304 Chemical Equilibrium

60
Chapter

E3
Chemical Equilibrium

Whenever we hear the word Equilibrium immediately a (d) Esterification, e.g.,

opposing forces. For chemical reactions also this is true. A

reaction also can exist in a state of equilibrium balancing
forward and backward reactions.
ID
picture arises in our mind an object under the influence of two
CH 3 COOH  C2 H 5 OH ⇌ CH 3 COOC 2 H 5  H 2 O

(e) Evaporation of water in a closed vessel, e.g.,

H 2 O(l) ⇌ H 2 O(g) Q
U
Reversible and Irreversible reactions
A chemical reaction is said to have taken place when the (2) Irreversible reactions : Reaction in which entire
concentration of reactants decreases, and the concentration of amount of the reactants is converted into products is termed as
YG

the products increases with time. The chemical reactions are irreversible reaction.
classified on the basis of the extent to which they proceed, into (i) Characteristics of irreversible reactions
the following two classes;
(a) These reactions proceed only in one direction (forward
(1) Reversible reactions : Reaction in which entire
direction),
amount of the reactants is not converted into products is termed
as reversible reaction. (b) These reactions can proceed to completion,
D

(i) Characteristics of reversible reactions (c) In an irreversible reaction, G < 0,

(a) These reactions can be started from either side, (d) The arrow () is placed between reactants and
(b) These reactions are never complete, products,
U

(c) These reactions have a tendency to attain a state of

(ii) Examples of irreversible reactions
equilibrium, in which Free energy change is zero (G = 0),
(a) Neutralisation between strong acid and strong base
(d) This sign (⇌) represents the reversibility of the e.g.,
ST

reaction,
NaOH  HCl  NaCl  H 2 O 13 .7 kcal
(ii) Examples of reversible reactions
(a) Neutralisation between an acid and a base either of (b) Double decomposition reactions or precipitation
which or both are weak e.g., reactions e.g.,

CH 3 COOH  Na OH ⇌ CH 3 COONa  H 2 O BaCl 2 (aq )  H 2 SO 4 (aq )  BaSO 4 (s)  2 HCl(aq )

(b) Salt hydrolysis, e.g., (c) Thermal decomposition, e.g.,

Fe Cl3  3 H 2 O ⇌ Fe OH 3  3 HCl MnO2 ,
2 KClO 3 (s)   2 KCl (s)  3O2 
(c) Thermal decomposition, e.g.,
(d) Redox reactions, e.g.,
PCl 5 ( g ) ⇌ PCl 3 ( g )  Cl 2 ( g ) Q
SnCl 2(aq )  2 FeCl 3 (aq)  SnCl 4 (aq)  2 FeCl 2(aq)
 Chemical Equilibrium 305

Equilibrium and Its dynamic nature k f [ A]a [B]b  k b [C]c [D]d

“Equilibrium is the state at which the concentration of kf [C]c [D]d
reactants and products do not change with time. i.e.  Kc 
kb [ A]a [B]b
concentrations of reactants and products become constant.”
Where, K c is called equilibrium constant.
Products
In terms of partial pressures, equilibrium constant is
denoted by K p and
Concentration

PCc PDd
Kp 
PAa PBb
Reactants
In terms of mole fraction, equilibrium constant is

60
denoted by K x and
Time Equilibrium state
The important characteristics of equilibrium state are, (X C )c (X D )d
Kx 
(1) Equilibrium state can be recognised by the constancy (X A )a (X B )b
of certain measurable properties such as pressure, density, Relation between Kp, Kc and Kx
colour, concentration etc. by changing these conditions of the K p  Kc (RT )n

E3
system, we can control the extent to which a reaction proceeds.
K p  K x (P)n
(2) Equilibrium state can only be achieved in close vessel.
(3) Equilibrium state is reversible in nature. n = number of moles of gaseous products – number of
moles of gaseous reactants in chemical equation.
(4) Equilibrium state is also dynamic in nature. As a general rule, the concentration of pure solids and
(5) At equilibrium state, pure liquids are not included when writing an equilibrium
Rate of forward reaction = Rate of backward reaction
(6) At equilibrium state, G = 0, so that H = TS.
ID
equation.

Value
of n
Relation
between Kp and
Kc
Units of Kp Units of Kc
U
Rate of reaction

0 Kp = K c No unit No unit
G= 0 >0 Kp > K c (atm)n (mole l–1)n
<0 Kp < K c (atm)n (mole l–1)n
Equilibrium state
YG

Characteristics of equilibrium constant

Time (1) The value of equilibrium constant is independent of
the original concentration of reactants.
Law of mass action and Equilibrium constant
(2) The equilibrium constant has a definite value for
On the basis of observations of many equilibrium every reaction at a particular temperature. However, it varies
reactions, two Norwegian chemists Goldberg and Waage with change in temperature.
suggested (1864) a quantitative relationship between the rates
D

(3) For a reversible reaction, the equilibrium constant for

of reactions and the concentration of the reacting substances.
the forward reaction is inverse of the equilibrium constant for
This relationship is known as law of mass action. It states that
the backward reaction.
“The rate of a chemical reaction is directly proportional
U

1
to the product of the molar concentrations of the reactants at a In general, K forward reaction 
constant temperature at any given time.” K backward reaction

The molar concentration i.e. number of moles per litre is also (4) The value of an equilibrium constant tells the extent
ST

called active mass. It is expressed by enclosing the symbols of to which a reaction proceeds in the forward or reverse
formulae of the substance in square brackets. For example, molar direction.
concentration of A is expressed as [A]. (5) The equilibrium constant is independent of the
Consider a simple reversible reaction presence of catalyst.
(6) The value of equilibrium constant changes with the
aA  bB ⇌ cC  dD (At a certain temperature) change of temperature. Thermodynamically, it can be shown
According to law of mass action that if K 1 and K 2 be the equilibrium constants of a reaction at

Rate of forward reaction  [ A]a [B]b  k f [ A]a [B]b absolute temperatures T1 and T2 . If H is the heat of reaction
at constant volume, then
Rate of backward reaction  [C]c [D]d  k b [C]c [D]d 1
 H 1
log K 2  log K1     (Van’t Hoff equation)
At equilibrium , 2 .303 R  2
T T1
Rate of forward reaction = Rate of backward reaction
 306 Chemical Equilibrium
The effect of temperature can be studied in the following (2) Predicting the direction of reaction : The
three cases concentration ratio, i.e., ratio of the product of concentrations of
(i) When H  0 i.e., neither heat is evolved nor products to that of reactants is also known as concentration
absorbed quotient and is denoted by Q.
log K 2  log K1  0 or log K 2  log K1 or K 2  K1 [ X ][Y ]
Concentration quotient, Q  .
Thus, equilibrium constant remains the same at all [ A][B]
temperatures. It may be noted that Q becomes equal to equilibrium
(ii) When H = +ve i.e., heat is absorbed, the reaction is constant (K) when the reaction is at the equilibrium state. At
endothermic. The temperature T2 is higher than T1 . equilibrium, Q  K  K c  K p . Thus,

log K 2  log K1  ve or log K 2  log K1 or K 2  K1

60
(i) If Q > K, the reaction will proceed in the direction of
The value of equilibrium constant is higher at higher reactants (reverse reaction).
temperature in case of endothermic reactions. (ii) If Q < K, the reaction will proceed in the direction of
(iii) When H = – ve, i.e., heat is evolved, the reaction is the products (forward reaction).
exothermic. The temperature T2 is higher than T1 . (iii) If Q = K, the reaction mixture is already at

E3
log K 2  log K1  ve or log K1  log K 2 or K1  K 2 equilibrium.
Thus, a reaction has a tendency to form products if Q < K
The value of equilibrium constant is lower at higher
temperature in the case of exothermic reactions. and to form reactants if Q > K.

(7) The value of the equilibrium constant depends upon

the stoichiometry of the chemical equation.
For the reaction
2SO 3 (g) ⇌ 2SO 2 (g)  O2 (g) and SO 3 (g) ⇌ SO 2 (g)  1 / 2O2 (g)

[SO 2 ]2 [O 2 ] [SO 2 ][O 2 ]1 / 2

ID Q Kc Q Kc Q Kc

K and K  
U
2
[SO 3 ] [SO 3 ]
Reactants  Products Equilibrium Reactants  Products
Q<K Q=K Q>K
K   K or (K ) 1/2
(Forward reaction) (At (Reverse reaction)
equilibrium)
YG

(i) Similarly, if a particular equation is multiplied by 2, Fig. 8.1

the equilibrium constant for the new reaction (K) will be the
Types of equilibria
square of the equilibrium constant (K) for the original reaction
i.e., K   K 2 The equilibrium between different chemical species
present in the same or different phases is called chemical
(ii) If the chemical equation for a particular reaction is
equilibrium. There are two types of chemical equilibrium.
written in two steps having equilibrium constants K1 and K 2 ,
(1) Homogeneous equilibrium : The equilibrium
D

then the equilibrium constants are related as K  K1  K2

reactions in which all the reactants and the products are in the
Applications of equilibrium constant same phase are called homogeneous equilibrium reactions.
(1) Judging the extent of reaction C 2 H 5 OH (l)  CH 3 COOH (l) ⇌ CH 3COOC 2 H5 (l)  H 2O(l)
U

(i) If K c  10 3 , products predominate over reactants. If

N 2 (g)  3 H 2 (g) ⇌ 2 NH 3 (g)
K c is very large, the reaction proceeds almost all the way to
completion. 2SO 2 (g)  O 2 (g) ⇌ 2SO 3 (g)
ST

(ii) If K c  10 3 , reactants predominate over products. If (2) Heterogeneous equilibrium : The equilibrium
K c is very small, the reaction proceeds hardly at all. reactions in which the reactants and the products are present in
different phases are called heterogeneous equilibrium reactions.
(iii) If K c is in the range 10 3 to 10 3 , appreaciable
concentration of both reactants and products are present. 2 NaHCO 3 (s) ⇌ Na 2 CO 3 (s)  CO 2 (g)  H 2 O (g)

Kc Ca(OH )2 (s)  H 2 O (l) ⇌ Ca 2  (aq)  2OH  (aq)

Reaction
proceeds hardly 103
Reaction proceeds CaCO 3 (s) ⇌ CaO (s)  CO 2 (g)
10–3 to completion
at all
Both reactants and
products are present H 2 O (l) ⇌ H 2 O (g)
at equilibrium
 Chemical Equilibrium 307

Table : 8.1 Homogeneous equilibria and equations for equilibrium constant (Equilibrium pressure is P atm in a V
L flask)
n  0 ; K p  Kc n  0 ; K p  Kc n  0; K p  Kc

H 2 + I2 ⇌ 2 HI N 2  3 H 2 ⇌ 2 NH 3 2 SO 2  O2 ⇌ 2 SO 3 PCl 5 ⇌ PCl 3  Cl 2
(g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (g)
(g)

Initial mole 1 1 0 1 30 2 1 0 1 0 0
Mole at (1–x) (1– x) 2x (1–x) (3–3x) 2x (2–2x) (1–x) 2x (1–x) x x
Equilibrium
Total mole at 2 (4 – 2x) (3 – x) (1 + x)
equilibrium

60
Active  1  x   1  x   2x   2  2x   1  x 
1  x  1  x  2x  2x  1  x  x x
masses       3               
 V   V  V  V   V   V   V   V   V   V  V V
Mole fraction 1  x  1  x  2x 1x 31 x  x  2  2x   1  x   2x  1 x   x   x 
                 
 2   2  2 2 2  x  2  2  x  (2  x )  3x  3 x 3 x 1  x  1  x  1  x 

E3
Partial 1  x   1  x   2x   1  x   3(1  x )  Px  2  2x  1x   2x  1 x   x   x 
pressure
p  p  p  P   P 
  P  P   P  P  P  P 
 2   2   2   2(2  x ) _   2(2  x )  (2  x )  3x  3 x 3 x 1 x  1 x  1 x 
Kc 4x2 4 x 2V 2 x 2V x2
1  x  2 27 1  x  4 1  x  3 1  x  V
16 x 2 2  x  2 x 2 3  x 
Kp 4x2
1  x  2 27 1  x  P 4 2
ID
Table : 8.2 Heterogeneous equilibria and equation for equilibrium constant (Equilibrium pressure is P atm)
P 1  x  3

Px 2
1  x2 

NH 4 HS (s) ⇌ NH 3 (g) + H 2 S (g) C(s)  CO2 (g) ⇌ 2 CO (g) NH 2CO2 NH 4 (s) ⇌ 2 NH 3 (g)  CO2 (g)
U
Initial mole 1 0 0 1 1 0 1 0 0
Mole at equilibrium (1–x) x x (1–x) (1–x) 2x (1–x) 2x x
YG

Total moles at equilibrium 2x (1+x) 3x

(solid not included)
Mole fraction x 1 1 1  x   2x  2 1
    
2x 2 2 1  x  1  x  3 3
Partial pressure P P 1  x   2x  2P P
P  P 
2 2 1  x  1  x  3 3
D

Kp P2 4P x2 4 P3
4 (1  x 2 ) 27
U

Relationship between equilibrium constant and For components in solution: a  molar concentration.
G° Le-Chatelier's principle
G for a reaction under any condition is related with G° Le-Chatelier and Braun (1884), French chemists,
ST

by the relation, G  G  2.303 RT log Q made certain generalizations to explain the effect of changes in
Standard free energy change of a reaction and its concentration, temperature or pressure on the state of system in
equilibrium constant are related to each other at temperature T equilibrium. When a system is subjected to a change in one of
by the relation, G o  2 .303 RT log K these factors, the equilibrium gets disturbed and the system
readjusts itself until it returns to equilibrium. The generalization
For a general reaction aA  bB ⇌ cC  dD
is known as Le-Chatelier's principle. It may be stated as :
(aC )c (aD )d
K “Change in any of the factors that determine the
(a A )a (aB )b
equilibrium conditions of a system will shift the equilibrium in
Where a represent the activity of the reactants and such a manner to reduce or to counteract the effect of the
products. It is unit less. change.”
For pure solids and liquids: a  1 .
For gases: a  pressure of gas in atm.
 308 Chemical Equilibrium
The principle is very helpful in predicting qualitatively
the effect of change in concentration, pressure or temperature
on a system in equilibrium.

Table : 8.3 The effect of varying conditions on the equilibrium a A + b B ⇌ c C + d D, n = (c + d) – (a + b)

Change imposed on the Equilibrium position moves Equilibrium constant Any other points
system in equilibrium
Conc. of A and/or B increased To right No change No change
Conc. of C and /or D To left No change No change
increased
Pressure increased To right if (c  d )  (a  b ) , i.e. n  ve No change Very little effect, if any, on

60
No change reactions in liquid solution.
To left if (c  d )  (a  b ) , i.e. n  ve
No change
No change if (c  d )  (a  b ) , i.e. n  0
Temperature increased To left if H  ve (exothermic) Value decreased Equilibrium achieved faster
To right if H  ve (endothermic) Value increased

E3
Addition of catalyst No change No change Equilibrium achieved faster
(v) Dissociation of phosphours pentachloride
Application of Le-Chatelier's principle
PCl 5 ⇌ PCl 3  Cl 2  15 kcal
The Le-Chateliers principle has a great significance for the 1 vol 1 vol 1 vol
chemical, physical systems and in every day life in a state of (a) Low pressure or high volume of the container, n  0
equilibrium.
(1) Applications to the chemical equilibrium
(i) Synthesis of ammonia (Haber’s process)
N 2  3H 2
1 vol 3 vol
⇌ 2 NH 3  23 kcal (exothermic)
2 vol
ID (b) High temperature (c) Excess of PCl 5 .
(2) Applications to the physical equilibrium
(i) Melting of ice (Ice – water system)
Ice ⇌ Water  x kcal
U
(Greater Volume) (Lesser Volume)
(a) High pressure (n  0)
(In this reaction volume is decreased from 1.09 c.c. to
(b) Low temperature 1.01 c.c. per gm.)
(c) Excess of N 2 and H 2
YG

(a) At high temperature more water is formed as it

absorbs heat.
(d) Removal of NH 3 favours forward reaction.
(b) At high pressure more water is formed as it is
(ii) Formation of sulphur trioxide accompanied by decrease in volume.
2 SO 2  O 2 ⇌ 2SO 3  45 kcal (exothermic) (c) At higher pressure, melting point of ice is lowered,
2 vol 1 vol 2 vol
while boiling point of water is increased.
(a) High pressure (n  0) (ii) Melting of sulphur : S (s) ⇌ S (l)  x kcal
D

(b) Low temperature (This reaction accompanies increase in volume.)

(c) Excess of SO 2 and O 2 , favours the reaction in (a) At high temperature, more liquid sulphur is formed.
forward direction. (b) At higher pressure, less sulphur will melt as melting
U

(iii) Synthesis of nitric oxide increases volume.

(c) At higher pressure, melting point of sulphur is
N 2  O2 ⇌ 2 NO  43 . 2 kcal (endothermic )
1 vol 1 vol 2 vol
increased.
(iii) Boiling of water (water- water vapour system)
ST

(a) High temperature

Water ⇌ Water Vapours  x kcal
(b) Excess of N 2 and O 2 (Low volume) (Higher volume)

(c) Since reaction takes place without change in volume (It is accompanied by absorption of heat and increase in
i.e., n  0 , pressure has no effect on equilibrium. volume.)
(iv) Formation of nitrogen dioxide (a) At high temperature more vapours are formed.
(b) At higher pressure, vapours will be converted to liquid
2 NO  O 2 ⇌ 2 NO 2  27 .8 Kcal
2 vol 1 vol 2 vol
as it decreases volume.
(c) At higher pressure, boiling point of water is increased
(a) High pressure (principle of pressure cooker).
(b) Low temperature (iv) Solubility of salts : If solubility of a salt is
(c) Excess of NO and O 2 favours the reaction in forward accompanied by absorption of heat, its solubility increases with
direction. rise in temperature; e.g., NH 4 Cl, K2 SO 4 , KNO 3 etc.
 Chemical Equilibrium 309

KNO 3(s)  (aq)  KNO 3(aq)  x kcal decreased and dissolved CO2 gas escapes out with a fizze.
 Increase in pressure favours melting of ice into water
On the other hand if it is accompanied by evolution of
heat, solubility decreases with increase in temperature; e.g.,
 Flash evaporation is a technique generally used for
concentrating certain aqueous solutions which cannot be
CaCl 2 , Ca(OH )2 , NaOH , KOH etc. concentrated by normal boiling.
Ca(OH )2( s)  (aq)  Ca(OH )2 (aq)  x kcal  Freeze drying is a technique where water is made to
sublime off at a temperature below 0°C.
Relation between vapour density and
Degree of dissociation
In the following reversible chemical equation.
A ⇌ yB

60
Initial mol 1 0
At equilibrium (1–x) yx x = degree of Reversible and Irreversible reaction
dissociation
Number of moles of A and B at equilibrium 1. A reversible reaction is one which
 1  x  yx  1  x (y  1) [MP PET 1986]

E3
If initial volume of 1 mole of A is V, then volume of (a) Proceeds in one direction
equilibrium mixture of A and B is,  [1  x (y  1)]V (b) Proceeds in both directions
Molar density before dissociation, (c) Proceeds spontaneously
molecular weight m (d) All the statements are wrong
D 
volume V 2. Which of the following is a characteristic of a reversible
Molar density after dissociation, reaction [AFMC 1993]

d

reactant.
D
m D
;  [1  x (y  1)] ; x 
[1  x (y  1)]V d

is also called Van’t Hoff factor.

Dd
d(y  1)
y is the number of moles of products from one mole of
ID3.
(a) Number of moles of reactants and products are equal
(b) It can be influenced by a catalyst
(c) It can never proceed to completion
(d) None of the above
The reaction CaCO 3 ⇌ CaO  CO 2 (g) goes to
U
d
completion in lime kiln because
M m [MP PMT/PET 1988; CPMT 1990]
In terms of molecular mass, x 
(y  1) m (a) Of the high temperature
Where M  Initial molecular mass, (b) CaO is more stable than CaCO 3
YG

m  molecular mass at equilibrium (c) CaO is not dissociated

Thus for the equilibria (d) CO 2 escapes continuously
(I) PCl 5(g) ⇌ PCl 3(g)  Cl 2(g) , y  2
4. In the given reaction N 2  O 2 ⇌ 2 NO , equilibrium
(II) N 2 O 4 (g) ⇌ 2 NO 2(g) , y  2 means that [
1 (a) Concentration of reactants is changing where as
(III) 2NO 2 ⇌ N 2 O 4 , y  concentration of products is constant
2
D

(b) Concentration of all substances is constant

Dd 2(d  D)
 x (for I and II) and x  (for III) (c) Concentration of reactants is constant where as
d d concentration of products is changing
Also D  2  Molecular weight (theoretical value) (d) Concentration of all substances is changing
U

d  2  Molecular weight (abnormal value) of the mixture. 5. Which of the following reactions is reversible
[MADT Bihar 1980]
(a) H 2  I 2  2 HI
ST

(b) H 2 SO 4  Ba (OH )2  BaSO 4  2 H 2 O

(c) NaCl  AgNO 3  NaNO 3  AgCl
(d) Fe  S  FeS
 Pure ice can be made to melt at a temperature slightly 6. All reactions which have chemical disintegration
below 0°C by increasing the pressure. As the water so [MP PMT 1990]
obtained on melting is below 0°C, it refreezes when (a) Is reversible
pressure is reduced. It is called regelation of ice. (b) Is reversible and endothermic
 Increase in external pressure always increases the boiling (c) Is exothermic
point and vice-versa. (d) Is reversible or irreversible and endothermic or
 If the reaction is multipled by 2, the equilibrium constant is exothermic
squared. 7. Amongst the following chemical reactions the irreversible
 When a bottle of coca or beer is opened, the pressure is reaction is [MP PMT 1999]
 310 Chemical Equilibrium
(a) H 2  I 2 ⇌ HI
(b) AgNO 3  NaCl ⇌ AgCl  NaNO 3
(c) CaCO 3 ⇌ CaO  CO 2
(d) O2  2SO 2 ⇌ 2SO 3

60
E3
ID
U
YG
D
U
ST