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2016-2017

CHEMICAL EQUILIBRIUM

(Lecture Notes)

CONTENTS
1.

Equilibrium in physical and chemical processes.

2.

Dynamic nature of equilibrium.

3.

Law of mass action.

4.

Equilibrium constant.

5.

Effect of temperature on equilibrium constant.

6.

Thermodynamics of equilibrium.

7.

Factors affecting equilibriumLe Chateliers principle.

8.

Concept of Simultaneous Equilibrium.

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INTRODUCTION
When reactants are mixed under a certain set of conditions, the following questions arise:
Will a reaction occur among all the reactants?
Chemical Energetics
If the reaction takes place, what is its rate?
Chemical Kinetics
To what extent will the reaction proceed?
Chemical Equilibrium
A System at equilibrium has no tendency to change in either direction (forward or reverse), such a system
remains in its current state until it is disturbed by changing the conditions, such as raising the temperature,
decreasing the volume or adding more reactants.
At equilibrium state both the forward and backward reactions move with equal speeds. i.e., the rate of
disappearance of reactants is exactly equal to the rate of appearance of reactants from the products.
or
The state at which concentrations of reactants and products do not change with time is known as a state
of chemical equilibrium.
The state of equilibrium is recognized by the constancy of certain measurable properties such as
pressure, density, color, etc., besides concentration of reactants and products.
By changing conditions of the system such as temperature, pressure, concentration of reactants and by
changing concentration of products by removing them from the site of reaction, etc., the extent to which
a reaction can proceed can be controlled.
Thus, the study of chemical equilibrium helps in the elucidation of the optimum conditions for the greater
yields of the products in the case of reactions which attain equilibrium in the course of reaction.
The equilibrium established in physical processes is called physical equilibrium and equilibrium
established in chemical processes is termed chemical equilibrium.

EQUILIBRIUM INVOLVING PHYSICAL CHANGES


Most familiar types of equilibria involving physical changes are the following:
Equilibrium between a solid and its liquid: Solid
Equilibrium between liquid and its vapors: Liquid

Liquid (Fusion equilibrium)


Gas (Vaporization equilibrium)

Equilibrium between a solid and its saturated solution: Solute(s)


Equilibrium between a gas and its saturated solution: Solute (g)

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Solution(aq) (Solubility equilibrium)


Solution (aq) (Solubility equilibrium)

EQUILIBRIA INVOLVING CHEMICAL SYSTEMS


IRREVERSIBLE AND REVERSIBLE REACTIONS
IRREVERSIBLE REACTIONS
The chemical reactions which proceed in such a way that initial substances (reactants) are nearly completely
converted into products, i.e., the reactions that proceed in one direction only are called irreversible reactions.
In such reactions products do not react together to form reactants again, i.e., the reaction does not move in
reverse direction.
For example,
BaSO4 + 2NaCl
BaCl2 + Na2SO4
2KClO3
2KCl + 3O2
N2 + 2H2O
NH4NO2
AgCl + NaNO3
AgNO3 + NaCl
Na2 SO4 + 2 H2O
H2SO4 + 2NaOH
SnCl4 + 2FeCl2
SnCl2 + 2 FeCl3
2MgO
2Mg + O2
REVERSIBLE REACTIONS
The chemical reactions which take place in both directions under similar conditions are called reversible
reactions.

Note:
Reversible reactions do not proceed to completion.
For a chemical reaction to be reversible it must be carried out in a closed vessel.
The reaction, proceeding from left to right is conventionally the forward reaction and the reaction
proceeding from right to left is called the reverse or backward reaction.
The sign (

) represents the reversibility of the reaction.

For example,
2HI
H2 + I2
PCl5

PCl3 + Cl2

CH3COOH + C2H5OH
NH4HS

CH3COOC2H5 + H2O

NH3 + H2S

Reversible chemical reactions are classified into two types: Heterogeneous and homogeneous.
HETEROGENEOUS REACTIONS
Reversible reactions in which more than one phase is present i.e., all the reactants and products are
not present in the same physical state are known are heterogenous reactions.
For example,
MgCO3(s)
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MgO(s) + CO2(g)

2Na2O2(s) +2H2O(l)
3Fe(s) + 4H2O (g)

4NaOH(l) + O2 (g)
Fe3O4 (s) + 4H2(g)

HOMOGENEOUS REACTIONS
Reversible reactions in which only one phase is present, i.e., all the reactants and products are in the
same physical state are known are homogenous reactions.
For example,
H2(g) + I2(g)

2HI(g)

CH3COOH(l) + C2H5OH(l)

CH3COOC2H5(l) + H2O (l)

Homogeneous reversible reactions are further classified into three types:


Case 1: Homogeneous reversible reactions where there is no change in number of molecules.
For example,
H2 + I2
2HI
2NO

N2 + O2

CH3COOH + C2H5OH

CH3COOC2H5 + H2O

Case 2: Homogeneous reversible reactions where there is an increase in number of molecules.


For example,
PCl5
PCl3 + Cl2
2NH3

N2 + 3H2

Case 3: Homogeneous reversible reactions where there is a decrease in number of molecules.


For example,
N2 + 3H2
2NH3
2SO2+ O2

2SO3

Note:
It is interesting to note that a reversible reaction becomes irreversible if one of the products (which is in
a gaseous state) is allowed to escape out.
For example, the decomposition of CaCO3 becomes irreversible if CO2 is allowed to escape.

STATE OF CHEMICAL EQUILIBRIUM


Consider a general reversible reaction in a closed vessel.
A+B

C+ D

In the initial state, only A and B are present, both react with each other, i.e., rate of forward reaction is maximum
as only the concentrations of A and B are involved (in the beginning, the concentrations of products C and D is
zero).
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As soon as the products C and D are produced, the backward reaction begins to take place.
As time passes, the rate of forward reaction decreases as the concentrations of A and B decrease while the rate
of backward reaction increases as the concentrations of products C and D increase.
Ultimately, a stage comes when the rate of forward reaction becomes equal to the rate of backward reaction.
This state is called the equilibrium state.
At equilibrium state,
Rate of forward reaction = Rate of backward reaction.

Time
Thus, chemical equilibrium in a reversible reaction is the state at which both forward and backward reactions
(or two opposing reactions) occur at the same speed.

Note:
This state of equilibrium will continue indefinitely if the conditions such as temperature and concentration
are not changed.
At the state of equilibrium, the concentrations of reactants and products in the reaction mixture attain a
constant value and the concentrations do not change with time.
Example 1: Reaction between Hydrogen and Iodine.
When hydrogen gas and iodine vapors are heated in a closed vessel at a constant temperature, 717K, the two
react to form hydrogen iodine.
The reactions involved is: H2(g) + I2 (g)

2HI (g)

In the initial stage, the color of the reaction mixture is deep violet due to the presence of large amounts of
iodine.
But as the reaction progresses, the intensity of the color decreases as more and more iodine is converted into
hydrogen iodine.
After some time, the intensity of the color of the reaction mixture becomes constant. The constancy of intensity
of color indicates that the concentrations of both reactants and products have become constant and state of
equilibrium has been attained.
Example 2: Decomposition of Calcium Carbonate.
Solid calcium carbonate is taken in a closed tube connected to a manometer as shown in the figure and is heated
at 1073K in a furnace.
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Calcium carbonate decomposes into solid calcium oxide and gaseous carbon dioxide according to the equation:
CaCO3(s)
CaO(s) +CO 2(g)
Pressure is developed in the tube due to formation of CO2 and as the decomposition of calcium carbonate
continues, the pressure goes on increasing.
After some time, it is observed that pressure becomes constant at constant temperature even though, calcium
carbonate is still present.
This means that the amount of CO2 produced has become constant. The constancy of pressure indicates that
state of equilibrium has been attained.

CHARACTERISTICS OF EQUILIBRIUM STATE


Equilibrium state can only be achieved if a reversible reaction is carried out in a closed space, i.e., neither
Product can leave nor any reactant from outside can enter the space. If the system is not closed, some of
the products may escape and thus, backward reaction will not occur.
Chemical equilibrium, at a given temperature, is characterized by constancy of certain properties such
as pressure, concentration, density and color.
Chemical equilibrium can be attained from either side, i.e., from the side of reactants or products.
2HI

H2 + I2

or

H2 + I2

2HI

At equilibrium, each reactant and each product has a fixed concentration and this is independent of the fact
whether we start the reaction with the reactants or with the products.
The presence of a catalyst does not change the equilibrium state, as the catalyst affects the forward reaction
to the same but it helps in attaining it rapidly.
Equilibrium state can be attained in a lesser time by the use of a positive catalyst, i.e., the relative
concentrations of reactants and products remain the same irrespective of the presence or absence of a catalyst.
It is dynamic in nature, i.e., both the reactions move with same speed. However, the reaction seems to have come
to stand still because the concentrations of reactants and products do not change.
At equilibrium, the free energy change of the system is zero, i.e., G = 0 .

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LAW OF MASS ACTION


According to the law of mass action At a given temperature, the rate of a reaction at a particular instant is
proportional to the product of the active masses of the reactants at that instant raised to powers which are
numerically equal to the numbers of their respective molecules in the stoichiometric equation describing the
reaction.
Consider the following general reaction:
Products
m1A1 + m2A2 + m3A3 + .
Acc. to the Law of Mass Action,
Rate of forward reaction, rf A1

m1

A 2 A3
m2

Rate of forward reaction, rf =k f A1

m1

m3

A 2 A3
m2

m3

THE LAW OF CHEMICAL EQUILIBRIUM (APPLICATION OF LAW OF MASS ACTION)


Consider a reversible homogeneous reaction which has attained equilibrium state at a particular temperature.
A+B
C+D
Let the active masses of A, B, C and D be [A], [B], [C] and [D] respectively at equilibrium.
According to law of mass action,
Rate of forward reaction, rf [A][B]

Similarly,

rf =k f [A][B]
Rate of backward reaction, rb [C][D]

rb =k b [C][D]

where,
k f is the velocity constant for forward reaction, k b is the velocity constant for backward reaction.
Rate of forward reaction decreases and that of backward reaction increases with passage of time as shown below
graphically.

(Equilibrium)
Time

At equilibrium,
Rate of forward reaction = Rate of backward reaction

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k f [A][B] = k b [C][D]

k f C[D]
=
k b A [B]

k f and k b are both constants, the ratio

kf
is also a constant say Kc,
kb
Kc =

C[D]
A [B]

where,
Kc is known as equilibrium constant.

Note:
Kc has a definite value for every chemical reaction at a given temperature regardless of the concentration of
the reactants.
Considering a general homogeneous reversible reaction of the type
m1A1 + m2A2 + m3A3 +

n1B1 + n2B2 + n3B3 +

Rate of forward reaction,

rf =k f [A1 ]m1 [A 2 ]m2 [A3 ]m3 ....


Rate of backward reaction,

rb =k b [B1 ]n1 [B2 ]n 2 [B3 ]n3 ....


At equilibrium,

rf = rb

k f [A1 ]m1 [A 2 ]m2 [A3 ]m3 ....= k b [B1 ]n1 [B2 ]n 2 [B3 ]n3 ....

[B1 ]n1 [B2 ]n 2 [B3 ]n3 ....


kf
=K c =
kb
[A1 ]m1 [A 2 ]m2 [A3 ]m3 ....

The equilibrium constant may be defined as the ratio between the products of the molar concentration of
the products to that of the product of the molar concentrations of the reactants with each concentration term
is raised to a power equal to stoichiometric coefficient in the balanced chemical equation.

Note:
The equilibrium constant, at a given temperature, is the ratio of the rate constants of forward and backward
reactions.
The value of equilibrium constant is independent of the following factors:
(i) Initial concentrations of the reactants involved.
(ii) The presence of a catalyst.
(iii) The direction from which the equilibrium has been attained.
(iv) The presence of inert materials.

EQUILIBRIUM CONSTANT IN TERMS OF PARTIAL PRESSURES OR MOLE FRACTIONS


When the reactants and products are in gaseous state, the partial pressures can be used instead of concentrations at
a definite temperature, as the partial pressure of a substance is proportional to its concentration in the gas phase.
Consider a general reversible homogeneous gaseous reaction
m1A1 + m2A2 + m3A3 +
n1B1 + n2B2 + n3B3 +
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Let the partial pressures of various reactants and products be p A1 , p A 2 , p A3 , .. . and


respectively at equilibrium.

p B1 , p B2 , p B3 .

The equilibrium constant for the reaction,

Kp =

(p B1 ) n1 (p B2 ) n 2 (p B3 ) n3 .....
(p A1 ) m1 (p A2 ) m2 (p A3 ) m3 .....

The value of Kc for the above reaction can be given as:

Kc =

[B1 ]n1 [B2 ]n 2 [B3 ]n3 .....


[A1 ]m1 [A 2 ]m2 [A3 ]m3 .....

For an ideal gas,

PV = nRT
n
P = RT
V
= Active mass RT

where,
n = number of moles, V= volume in litres.
n

= molar concentration or active mass.


V
Substituting the values of partial pressures in the expression of K p , we get

([B1 ]RT)n1 ([B2 ]RT)n 2 ([B3 ]RT)n3 .....


Kp =
([A1 ]RT)m1 ([A 2 ]RT) m2 ([A3 ]RT) m3 .....
n g

K p =K c (RT)

where,
n g = total number of molecules of gaseous products total number of molecules of gaseous reactants.
RELATIONSHIP BETWEEN KP AND KC
Case 1: n g = 0

K p =K c
For example,
H2 + I2
2HI
Case 2: n g = +ve or n g > 0,

K p >K c
For example,
PCl5
PCl3 + Cl2
Case 3: n g = -ve or n g < 0,

K p <K c
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For example,
N2 + 3H2

2NH3

Consider a general reversible homogeneous gaseous reaction


m1A1 + m2A2 + m3A3 +
n1B1 + n2B2 + n3B3 +
For the above chemical equilibrium, equilibrium constant in terms of mole fraction can be expressed as

Kx =

( B1 ) n1 ( B2 ) n 2 ( B3 ) n3 .....
( A1 ) m1 ( A2 ) m2 ( A3 ) m3 .....

pi = i PT

K p = K x (PT )

n g

Note:
When, n g = 0

Kc = Kp = K x

WRITING EXPRESSION FOR EQUILIBRIUM CONSTANT


While writing equilibrium expressions, the following conventions are followed:
1. In case a solid is involved in the equilibrium, its concentration remains constant, no matter how much of
it is present. Therefore, by convention, the concentrations of all solids are taken as unity, i.e., [Solid] = 1.
For example,
CaCO3(s)
K=

CaO(s) + CO2(g)
[CaO(s) ][CO 2 g ]

[CaCO3s ]

[CaO(s)] and [CaCO3(s)] =1

K c = [CO2 ]

or

Kp = PCO2

2. In case, a liquid is in equilibrium with a gas or gases, the concentration of pure liquid is taken as unity.
For example,
H 2 O l
H 2 O g
K=

[H 2 O(g) ]
[H 2 O(l) ]

[H2O(l)] =1)

K c = [H 2O(g) ]
or

K p = PH2O

3. For the equilibrium in aqueous medium, if H2O is also involved in equilibrium, its concentration is taken
as constant as it is present in a large quantity.
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For example,

HCl H 2O

H3O Cl

H 3O + [ Cl- ]
K=
HCl[H 2O]

( [H2O] = Constant)
H 3O + [ Cl- ]
K[H2O] = Kc =
HCl
4. For the equilibrium in aqueous medium, if H2O is involved in equilibrium, but is produced during the
course of the reaction, the concentration of H2O is not considered unity as it is not present in a large
quantity.
For example,
CH3COOH + C2H5OH
CH3COOC2H5 + H2O

Kc =

[CH 3COOC 2 H 5 ][H 2 O]


CH3COOH [C2 H5OH]

UNITS OF EQUILIBRIUM CONSTANT


The units of equilibrium constant vary in case of different reactions.
Case 1: The equilibrium constant K has no unit for a reaction in which the total number of moles of
reactants and products are same.
For example:
[HI]2
(No unit)
H 2 g I 2 g
2HI g ; Kc =
H 2 [I2 ]
[NO]2
(No unit)
N 2 [O2 ]
Case 2: Kc will have units for a reaction in which total number of moles of reactants and products are
different.
For example:
PCl3 [Cl2 ] mol L-1
PCl5 g
PCl3 g Cl 2 g ; Kc =
[PCl5 ]
N 2 g O 2 g

N 2 g 3H 2 g

2NO g ;

Kc =

2NH 3 g ; Kc =

[NH 3 ]2
mol-2 L2
[N 2][H 2 ]3

Note:
n

In general the unit of K c = (mol L-1 ) g


where
n g = number of moles of gaseous products Number of moles of gaseous reactants.
The above relation can be used in aqueous systems also.
where
n g = number of moles of aqueous products Number of moles of aqueous reactants
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n g

n g

In general the unit of Kp = (atm)


or (bar)
or (mmHg) g
where
n g = Number of moles of gaseous products Number of moles of gaseous reactants.

CHARACTERSTICS OF EQUILIBRIUM CONSTANT

The equilibrium constant expression for a given reaction is independent of the reaction mechanism
.i.e the path followed by the reaction.
Equilibrium constant for a particular reaction does not change with time.
The numerical value of equilibrium constant is independent of the initial concentrations of reactants
and products (if any).
The value of equilibrium constant is a characteristic quantity for a given reaction at a given
temperature, however Kx depends on total pressure.
The numerical value of equilibrium constant is not influenced by the presence of a catalyst, however
the presence of a catalyst helps in attaining equilibrium faster.
The magnitude of equilibrium constant is a measure of the extent to which a given reaction has taken
place at equilibrium.

A very high value of equilibrium constant (>103) shows that reaction has gone almost to
completion.

A very low value of equilibrium constant (< 10-3) shows that reaction has gone almost to
completion.

Intermediate values of equilibrium constant (103-10-3) shows that the concentration of


reactants and products are comparable.
The equilibrium constant expression depends on the stoichiometry of the balanced chemical equation.
If an equilibrium is reversed, the equilibrium constant value gets inversed.
If any two equilibriums are added, to get another equilibrium, then the equilibrium constant for the
new equilibrium is the product of the equilibrium constant of the original equilibriums that were
added.
If any two equilibriums are subtracted, to get another equilibrium, then the equilibrium constant for
the new equilibrium is the ratio of the equilibrium constant of the original equilibriums that were
added.
In case if the stoichiometric coefficients in a reaction are multiplied by a small integer, the
equilibrium constant for the new reaction will have the same integer raised to the power of the
equilibrium constant of the original reaction.
In case if the stoichiometric coefficients in a reaction are divided by a small integer, say n, the
equilibrium constant for the new reaction will be the nth root of the equilibrium constant of the
original reaction.

SOLVED EXAMPLES
Example 1: The expression of equilibrium constant for a reaction is: Kc =

I2 [H5 IO6 ]5

[IO3- ]7 [H 2O]9 [H + ]7
Write down the balanced chemical equation corresponding to this expression.
Solution: The balanced chemical equation for the given expression will be:
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7IO3(aq)
+9H 2 O(l) +7H + (aq)

I 2(aq) +5H5 IO6(aq)

Example 2: Water gas shift reaction: CO(g) + H2O(g)


CO2(g) + H2(g), is used in industries to prepare
hydrogen. At equilibrium, following concentrations were found for this reaction at 500C.
[CO] = 0.18 M, [H2O] = 0.0411 M, [CO2] = 0.15 M and [H2] = 0.20 M. What is the value of Kc for this
reaction?
Solution: For the given reaction: CO(g) + H2O(g)
CO2(g) + H2(g)

Kc =
=

CO2 [H 2 ]
CO[H 2O]
0.15 0.2
4.055
0.18 0.0411

1
3
N2 H2
NH3 , write down the expressions for
2
2
equilibrium constants K c and K 'c . How is K c related to K 'c ?
Solution:
For the reaction: N2 + 3H2
2NH3
[NH3 ]2
. . . (i)
Kc =
N 2 [ H 2 ]3

Example 3: For the reactions, N2 + 3H2

And for the reaction:

1
3
N2 H2
2
2

2NH3 and

NH3

[NH 3 ]

K 'c =

1
2

[N 2 ] [H 2 ]

3
2

. . . (ii)

Squaring equation (ii) we get,


( K 'c )2 =

[NH 3 ]
[N 2 ][H 2 ]3

. . . (iii)

Equations (i) and (iii) are same, thus, K c = ( K 'c )2

K c = Kc

Example 4: The equilibrium constant for the reaction, N2 + 2O2


2NO2 at a particular temperature is 100.
Write down the equilibrium constant expressions for the following reactions and determine the value of
equilibrium constants for the respective equilibriums.
2NO2
N 2 2O 2
.. . (1)

NO2

N 2 O2

. (2)

Solution:
The equilibrium constant for the reaction: N2 + 2O2
2NO2
2
[NO2 ]
Kc =
= 100 . . . (i)
N 2 [ O2 ]2
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The equilibrium constant equation for reaction (i)


N 2 [ O 2 ]2

K1 =
[NO2 ]2
This is reciprocal of Eqn. (i)
1
1
=
= 1 10-2
K1 =
K c 100
The equilibrium equation for the reaction (2)

N2

1/2

K2 =

. . . (ii)

[ O2 ]

. . . (iii)

[NO2 ]

K1 = 102 = 10-1 = 0.1

Comparing Eqns. (ii) and (iii) we get, K2 =

1
1
1
N 2 g O2 g Br2 g
2
2
2
298K.The equilibrium constants for the following reactions: 2NO g
Example 5: Determine Kc for the reaction:

1
NO g Br2 g
2
Solution:

NOBr g from the following data at


N 2 g O 2 g and

NOBr g are 2.4 x 1030 and 1.4 respectively.

The net reaction is:

1
1
1
N 2 g O2 g Br2 g
2
2
2
Kc =

NOBr g

[NOBr]
[N 2 ] [O 2 ]1/2 [Br]1/2
1/2

Considering the given equations:


2NO g
N 2 g O 2 g
; Kc = 2.4 1030
N 2 g O 2 g

2NO g

; K 'c =

1
2.4 1030
1

1
1
The equilibrium constant for the equilibrium N 2 g O2 g
2
2
[NO]
= K ''c = 0.6455 10-15
1/2
1/2
[N 2 ] [O 2 ]
1
For the equilibrium: NO g Br2 g
2

i.e

The equilibrium constant expression K '''c =

2
NO g =
30
2.4 10
= 0.6455 10-15

. . . (i)

NOBr g

[NOBr]
= 1.4 . . . (ii)
NO[Br2 ]1/2
[NO]
[NOBr]

1/2
1/2
[N 2 ] [O 2 ]
NO[Br2 ]1/2
= 0.6455 10-15 1.4

Multiplying both equations we get, K ''c K '''c =

K c(net) =

[NOBr]
=0.9037 10-15
[N 2 ] [O 2 ]1/2 [Br2 ]1/2
1/2

Example 6: The value of Kc for the reaction: N2(g) + 3H2(g)

2NH3(g), is 0.50 at 400C. Find the value of Kp

at 400C when concentrations are expressed in mol litre-1 and pressure in atmosphere.
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Solution:
Given:
Kc = 0.50, R = 0.082 litre atm mol-1K-1
T = (400+273) = 673 K, n g = 2- 4 = -2
Kp = 0.05 (0.082 673)-2
n

Applying the relationship Kp = Kc(RT ) g


= 0.50(55.185)-2 = 1.64 10-4atm-2
Example 7: At 25C, Kp for the reaction: N 2 O 4 g

2NO 2 g , has a value of 0.14 atm. Calculate the value of

Kc in which the concentration is measured in terms of molL-1.


Solution:
For the given reaction: N 2 O 4 g
2NO 2 g

n g = 2 1 = 1
n

We know that, Kp = Kc (RT ) g


Kp
0.14
=
= 5.73 10-3 mol L-1
Kc =
n g
(0.022 298)1
(RT)
Example 8: At 25C, the equilibrium constants for the following reactions are as shown:
2CO g O 2 g
2CO 2 g ;
Kc = 3.3 1091 . . . (i)
2H 2 g O 2 g

Kc = 9.1 1080

2H 2 O g ;

Use these data to calculate the Kc for the reaction: H 2 O g CO g


Solution:
Dividing Eqn. (i) by 2, we get, CO g O 2 g

. . . (ii)

CO 2 g H 2 g

CO 2 g

Kc = [3.3 1091]1/2 . . . (iii)


Reciprocating and dividing equation (ii) by 2, we get, H2O(g)

H2(g) + 2O2(g)

2
...
Kc =
(iv)
80
9.110
Adding equation (ii) and (iii), we get, H2O(g) + CO(g)
CO2(g) + H2(g)

1
Kc = (3.3 1091)1/2
80 1/2
(9.110 )
45
5.744 10
=
= 1.9 105
40
3.016 10
Example 9: At certain temperature, the reaction: CO(g) + 2H2(g)
CH3OH(g) has Kc = 0.5. If the reaction has
equilibrium concentration of CO and H2 as 0.18 M and 0.22 M respectively. What is the equilibrium
concentration of CH3OH?
Solution:
For the given reaction: CO(g) + 2H2(g)
CH3OH(g)
Page 16 of 46

Kc =

[CH 3OH]
CO [H 2 ]2

. . . (i)

Given, Kc = 0.5, [CO] = 0.18 M, [H2]= 0.22 M.


From Eqn.(i) we get,
0.5 =

[CH3OH]
0.18 (0.22) 2

[CH3OH] = 4.356 10-3 L2mol-2

PROBLEMS FOR PRACTICE


1.
2.
3.
4.

Give two examples in which equilibrium constant Kp and Kc are equal.


Ans. H2(g) + I2 (g)
2HI (g), N2(g) + O2 (g)
Is the reaction between ethyl acetate and water attains equilibrium in open vessel?
CH3COOC2H5 ( l ) + H2O ( l )
CH3COOH ( l ) + C2H5OH ( l )

6.

4NH3 (g)
Ans. (i) 0.024

8.

(ii) 6.4

(iii) 1.68 103

Kp for the reaction N2O4 (g)


2NO2 (g) is 0.157 atm at 27C and 1 atm pressure. Calculate Kc for the
reaction.
Ans. 6.37 10-3 mol L-1
The value of the equilibrium constant for the reaction: H2 (g) + I2 (g)
2HI (g) at 720K is 48. What is
the value of the equilibrium constant for the following reaction: 2HI (g)

7.

Ans. Yes

At 700 K, the equilibrium constant Kp for the reaction: 2SO3 (g)


2SO2 (g) + O2 (g) is 1.80 10-3 kPa.
What is the value of Kc for the reaction at same temperature?
Ans. Kc = 3.09 10-7 M
For the reaction: N2 (g) + 3H2 (g)
2NH3 (g), at 400K, Kp = 41. Find the value of Kp for each of the
following reactions at same temperature.
(i) 2NH3 (g)
N2 (g) + 3H2 (g)
1
3
(ii) N 2( g ) H 2( g )
NH 3( g )
2
2
(iii) 2N2 (g) + 6H2 (g)

5.

2NO(g)

H2 (g) + I2 (g)?

Ans. 0.02

The equilibrium concentrations of NO2 and N2O4 at 142C for the reaction: 2NO2 (g)
N2O4 (g)
-1
-1
are: 0.710 mol L and 0.145 mol L respectively. What is the value of the equilibrium constant of the
given reaction?
Ans. Kc = 0.204 mol L-1
The equilibrium constant for the reactions have been measured at 823 K.
CoO (s) + H2 (g)
Co (s) + H2O (g)
; K = 67
CoO (s) + CO (g)
Co (s) + CO2 (g)
; K = 490
From the given data, calculate the equilibrium constant for the reaction:
CO2 (g) + H2 (g)
CO (g) + H2O (g)
Ans. 0.136

Page 17 of 46

EQUILIBRIUM CONSTANT EXPRESSIONS FOR SOME COMMON EQUILIBRIA


CASE 1: HOMOGENEOUS GASEOUS EQUILIBRIUM
Case 1: Gaseous reactions where the total number of molecules of reactants is equal to those of products,
i.e., n g = 0.
Example: Synthesis of hydrogen iodine:
The formation of hydrogen iodide from hydrogen and iodine is represented by the equation:
H 2 g I 2 g
2HI g
Let a start be made with a gram moles of hydrogen and b gram moles of I2.
These are heated in a sealed bulb having volume V liters by keeping the bulb in a thermostat till equilibrium
is established.
If at equilibrium, x moles of each of H2 and I2 have reacted, 2x moles of HI will be formed.

Initial no. of moles

H2
a

No. of moles at equilibrium (a-x)

I2
b

2HI
0

(b-x)

2x

Thus, the active masses of various reactants and products at equilibrium are:
a-x
-1
[H2] =
mol L
V
b-x
-1
[I2] =
mol L
V
2x
[HI] = mol L-1
V
Applying the law of mass action,
2
2x

[HI]2
V
Kc =
=
H 2 [I2 ] a-x b-x

V V
4x 2
Kc =
a-x b-x
When a = b =1,
4x 2
Kc =
2
1-x
Calculation of Kp:
The equilibrium constant, Kp, can also be calculated considering partial pressures of reactants and products at
equilibrium.
H2
+
I2
2HI
Initial no. of moles
a
b
0
Page 18 of 46

No. of moles at equilibrium (a-x)

(b-x)

2x

Total number of moles at equilibrium = (a-x) + (b-x) + 2x = (a+b)


Let the total pressure of the system at equilibrium be P atmospheres.
(a-x)
P
(a+b)
(b-x)
Partial pressure of I2, PI2 =
P
(a+b)
2x
Partial pressure of HI, PHI =
P
(a+b)

Partial pressure of H2, PH2 =

2x 2
2

P
(PHI )
a+b

Kp =
=
a-x
b-x
PH2 (PI2 )

P
P
a+b
a+b
4x 2
Kp =
a-x b-x

Kp = Kc

Note:
For all gaseous reactions where n g = 0, Kp and Kc are identical.
For all reactions where n g = 0, Kc or Kp has no units.
Case 2: Gaseous reactions where the total number of molecules of products is more than those of reactants,
i.e., n g > 0.
Example: Dissociation of PCl5:
The dissociation of PCl5 takes place according to the equation:
PCl5

PCl3 + Cl2

Let a moles of PCl5 be taken in closed vessel of volume V litres. It is heated and by the time equilibrium is
established, x moles are dissociated into PCl3 and Cl2.
Since one molecule of PCl5 on dissociation gives one molecule of PCl3 and one molecule of Cl2, thus, x moles
of PCl5 will give x moles of PCl3 and x moles of Cl2.

PCl5
Initial no. of moles
a
No. of moles at equilibrium (a-x)
At equilibrium,
x
x
a-x
[PCl5] =
, PCl3 = , Cl 2 =
V
V
V
Applying law of mass action, we get,
Page 19 of 46

PCl3
x

Cl2
x

Kc =

x
2
V = x
(a-x)
a-x V
V

PCl3 [Cl2 ] = V
[PCl5 ]

when a =1,
Kc =

x2
1-x V

Calculation of Kp:
Let the total pressure at equilibrium be P.
Total number of moles at equilibrium = (a-x) + x + x = (a+x)
x
a-x
x
p PCl5 =
pCl2 =
P
P ; p PCl3 =
P;
a+x
a+x
a+x
x
x
P

P
p PCl3 pCl2
a+x
a+x

=
Kp =
p PCl5
a-x

P
a+x
x 2P
Kp =

a-x a+x

Note:
Kc or Kp will have units for a reaction such as dissociation of PCl5 as the total number of moles of products
and reactants are different.
mol mol
[PCl3 ] [ Cl2 ] litre litre
K c=
= [mol/litre]
=
[PCl5 ]
mol
litre
p PCl3 p PCl3
atm atm
Similarly, Kp =
=
=atm
p PCl5
atm
In such reactions, Kp > Kc as n g > 0.
Case 3: Gaseous reactions where the total number of molecules of reactants is more than total number of
molecules of products, i.e., n g < 0.
Example: Synthesis of ammonia:
The formation of ammonia from nitrogen and hydrogen is represented by the equation:
N2 + 3H2
2NH3
Let a start be made by mixing a g moles of N2 and b g moles of hydrogen in a closed vessel of V litres.
By the time equilibrium is established x g moles of nitrogen have combined with 3x g moles of hydrogen
and produced 2x g moles of ammonia.
N2
Page 20 of 46

3H2

2NH3

Initial no. of moles


a
No. of moles at equilibrium (a-x)
At equilibrium,
b-3x
a-x
[N2] =
; [H2] =

V
V
Applying law of mass action,

b
(b-3x)

0
2x
; [NH3] =

Kc =

2x
V

[NH3 ]2
N 2 [H 2 ]3
2

2x

V
=
3
a-x b-3x

V V
4x 2 V 2
=
a-x (b-3x)3

If a=1 and b=3 then,

4x 2 V 2
Kc =
27(1-x) 4

Note:
In such reactions, Kp < Kc as n g < 0.
Kc or Kp will have units as the total number of moles of products and reactants are different
2
mol

[NH3 ]2
litre
Kc =
=
= mol-2 litre2
N 2 [H 2 ]3 mol mol 3

litre litre
(p NH3 )3
atm 2
=
=atm -2
Similarly, Kp =
3
3
(p N2 ) (p H2 )
atm atm

CASE 2: HOMOGENEOUS LIQUID PHASE EQUILIBRIUM


Example: Formation of Ethyl acetate:
The reaction between alcohol and acid to form ester is an example of homogeneous equilibrium in liquid
system:
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
Let a start be made by mixing a g moles of an acid and b g moles of an alcohol.
By the time, equilibrium is established, x g moles of ester and x g moles of water are formed, i.e., x moles of
acid and x moles of alcohol have been consumed. Let V be the total volume.
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
Initial no. of moles
a
b
No. of moles at eq
(a-x)
(b-x)
x
x
At equilibrium, the active masses of reactants and products are:
x
x
a-x
b-x
[CH3COOH] =
; [C2H5OH] =
; CH3COO2H5] =
; [H2O] =

V
V
V
V
Applying law of mass action,
Page 21 of 46

x
x

[ester][water]
V V
=
Kc =
a-x
acid
[alcohol]

b-x

V V
x2
Kc =
a-x ( b-x)

If a = b =1, then,

Kc =

1
(1-x) 2

Note:
Since for the above equilibrium Kc expression does not involve the volume term, Kc is not affected by the
changes in volume. Kc has no units.
For the reaction: Fe3 aq SCN aq
FeSCN 2 aq
Kc =

[FeSCN 2+ aq ]

(Unit = mol-1 L)

Fe aq [ SCN aq ]

For the reaction: NH3(aq) +H 2 O(l)


K=

3+

[NH +4 aq ][ OH - aq ]
[NH 3 aq ]

NH 4+ (aq) +OH - (aq)

(Unit = mol L-1)

[H2O(l)] = constant

CASE 3: HETEROGENEOUS EQUILIBRIUM


Example: Decomposition of solid NaHCO3 to produce solid Na2CO3, gaseous CO2 and H2O.
2NaHCO3s

Applying the law of mass action,


K=

Na 2CO3s CO 2 g H 2O g

Na 2CO3 CO2 [H 2O]

[NaHCO3 ]2
It involves two pure solids, Na2CO3 and NaHCO3. It is customary not to include the concentrations of pure
solids in equilibrium expressions.
K[NaHCO3 ]2
= CO2 [H 2O]

[Na 2 CO3 ]

Kc = CO 2 [H 2O]

In terms of partial pressures we have,


Kp = PCO2 PH2O
EXAMPLES OF HETEROGENEOUS EQUILIBRIUM
Decomposition of CaCO3: CaCO3s
Page 22 of 46

CaOs CO 2 g

Kc = [CO2]

or Kp = PCO2

Reaction of steam on heated iron: 3Fes 4H 2 O g


Kc =

Fe3O 4s 4H 2 g

[PH2 ]4
[H 2 ]4
or
K
=
p
[H 2O]4
[ PH2O ]4

Reaction of steam on heated carbon: Cs H 2 O g


Kc =

[CO][H 2 ]
[H 2O]

CO g H 2 g

or Kp =

Dissociation of ammonium carbamate: NH 2 COONH 4s

PCO PH 2
PH2O
2NH 3 g CO 2 g

Kc = [NH3]2 [CO2] or Kp = (PNH3 )2 (PCO2 )


Dissociation of ammonium hydrogen sulphide: NH 4 HSs

NH 3 g H 2S g

Kc = [NH3] [H2S] or Kp = PNH3 PH2s


ALTERNATE METHOD FOR THE CALCULATION OF KP:
Let us consider a gaseous reaction:
n1A g n 2 B g

n 3C g n 4 D g

where,
n g = n 3 +n 4 - (n1 +n 2 )
Equilibrium constant Kp may be calculated as,

n nC3 n nD4

P
T
Kp = n1
n2
nA nB n

n g

where,
P = Pressure at equilibrium.
n = Total no. of moles at equilibrium.

DEGREE OF DISSOCIATION ( )
Degree of dissociation =

No.of moles of substance dissociated at equilibrium


No.of moles of substance taken initially

Note:
The no. of moles dissociated is same as Degree of dissociation when then the no. of moles taken initially is unity,
else the no. of moles dissociated is the product of Degree of dissociation and the no. of moles taken initially.

Page 23 of 46

MEASUREMENT OF DEGREE OF DISSOCIATION


Case 1: From Vapor density measurements:
Let a moles of PCl5 be taken in closed vessel of volume V liters. Let be the degree of dissociation
of PCl5.
PCl5 ( g )
PCl3 ( g ) + Cl2 ( g )
Initial no. of moles
a
Total no. of moles initial = a
No. of moles at equilibrium (a-a )
a
a
Total no. of moles at equilibrium = a + a
Assuming that all the gases behave ideally, from the ideal gas equation we have,

V
2n
1
V.D
n
Vapor density initial
No.of moles at equilibrium
=
Vapor density at equilibrium
Initial no.of moles
V.D =

D a + a
=
d
a
D-d
=
d

where,
D Initial vapor density.
d- Equilibrium vapor density.

M-mavg
mavg

where,
M Initial molecular mass.
m avg - Average molecular mass.
Case 2: From Pressure Temperature measurements:
Let a moles of PCl5 be taken in closed vessel of volume V litres. Let be the degree of dissociation of
PCl5.
PCl5 ( g )
PCl3 ( g ) + Cl2 ( g )
Initial no. of moles
a
Total no. of moles initial = a
No. of moles at equilibrium (a-a )
a
a
Total no. of moles at equilibrium = a+a
Assuming that all the gases behave ideally, from the ideal gas equation we have,
P1V = aRT1
..(i)

P2 V = (a+a)RT2
Dividing eq. (ii) by eq. (i) we get,
=
Page 24 of 46

P2 T1 - P1T2
P1T2

..(ii)

where,
P1, P2, T1, T2 - Initial and equilibrium Pressures and Temperatures respectively.

SOLVED EXAMPLES
Example 9. Write down equilibrium constant expression for the following:
(i) 2PCl3 g O 2 g
2POCl3 g
(ii) 2SO3 (g)

2SO2 (g) + O2 (g)

(iii) H2O (g) + Cl2O (g)


(iv) 2NaNO2 (s) + O2 (g)
(v) CuSO4. 5H2O (s)
Solution:
[ POCl3 ]2
(i) Kc =
[PCl3 ]2 [ O 2 ]

2HOCl (g)
2NaNO3 (s)
CuSO4 (s) + 5H2O (g)

[ SO2 ]2 [ O2 ]
(ii) Kc =
[SO3 ]2
[HOCl]2
(iii) Kc =
H 2O Cl2O
(iv) Kc =

[ NaNO3 ]2
1
=
2
[ O2 ]
[ O2 ][NaNO2 ]

(v) Kc =

[ CuSO4 ] [ H 2O]5
= [ H 2O]5
CuSO4 . 5H 2O

Example 10. 0.5 moles of hydrogen and 0.5 mole of iodine react in a 10 liters evacuated vessel at 448C,
hydrogen iodide is formed. The equilibrium constant. K for the reaction is 50
(i) Calculate the number of moles of iodine which remain unreacted at equilibrium?
(ii) What is the value of Kp?
Solution:
(a)
H2
+
I2
2HI
Initial moles
0.5
0.5
0
No. of moles at equilibrium (0.5 x)
(0.5- x)
2x

4x 2
Kc =
= 50
0.5-x 0.5-x
2x
= 50 = 7.07
0.5-x
2x = 0.5 x 7.07 7.07 x

2x + 7.07 x = 0.5 x 7.07


0.5 7.07
= 0.39 mole
x=

9.07
No. of mole of I2 at equilibrium = (0.5 0.39)
= 0.11 mole
n g
K
=
K
RT

c
(b) p
Page 25 of 46

n g = 0,

Kp = Kc = 50

Example 11. 13.8 g of N2O4 (g) was placed in a 1L reaction vessel at 400 K and allowed to attain equilibrium:
N2O4 (g)
2NO2 (g)
The total pressure at equilibrium was found to be 9.15 bar. Calculate Kc, Kp and partial pressure at equilibrium.
Solution:
Mass
Number of moles of N2O4, n =
Molecular mass
13.8
=
= 0.15
92
PV = nRT
Px1 = 0.15 0.083 400
P = 4.98 bar
The reaction is: N2O4 (g)
2NO2 (g)
to
4.98
0
teq
(4.98 x)
2x
Total pressure = PN2O4 +PNO2
= 4.98 x + 2x = (4.98 + x)
9.15 = 4.98 + x

x = 4.17 bar

PNO2 = 2x = 2 4.17 = 8.34 bar

PN2O4 = 4.98 x = 4.98 4.17 = 0.81 bar

PNO2 2
Kp =
PN O
2 4
(8.34) 2
=
= 85.87 bar
0.81

Kp = Kc (RT)
Kc =

Kp
(RT)

n g

n g

85.87
2.586 = 2.6 M
(0.083 400)1

Example 12. 3 g moles of phosphorus pentachloride is heated in a flask of 4 liters volume. At equilibrium, it
dissociates to give 40% of phosphorus trichloride and chlorine. Calculate the equilibrium constant.
Solution:
Degree of dissociation = 0.4
Given, a =3, x= 0.4 and V =4
PCl5
PCl3 +
Cl2
At equilibrium
a(1- x )
ax
ax
At equilibrium,
3(1 0.4) 3 0.6
[PCl5] =
=
mol L-1
4
4
Page 26 of 46

3 0.4
mol L-1
4
3 0.4
[Cl2] =
mol L-1
4
Applying law of mass action, we get,
PCl3 [ Cl2 ]
Kc =
[PCl5 ]
30.430.4
=
= 0.2 mollitre-1
430.6
[PCl3] =

Example 13. N2O4 is 25% dissociated at 37C and one atmospheric pressure. Calculate: (i) Kp (ii) The
percentage dissociation at 0.1 atmosphere and 37C.
Solution:
N2O4
2NO2
Initial
1
0
At equilibrium
(1- x )
2x
Total moles = (1- x ) + 2 x = (1+ x )
2
1-x
PN2O4 =
P
P , PNO2 =
1+x
1+x

Given, x = 0.25 and P =1 atm.


1-0.25
PN2O4 =
1= 0.6 atm.
1+0.25
2 0.25
1= 0.4 atm
PNO2 =
1+0.25

PNO2 2 0.4 0.4


= 0.267 atm
Kp =
=
PN O
0.6
2 4
Let the degree of dissociation of N2O4 at 0.1 atm be , then
2
1-
0.1
PN2O4 =
0.1 and PNO2 =
1+
1+
2
2

(0.1)
1+
Kp =

1-

0.1
1+
4 2 0.1
0.4 2
=
=
1- ( 1+ ) (1-)2

Page 27 of 46

0.4 2
(1-) 2
0.267 = 0.667 2
= 0.632

0.267 =

Hence, dissociation of N2O4 = 63.2%


Example 14. 1.0 moles of nitrogen and 3.0 moles of PCl5 are placed in 100 liters vessel heated to 227C. The
equilibrium pressure is 2.05 atm. Assuming ideal behavior, calculate the degree of dissociation for PCl5 and Kp
for the reaction, PCl5
PCl3 + Cl2.
Solution:
PCl5
PCl3 + Cl2
Initial
3
0
0
At equilibrium
3(1-x)
3x
3x
(x= degree of dissociation)
Total moles at equilibrium = 3(1-x) + 3x + 3x = 3 (1-x)
Since 1 mole of nitrogen is present, hence, actual total number of moles are equilibrium = 3(1+x) + 1
According to gas equation: PV = nRT
Given, P = 2.05 atm, V= 100 liters, R= 0.082 and T = (273 + 227) = 500K.
2.05100
5
n =
0.082 500
3(1-x) +1 =5
3x =1 or x = 0.333
3(1+x) + 1 =3 +3 x 0.333 +1 = 4 + 0.999

At equilibrium,
3(1-x)
2.05
PPCl5 =
(3x+4)
3x
2.05
PPCl3 =PCl2 =
3x+4

3x
3x
2.05
2.05
3x+4
3x+4

Kp =
3(1-x)
2.05
(3x+4)
3 (0.333) 2 2.05
9x 2 2.05
=
= 0.204 atm.
Kp =
3 3x+4 ( 1-x)
4+0.999 (0.667)
Example 15. For a gas phase reaction, 3H2 + N2
2NH3. The partial pressures of H2 and N2 are 0.4 and 0.8
atmosphere, respectively. The total pressure of the entire system is 2.8 atmosphere. What will be the value of Kp
if all the concentrations are given in atmosphere?
Solution:
N2 + 3H2
2NH3
Partial pressures at equilibrium
0.8
0.4
1.6
Applying law of mass action,
(PNH )2
1.6 1.6
3
Kp =
=
3
0.8 0.4 0.4 0.4
PN 2 ( PH 2 )

= 50 atm-2
Page 28 of 46

Example 16. One mole of nitrogen and three moles of hydrogen are mixed in a 4 liters container. If 0.25 per
cent of nitrogen is converted to ammonia by the following reaction: N2 + 3H2
2NH3
Calculate the equilibrium constant (Kc) in concentration units. What will be the value of K for the following
1
3
equilibrium: N 2 H 2
NH3 ?
2
2
Solution:
N2
+
3H2
2NH3
No. of moles at equilibrium
(1-x)
(3 3x)
2x
(3 0.0075)
(1 0.0025)
(0.0050)
Molar Concentration
( x = 0.0025)
4
4
4
Applying law of mass action,
2
0.0050

[NH3 ]2
4
Kc =
=
= 1.49 10-5 lit2 mol-2
3
3
N 2 [H 2 ] 0.9975 2.9925

4 4
1
3
NH3 is equal to K c
K for the reaction, N 2 H 2
2
2
K =

K c = 1.49 10-5 = 3.86 10-3 lit mol-1

Example 17. In an experiment, one mole of acetic acid and one mole of alcohol were allowed to react until
equilibrium was established. The equilibrium mixture was found to contain 2/3 mole of ester. Calculate the
equilibrium constant of the reaction.
Solution:
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
Initial no. of moles
1
1
0
0
2
2
2
2

No. of moles at equilibrium


1
1
3
3
3
3
1
2
1
2
Molar conc. at equilibrium
3V
3V
3V
3V
Applying law of mass action, we get

2
2

[ester] [ water] 3V
3V = 4
Kc =
=
acid [alcohol] 1 1
3V 3V
Example 18. In an experiment, starting with 1 mole of ethyl alcohol, 1 mole of acetic acid and 1 mole of water
at 100 , the equilibrium mixture on analysis shows that 54.3% of the acid is esterified. Calculate the
equilibrium constant of this reaction.
Solution:
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
Initial no. of moles
1
1
0
1
No. of moles at equilibrium
1- x
1- x
x
1+ x
0.543
1+0.543
No. of moles at equilibrium 1 0.543 1- 0.543
Given, x = 0.543

Page 29 of 46

Applying law of mass action, we get


Kc =

ester water
acid alcohol

0.5431.543
4.0
0.457 0.457

Example 19. The equilibrium constant for the reaction: CH3COOH + C2H5OH
CH3COOC2H5 + H2O
is 4. What will be the composition of the equilibrium mixture when one mole of acetic acid is taken along with
4 moles of ethyl alcohol?
Solution:
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
Initial no. of moles
1
4
0
0
No. of moles at
1x
4-x
x
x
Equilibrium
ester water

x2
Kc =
=
=4
acid alcohol 1-x 4-x
x 2 = 4 1-x 4-x
x = 0.93 or 5.7366

The value 5.7366 is not possible, hence x = 0.93.


Thus, the composition of mixture at equilibrium is:
[CH3COOH] = (1-0.93) = 0.07 mole
[C2H5OH] = (4 0.93) = 3.07 mole
[CH3COOC2H5] = 0.93 mole
[H2O] = 0.93 mole
Example 20. At a certain temperature, equilibrium constant (Kc) is 16 for the reaction:
SO2 (g) + NO2 (g)
SO3 (g) + NO (g)
If we take one mole of each of the four gases in a one litre container, what would be the equilibrium
concentration of NO and NO2?
Solution:
SO2 (g) + NO2 (g)
SO3 (g) + NO (g)
Initial concentration
1
1
1
1
Equilibrium concentration 1- x 1-x
1+ x
1+x
Applying law of mass action,
Kc =

SO3 NO = 1+x 1+x =16


SO2 NO2 1-x 1-x

1+x
=4
1-x
3
x = = 0.6
5
Conc. of NO2 at equilibrium = (1- 0.6) = 0.4 mole
Conc. of NO at equilibrium = (1+ 0.6) = 1.6 mole

Page 30 of 46

Example 21. What is the per cent decomposition of H2S if 1.0 mole of H2S is introduced into a 1.1 liter vessel
at 1000 K? Kc for the reaction: 2H2S (g)
2H2 (g) + S2 (g) is 1 10-6
Solution:
2H2S (g)
2H2 (g) + S (g)
Initial no. of moles
1
0
0
No. of moles at equilibrium
(1-x)
x
x/2
where x is the no. of moles of H2S dissociated = degree of dissociation of H2S.
At equilibrium,
x
1- x
x
[H2S] =
, [H2] =
and [S2] =
1.1
21.1
1.1

Applying law of mass action, we get


2
x
x

[H 2 ] [ S2 ] 1.1 2.2
Kc =
=
2
[H 2S]2
1-x

1.1
x3
1.0 10-6 =
2.2 ( 1-x) 2
As x is very small, (1- x ) 1
x3
Kc =
2.2
x = 1.3 x 10-2
% decomposition of H2S = 13%
Example 22. A mixture of SO3, SO2 and O2 gases is maintained in a10 litre flask at a temperature at which the
equilibrium constant for the reaction is 100: 2SO2 (g) + O2 (g)
2SO3 (g)
(i) If the number of moles of SO2 and SO3 in the flask are equal, how many moles of O2 are present?
(ii) If the number of moles of SO3 in the flask is twice the number of moles of SO2, how many of oxygen
are present?
Solution:
(i) At equilibrium, let the number of moles of each of SO2 and SO3 for the below equilibrium be n1 and of
oxygen n2,
2SO2 (g) + O2 (g)
2SO3 (g)
n2
n1
n1
[SO2] =
, [O2]=
, [SO3] =
10
10
10
Applying law of mass action, we get
2
n1

[SO3 ]2
10
=100
Kc =
=
2
[SO2 ] [O2 ] n1 2 n 2

10 10
n2 = 0.1 mole
i.e The no. of moles of Oxygen at equilibrium = 0.1 mole
Page 31 of 46

(ii) Let the number of moles of SO2 and O2 be n1 and n2 respectively


Number of moles of SO3 = 2n1
2

2n1

10

Kc =
2
n1 n 2

10 10
n2= 0.4 mole

i.e The no. of moles of Oxygen at equilibrium = 0.4 mole


Example 23. Ammonium hydrogen sulphide dissociates according to the equation:
NH4HS (s)
NH3 (g) + H2S (g)
If the observed pressure at equilibrium is 1.12 atm. At 380 K. what is the equilibrium constant, Kp, of the reaction.
Solution:
NH4HS (s)
NH3 (g) + H2S (g)
1
PNH3 = PH2S = 1.12 = 0.56 atm
2
K p = PNH3 PH2S = 0.56 0.56 = 0.3136 atm 2
Example 24. A sample of CaCO3 (s) is introduced into a sealed container of volume 0.654 liters and heated to
1000K until equilibrium is reached.
The equilibrium constant for the reaction: CaCO3 (s)
CaO (s) + CO2 (g) is 3.9 10-2 atm at this temperature.
Calculate the mass of CaO present at equilibrium.
Solution:
CaCO3 (s)
CaO (s) + CO2 (g), K p = PCO2
Let the number of moles of CO2 be formed = n
PCO2 V 3.9 10-2 0.654
n=
=
RT
0.0821000
-4
n = 3.11 10 mol
The amount of CaO (s) formed will also 3.11 10-4 mol
Mass of CaO formed = 3.11 10-4 56
= 0.0174 g

PROBLEMS FOR PRACTICE


9. What will be the units of Kp for the following reactions?
(i) N2 (g) + 3H2 (g)
2NH3 (g)
10.
11.

(ii) N2 (g) + O2 (g)


2NO (g)
- Ans. (i) atm-2 (ii) unit less
2 mole PCl5 were introduced in a 2L flask and heated at 625 K to establish equilibrium when 60% of
PCl5 was dissociated into PCl3 and Cl2. Find the value of equilibrium constant.
Ans. 0.9
50 g CaCO3 are heated to 1073K in a 5 L vessel. What percentage of CaCO3 would decompose at
equilibrium? The value of Kp for the reaction: CaCO3 (s)
CaO (s) + CO2 (g) is 1.15atm at 1073 K.
- Ans. 13 %

Page 32 of 46

12.
13.

14.
15.

Calculate the degree of dissociation of HI at 450C if the equilibrium constant for the dissociation of HI:
2HI (g)
H2 (g) + I2 (g) is 0.263.
- Ans. 0.51
When PCl5 is heated in a closed container at 575 K, the total pressure at equilibrium is found to be 1 atm
and partial pressure of Cl2 is found to be 0.324 atm. Calculate the equilibrium constant (Kp) for the
decomposition reaction.
- Ans. 0.298
Under what pressure, must an equimolar mixture of PCl3 and Cl2 be placed at 250C in order to obtain
PCl5 at 1 atm? Given Kp for dissociation of PCl5 is 1.78atm.
- Ans. 4.66 atm
The equilibrium constant of the reaction: H2 (g) + I2 (g)
2HI (g) is 64 at 717 K. Starting from 6 moles
of H2 and 3 moles of I2 in a one liter vessel at this temperature, calculate the equilibrium concentration
of each of components.
- Ans. [H2] = 3.16 M, [I2] = 0.16 M, [HI] = 5.68 M

EXTENT OF REACTION AND EQUILIBRIUM CONSTANT


The magnitude of the equilibrium constant K, indicates the relative amount of the products and the reactants
of a reaction present at equilibrium.
i.e. Large magnitude of K indicates that larger amounts of products are formed by the time equilibrium is
established and smaller value of K indicates that at equilibrium lesser amount of products are present.
Case 1: If Kc > 103 then products are dominant, i.e., greater the value of K, nearer is the reaction to completion.
H2 (g) + Cl2 (g)

2HCl (g)

; Kc = 4 1031 at 300K

H2 (g) + Br2 (g)


1
H2 (g) + O 2 (g)
2

2HBr (g)

; Kc = 5.4 1018 at 300K

H2O (g)

; Kc = 2.47 1047 at 500 K

Case 2: If Kc < 10-3, then reactants are dominant in the reaction mixture. i.e., when Kc is very small in
magnitude, the reaction rarely proceeds for completion.
N2 (g) + O2 (g)
H2O (g)

2NO (g)
1
H2 (g) + O 2 (g)
2

; Kc = 4.8 10-31 at 298 K


; Kc = 4.1 10-48 at 500K

Case 3: If the value of Kc lies in the range of 10-3 to 103 then appreciable amount of reactants and products
are present.
H2 (g) + I2 (g)
N2O4 (g)

2HI (g)
2NO2 (g)

; Kc= 57 at 700 K
; Kc = 4.64 10-3 at 298 K

MASS ACTION RATIO (REACTION QUOTIENT)


Mass action ratio or Reaction Quotient is used to predict the direction of the reaction.
Let us consider a reversible process.
A+B
C+D
C[D]
Reaction Quotient,
Q=
A [B]

Page 33 of 46

Reaction Quotient is defined as the ratio of product of concentration of products to the product of
concentration of reactants where each concentration term being raised to its stoichiometric co-efficient and
where the concentration refers to the concentration at any point of time.
Note:
Reaction quotient Q unlike equilibrium constant for a reaction is a variable quantity and at t = 0, Q = 0.
Q = Qc when concentration is taken in terms of moles/liter.
Q = Qp when partial pressure is taken in place of concentration.
Case 1: When Q (Reaction quotient) = K (equilibrium constant), then reaction is at equilibrium and the
reaction neither moves in the forward direction nor in the backward direction.
Case 2: When Q < K , then again the reaction is not at equilibrium and the reaction moves in the forward
direction.
Case 3: When Q > K , then reaction is not at equilibrium and the reaction moves in the backward direction.

SOLVED EXAMPLES
Example 25. Here are some reactions and their equilibrium constant.
2CH4 (g)
C2H6 (g) + H2 (g)
; Kc = 9.5 10-13
CH3OH (g) + H2 (g)

CH4 (g) + H2O (g)

; Kc = 3.6 1020

H2 (g) + Br2 (g)


2HBr (g)
; Kc = 2 109
Arrange these reactions in order of their increasing tendency to go towards completion.
Solution:
Greater is the value of equilibrium constant, nearer is the reaction to completion. Thus, the increasing tendency
of reactions to go towards completion will be: (a) < (c) < (b)
Example 26. Which of the following reactions tends to proceed farthest from completion?
H2 (g) + Br2 (g)
2HBr (g)
; Kc= 1.4 10-21
2NO (g)

N2 (g) + O2 (g)

; Kc = 2.1 1030

2BrCl (g)
Br2 (g) + Cl2 (g)
; Kc = 0.145
Solution:
The reaction: H2 (g) + Br2 (g)
2HBr (g), Kc = 1.4 10-21, has lowest value of equilibrium constant hence it
will be farthest from completion.
Example 27. At a certain temperature, Kc = 0.18 for the equilibrium.
PCl3 (g) + Cl2 (g)
PCl5 (g)
At a certain instant: [PCl3] = 0.042 M, [Cl2] = 0.024 M, [PCl5] = 0.005 M
(i) Is the system in a state of equilibrium?
(ii) If not, in which direction the reaction will proceed to come to equilibrium?
Solution:
PCl5 = 0.005 = 4.96
Qc =
PCl3 Cl2 0.042 0.024
Qc = K c
Page 34 of 46

Thus, the reaction is not at equilibrium and it will proceed in backward direction to attain equilibrium.
Example 28. At 460C, the reaction: SO2 (g) + NO2 (g)
NO (g) + SO3 (g) has Kc = 85.A reaction flask at
460C contains these gases at the following concentrations:
[SO2] = 0.0025 M, [NO2] = 0.0035 M, [NO] = 0.025 M, [SO3] = 0.04 M. Find out whether the reaction is at
equilibrium? If not, in which direction will a spontaneous change occur to go to equilibrium?
Solution:
NO[SO3 ] = 0.025 0.04 = 114.28
Qc =
SO2 [ NO2 ] 0.0025 0.0035

Qc > K c , the reaction is not at equilibrium, the reaction will proceed spontaneously in backward direction to
go to equilibrium.
Example 29. At 448C, the equilibrium constant ( K c ) for the reaction: H2 (g) + I2 (g)
2HI (g) is 50.5.
Predict the direction in which the reaction will proceed to reach equilibrium at 448C, if we start with
2.0 10-2 mol of HI, 1.0 10-2 mol of H2 and 3.0 10-2 mol of I2 in a 2.0 L container?
Solution:
The initial concentrations are:
2.0 10-2
[HI] =
=1.0 10-2 mol L-1
2
1.0 10-2
[H2] =
=0.510-2 mol L-1
2
3.0 10-2
[I2] =
=1.5 10-2 molL-1
2
(1.010 -2 ) 2
[HI]2
Reaction quotient, Qc =
=
= 1.33
H 2 [I2 ] 0.510-2 (1.510 -2 )

Qc = K c , the reaction will proceed in the forward direction in order to attain equilibrium, so that Qc becomes
equal to K c .
Example 30. The equilibrium constant at 278K for: Cu (s) + 2Ag+ (aq)
Cu2+(aq) + 2Ag (s) is 2.0 1015.
In a solution in which copper has displaced some silver ions from the solution, the concentration of Cu2+ ion is
1.8 10-2 molL-1 and the concentration of Ag+ ions is 3.0 10-9 molL-1. Is the system at equilibrium?
Solution:
For the reaction, Cu (s) + 2Ag+ (aq)
Cu2+ (aq) + 2Ag (s)
[Cu 2+ (aq) ]
1.8 102
The concentration ratio, Qc =
=
= 2 1015
[Ag + aq ]2 ( 3.0 109 ) 2

Qc = K c , the system is at equilibrium.

EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT


Vant Hoff gave following relation between the equilibrium constant and heat of reaction.
d(lnK) H
=
dT
RT 2
On integration within proper limits, we get,
H
log10 K = log10 A..(i)
2.303 RT
Page 35 of 46

where,
H -Heat of reaction at constant pressure.
A is a constant which is the ratio of the no. of collisions of the forward reaction to that of the backward
A
reaction i.e. A= f
Ab
1
Eq. (i) is an equation of the type, y = mx + c and hence a plot of log10 K vs gives a straight line with slope
T
H
and y-intercept log10 A .
2.303 R

Writing eq. (i) for two different temperatures T1, T2 and assuming that both A and H remains constant in
the temperature range, we get,
KT
H 1 1
log10 2 =
K T 2.303 R T1 T2
1
where,
K T1 and K T2 are the equilibrium constants of a reaction at temperature T1 and T2 (T2 > T1).
The effect of temperature can be studied in the following three cases:
Case 1: H = 0, i.e., neither heat is evolved, nor absorbed.

logK T2 log K T1 0

logK T2 log K T1

K T2 K T1

Case 2: H > 0, i.e., heat is absorbed, i.e., endothermic reaction.

logK T2 log K T1 ve

K T2 > K T1
The value of equilibrium constant is higher at higher temperature in the case of endothermic reactions.
Case 3: H < 0, i.e., heat is evolved, i.e., exothermic reaction.

logK T2 log K T1 ve

K T2 < K T1
The value of equilibrium constant is lower at higher temperature in the case of exothermic reactions.

Page 36 of 46

THERMODYNAMICS OF EQUILIBRIUM
According to thermodynamics,

G = G 0 + RT lnQ
.(i)

G = G 0 + 2.303RT log10Q
where,
G - Gibbs free energy change, a measure of the amount of useful work that could be derived from a system.
Q - Reaction quotient.
At equilibrium, G = 0 and Q = K

.(ii)

G 0 = -2.303RT log10 K

Note:
If G 0 = -ve, K > 1 , forward reaction is thermodynamically feasible.
If G 0 = +ve, K < 1 , backward reaction is thermodynamically feasible.
G 0 can also be given by,
G 0 = H 0 - TS0

(iii)

From eq. (ii) and (iii)


H 0 -TS0 = -2.303RT log10 K

log10 K= -

H 0
S0
+
2.303RT 2.303R

SOLVED EXAMPLES
1
3
N2 (g) + H2 (g)
NH3 (g) is -16.5 kJ mol-1. Find out Kp for the reaction at 25C.
2
2
0
Also report Kp and G for N2 (g) + 3H2 (g)
2NH3 (g) at 25 C.
Solution:

G
16.5 10 3
log Kp = =
2.8917
2.303 RT 2.3038.314 298
Kp = 779.41
Kp for reaction N2 (g) + 3H2 (g)
2NH3 (g) is equal to (7.79.41 ) 2 = 6.07 105
G 0 = - 2.303 8.314 298 log 6.07 105
= -32.998 kJmol-1
Example 31. G 0 for

Example 32. The value of Kp for this reaction is 1.7 1012 at 25C. What is G 0 for the reaction at this
temperature, expressed in kJmol-1?
Solution:
G 0 = -2.303 RT logK
Given: R = 8.314 JK-1 mol-1, T = 298K, K = 1.7 1012
Putting these values in Eqn.(i), we get,
G 0 = -2.303 8.314 298 log 1.7 1012
= -69785 J mol-1= -69.785 kJmol-1
Page 37 of 46

Example 33. In the reaction: 2N2O (g)


2N2 (g) + O2 (g), H 0 = -163kJ mol-1, S0 = +148 JK-1mol-1.
What is the value of equilibrium constant at 25C?
Solution:
G 0 = H 0 - T S0
. . . (i)
0
0
3
-1
-1
-1
Given, H = -163 10 J mol , S = +148 JK mol , T= 298 K
From Eqn. (i),
G 0 = (-163 103) (298 148)
= -207104 J mol-1
Equilibrium constant can be calculated as:
- G
K = antilog

2.303 RT
207104

= antilog

2.303 8.314 298


= antilog (+36.29)
= 1.94 1036

PROBLEMS FOR PRACTICE


17.

The equilibrium constant K p for reaction is 3 at 673 K and 4 at 773 K. Calculate the value of H 0 for the reaction.
Ans. 12.45 kJ

18.

The standard free energy change for the reaction: 2H2O (l)
value of equilibrium constant K for the reaction at 298 K.

19.

Calculate the value of equilibrium constant Kc for the reaction, 2NOCl (g)
The standard Gibbs free energy change for the reaction is 28.4 kJ mol-1

20.

Methanol, a potential replacement of petrol is made by following reaction: CO (g) + 2H2 (g)
At 25oC, this reaction has Kp =6.25 10-3. Calculate Go for this reaction.

2H2 (g) + O2 (g) is 474.4 kJ mol-1. Calculate the


Ans.7.2 10-84
2NO (g) + Cl2 (g) at 400 K.
Ans. 1.96 10-4
CH3OH (g)
Ans. 12.576 kJ mol-1

Le CHATELIERS PRINCIPLE
There are three main factors which can change the state of equilibrium in a reversible system, these are:
concentration, pressure and temperature.
According to Le Chateliers principle, If a system at equilibrium is subjected to a change of concentration,
pressure or temperature, the equilibrium shifts in the direction that tends to undo the effect of the change.
EFFECT OF CONCENTRATION
If an additional amount of a reactant or product is added to the system, the stress is relieved as the reaction that
consumes the added substance occurs more rapidly than its reverse reaction.
In general, in a chemical equilibrium, increasing the concentration of the reactants results in shifting the
equilibrium in favor of products while increasing concentrations of the products results in shifting the equilibrium
in favor of reactants.
The effect of change in concentration can be explained on the basic of following experiment involving the
reaction:
2
Fe3
SCN
FeSCN
Pale yellow aq

Page 38 of 46

Colorless aq

Reddish brown

aq

To the above equilibrium, when some quantity of potassium sulphocyanide is added, the color of the solution
darkens immediately showing that the concentration of [FeSCN]2+ ions has increased, i.e., the equilibrium shifts
towards right hand side.
Similarly, by adding ferric chloride, the colour of the solution deepens due to the formation of more of
[FeSCN]2+ ions. Thus, on an increase in concentration of either SCN- ions or Fe3+ ions (i.e., reactants), the
extend of forward reaction increases as to relieve the system from the effect of the increase in concentration of
SCN- or Fe3+ ions. This is in accordance with Le Chateliers principle.
Again, if to the solution a small amount of potassium ferro-sulphocyanide is added, the darkness of the solution
decreases, i.e., by increasing concentration of [FeCNS]2+ ions, the reaction moves towards left-hand side in
order to decrease the concentration of added [FeCNS]2+ ions. Thus, the equilibrium shifts towards the reactant
side.

Note:
In case of systems involving gaseous substances, the concentrations can also be taken as partial pressures of
the substances.
The effect of change in concentration on equilibrium can be illustrated with some examples from everyday life.
Faster drying of clothes when there is a breeze or when we keep on shaking it:
On shaking the cloth or when there is a breeze, the water vapors of the nearby air are removed. In order to reestablish the equilibrium, the wet cloth loses more water in the vapor state to saturate the surrounding air and
hence gets dried.
Sweating is more on a humid day but a fan provides relief:
When the surrounding air has large amount of water vapor, water from the skin does not evaporate quickly, i.e.,
sweating occurs. However, a fan helps by removing water vapor from the area near the skin and, thus
evaporation starts from the skin in order to re-establish equilibrium.
Transport of oxygen by hemoglobin in blood:
The inhaled oxygen combines with hemoglobin in the lungs according to the following reaction:
Hb s O 2 g
HbO 2s
In the tissues, the partial pressure of oxygen is low and when the Oxyhemoglobin reaches the tissues, the
equilibrium shifts towards left so that some of the Oxyhemoglobin breaks us with the release of oxygen. The
same blood when returns to the lungs, on account of high partial pressure of oxygen there, the equilibrium favor
the formation of Oxyhemoglobin. In this way, oxygen is supplied to every part of the body with the help of
blood (i.e., hemoglobin).
Removal of carbon dioxide from the tissues by blood:
The equilibrium is: CO2 (g) + H2O (l)
H2CO3 (aq)
H+ (aq) + HCO3- (aq)
Carbon dioxide dissolves in blood on account of high partial pressure of carbon dioxide in tissues.
The same blood, when comes to lungs, releases the dissolved carbon dioxide as the partial pressure of carbon
dioxide is low here.
Sweet substances cause tooth decay:
An enamel of insoluble substance called hydroxyapatite, Ca5(PO4)3(OH), is present in the form of a thin coating
Page 39 of 46

on our teeth. It exists in equilibrium with its ions in the mouth.


Demineralisation
Ca 5 PO 4 3 OH Remineralisation 5Ca 2 3PO 43 OH
The forward reaction (dissolution) is termed demineralization and the backward reaction (formation) is called
remineralization. When sugar substances are taken, these are absorbed on teeth and if not removed these get
fermented producing H+ ions. The H+ ions disturb the above equilibrium by combining with OH- ions to form
water and with PO34 ions to form HPO 24 ions. Thus, the sweet substances shift the above equilibrium to the
right-hand side, thereby causing tooth decay.
EFFECT OF PRESSURE
If a system in equilibrium consists of gases, then the concentrations of all the components can be altered by
changing the pressure.
When the pressure on the system is increased, the volume decreases proportionately and the total number of
moles per unit volume will now be more than before.
According to Le Chateliers principle, the equilibrium will shift in the direction in which there is decrease in
number of moles, i.e., towards the direction in which there is decrease in volume.
Case 1: In case of reactions where n g < 0, high pressure favors the shift of equilibrium towards products.

N 2 g +3H 2 g

2NH3 g

4moles

2moles

2SO2 g +O2 g

2SO3 g

3 moles

2moles

Case 2: In case of reactions where n g > 0, high pressure favors the shift of equilibrium towards reactants.

PCl5 g

PCl3 g +Cl2 g

1mole

2moles

N 2O4 g
1mole

2NO 2
2 moles

Case 3: In case of reactions where n g = 0, there will be no effect of pressure on the equilibrium.

H 2 g +I 2 g

2HI g

2moles

2moles

N 2 g +O2 g

2NO g

2moles

2moles

EFFECT OF TEMPERATURE
If in a reversible reaction, if the forward reaction is exothermic, the backward reaction will always be
endothermic and vice versa.
When heat energy is supplied, the system can relieve itself from the stress if the reaction which absorbs heat
moves faster, i.e., endothermic reaction is always favored with increase of temperature.
Note:
In the case of reversible reactions, the heat change ( H ) indicated in the equation is always for the forward
reaction.

Page 40 of 46

Case 1: In the case of endothermic reactions (H > 0) high temperature is favorable as K T2 > K T1 .
N 2 g O 2 g
PCl5 g

2NO g
PCl3 g +Cl2 g

; H = + 180 kJ
; H = + 63 kJ

Case 2: In the case of exothermic reactions (H < 0) high temperature is favorable as K T2 < K T1 .
2SO 2 g O 2 g

2SO3 g

; H = -189 kJ

EFFECT OF ADDITION OF AN INERT GAS ON EQUILIBRIUM


The effect of addition of an inert gas (i.e., a gas which does not react with any of the substances involved in the
reversible reaction) on equilibrium can be discussed under different conditions as described below:
Case 1: Addition of an Inert Gas at Constant Volume:
Let us consider a gaseous reaction:
n1A g n 2 B g

n 3C g n 4 D g

n nC3 n nD4 PT ng

Kp= n1

n A n Bn 2 n
where,
n g = n 3 +n 4 - (n1 +n 2 )
When no moles of an inert gas is added to the equilibrium system at constant volume, then the total no. of
moles increases ( n ) and as a result the total pressure ( PT ) of the system will increase.

PT n
PT
=constant

n
The concentrations of the reactants and product (i.e., the active masses) are not affected. Hence, under these
conditions, there will be no effect on the equilibrium.
Case 2: Addition of an Inert Gas at Constant Pressure:
When an inert gas is added to the equilibrium system at constant pressure, the volume increases. On account of
this, the number of moles per unit volume (i.e., active masses) of various reactants and products will decrease.
In order to overcome this stress, the equilibrium will shift to the direction in which there is increase in the
number of moles of gases.
For the equilibrium,
2SO3 (g)
2SO2 (g) + O2 (g)
The addition of an inert gas at constant pressure will shift the equilibrium in the forward direction.
The addition of inert gas is favorable for any reaction where n g > 0.
For the equilibrium,
N2 (g) + 3H2 (g)
2NH3 (g)
The addition of an inert gas at constant pressure will shift the equilibrium to the backward direction.
The addition of inert gas is unfavorable for any reaction where n g < 0.
Page 41 of 46

For the equilibrium,


H2 (g) + I2 (g)
2HI (g)
The addition of an inert gas at constant pressure will have no effect on the equilibrium as the number of moles
of reactants and products are same.
The addition of inert gas has no effect on equilibrium for any reaction where n g = 0.
EFFECT OF ADDITION OF AN INERT GAS ON EQUILIBRIUM
CONDITION
Constant Volume
n g = 0, +ve or ve
Constant Pressure
n g = 0

EFFECT ON EQUILIBRIUM
No effect
No effect

Constant Pressure

n g > 0

Forward shift

Constant Pressure

n g < 0

Backward shift

EFFECT OF A CATALYST ON EQUILIBRIUM


For reversible reactions, the catalyst not only increases the rate of forward reaction but also the rate of backward
reaction to the same extend and hence cannot change the equilibrium position or equilibrium constant of a
reaction.
The presence of a catalyst however helps to reduce the time taken for the equilibrium to be established and also
helps to carry out the reaction at a low temperature.
APPLICATIONS OF Le CHATELIERS PRINCIPLE
PHYSICAL EQUILIBRIA
Case 1: Ice-Water System (Melting of Ice):
Heat

Water
The change can be represented as: Ice
In this change, heat is absorbed (endothermic) and there is decrease in volume.
According to Le Chateliers Principle, the favorable conditions for the melting of ice are:
High pressure
High temperature.
Case 2: Water-water vapor system (Vaporisation of water):
Heat

The change can be represented as: Water


Water vapour
This change is endothermic (heat is absorbed) and there is increase in volume.
According to Le Chateliers Principle, favorable conditions for the conversion of water into water vapor are:
High temperature
Low pressure.
Case 3: Solubility of substances:
When solid substances are dissolved in water, either heat is evolved (exothermic) or heat is absorbed (endothermic).
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Consider the dissolution of KCl, when this is dissolved, heat is absorbed.


Heat
KCl aq
KCl aq
(Endothermic)
In such cases, solubility increases with increase in temperature.
Consider the cases of KOH, when this is dissolved, heat is evolved.
KOH + aq
KOH (aq)
(Exothermic)
In such cases, solubility decreases with increase in temperature.
Case 4: Solubility of gases in liquids:
When a gas dissolves in liquid, there is decrease in volume. Thus, increase of pressure will favor the dissolution
of gas in liquid.
CHEMICAL EQUILIBRIA
Case 1: Formation of HI: H 2 g I 2 g

2HI g 3000 cal

Effect of concentration: When concentration of H2 or I2 is increased at equilibrium, the system moves in a


direction which decreases the concentration, i. e., the rate of forward reaction increases thereby increasing the
concentration of HI.
Effect of pressure: As there is no change in the number of moles in the reaction, the equilibrium state remains
unaffected by change of pressure.
Effect of temperature: By increasing temperature, the equilibrium state shifts towards the reaction which
moves with absorption of heat. The formation of HI is an exothermic reaction. Thus, the backward reaction
moves faster when temperature is increased.
Case 2: Formation on nitric oxide: N 2 g O 2 g

2NO g 43200 cal

Effect of concentration: When concentration of N2 or O2 is increased, the system moves in a direction in which
N2 or O2 is used up, i.e., rate of forward reaction increases thereby increasing the concentration of NO.
Effect of pressure: In the formation of nitric oxide, the number of moles remains the same, i. e., no change in
volume occurs. Consequently, the equilibrium state is not affected by any change in pressure.
Effect of temperature: The formation of NO is endothermic in nature. If the temperature is raised, the
equilibrium shifts in the direction in which heat is absorbed. The concentration of NO will, therefore, be higher
at higher at higher temperature.
Case 3: Dissociation of PCl5: PCl5 (g)

PCl3 (g) + Cl2 (g) 15000 cal

Effect of concentration: When concentration of PCl5 is increased at equilibrium, the rate of forward reaction
increases as to decrease the added concentration. Thus, more of PCl3 and Cl2 are formed.
Effect of pressure: The volume increase in the dissociation of PCl5. When pressure is increased, the system
moves in the direction in which there is decrease in volume. Thus, high pressure does not favor dissociation of
PCl5.
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Effect of temperature: The dissociation of PCl5 is an endothermic reaction. Thus, increase of temperature
favors the dissociation.
Case 4: Synthesis of ammonia: N2 (g) + 3H2 (g)

2NH3 (g) + 22400 cal

Effect of concentration: When concentration of N2 or H2 is increased, the rate of forward reaction increases as
to consume the added substance. Thus, formation of ammonia increases.
Effect of pressure: During the formation of NH3, a decrease in volume occurs. When pressure is increased, the
system moves in direction in which there is decrease in volume. Thus, high pressure helps in the formation of
NH3.
Effect of temperature: The formation of NH3 is an exothermic reaction. Thus, low temperature will favor the
formation of NH3.

SOLVED EXAMPLES
Example 34. Consider the reaction, 2SO2 (g) + O2 (g)
2SO3 (g) + 189.4 kJ. Indicate the direction in which
the equilibrium will shift when:
(i) Temperature is decreased
(ii) Volume is decreased
(iii) A catalyst is added
(iv) Pressure is increased
(v) Concentration of O2 is increased
(vi) Argon gas is added at constant volume
(vii) Argon gas is added at constant pressure.
Solution:
(i) The reaction is exothermic in nature. The equilibrium will shift to the forward direction.
(ii) The equilibrium will shift to right. On decreasing volume, the number of moles per unit volume increase.
The stress will be relieved if the reaction moves in the direction where lesser number of molecules are formed.
(iii) Equilibrium is not affected but it is achieved quickly.
(iv) The equilibrium will shift towards right, i.e., towards the side where there is decrease in volume.
(v) The equilibrium will shift to the forward direction as the added oxygen is used up.
(vi) There is no effect on the equilibrium as the active masses of the reactants and products remain the same.
(vii)The addition of argon increases the volume, hence the equilibrium will shift towards
left where more molecules are produced.

PROBLEMS FOR PRACTICE


21.

22.

How will the equilibrium: CH4 (g) + 2H2S (g)


CS2 (g) + 4H2 (g), be affected by the following?
(i) Addition of CH4 (g)
(ii) Addition of CS2 (g)
(iii) Removal of CS2 (g)
(iv) Decreasing the volume of the container.
(v) Increasing the temperature (the forward reaction is endothermic).
Ans. Forward shift in (a), (c), (e), backward shift in (b), (d)
The reaction CO (g) + 2H2 (g)
CH3OH (g) has Ho = -18 kJ mol-1. How will the amount of CH3OH
present at equilibrium be affected by the following?
(i) Adding CO (g)
(ii) Removing H2 (g)

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(iii) Decreasing the volume of the container


(iv) Adding a catalyst
(v) Increasing the temperature
Ans. Forward shift in (a), (c), backward shift in (b), (e), (d) Catalyst does not change the position
of equilibrium.

SIMULTANEOUS EQUILIBRIUM
If in any container, if there are two or more equilibria existing simultaneously involving one or more than one
common species, then in both/all the equilibrium the concentration of the common species is the total
concentration of that species due to all the equilibria under consideration.

Example 35. 102g of solid NH4HS is taken in a 2 liters evacuated flask at 570C. Following two equilibria exist
simultaneously.
NH 4 HS (s)
NH 3 (g) H 2 S (g)

1
3
N 2 (g) H 2 (g)
2
2
One mole of the solid decomposes to maintain both the equilibria and 0.75 moles of H2 was found at the
equilibrium, then find the equilibrium concentration of all the species and Kc for both the reaction.
Solution:
NH3 (g)

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