1

Chemical Equilibrium
2
CONTENTS
12.1 The Concept of Equilibrium
12.2 The Equilibrium Constant
12.3 Heterogeneous Equilibria
12.4 Calculating Equilibrium Constants
12.5 Application of Equilibrium Constants
12.6 Le Chteliers Principle

3
Learning Outcomes
Student should be able to use concept of
equilibrium to calculate equilibrium constant and
equilibrium concentrations.
Able to apply Le Chaterliers Principle to predict
the direction of a reaction hence apply it in
commercial sense in increasing yield, reduce cost
etc.
Differentiate homogenous and heterogeneous
equilibria, reaction quotient and Equilibrium
constant
4
12.1 The Concept of Equilibrium
Consider Colorless frozen N
2
O
4
.
At room temperature, it decomposes to
brown NO
2
.
N
2
O
4
(g) 2NO
2
(g)
At some time, the color stop changing and
we have a mixture of N
2
O
4
and NO
2
.

the concentration of all reactants and
products no longer change with time.
N
2
O
4
(g) 2 NO
2
(g)
5
12.1 The Concept of Equilibrium
N
2
O
4
(g) 2 NO
2
(g)
Chemical equilibrium is the point at which
the concentrations of all species are
constant. (concentrations of reactants and
products cease to change with time)

Chemical equilibrium occurs
opposing reactions are proceeding at equal
rate.
Rate
forward
= Rate
reverse

6
N
2
O
4
(g) - colorless
NO
2
(g) - reddish brown
Concentration (color) remains constant at equilibrium
7
time
8
12.1 The Concept of Equilibrium
Consider a simple reaction: A(g) B(g)
We can write rate expressions for each reaction:

Forward reaction: A B
Rate = k
f
[A] k
f
= rate constant (forward reaction)
Reverse reaction: B A
Rate = k
r
[B] k
r
= rate constant (reverse reaction)

9
12.1 The Concept of Equilibrium
For gaseous substances we can use the ideal
gas equation to convert between concentration
and pressure:
PV=nRT so M(Molarity) = (n/V) =(P/RT)
For substances A and B:

[A] = (P
A
/RT) and [B] = (P
B
/RT)
Rate
fwd
= k
f
(P
A
/RT) and Rate
rev
= k
r
(P
B
/RT)

10
12.1 The Concept of Equilibrium
Place some pure compound A into a closed
container.
As A reacts to form B, the partial pressure of A
will decrease and the partial pressure of B will
increase.
Expect forward reaction rate to slow and reverse
reaction rate to increase.
Eventually, we get to equilibrium where forward
and reverse rates are equal.


11
Haber Process

N
2
(g) + 3H
2
(g) 2NH
3
(g)

The reaction is carried
out under conditions of
high pressure and high
temperature. Equilibrium
can be established either
by starting with N
2
and
H
2
or by starting only
with NH
3
.

12
12.1 The Concept of Equilibrium
At Equilibrium:


Rearrange:
a constant

This mixture is called an equilibrium mixture.
This is an example of dynamic equilibrium.

RT
P
k
RT
P
k
B
r
A
f
=
( )
( )
= = =
r
f
A
B
A
B
k
k
P
P
RT P
RT P
/
/
13
12.2 The Equilibrium Constant, K

We can write an expression for the relationship
between the concentration of the reactants and
products at equilibrium.
This expression is based on the law of mass
action.
For a general reaction:
aA + bB cC + dD
Equilibrium expression:
| | | |
| | | |
b a
d c
B A
D C
K =
14
12.2 The Equilibrium Constant, K

When the reactions and products are all in
gaseous form, equilibrium constant is expressed
in terms of partial pressures of the gases.




The value of K
eq
does not depend on the initial
concentrations of reactants and products.
( ) ( )
( ) ( )
b
B
a
A
d
D
c
C
P P
P P
K =
15
12.2 The Equilibrium Constant, K

When the reactants and products are all
in aqueous form, K
c
is used for equilibrium
constant.
c indicates the molar concentration (M)
When the reactants and products are all
in gaseous form, K
p
is used for equilibrium
constant.
p indicates the partial pressures of the
gases.
16
12.2.1 The Magnitude of Equilibrium
Constants, K

K is the ratio of products to reactants.
The larger K the more products are present at
equilibrium.
The smaller the K the more reactants are
present at equilibrium.
If K >> 1, then products dominate at equilibrium
and equilibrium lies to the right.
K << 1, then reactants dominate at equilibrium
and equilibrium lies to the left.

17
The range of equilibrium
constants, K

A: reaches equilibrium, little product.
K

= 1/49
B:reaches equilibrium, nearly all product
K

= 49/1
C: reaches equilibrium with significant
concentrations of reactant & product.
K

= 25/25 =1
18
12.2.2 The Direction of the Chemical
Equation and K

An equilibrium can be approached from any
direction:
Eg: N
2
O
4
(g) 2 NO
2
(g)
The equilibrium constant for this reaction (at
100C) is:


49 . 6
) (
) (
4 2
2
2
= =
O N
NO
p
P
P
K
19
12.2.2 The Direction of the Chemical
Equation and K
eq
For the reverse reaction:
2 NO
2
(g) N
2
O
4
(g)
The equilibrium constant for this reaction (at
100C) is:



The equilibrium constant for a reaction in one
direction is the reciprocal of the equilibrium
constant of the reaction in the opposite direction.

154 . 0
) (
) (
2
2
4 2
= =
NO
O N
p
P
P
K
20
12.3 Heterogeneous Equilibria
Equilibria in which all reactants and products are
present in the same phase are called
homogeneous equilibria.
Equilibria in which one or more reactants or
products are present in a different phase are
called heterogeneous equilibria.
Consider:
CaCO
3
(s) CaO(s) + CO
2
(g)
Experimentally, the amount of CO
2
does not
depend on the amounts of CaO and CaCO
3
.
WHY?
21
12.3 Heterogeneous Equilibria
The concentration of a pure solid or pure liquid
equals its density divided by its molar mass.
Neither density nor molar mass is a variable
thus the concentrations of solids and pure
liquids are constant.

| |
| |
3
2
CaCO
P CaO
K
CO
=
22
12.3 Heterogeneous Equilibria
CaO and CaCO
3
are pure solids and have
constant concentrations.



Rearrange:

( )
( ) 2 constant
P 1 constant
K
2
CO
=
( )
( )
( )
2
2
1 constant
2 constant
K K
'
CO p
CO
P K Theref ore
P
=
= =
23
12.3 Heterogeneous Equilibria
If a pure solid or pure liquid is involved in the
heterogeneous equilibrium, its concentration is
not included in the equilibrium constant
expression.
The amount of CO
2
formed (pressure of CO
2
)
will not depends on the amounts of CaO and
CaCO
3
present.
However, they do participate in the reaction and
must be present for an equilibrium to be
established.
24
12.3 Heterogeneous Equilibria
f




25
12.4 Calculating Equilibrium Constants, K

Steps:
Tabulate initial and equilibrium concentrations (or
partial pressures) for all species in the equilibrium.
If an initial and an equilibrium concentration is given
for a species, calculate the change in concentration.
Use the coefficients in the balanced chemical
equation to calculate the changes in concentration of
all species.
Deduce the equilibrium concentrations of all species.
Use these equilibrium concentrations to calculate the
value of the equilibrium constant.


26
Example 1

A mixture of hydrogen and nitrogen in a
reaction vessel is allowed to attain
equilibrium at 472C. The equilibrium
mixture of gases was analysed and found to
contain 7.38 atm H
2
, 2.46 atm N
2
, and 0.166
atm NH
3
. From these data, determine K
p
for

N
2
(g) + 3H
2
(g) 2NH
3
(g)


27
Answer 1
N
2
(g) + 3H
2
(g) 2NH
3
(g)




( )
( )( )
( )
( )( )
5
3
2
2
10 79 . 2
38 . 7 46 . 2
166 . 0
3
2 2
3

=
=
=
H N
NH
p
P P
P
K
28
Example 2

Enough ammonia is dissolved in 5.00 L of
water at 25C to produce a solution that is
0.0124 M in ammonia. The solution is then
allowed to come to equilibrium. Analysis of
the equilibrium mixture shows that the
concentration of OH
-
is 4.64 10
-4
M.
Calculate K
c
at 25C for the reaction:

NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)


29
Answer 2
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)

Initial

Change

Eqm



4.64 10
-4
M
0.0124 M
0 M
0 M
30
Answer 2
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)

Initial

Change

Eqm



4.64 10
-4
M
0.0124 M
0 M
0 M
+4.6410
-4
M
+4.6410
-4
M
-4.6410
-4
M
0.0119 M
4.64 10
-4
M
31
Answer 2
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)



| || |
| |
( )
( )
5
2
4
3
4
10 81 . 1
0119 . 0
10 64 . 4

+
=

=
=
c
c
K
NH
OH NH
K
32
Exercise 1
Methanol is produced commercially by the
catalysed reaction of carbon monoxide and
hydrogen: CO(g) + 2H
2
(g) CH
3
OH(g). An
equilibrium mixture in a 2.00 L vessel is found to
contain 0.0406 mol CH
3
OH, 0.170 mol CO, and
0.302 mol H
2
at 500 K. Calculate K
p
at this
temperature.
(Answer = 6.22 10
-3
)



33
12.5 Application of Equilibrium Constants, K

The equilibrium constant can be used:

(i) to predict the direction in which a reaction
mixture will proceed to achieve
equilibrium.

(ii) to calculate the concentrations of
reactants and products once equilibrium
has been reached.


34
12.5.1 To Predict the Direction of Reaction:
Writing Reaction Quotient

Consider: aA + bB pP + qQ


Q is the called reaction quotient.
a,b,p and q are the coefficients in the balanced
chemical equation.
The reaction quotient will equal the equilibrium
constant, K, only if the system is at equilibrium:
Q = K at equilibrium.


| | | |
| | | |
b a
q p
B A
Q P
Q =
35
12.5.1 To Predict the Direction of
Reaction: Example
N
2
(g) + 3H
2
(g) 2NH
3
(g)

A mixture of 2.00 mol H
2
; 1.00 mol of N
2
and
2.00 mol of NH
3
in a 1.00L container is at
472C. K
p
for the reaction at this temperature
is 2.75 10
-5
.

Will N
2
and H
2
react to form more NH
3
?


36
Answer
N
2
(g) + 3H
2
(g) 2NH
3
(g)

First, write the equilibrium-constant expression, K
p
(or
Q):



To calculate the partial pressure of each gases, use
PV=nRT (P
H2
= 122 atm, P
N2
= 61.2 atm, P
NH3
= 122
atm)




( )
( )( )
3
2
2 2
3
H N
NH
P P
P
Q =
37
Answer
Inserting the values into the reaction quotient, Q =
1.34 10
-4
.
Compare with K
p
value, K
p
=2.75 10
-5
.
Therefore the quotient will need to decrease for the
system to achieve equilibrium.
Can be achieved if decrease the pressure of NH
3
or
increase the pressures of H
2
and N
2
.
Thus the reaction proceeds toward equilibrium by
producing H
2
and N
2
from NH
3
, i.e. the reaction
proceeds from right to left.



38
12.5.1 To Predict the Direction of Reaction



If Q < K,.. more
product forms

If Q > K,. more
reactant forms

If Q = K

, no net
change
] tan [Re
] [Pr
] tan [Re
] [Pr
ts ac
oducts
Q
ts ac
oducts
K
eq
=
=
39
12.5.2 Calculating Equilibrium
Concentrations
The same step used to calculate the equilibrium
constants.
Generally, we do not have a number for the change
in the concentration.
Therefore we need to assume that x mol/L of the
species is formed (or used).
The equilibrium concentrations are given as
algebraic expressions.


40
Example
A 1.000L flask is filled with 1.00 mol of
H
2
and 2.00 mol of I
2
at 448C. K
p
for
the reaction at 448C is 50.5.
H
2
(g) + I
2
(g) 2HI(g)
Question:
What are the partial pressures of H
2
, I
2

and HI in the flask at equilibrium?
41
First, calculate the initial partial pressures of H
2
and I
2

using PV=nRT. (P
H2
= 59.17 atm, P
I2
= 118.4 atm).
Second, construct a table that consists of initial partial
pressures.

Initial 59.17 atm 118.4 atm 0 atm
Change
Equilibrium
H
2
(g) + I
2
(g) 2HI(g)
Answer
42
From the equation, 1 mol of H
2
+ 1 mol of I
2
will
produce 2 moles of HI.
The partial pressures of H
2
and I
2
will decrease and the
partial pressure of HI will increase.

Initial (atm) 59.17 118.4 0
Change (atm) - x -x +2x
Equilibrium (atm) 59.17 x 118.4 x 2x
H
2
(g) + I
2
(g) 2HI(g)
Answer
43
Substitute the values into equilibrium-constant
expression, K
p
(value is 50.5).

Answer
( )
( )( )
( )
( )( )
5 . 50
4 . 118 17 . 59
2
2 2
2 2
=

= =
x x
x
P P
P
K
I H
HI
p
( )
3 . 55 6 . 137
2
4
0 10 54 . 3 10 97 . 8 5 . 46
10 01 . 7 6 . 177 5 . 50 4
2
5 3 2
3 2 2
or x
a
ac b b
x use then
x x
x x x
=

=
= +
+ =
44
Substitute x values into the expressions for equilibrium
partial pressures.
Using x = 137.6 will lead to negative partial pressures
of H
2
and I
2
which are not chemically meaningful. So x
= 55.3.
P
H2
= 59.17 x = 3.87 atm, P
I2
= 118.4 x = 63.1 atm,
P
HI
= 2x = 110.6 atm.
Check:
Answer
( )
( )( )
( )
( )( )
1 . 50
1 . 63 87 . 3
6 . 110
2 2
2 2
= = =
I H
HI
p
P P
P
K
45
12.6 Le Chteliers Principle
If a system at equilibrium is disturbed by a change in
temperature,
Pressure (by changing the volume),
the concentration of one of the components (adding or
removing)
the system will shift its equilibrium position to reduce the effect
of the disturbance.
Changes in concentration or pressure cause shifts in
equilibrium but K remains constant.
Change in temperature increases or decreases the K value.
46
12.6.1 Change in Reactant or Product
Concentrations
A system at equilibrium:
- if we add a substance (a reactant or a
product) the reaction will shift
reestablish equilibrium by consuming
part of the added substance.
- removal of a substance reestablish
by forming more of the substance.

47
N
2
(g) + 3H
2
(g) 2NH
3
(g)

i) Addition of H
2

shift to reduce H
2
conc.
More NH
3
will form
N
2
will be reduced
ii) Addition of NH
3
shift to reduce NH
3
conc.
added NH
3
will decompose
to form N
2
and H
2
iii) Removal of NH
3
shift from left to right -
formation of more NH
3
.
C
o
n
c
e
n
t
r
a
t
i
o
n

Time
Initial
Equilibrium
H
2

NH
3

N
2

H
2
added at this
time
Equilibrium
reestablished
Example:
48
12.6.2 Change in Pressure
Pressure will change if volume of the
container changes.
Volume decreases pressure increases
equilibrium will shift towards the less
number of gas molecules
Volume increases pressure decreases
equilibrium shift towards the more number
of gas molecules

49
12.6.2 Change in Pressure
E.g: PCl
5
(g) PCl
3
(g) + Cl
2
(g)

No. of gas molecules is more on RHS
P |, equilibrium shift to LHS producing more
PCl
5
(g)
P +, equilibrium shift to RHS producing PCl
3
(g)
+ Cl
2
(g)
No change will occur if we increase the total
pressure by the addition of a gas that is not
involved in the reaction.
50
Changes in concentration or total pressure cause
shifts in equilibrium without changing the value of
K
eq
.
Applying Le Chteliers principle:
Consider heat as a chemical reagent.

Endothermic reaction (heat as a reactant)
A + B + Heat C

Exothermic reaction (heat as a product)
A + B C + Heat

12.6.3 Change in Temperature
51
When the temperature is increased, the
equilibrium shifts in the direction that absorbs
heat.
In an endothermic reaction, AH>0:
- increasing temperature or adding heat, the
equilibrium shifts to the right (product) and K
increases.

In an exothermic reaction, AH<0:
- increasing temperature or adding heat, the
equilibrium shifts to the left (reactant) and K
decreases.
12.6.3 Change in Temperature
52
Endothermic
A + B + Heat C
Exothermic
A + B C + Heat
Increase Increase
Decrease
Reaction K

Temperature
Decrease
Decrease
Increase
Increase
Decrease
12.6.3 Change in Temperature
53
Example
Consider the following equilibrium.
N
2
O
4
(g) 2NO
2
(g) AH = +58.0 kJ.

Which direction will the equilibrium shift if:
a) N
2
O
4
is added
b) NO
2
is

removed
c) N
2
is added
d) the volume is increased.
e) the temperature is decreased
54
a) N
2
O
4
is added
Concentration of N
2
O
4
increases, reaction
shifts to the right to decrease back N
2
O
4.


b) NO
2
is

removed

Concentration of NO
2
decreases, reaction
shifts to the right to increase back NO
2
.
c) N
2
is added

No effect, no shift in equilibrium position
N
2
O
4
(g) 2NO
2
(g) AH = +58.0 kJ
( )
( )
4 2
2
O N
2
p
P
P
K
NO
=
Answer
55
d) The volume is increased.
V | P +, the equilibrium shifts in the direction to
increase P by producing more gas molecules. It
shifts to the right, 1 mol N
2
O
4
molecules
generates 2 mol NO
2
molecules

e) the temperature is decreased.
The reaction is endothermic, heat is a reactant.
Equilibrium shifts to the left, forming more N
2
O
4
,
decreasing K
p
.
N
2
O
4
(g) 2NO
2
(g) AH = +58.0 kJ
Answer
56
12.6.4 The Effect of Catalyst
A catalyst lowers the activation energy
barrier for the reaction.
Therefore, a catalyst will decrease the time
taken to reach equilibrium.
The catalyst has no effect on the equilibrium
position.
A catalyst does not effect the composition of
the equilibrium mixture.
57
Haber synthesis of ammonia
Ammonia is used for production of fertilizer, explosives
and polymers.
58
N
2
(g) + 3H
2
(g) 2NH
3
(g) AH = -91.8 kJ/mol
59
Haber Process
60
Example
Methanol (CH
3
OH) is manufactured by reaction of carbon
monoxide with hydrogen in the presence of a ZnO/Cr
2
O
3

catalyst

CO (g) + 2H
2
(g) CH
3
OH (g) AH
o
= - 91 kJ

Does the amount of methanol (CH
3
OH) INCREASE,
DECREASE or REMAIN THE SAME when an
equilibrium mixture of reactants and product is subjected to
the following changes?

The temperature is increased.
CO is added.
The volume of the vessel is decreased.
The catalyst is removed
61
Answer
Decrease. Because the reaction is exothermic.
Reaction goes to the left (endothermic) to
reduce back the T, K
p
decreases, so
concentration decreases.
Increase. Because CO is a reactant, increasing
CO, shift equilibrium to right.
Increase. When the volume decreases, pressure
increases. The reaction shifts to the sides with
fewer molecules i.e. shifts to the right.
Remains the same. Additional or removal of a
catalyst does not affect the equilibrium
composition.
62


END of CHAPTER 12