Chemical Equilibrium

Whats Chemical Equilibrium:

Thermodynamics:
Spontaneous S total
0

G system
0

Equilibrium S total
0 or G system
0

Kinetics:
Concept introduced by A. W. Williamson in 1851 during
study esterifications
Forward reaction rate = Reverse reaction rate
Equilibrium (at a specified temperature)
Reaction rates are not ceased when equilibrium is
reached.
Chemical equilibrium Dynamical equilibrium
Expression of Equilibrium Constant:
Considering a stoichiometric reaction: aA bB yY zZ

Forward reaction rate: r k A B

a b

1 1

Reverse reaction rate: r k Y Z

y z

-1 -1

At equilibrium, r r
1 1

k1 Y Z
y z

a b Kc
k1 A B

(A) Types of equilibrium constant:

1
 Kc; Kp; Ksp
(B) The factors that affect equilibrium constant:
Temperature; Reacting species
Chemical Potential:
G U H A

n n n n
i
i T , P , ni n j i S , V , ni n j i S , P , ni n j i T , V , ni n j

At constant P and T, the direction of reaction is determined by the

chemical potential, . i

(A) Chemical potential for ideal solution:

( T , P ) ( T , P ) RT n x
i
*

i i
ideal solution
where (T , P)
*
i is the chemical potential of the pure substance
i when it is at the temperature T and pressure P.
xi is the mole fraction of substance i in the solution.
(B) Chemical potential for non-ideal solution:
For non-ideal solution, the chemical potential of substance i
is defined by:
( T , P ) ( T , P ) RT n a (definition of ai)
i i
*
i

where is the chemical potential of the pure substance i.

*
i

ai is the activity.
Extent of reaction:
The degree of reaction progress
The ratio of the amount of any species produced/formed to
the its stoichiometric coefficient

2
 e.g. A B Y Z
A B Y Z

n A n B
for reactants:
A B

nY n Z
for products:
Y Z

The general equilibrium expression:

Consider a closed system in which a single reaction occurs in a
single phase. If an infinitesimal amount of reaction takes place at
constant T and P, the change in the Gibbs energy is given by:
N

dG dn i i
i 1

where N is the number of species involved in the reaction;

dni is the differential change in the amount of the i-th
species.
The differential change in the amount of a species I is given
by dn d .
i i

G N

Thus, we can identify i i

T,P
i 1

The quantity G is the rate of change of Gibbs energy per

T ,P

mole of reaction.
G 0 (forward reaction spontaneous)
T ,P

G 0 (backward reaction spontaneous)
T ,P

G 0 (equilibrium)
T ,P

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 The chemical potential of a species is expressed by,
( T , P ) ( T , P ) RT n a
i
*
i i

N N

At equilibrium, RT na 0
o
i i i i,eq
i 1 i 1

-RT n a
N
o i
i i i,eq
i 1 i 1

Define the equilibrium constant K of the reaction as

N

K a i 1
i
i,eq

and the quantity is the standard reaction Gibbs energy, G

o o

i i r
i 1

.
Therefore, we can obtain
G RT n K
r
o

(A) Equilibri
um in pure gases:
Pi fi
a o ( ideal gas ) or a i
f
o ( real gas)
i
P
i i
P N
f
N

K P i
(ideal gas) or K P i
(real gas)
P i 1 o
eq
f i 1 o
eq

(B) Equilibri
um in pure condensed phases:
Substances that are pure liquids or solids contribute a factor nearly
equal to unity to the equilibrium constant expression. To a good
approximation, they can be omitted from it, i.e.
a 1i (pure liquid or solid)
(C) Equilibri
4
 um in solution:
a x ( ideal solution )
i i or a m ( real solution)
i i i

K x (ideal solution) or K m (real solution)

N N
i i

a i eq a i i eq
i 1 i 1

Equilibrium constant in concentration units:

For a general reaction: A B Y Z A B Y Z

n
PV nRT P RT = CRT
V

P P C C uY uZ uY uZ

C C RT K RT
uY uZ uA uB u
K P
Y
uA
Z
uB
Y
uA
Z
uB C
P P A B eq A B eq

RT
u
K K P C

where = the stoichiometric sum ()

KC is dependent on T only.
Equilibrium constant in mole fraction:
From Daltons law: P yPi i

P P y y Y Z Y Z

P K P
Y Z A B
K
Y Z Y Z

P P y y
P A B A B y
A B eq A B eq

K K P

P y

Ky is dependent on T and P.
Units:
Thermodynamic equilibrium constant is dimensionless, but
practical equilibrium constant is not.
Ex.1: A B Z

5
 Z

1

A B ; K C
K
C
mole
liter
Ex. 2: A BY Z

K
Y Z
C
A B ; Kc is dimensionless
In general, K ( unit ) u

K depends on how the stoichiometric equation is written:

Z
2

Ex.: A 2Z K C

A
G RT nK
0
1
0
C

Z
1 A Z K G RT nK
0 0

A
C 1
2 2 2 C

K K
1
; G 1 G 0
2 0

C C
2
2 1

B C
Ex.: A BC K 1C
A

B Y
C BY K 2C
C
B Y K
2

A 2B Y K K
C
A 1C 2C

Determination of equilibrium constant:

(A) From
Gibbs energy: G RT n K
o

The Gibbs energy can be determined by:

From standard Gibbs energy of formation:
G G
o
i
0
f ,i
i

From reaction enthalpy: G H TS

0 0 0

6
 From electromotive force: G zFE
0

(B) From the

reaction extent:
Procedures:
Given the equilibrium extent of reaction,
To express the equilibrium pressure of various
components in terms of
To determine the equilibrium constant in terms of
Ex.: N O
2 4( g )
2NO 2( g ) the total equilibrium pressure = P
initial 1 mole 0 mole the reaction extent =
final (1-) mole 2 mole
1 2
Pequilibrium 1
P
1
P

2
2
P
1
2
PNO 4
2

K 2
P
1
P
1
2
PN O
2 4
P
1

Ex. The Gibbs energies of formation of NO2(g) and N2O4(g) are 51.3
kJ/mole and 102.0 kJ/mole, respectively, in the standard state,
(a) Calculate
Kp and Kc for the reaction N O 2 4( g )
2NO
2( g ) if the gas is ideal.
(b) Calculate
Kx at 1 bar pressure.
(c) At what
pressure is N2O4 50% dissociated?
(d) What is

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 if the standard state is 1 mole liter ?

Sol: (a) G 2 51. 3 102 . 0 0 . 6 kJ mole

0

G
0
600
n K 0
P
0 . 242 ;
RT 8 . 3145 298 . 15

K 0 .785 bar
0
P

K K RT K RT
u

P C C

0 . 785 10
0 5
KP
K
0
3 . 17 10 mole
2
C
RT 8 . 3145 298 . 15 liter

(b)
K K P
u

P y
K P y

KP
K y
0 .785
P

(c)
4
2

K P
P ; =0.5; Kp= 0.785 bar
1
2

4 0.5
2

0 .785 P P = 0.589 bar

1 0.5
2

(d)
G RT nK 8 . 3145 298 . 15 n 3 .17 10
0
C
2

joule
= 8555
mole

Ex. Write down the expression of equilibrium constant for

CaCO 3( S )
CaO (S)
CO 2( g )

Assumed CO2(g) is ideal gas.

8
 Sol: a CaCO3
1 and a CaO
1 K P
P CO2

Ex. At 1393K,
Fe O
2 3( S )
3CO ( g)
2Fe (S)
3CO 2( g ) K1=0.0467
2CO 2( g )
2CO ( g)
O 2( g ) K2 =1. 4 10 12

What is the equilibrium pressure of O2(g) in a vessel containing

Fe2O3(g) and Fe(s) at equilibrium at 1393 K?
Sol: The total reaction is
Fe O 2 3( S )
3CO ( g)
2Fe (S)
3CO 2( g ) 2
2CO 2( g )
2CO ( g)
O 2( g ) 3
2Fe O 2 3( S )
4Fe (S)
3O 2( g ) K K K 1
2 3
2

K 0 . 0467 1. 4 10
2 3
12
6 . 01 10 39

K P 3
O2

P 6 . 01 10
1

O2
39 3
1. 82 10 bar 13

Effect of pressure on equilibrium:

For an ideal mixture of ideal gases, the equilibrium constant can be
expressed in terms of the individual mole fraction and the total
pressure of the system; i.e. K K P

P y

if 0 ; K isindependent of pressure
y

equilibrium doesnt shift

if 0 ; K islower when pressureis higher
y

equilibrium toward reactants

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 if 0 ; K is higher when pressureis higher
y

equilibrium toward products

Effect of volume on equilibrium:
nRT
V
P

if 0 ; K isindependent of volume
y

equilibrium doesnt shift

if 0 ; K islower when volumeislower
y

equilibrium toward reactants

if 0 ; K is higher when volumeislower
y

equilibrium toward products

Effect of inert gas on equilibrium:
i
n P

K P y P P n
i i i
i
P i i
n n i
i i i
i
i i
i
i

K K
P n

n i
i

if 0 ; K isequal to K
n P

equilibrium doesnt shift

if 0 ; adding inert gas is to increase n i
i

Kn increasing; equilibrium toward products

if 0 ; adding inert gas is to increase n i
i

Kn decreasing; equilibrium toward reactants

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 Effect of temperature on equilibrium:
G 0
H
0

From the Gibbs-Helmholtz equation: T T

P
2
T

G RT n K
o 0
P

G nK H
0 0 0

R P

T T T T
2
P P

nK H
0 0

T
RT
P
2 called the vant Hoff equation.
P

if H 0 0
(exothermic reaction), K 0
P decreases when T is
increasing equilibrium toward reactants
if H 0 0
(endothermic reaction), K 0
P increases when T is
increasing equilibrium toward products
if H 0
is independent of temperature, then
H S
0 0

n K 0
P

RT R

H S
0 0

(slope = R
and intercept = R
)

if H 0
is a function of temperature, i.e. C d eT fT
P
2

1 1
H ( T ) H 25C d T 298.15 1
0

e T
2
288.15 f 2

m m
2 T 298. 15

then, the equation can be integrated to be:

1 H
0 2
d d 298 . 15 e 298 . 15 e f f
nKP 2m dT C
0
3 2
R T 298 . 15 T
2 2
T T 2 2T T

If H , d , e , and f are known , KP can be calculated at any other

0
m

temperature.
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 if Ky instead of Kp: K K P

P y

nK
0
H
0

T RT
y
2
P

if Kc instead of Kp: RT
u
K K
P C

nK U
0 0

T
RT
2
P

Le Chatelier Principle:
When an independent variable of a system at equilibrium is
changed, the equilibrium shifts in the direction that tends to
reduce the effect of the change.
When total pressure is increased, the equilibrium shifts in
the direction to reduce the number of molecules.
An increase in temperature at constant pressure in a closed
system shifts the equilibrium in the direction in which the
system absorbs heat from the surroundings.

Ex.: Consider that a dissociation reaction of water becomes O2 and

H2 : H O H 1 O H 57 . 8 Kcal
0
2 ( g) 2( g )
2 2( g ) r
mole
(a) will the
dissociation increase or decrease if the pressure is
reduced?
(b) will the
dissociation increase or decrease if argon gas is added,

12
 holding the total pressure equal to 1 bar?
(c) will the
dissociation increase or decrease if the pressure is raised
by addition of argon at constant volume to the close
system?
(d) will the
dissociation increase or decrease if oxygen gas is added?
(e) will the
dissociation increase or decrease if temperature is raised?
Sol: (a) increase; (b) increase; (c) no change; (d) decrease;
(e) increase.
Coupling of reactions:
If two reactions exist in a chemical system, one of reaction
product is the reactant of another reaction. This is called the
coupling of reactions.
e.g. A + B = L + M K1 < 1
L+C=N+Q K2 > 1
A + B + C = M + N + Q K3 = K 1 K2 > 1
The importance of the coupling of reaction is to increase the
production rate of product M.

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