CHEMICAL EQUILIBRIUM

- is the state that exists when two opposing reactions are proceeding at the same rate

From Law of Mass Action

aA + bB + …  cC + dD + …

Rf = kf [A]a [B]b

For Chemical Equilibrium

aA + bB + …  cC + dD + …

Rf = R b

kf [A]a [B]b = kb [C]c [D]d

rearranging

kf

C   D 
c d

kb  A a  B  b

Keq 
 C   D
c d

 A a  B  b
The thermodynamic approach

GA = GAo + RTln aA

GB = GBo + RTln aB

GC = GCo + RTln aC

GD = GDo + RTln aD

G = [cGC + dGD ] - [aGA + bGB ]

=[ c(GCo + RTln aC) + d(GDo + RTln aD]

- [ a(GAo + RTln aA) + B(GBo + RTln aB]

G = [( cGCo + dGDo) - (aGAo + bGBo)]

+ [(cRTln aC + dRTln aD) - (aRTln aA + bRTln aB)
 aCc .a Dd
G  G o  RT ln
a Aa .a Bb

Note: Activities are those of the products at the end of the reaction and of the reactants
at the start of the reaction.

At equlibrium

G = 0

aCc .aDd
 G o  RT ln
aAa .aBb

Note: Activities are those of the products and of the reactants at equilibrium.

At a fixed T, P, and V Go and R are constant

aCc .aDd
 Ka  a b
a A .aB

G o  RT ln Ka

 G o 
Ka  exp 
 RT 

This equation relates the thermodynamic equilibrium constant of a reaction at a

temperature T, to the free energy in the standard state for the reaction.

Equilibrium Constant expressions for a Gas Reactions

From Lewis Fugacity Rule

f
φ ; a = P
P

Ka 
 φP  Cc  φP  dD

 φP  aA  φP  Bb

φCc φDd PCc PDd

Ka  .
φ Aa φBb PAa PBb
 Ka = K . Kp

For an ideal gas or real gas at zero pressure

 = 1, thus K = 1

therefore

Ka = Kp

In terms of concentration

Kc 
 C   D
c d

 A a  B  b
Relationship between Kp and Kc

From PV = nRT

nRT
P  CRT
V

Kp 
 C RT  c   DRT  d
  ART  a   B RT  b

Kp 
C  c  D d .  RT  c RT d 
 A a B  b  RT  a  RT  b

Kp  Kc.
 RT  c d
 RT  a b

Kp  Kc  RT 
ng

In terms of mole fractions

From
PCc PDd
Kp  a b
PA PB
  xPT  Cc  xPT  dD
Kp   KxPT c d   a b 
 xPT  aA  xPT  Bb
Kp  KxP n

Interpretation of value of the Equilibrium Constant

If K is large the reaction favors the formation of the products.

If K is small the reaction does go to appreciable extent under a given condition.

Determination of Equilibrium Constant

Problem: Calculate Ka, K, Kp, Kx, and Kc at 25oC and 1.0 bar total pressure for the reaction

H2(g) + ½ O2(g)  H2O(g) Go = -228.572 kJ

(H2O) = 0.98 (H2) = 1 (O2) = 1

Solution:

 G o 
a. Ka  exp 
 RT 

 
  228 . 572 kJ 
Ka  exp   
  kJ  
  8 . 314 x10 3
  298 . 15 K  
  K  mol  

Ka = 1.1125 x 10 40

 0.98
b. Kφ  1
1.01.0 2
K = 0.98

c. Ka = K.Kp

1.1125 x10 40
Kp 
0.98

Kp = 1.135 x 1040

d. Kx = Kp P-n
 = 1.135 x 1040 (1bar)0.5
1.135 x 1040

e. Kc = Kp(RT)-n

Kc = 1.135 x 1040 [(0.08314 L-bar K-mol-) (298.15K)]0.5

Kc = 2.2797 x 1039

Homogeneous Chemical Equilibrium

(Gaseous Reaction)

I. Reaction without change in the number of molecules

A2(g) + B2(g)  2AB(g)

Kp  Kc  RT  since n = 0
ng

Kp  Kc

II. Reaction with changes in the number of molecules

A(g)  B(g) + C(g)

Basis: 1 mole
A(g)  B(g) + C(g)
Initial 1n 0 0
Change amount -  
Equilibrium 1-  
1+ 1+ 1+

PB .PC  x B PT  x C PT   x C  x D  PT
Kp   
PA  x A PT  xA 
ξ ξ
. PT
1 ξ 1 ξ
Kp 
1 ξ
1 ξ
 ξ 2 PT
Kp 
1  ξ 1  ξ 

Calculation of Keq from

1. Composition of the equilibrium mixture
2. Extent of dissociation
3. Equilibrium density
M  M2
ξ  1 where M1 – molar mass of the undissociated reactant
M2
M2 – average molar mass of the equilibrium mixture

Heterogeneous Chemical Equilibrium

Consider the reaction

CuO(s) + H2(g)  Cu(s) + H2O(g)

aCu .aH2O
Ka 
aCuO .aH2

but
aCu = aCuO = 1

aH2O
Ka 
aH2
if the gases behaves ideally

PH2O
Kp 
PH2

Effect of Temperature on the Equilibrium Constant

G o  RT ln Ka

G o
ln Ka  
RT
Differentiation with respect to temperature
  G 
d 
d ln K 1  T 

dt R dT

From Gibb’s Helmholtz equation

  G  
d T   H
  
  2
 dT  T
 
 P

d ln K 1  H 
   2 
dt R T 

Integrating between limits K1 to K2 and T1 to T2

K2 T2 H dT
K1
d ln K  
T1 R T2

K2 H  1 1
ln    
K1 R T 2 T1 

Effect of Pressure, Initial Composition and Inert Gases on the Equilibrium Composition
(The Le Chatelier – Braun Principle)

The effect of pressure and temperature on a system in equilibrium can be quantitatively

determined by the use of Le Chatelier – Braun Principle

- states that whenever stress is applied on any system in a state of equilibrium, the system
will always react in a direction which will tend to counteract the applied stress, thus if pressure is
applied to a system, the tendency of the stress will be to decrease the volume and hence that
reaction in the system will take place which will favor the smaller volume.