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CHEMICAL EQUILIBRIUM
(Lecture Notes)
CONTENTS
1.
2.
3.
4.
Equilibrium constant.
5.
6.
Thermodynamics of equilibrium.
7.
8.
Page 2 of 46
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.
Page 3 of 46
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 (
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)
Page 4 of 46
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)
N2 + O2
CH3COOH + C2H5OH
CH3COOC2H5 + H2O
N2 + 3H2
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.
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).
Page 5 of 46
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.
Page 6 of 46
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.
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 .
Page 7 of 46
m1
A 2 A3
m2
m1
m3
A 2 A3
m2
m3
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
Page 8 of 46
k f [A][B] = k b [C][D]
k f C[D]
=
k b A [B]
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 +
rf = rb
k f [A1 ]m1 [A 2 ]m2 [A3 ]m3 ....= k b [B1 ]n1 [B2 ]n 2 [B3 ]n3 ....
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.
p B1 , p B2 , p B3 .
Kp =
(p B1 ) n1 (p B2 ) n 2 (p B3 ) n3 .....
(p A1 ) m1 (p A2 ) m2 (p A3 ) m3 .....
Kc =
PV = nRT
n
P = RT
V
= Active mass RT
where,
n = number of moles, V= volume in litres.
n
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
Page 10 of 46
For example,
N2 + 3H2
2NH3
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
CaO(s) + CO2(g)
[CaO(s) ][CO 2 g ]
[CaCO3s ]
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.
Page 11 of 46
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 =
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
n g
n g
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.
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:
Page 13 of 46
7IO3(aq)
+9H 2 O(l) +7H + (aq)
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
1
3
N2 H2
2
2
2NH3 and
NH3
[NH 3 ]
K 'c =
1
2
[N 2 ] [H 2 ]
3
2
. . . (ii)
[NH 3 ]
[N 2 ][H 2 ]3
. . . (iii)
K c = Kc
NO2
N 2 O2
. (2)
Solution:
The equilibrium constant for the reaction: N2 + 2O2
2NO2
2
[NO2 ]
Kc =
= 100 . . . (i)
N 2 [ O2 ]2
Page 14 of 46
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 ]
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:
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
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
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
K c(net) =
[NOBr]
=0.9037 10-15
[N 2 ] [O 2 ]1/2 [Br2 ]1/2
1/2
at 400C when concentrations are expressed in mol litre-1 and pressure in atmosphere.
Page 15 of 46
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
n g = 2 1 = 1
n
Kc = 9.1 1080
2H 2 O g ;
. . . (ii)
CO 2 g H 2 g
CO 2 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)
[CH3OH]
0.18 (0.22) 2
6.
4NH3 (g)
Ans. (i) 0.024
8.
(ii) 6.4
7.
Ans. Yes
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
H2
a
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
(b-x)
2x
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
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
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
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 ]
3+
[NH +4 aq ][ OH - aq ]
[NH 3 aq ]
[H2O(l)] = constant
Na 2CO3s CO 2 g H 2O g
[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]
CaOs CO 2 g
Kc = [CO2]
or Kp = PCO2
Fe3O 4s 4H 2 g
[PH2 ]4
[H 2 ]4
or
K
=
p
[H 2O]4
[ PH2O ]4
[CO][H 2 ]
[H 2O]
CO g H 2 g
or Kp =
PCO PH 2
PH2O
2NH 3 g CO 2 g
NH 3 g H 2S 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 =
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
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)
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
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 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
(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 =
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 =
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
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
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
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
[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
2n1
10
Kc =
2
n1 n 2
10 10
n2= 0.4 mole
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
2HCl (g)
; Kc = 4 1031 at 300K
2HBr (g)
H2O (g)
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
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
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)
; Kc = 3.6 1020
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
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
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)
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
2.303 RT
207104
= antilog
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.
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
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
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
EFFECT ON EQUILIBRIUM
No effect
No effect
Constant Pressure
n g > 0
Forward shift
Constant Pressure
n g < 0
Backward shift
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
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)
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)
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.
22.
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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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