reaction
According to the Law of active mass,
V
f
[A]
a
[B]
b
and V
r
[C]
c
[D]
d
V
f
= K
f
[A]
a
[B]
b
and Vr = K
r
[C]
c
[D]
d
And at equilibrium V
f
= V
r
Hence K
f
[A]
a
[B]
b
= K
r
[C]
c
[D]
d
Where K
f
= constant for forward reaction K
r
= constant for reverse reaction
[ ] [ ]
[ ] [ ]
c d
f
a b
r
K
C D
K
A B
=
[ ] [ ]
[ ] [ ]
c d
c
a b
C D
K
A B
=
f
r
K
Kc
K
1
=
(
]

This equation is called equation of law of chemical equilibrium.

If, at equilibrium, the concentration of the reactants is expressed in terms of Mole/Litre [c] then
the equilibrium constant Keq = Kc and if the concentration is expressed as partial pressure, then
Keq = Kp.
( ) .( )
( ) .( )
c d
C D
eq p
a b
A B
P P
K K
P P
= =
Equation of chemical reaction Equilibrium constant
a A + bB c C + d D
Kc
c C + d D a A + bB '
1
c
c
K
K
=
(n)c C + (n)d D (n)a A + (n)bB ( )
n
c c
K K =
Nirav Sir Page 8
Derive relationship Between Kc and Kp
If the components of a chemical reaction, at equilibrium, are in form of solid, liquid or gas it Kc can
be obtained.
However if one of the components is in gaseous form. its equilibrium constant Kc and Kp can be
calculated. For a chemical reaction, it is not essential to have both Kc and Kp should be same.
The relationship between them (Kp and Kc) can be obtained considering a simple reaction as
follows.
a A
(g)
+ b B
(g)
c C
(g)
+ d D
(g)
At equilibrium, the concentration of A, B, C and D in terms of mole / Litre are respectively C
A
C
B
C
C
and C
D
we get equilibrium constant as
( ) ( )
( ) ( )
c d
C D
c
a d
A D
C C
K
C C
=
Here, at equilibrium, all the components i.e., reactants and products, are in gaseous form and so by
taking their concentration in partial pressures as P
A
, P
B
, P
C
and P
D
we get
( ) ( )
( ) ( )
c d
C D
p
a b
A B
P P
K
P P
= __________( )
If both reactants and products are in gaseous states and they behave as ideal gases, then by
associating the general gas equation with it, we get PV = nRT
P =
v
n
RT By putting
v
n
c = we get P = CRT
In replacing the concentrations of A. B. C and D as C
A
. C
B
,. C
C
and C
D
we get the equation as under:
P
A
=C
A
RT , P
B
=C
B
RT, Pc =C
C
RT and P
D
=C
D
R
On substituting these values of partial pressures in the above reaction we get
( ) ( )
( ) ( )
c d
C D
p
a b
A B
C RT C RT
K
C RT C RT
=
( )
( )
( ) ( ) ( )
( ) ( ) ( )
c d c d
C D
p
a b a b
A D
C C RT
K
C C RT
+
+
=
( ) ( )
( ) ( )
( )
( ) ( )
c d
c d a b C D
p
a b
A D
C C
K RT
C C
+ +
=
( )
( ) ( )
( )
( ) ( )
g
c d
n
C D
p
a b
A D
C C
K RT
C C
A
=
but (c+d) (a+b) =(gaseous moles of products) - (gaseous moles of reactants) = n
Kp = Kc (RT)
n(g)
If n
(g)
= 0 then Kp = Kc (e.g N
2(g)
+ O
2(g)
2NO
(g)
)
If n
(g)
> 0 then Kp > Kc (e.g. CaCO
3(s)
CaO
(s)
+ CO
2(g)
)
If n
(g)
< 0 then Kp < Kc (e.g. N
2 (g)
+ 3H
2 (g)
2NH
3 (g)
)
Derive relation between Kp and Kx
Consider a simple reaction as follows.
a A
(g)
+ b B
(g)
c C
(g)
+ d D
(g)
Here, at equilibrium, all the components i.e., reactants and products, are in gaseous form and so by
taking their concentration in partial pressures as P
A
, P
B
, P
C
and P
D
we get
( ) ( )
( ) ( )
c d
C D
p
a b
A B
P P
K
P P
= __________( )
Nirav Sir Page 9
Here, at equilibrium, all the components i.e., reactants and products, are in gaseous form and so by
taking their concentration in mole fraction as X
A
, X
B
, X
C
and X
D
we get
( ) ( )
( ) ( )
c d
C D
x
a b
A B
X X
K
X X
=
According to Dalton's law of partial pressures, if the total pressure is P atmosphere, the partial
pressures of reactants A and B and partial pressures of products C and D will be X
A
P, X
B
P, XcP and
X
D
P respectively, where X is mole fraction.

( ) ( )
( ) ( )
c d
C D
p
a b
A B
X P X P
K
X P X P
=

( ) ( )
( ) ( )
.
( ) ( )
c d
c d a b C D
p
a b
A B
X X
K P
X X
+ +
=

( )
.
g
n
p x
K K P
A
=
DECOMPOSITION CONSTANT IN HETEROGENEOUS CHEMICALEQUILIBRIUM
Equilibrium Constant for Decomposition of Solid Calcium Carbonate
In a closed system, at a given temperature, solid calcium carbonate decomposes into solid calcium
oxide and gaseous carbon dioxide on heating.
CaCO
3(s)
CaO
(s)
+ CO
2(g)
According to the Law of active mass
The rate of forward reaction V
f
[CaCO
3
]
The rate of reverse reaction V
r
[CaO] [CO
2
]

V
f
= K
f
[CaCO
3
] and V
r
= K
r
[CaO] [CO
2
]
Where K
f
= Constant for forward reaction
Where K
r
= Constant for reverse reaction
At equilibrium, the forward reaction rate and reverse rate being equal V
f
= V
r
K
f
[CaCO
3
] = K
r
[CaO] [CO
2
]

2
3
[ ][ ]
[ ]
f
r
K
CaO CO
K CaCO
=
By replacing
f
c
r
K
K
K
= where we get
2
3
[ ][ ]
[ ]
c
CaO CO
K
CaCO
=
Now, CaO and CaCO
3
are solid substances. Here the concentration of solid substances will be equal
to their densities and at a given temperature, the density is constant, we will have,
3
2
[ ]
c
density of CaCO
K CO
density of CaO
=
Here, CO
2
is gas and if its concentration is taken as its partial pressure then we get a new constant
Kp.

2
P CO
K P =
Based upon the above, we can get equations for the decomposition constant of compounds like
NH
4
SH and NH
4
COONH
2(s)
which can undergo decomposition.
Their decomposition reactions are as under:
NH
4
HS
(s)
NH
3(g)
+ H
2
S
(g)
NH
4
COONH
2(s)
2NH
3(g)
+ CO
2(g)
Derive equation of equilibrium constant for decomposition of solid ammonium carbamate.
Nirav Sir Page 10
In a closed system, at a given temperature, solid ammonium carbamate decomposes into gaseous
ammonia and carbon dioxide on heating.
NH
4
COONH
2(s)
2NH
3(g)
+ CO
2(g)
According to the Law of active mass
The rate of forward reaction V
f
[NH
4
COONH
2(s)
]
The rate of reverse reaction V
r
[NH
3(g)
]
2
[CO
2
]

V
f
= K
f
[NH
4
COONH
2(s)
] and V
r
= K
r
[NH
3(g)
]
2
[CO
2
],
Where K
f
= Constant for forward reaction
Where K
r
= Constant for reverse reaction
At equilibrium, the forward reaction rate and reverse rate being equal V
f
= V
r
K
f
[NH
4
COONH
2(s)
] = K
r
[NH
3(g)
]
2
[CO
2
]

2
3 2
4 2
[ ] [ ]
[ ]
f
r
K
NH CO
K NH COONH
=
By replacing
f
c
r
K
K
K
= where we get
2
3 2
4 2
[ ] [ ]
[ ]
C
NH CO
K
NH COONH
=
Now, NH
4
COONH
2
is solid substance. Here the concentration of solid substance will be equal to its
density and at a given temperature, the density is constant, we will have
2
4 2 3 2
[ ] [ ]
C
K density of NH COONH NH CO =
Here, NH
3
and CO
2
are gases and if their concentrations are taken as their partial pressure then we
get a new constant Kp.

3 2
2
( ) ( )
P NH CO
K P P =
Above equation indicates that equilibrium constant is depending only on the partial pressure of
ammonia and carbon dioxide.
Derive equation of equilibrium constant for decomposition of solid ammonium hydrogen sulphide. (H.W.)
State the characteristics of equilibrium constant
At a given temperature, for every chemical reaction at equilibrium, the value of equilibrium
constant is always constant.
If, for a chemical reaction at equilibrium, the value of Kc is high the conversion of reactants into
products is high and if the value of Kc is low, conversion of reactants into products is low.
The value of equilibrium constant is independent of the initial concentration of the reactants.
The equilibrium constant for the reverse reaction is equal to the inverse of the equilibrium constant
for the forward reaction.
Kc (forward reaction rate) =
c
1
K ( ) reverse reactionrate
The value of K
eq
does not depend upon the catalyst.
Equilibrium constant of a chemical reaction concerned with heat is independent on temperature.
State Le-Chatelier's Principle
The effect of change of external factors like temperature and pressure over a chemical reaction at
equilibrium was given by Le-Chatelier and Braun in 1884. The Le-Chatelier's principle may be stated
in the following form.
"If any change occurs in one of the factors, such as temperature, pressure or concentration, under
which a system is in equilibrium, the system will tend to adjust it self so as to annul, as far as
possible, the effect of that change."
The same general conclusions may be reached in a qualitative manner.
Explain Effect of Concentration on Equilibrium
Nirav Sir Page 11
According to Le-Chatelier's principle if concentration of reactant is increased in system at
equilibrium then system tries to decrease it. In order to decrease the concentration of reactant rate
of forward reaction is increased so equilibrium is disturbed and it will shift into forward direction in
order to obtain new equilibrium state.
Now if concentration of reactant is decreased the equilibrium will disturb and shift into reverse
direction.
Similarly if in a system at equilibrium if concentration of product is increased then state of
equilibrium shift in the reverse direction and if concentration of product is decreased then state of
equilibrium shift in the forward direction.
Consider the following equilibrium at a given temperature
3 2
( )
( ) ( )
[ ( )]
aq
aq aq
Fe SCN Fe SCN
+ +

+

yellow colourless deep red
As an external factor, if a solution of ferric chloride is added to the system, the concentration of
3
( ) aq
Fe
+
will be increased. Now according to Le-Chatelier's principle, the system will try to
decrease the concentration of
3
( ) aq
Fe
+
ions. To do this the forward reaction will take place and so
more of
( ) aq
SCN

will react to form more of

2
( )
[ ]
aq
FeSCN
+
As result, the intensity of red colour of
the solution will be more.
If as an external factor, solution of KSCN is added to the solution the concentration of
( ) aq
SCN

ion will be increased. Now according to Le-Chatelier's principle, the system will try to decrease the
concentration of
( ) aq
SCN

ions. To do this the forward reaction will take place and so more of
3
( ) aq
Fe
+
will react to form more of
2
( )
[ ]
aq
FeSCN
+
as a result, the intensity of red colour of the
solution will be more.
Concentration of Rate of Equilibrium shift
in -----direction
Reactant increased Forward reaction increased Forward
Reactant decreased Reverse reaction increased Reverse
Product increased Reverse reaction increased Reverse
Product decreased Forward reaction increased Forward
Effect of Temperature on Equilibrium
Increase of temperature increases the reaction rate. This affects the equilibrium state.
N
2 (g)
+ O
2 (g)
+ heat 2 NO
(g)
This is an endothermic reaction. If temperature is increased as an external factor, the system will
try to decrease the temperature according to the Le-Chatelier's principle. This will enhance the
forward reaction which will result in utilizing the reactants and hence more of the products will be
formed. At the new equilibrium state the value of Kc will be higher.
Let us consider the following reaction which is exothermic in nature.
2 SO
2 (g)
+O
2 (g)
2SO
3 (g)
+ heat
According to Le Chatelier's principle, raising the temperature shifts the equilibrium to the left and
decreases the equilibrium concentration of the products. In other words, the concentration of the
products will be decreased and that of the reactants increased. Under such circumstances, the
value of Kc will decrease.
Forward
reaction
Effect of
temperature
Rate of Equilibrium
shift in -----
Value of K
eq
Nirav Sir Page 12
direction
Exothermic Increased Reverse reaction
increased
Reverse Decreased
Exothermic Decreased Forward reaction
increased
Forward Increased
Endothermic Increased Forward reaction
increased
Forward Increased
Endothermic Decreased Reverse reaction
increased
Reverse Decreased
Explain Effect of Pressure on Equilibrium
Effect of pressure is only exerted only in the system in which gaseous components involve.
If in the system at equilibrium pressure is increased then equilibrium will shift in the direction in
which total number of moles of gaseous component decreased.
Consider the reaction N
2 (g)
+ 3H
2 (g)
2NH
3 (g)
On increasing the pressure as an external factor on the above chemical reaction, at equilibrium, the
system will try to decrease the pressure according to Le-Chatelier's principle the pressure has
increased, the equilibrium now shifts in forward direction, a direction in which the number of
moles of the gas or pressure decreases.
This means that the concentration of the products will be increased and that of the reactants
decreased. Under the newly attained equilibrium the value of Kc will be constant.
It must be understood that if the number of the moles of both gaseous reactants and gaseous
products are equal in a chemical reaction at equilibrium state there will be practically no effect of
change of pressure on the system.
The effect of pressure is ignored on liquid and solid reactants and products. They are not affected
much by pressure changes.
n Effect of P Eq
m
shift in -----direction
n = 0 Increased No effect on eq
m
n < 0 Increased Forward direction
n > 0 Increased Reversed direction
Effect of Catalyst on Equilibrium
A catalyst does not affect equilibrium constant. It increases the rate of both the reactions (forward
and reverse) and simply allows a reaction to reach an equilibrium position more rapidly.
A catalyst has no effect on the equilibrium composition of a reaction mixture. The value of Kc
remains constant.
Q.22. Explain the effect of the external factor mentioned on the, chemical reactions given below under
the stated condition.
(1) H
2
O
(g)
+CO
(g)
H
2(g)
+ CO
2 (g)
(on introducing vapour)
(2) PCl
5(g)
PCl
3( g)
+ Cl
2 (g )
(removal of Cl
2
)
(3) H
2 (g)
+I
2 (g)
2HI
(g )
+ heat (decreasing temperature)
(4) CaCO
3(s)
CaO
(S)
+ CO
2(g)
- heat (increasing pressure)
(5) NH4CI
(s)
NH
3(g)
+ HCl
(g)
(lowering pressure)
(6) NH
4
COONH
2(S)
2NH
3(g)
+ CO
2(g)
(lowering pressure)
Ans:
(1)H
2
O
(g)
+CO
(g)
H
2(g)
+ CO
2 (g)
(on introducing vapour) :
Nirav Sir Page 13
On introducing water vapour at equilibrium, the concentration of reactants is increased. According
to Le-Chatelier's principle, to nullify this effect, forward reaction will occur, as a result, the
concentration of products will be increased. ,
(2) PCl
5(g)
PCl
3( g)
+ Cl
2 (g )
(removal of Cl
2
)
On removing Cl
2
gas from the system at equilibrium, the system will try to produce more and more
Cl
2
. This will enhance the forward reaction.
(3) H
2 (g)
+I
2 (g)
2HI
(g )
+ heat (decreasing temperature)
This reaction is exothermic. When temperature is decreased, according to Le-Chatelier's principle,
the system will try to produce more heat to increase the temperature. As a result, the forward
reaction will be favoured.
(4) CaCO
3(s)
CaO
(S)
+ CO
2(g)
- heat (increasing pressure)
Here Kp =Pco
2
. To increase the pressure, Pco
2
should increase. To maintain constant Kp the system
will favour reverse reaction. So excess of CO
2(g)
will combine with solid CaO to produce solid CaCO
3
.
(5) NH
4
Cl
(s)
NH
3(g)
+ HCl
(g)
(lowering pressure)
When pressure is decreased, to maintain constant Kp' more and more NH
4
Cl will be decomposed
into NH
3(g)
and HCl
(g)
i.e. forward reaction will be favoured.
(6) NH
4
COONH
2(S)
2NH
3(g)
+ CO
2(g)
(lowering pressure)
In this heterogeneous equilibrium, Kp =(P
NH3
)
2
Pco
2
. Now when pressure is decreased, according
to Le-Chatelier's principle, the equilibrium will be shifted in forward direction to increase the
equilibrium concentration of the products.
Que: The following equation represents a gaseous system at equilibrium:
2 SO
2 (g)
+O
2 (g)
2SO
3 (g)
+ heat
Indicate the direction in which the equilibrium will shift when the following changes are made:
(1) Concentration of SO
2
is increased.
(2) Temperature of the system is decreased.
(3) Total pressure is decreased.
Ans :
(1) When the concentration of SO
2
is increased, the equilibrium will shift in the direction of the
products, i.e. forward reaction rate will increase.
(2) The formation of SO
3
is an exothermic reaction. Therefore, when the temperature of the system
is decreased, the equilibrium shifts towards the forward direction and thus favours formation of
SO
3
.
(3) If the total pressure is decreased, the volume will increase, and the reaction will move in that
direction which favours the increase in volume, i.e., the dissociation of SO
3
will be favoured.
Que : With the help of Le-Chatelier's principle, predict the effect of (a) increasing the temperature; and
(b) decreasing the temperature on each of the following equilibrium systems:
(i) N
2(g)
+ 3H
2 (g)
2NH
3 (g)
(ii) N
2(g)
+ O
2 (g)
+ heat 2NO
(g)
(iii) H
2
O
(g)
H
2 (g)
+ O
2 (g)
- heat
(iv) 2CO
(g)
+ O
2 (g)
2CO
2 (g)
+ heat
(i) As the forward reaction is exothermic, an increase in temperature favours the backward reaction
and a decrease in temperature favours the forward reaction.
(ii) The reaction is accompanied by absorption of heat. So increase in temperature favours the
forward reaction and decrease in temperature favours the backward reaction.
(iii) This is similar to (ii).
(iv) This is similar to (i).
Give scientific reasons.
Nirav Sir Page 14
In a reaction under equilibrium, increase in concentration of any reactant increases the amount of the
product.
Sulphur trioxide (SO
3
) is formed on oxidation of sulphur dioxide by oxygen. The equilibrium for the
reaction can be expressed by the following equation:
2SO
2 (g)
+ O
2 (g)
2SO
3 (g)
At the time of equilibrium, if the amount of oxygen or sulphur dioxide is increased, according to Le-
Chatelier's principle, reaction equilibrium will adjust in such a way that the effect produced by the
addition of a reactant is nullified, i.e., the reactant is used up. As a consequence more SO
3
(product)
will be produced.
Thus increase in concentration of any reactant increases the amount of product.
Ice melts on applying pressure even below 0C.
Equilibrium between ice and liquid water can be represented by the following equation: ice
water
Here, when ice melts, there is decrease in volume. Thus, increase in pressure on ice-water system
causes the equilibrium to shift towards right side, i.e. in the direction where there is decrease in
volume. In other words, increase in pressure will cause the melting of ice. Hence, ice melts on
applying pressure even below 4C.
Pressure has no effect on the dissociation of hydrogen iodide HI.
Dissociation reaction of hydrogen iodide can be represented by the following equation: 2HI(g)
H
2(g)
+I
2(g)
The change of pressure plays an important role in those chemical equilibrium which involves
gaseous substances and proceed with a change in the number of moles of the gases. But in those
reactions in which there is no change in the number of moles of reactants and products, there will
not be any effect of pressure.
Here, in the above equation, the number of moles of reactants and products are the same, i.e.,
two. Hence, it is very clear that pressure has no effect on such equilibrium.
Equilibrium cannot be reached between water and its vapour in an open vessel.
Equilibrium between water and its vapour can be represented by the following equation: H
2
O
(l)
H
2
O
(s)
In this case, equilibrium is possible only if the rate of evaporation is equal to the rate of
condensation. But in an open vessel, the water molecules in gaseous phase get dispersed into a
large volume. So the rate of condensation from gas to liquid state can never be equal to the rate of
evaporation. Such systems are said to be open and equilibrium cannot be reached in such systems.
In this system, the water will get evaporated eventually. Moreover, equilibrium state can be
reached only in closed systems.