Chemical Equilibrium

Chapter 15
 Equilibrium

e.g. H2 (g) + I2 (g) 2HI (g)

NOTE:
Equilibrium is a dynamic process because reaction has not
stopped.
The reaction must occur in a closed system so that no
products or reactants are lost.
There is no overall change in the concentrations of products
or reactants at equilibrium.
Some reactions are not at equilibrium, but go to completion
( ).
 A B
At equilibrium: At equilibrium:
Rate of forward rxn Ratio [B]:[A] remains
= Rate of reverse rxn constant

Rxn rate depends on the Equilibrium

concentrations of the reagents mixture

The equilibrium condition can be reached from either direction.

 Dissociated to form Colour stops changing
Frozen N2O4 – brown NO2 gas above  [N2O4] and [NO2]
almost colourless boiling point constant

N2O4 (s) N2O4(g)  NO2(g) N2O4(g) NO2(g)

 Equilibrium Constant, KC
Consider the general reaction :
aA + bB cC + dD

[C]c [D]d Equilibrium-constant

Kc = expression
[A]a [B]b

Equilibrium Concentrations
constant are used

The equilibrium constant is the value obtained from the

equilibrium-constant expression when equilibrium
concentrations are substituted.
Kc is dimensionless!
Kc is temperature dependent!
Example:
Write the equilibrium-constant expression for the following
reaction:
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)

NOTE:
Products in the numerator; reactants in the denominator.
The equilibrium-constant expression depends only on the
stoichiometry of the reaction, not its mechanism.
Example: the catalytic methanation reaction
CO (g) + 3H2 (g) CH4 (g) + H2O (g)
Some equilibrium compositions for the methanation reaction:

CO (g) + 3H2 (g) CH4 (g) + H2O (g)

Starting Conc’s Equilibrium Conc’s Kc

Exp 1 0.1000 M CO 0.0613 M CO 3.93

0.300 M H2 0.1839 M H2
0.0387 M CH4
0.0387 M H2O

Exp 2 0.2000 M CO 0.1522 M CO 3.91

0.300 M H2 0.1566 M H2
0.0478 M CH4
0.0478 M H2O

Exp 3 0.1000 M CO 0.0613 M CO 3.93

0.100 M H2 0.1839 M H2
0.0387 M CH4
0.0387 M H2O
Equilibrium Constant using Pressures, KP
When products and reactants are gases, partial pressures
can be used instead of concentrations in the equilibrium
constant expression:

aA(g) + bB(g) cC(g) + dD(g)

(PC)c (PD)d PA is the partial pressure

Kp = of A in atmospheres etc.
(PA)a (PB)b

Indicates pressures are used

NOTE: K = Keq = equilibrium constant.

We express it as Kc or Kp to show whether concentrations or
partial pressures were used in its calculation.
For an ideal gas:
PV = nRT
 P = (n/V)RT = cRT c = concentration
 PA = [A]RT c = n/V

Thus: Kp = Kc(RT)n
where n = change in the number of moles of gas in the rxn

e.g. CO (g) + 3H2 (g) CH4 (g) + H2O (g)

n =

When n = 0
Example:
In the synthesis of ammonia from hydrogen and nitrogen,
Kc = 9.60 at 300oC.
N2(g) + 3H2(g) 2NH3(g)
Calculate Kp for the reaction at this temperature.
 Magnitude of Equilibrium Constants
Recall: In the equilibrium constant expression, products are
in the numerator and reactants are in the denominator.
[C]c [D]d
aA + bB cC + dD Kc =
[A]a [B]b

Keq …………….. Keq …………….

Product are favoured; Reactants are favoured;
m lies to the right m lies to the left
 Direction of Equilibrium and Keq
[C]c [D]d
aA + bB cC + dD Kc =
[A]a [B]b

Equilibrium constant for a reverse reaction:

cC + dD aA + bB
 Heterogeneous Equilibria
Homogeneous equilibria  equilibria that involves reactants
and products in a single phase only.

Heterogeneous equilibria  equilibria involving reactants

and products in more that one phase.

e.g. CaCO3 (s) CaO (s) + CO2 (g)

[CaO ][CO 2 ]
Kc 
[CaCO 3 ]

BUT how do we express the concentration of a solid???

Concentration of pure solid or liquid:
Density g/L
  mol / L
Molar mass g / mol

Molar mass is a constant and density is a constant at a given

temperature
 concentration of a pure solid or pure liquid is a
constant irrespective of how much of it is present.

[CaO ][CO 2 ] (cons tan t 1)[CO 2 ]

Kc   Kc 
[CaCO 3 ] (cons tan t 2)

K c  K c
(cons tan t 2)
  [CO 2 ]
(cons tan t 1)

When writing the equilibrium-constant expression for

heterogeneous equilibria, the concentration terms for pure
solids and pure liquids are omitted.
Example
Write the equilibrium-constant expression for the following
reaction:
3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
 Calculating Equilibrium Constants
Example:

Carbon dioxide decomposes at elevated temperatures to

carbon monoxide and oxygen:
2CO2(g) 2CO(g) + O2(g)
At 3000 K, 4.00 mol CO2 is placed into a 2.00 L container and
allowed to come to equilibrium. At equilibrium, 1.80 mol CO2
remains. What is the Kc at this temperature?
Application of Equilibrium Constants
Recall:
For Keq large  product are favoured; m lies to the right
For Keq small  reactants are favoured; m lies to the left

1) Predicting the direction of reaction

Suppose a gaseous mixture from an industrial plant has the
following composition at 1200 K:
0.0200 M CO 0.0200 M H2
0.00100 M CH4 0.00100 M H2O
Would the following reaction go forward or in reverse?
CO (g) + 3H2 (g) CH4 (g) + H2O (g)

To answer this question we need to calculate the reaction

quotient Q, and compare its value to that of Keq
 The reaction quotient (Q) is an expression that has the same
form as the equilibrium constant expression but whose
concentration values are not necessarily those at equilibrium.
CO (g) + 3H2 (g) CH4 (g) + H2O (g)

Kc = 3.93 for this reaction at 1200 K.

If Qc > Kc, the reaction will go left

If Qc < Kc, the reaction will go right
If Qc = Kc, the reaction is at m
2) Calculating equilibrium concentrations
Once you have determined the equilibrium constant for a
reaction, you can use it to calculate the concentrations of
substances in an equilibrium mixture.

Example
Nitrogen and oxygen form nitric oxide:
N2(g) + O2(g) 2NO(g)
If an equilibrium mixture at 25°C contains 0.040 M of N2 and
0.010 M of O2, what is the concentration of NO in this
mixture? Kc at 25°C is 1x10-30.
Example
Hydrogen iodide decomposes to hydrogen gas and iodine
gas.
2HI(g) H2(g) + I2(g)
At 800 K, the equilibrium constant for this reaction is 0.016. If
0.50 mol HI is placed in a 5.0 L flask, what will the
composition of the equilibrium mixture be?
 Le Chatelier’s Principle
When a system in chemical equilibrium is disturbed the
system shifts in equilibrium composition in a way that tends
to counteract this change.

Three ways the equilibrium can be disturbed:

1) Changing the concentrations by removing products or
adding reactants to the reaction vessel.
2) Changing the partial pressure of gaseous reactants and
products by changing the volume.
3) Changing the temperature.

 by changing the reaction conditions, you can increase or

decrease the yield of product
 1) Change in reactant or product concentrations
Consider the Haber process:
N2 (g) + 3H2 (g) 2NH3 (g)

If H2 is added while the

system is at equilibrium:
the system must consume
the H2 and form products
until a new equilibrium is
established
 [H2] and [N2] decreases
and [NH3] increases
The Haber process:
N2 (g) + 3H2 (g) 2NH3 (g)

If NH3 is removed from the equilibrium mixture:

 to increase the yield in an industrial process, reactants

have to be added and products removed
Example:

The Fischer-Tropsch process for the synthesis of gasoline

consists of passing a mixture of carbon monoxide and
hydrogen over an iron-cobalt catalyst.
A typical reaction that occurs in the process is as follows:

8CO(g) + 17H2(g) C8H18(g) + 8H2O(g)

Suppose the reaction mixture comes to equilibrium at 200°C,

then is suddenly cooled to room temperature where octane
liquifies. The remaining gases are then reheated to 200°C.

What is the direction of the reaction as equilibrium is

attained?
2) Effects of Volume and Pressure Changes
If the pressure is increased by decreasing the volume of a
reaction mixture, the reaction shifts in the direction of fewer
moles of gas.
Addition of an inert gas will increase the total pressure, but
will not affect the partial pressures and hence not shift the
equilibrium.

Example:
Let’s consider the reaction in the Fischer-Tropsch process:
8CO(g) + 17H2(g) C8H18(g) + 8H2O(g)

Would you expect more or less of the product octane, C8H18,

as the pressure increases?
3) Effects of Temperature Changes

For an exothermic reaction (H negative), the amount of

products are decreased at equilibrium by an increase in
temperature.
A+B C + D + heat

Also  temperature  ? Keq

For an endothermic reaction (H positive), the amount of

products are increased by a increase in temperature.
A + B + heat C+D

Also  temperature  ? Keq

Example:
One stage in the manufacture of sulphuric acid is the
formation of sulphur trioxide by the reaction of SO2 with O2.
Predict how the equilibrium composition of the reaction
mixture will change when the temperature is raised.
2SO2(g) + O2(g) 2 SO3(g) H = -198 kJ
4) The Effect of Catalysts

A catalyst increases the Uncatalyzed

rates of both the forward reaction
and the reverse reactions
Catalyzed
reaction

Self study: why is the use of a catalyst in the Haber process

so crucial?