Lecture 11

Chemical Equilibrium
Learning outcomes
• Define equilibrium condition.
• Derive equilibrium constant expression.
• Calculate equilibrium constants for heterogeneous equilibria.
• Calculate the reaction quotient.
• Study of some factors affecting equilibrium.
• Apply Le Chatelier’s principal.

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 Chemical reactions

Irreversible
Reactants Products
• Proceed in only one direction.
• Limiting reactant is completely
consumed in the reaction.
• Stoichiometric calculations are
performed to compute amount of
product.
Reversible
Reactants Products
• Most of the chemical reactions are
reversible.
• Reactants form products and then
products form reactants again.
• At equilibrium, equilibrium constant is
used to compute amount of product.
 What is Equilibrium?
• In a reversible reaction, at first reactants start to form products, then
as products are formed the reverse process takes place.
• Chemical equilibrium is achieved when the rate of forward reaction is
equal to the rate of backward reaction and the concentration of
reactants and products remain constant.

Reactants Products
Chemical equilibrium is a dynamic process, although at equilibrium there is no change in the
concentration of reactants and products but this doesn’t mean that the reaction stopped. The
reaction is continuously going on. As reactants are consumed to give products, the products at the
same rate react to form reactants again.
 Rate-time graph and Concentration –time graphs illustrating what
happens at equilibrium

At equilibrium, there is no
change in the concentration of
reactants and products.

In some reactions, at equilibrium, the concentration In other reactions, at equilibrium, the

of products is more than reactants. concentration of reactants is more than products.
Equilibrium favors product side. Equilibrium favors reactant side.
 The Equilibrium constant (K)
According to the law of mass action, for a reversible reaction at a state of equilibrium
and at constant temperature, a certain ratio of product and reactant concentrations
has a constant value, K (the equilibrium constant).
aA + bB cC + dD

  [ 𝐶 ]𝑐 [
𝐷 ]𝑑
Equilibrium expression K= • The bracketed terms mean Molar concentration.
𝑎 𝑏
[ 𝐴 ] [𝐵 ] • Molar concentration is moles/volume.

• The concentrations of the products are always
written in the numerator and the concentrations
of the reactants in the denominator.
• The equilibrium constant K, is a temperature
dependent numerical quantity.
• If one (or more) of the species in the equilibrium
expression is a pure liquid, a pure solid, or the
solvent present in excess, no term for this species
appears in the equilibrium- constant expression.
 Example:
Write the equilibrium expression for the following reaction:
4 NH3(g) + 7O2(g) 4NO2(g) + 6H2O(g)

4 6
[NO2 ] [H2O]
K 4 7
[NH3 ] [O2 ]
This reaction is an example of Homogenous equilibrium where all of the reactants and
products are at the same phase.

Heterogeneous equilibrium?
 Heterogeneous equilibrium
In heterogeneous equilibrium, the reactants and products of a reaction
are present in more than one phase (solid, liquid, gas).

Example:
Thermal decomposition of calcium carbonate to prepare lime.
CaCO3(s) CaO(s) + CO2(g)

K = [CO2]

The pure solids are not included in the equilibrium expression since
their concentrations cannot change.
Another example
Write a balanced equation for the decomposition of liquid water into gaseous hydrogen
and oxygen.
Then write the equilibrium expression for this reaction.
H2O(l) H2(g) + O2(g)

2H2O(l) 2H2(g) + O2(g)

K= [H2]2[O2]
What if the water was in the gaseous phase, how would the equilibrium
expression differ?

K= [H2]2[O2] / [H2O]2
 Example
H2 (g)+ F2 (g) 2HF(g)
The equilibrium constant, K, for the reaction has the value 2.1x103 at a particular
temperature. When the system is at equilibrium at this temperature, the concentrations of
H2 and F2 are both found to be 0.0021 M.
What is the concentration of HF in the equilibrium system under these conditions?
  [ 𝐻𝐹 ]2
𝑘=
[𝐻 2][𝐹2]
2.1x103 = [HF]2
[0.0021] [0.0021]

[HF] = 0.096 M
 An important rule
The K (equilibrium constant) for the following reaction is 4.63 x 10-3 at 25 ͦ C

N2O4 (g) 2NO2 (g)

  [NO 2]2
𝑘= ¿ = 4.63 x 10-3
[N 2O 4¿
Always when we write the equation in the opposite direction , the new K will
be the reciprocal of the first K
2NO2 (g) N2O4 (g)
  = 1 = 216
4.63 x 10-3
 Reaction quotient (Q)
• When the reactants and products • The reaction quotient is obtained by aA + bB cC + dD
of a given chemical reaction are substituting the initial given 𝑐 𝑑
mixed, it is useful to know concentrations into the equilibrium  
Q=[ 𝐶 ] 0
[ 𝐷0
]
whether the mixture is at expression instead of using 𝑎 𝑏
[ 𝐴 ]0 [ 𝐵0 ]
equilibrium or if not at equilibrium concentrations.
equilibrium, it is important to
know the direction in which the • After calculating the value
system must shift to reach of Q, you must compare it
equilibrium. to K
• The reaction quotient (Q) will
determine this.

Q=k Q<k Q>k

Reaction shifts forward Reaction shifts backward
Reaction is at towards product side to towards reactant side to
equilibrium reach equilibrium reach equilibrium
 Example
2NO2 (g) N2O4 (g) K = 216 at 25 ͦ C

If the following initial concentrations were mixed, determine if the reaction is at a state of
equilibrium and if not, predict in which direction the reaction will shift to reach equilibrium.

A) [NO2 ] = 0.1 M, [N2O4 ] = 2.9 M

0 0 B) [NO2 ] = 1.2 M, [N2O4 ] = 2.2 M C) [NO2 ]0= 0.1M, [N2O4 ] 0= 2.16M
0 0
 
0 Q = [2.2] = 1.53 Q = [2.16] = 216
0 [ 1.2]2 [ 0.1]2
Q<K Q=K
Q = [2.9] = 290 The concentrations of the
[ 0.1]2 products must be The reaction is at a
increased and the state of equilibrium.
Q>K concentrations of the
The concentrations of the products must be
reactants decreased to
decreased and the concentrations of the
reach equilibrium.
reactants increased to reach equilibrium.
The reaction shifts forwards (to the
The reaction shifts backwards (to the left). right).
 Equilibrium Constant in terms of
Pressure, K
 When the reactants and products in a chemical reaction are GASES,p
we can formulate the
equilibrium-constant expression in terms of PARTIAL PRESSURES.
Consider the following reaction where A, B, C and D are gases:

aA + bB cC + dD • PD is the partial pressure of D.

• PC is the partial pressure of C.
Equilibrium expression Kp = (PD)d (PC)c • PA is the partial pressure of A.
(PA)a (PB)b • PB is the partial pressure of b.

 It is possible to convert between K (equilibrium constant in terms

•
of molar concentrations)
and Kp through the following equation:

• ∆n is change in the number of moles of gas in the balanced equation.

Kp = k (RT) ∆n ∆n = (moles of gaseous products) – (moles of gaseous reactants)
• R is the universal gas constant (0.0821 L.atm/K.mol).
Kp = k (RT) (c+d) – (a+b) • T is the temperature in kelvin.
 Some factors that affect
chemical equilibrium
1- Effect of change of Concentration of reactants or products on equilibrium.

2- Effect of change of Temperature on equilibrium.

Based on Le Châtelier’s principle we can predict the effect of these

changes on the chemical equilibrium.

Le Châtelier’s principle states that if a change is imposed on a

system at equilibrium, the position of the equilibrium will
shift in a direction that tends to reduce that change.
 1- The effect of change in concentration of reactants
or products on
 Whenequilibrium
the concentration of reactants are increased, the equilibrium will shift forward to reduce that
change.
 When the concentration of the products are increased, the equilibrium will shift backwards to reduce that change

 When the concentration of reactants are decreased, the equilibrium will shift backwards to reduce that
change.
 When the concentration of the products are decreased, the equilibrium will shift forwards to reduce that change.

Important notes:
 If any of the reactants or products is a pure liquid or pure solid, since they have no effect on the
equilibrium position, so any change of its amount will not affect the equilibrium, there will be no shift in
the reaction.
 Although the change in concentration may alter the equilibrium position but they do not alter the value of
equilibrium constant.
For example:
The addition of a reactant shift the equilibrium position forwards but has no effect on the value of the
equilibrium constant, as the new equilibrium concentrations satisfy the original equilibrium constant.
1- The effect of change in concentration of reactants
or products on
equilibrium
• Example: For the synthesis of ammonia (Haber Reaction)
N2(g) + 3H2(g) 2NH3(g)

Suppose that there is an equilibrium position described by these concentration:

[N2] = 0.399M, [H2] = 1.197M , [NH3] = 0.202M
[NH3 ]2 (0.202) 2 2
K   5.96x10
[N2 ][H2 ]3 (0.399)(1. 197) 3

What will happen if 1.0mol/l N2 is suddenly injected into the system?

[NH3 ]02 (0.202) 2 2

Q   1.70x10
[N2 ]0 [H2 ]30 (1  0.399)(1.1 97) 3

As expected, Q is less than K because the concentration of N2 was increased.

The system will shift to the right to come to the new equilibrium position.
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1- The effect of change in concentration of reactants
or products on
equilibrium
Another example: Arsenic can be extracted from its ore by first reacting the
ore with oxygen to form As4O6, which is then reduced using carbon
As4O6(s) + 6C(s) As4(g) + 6CO(g)
Predict the direction of the shift of the equilibrium position in response to
each of the following changes in conditions:
a. Addition of carbon monoxide.
The equilibrium position will shift to the left.
b. Addition or removal of carbon or tetraarsenic hexoxide (As4O6).
No effect on the equilibrium.
C. Removal of gaseous arsenic (As4).
The equilibrium position will shift to the right.
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2- The effect of change in temperature of the
reaction on equilibrium
For an Endothermic reaction: H°= + ve kJ
 Treat energy as a reactant.
 As the temperature is increased, the equilibrium shifts to the right.
 As the temperature is decreased, the equilibrium shifts to the left.
556 kJ + CaCO3(s) CaO(s) + CO2(g) H°= 556 kJ
An increase in the temperature will cause the A decrease in the temperature will cause the
equilibrium to shift to the right and the value of k to equilibrium to shift to the left and the value of k to
increase. decrease.

For an Exothermic reaction: H°= - ve kJ

 Treat energy as a product.
 As the temperature is increased, the equilibrium shifts to the left.
 As the temperature is decreased, the equilibrium shifts to the right.
N2(g) + 3H2(g) 2NH3(g) + 92 kJ H°= -92 kJ
An increase in the temperature will cause the A decrease in the temperature will cause the
equilibrium to shift to the left and the value of k to equilibrium to shift to the right and the value of k to
decrease. increase.
2- The effect of change in temperature of the
reaction on equilibrium
• For each of the following reactions, predict how the
value of K changes as the temperature is increased.
• a. N2(g) + O2(g) 2NO(g) H°= 181kJ
• b. 2SO2(g) + O2(g) 2SO3(g) H°= -198kJ

• a. This is an endothermic reaction, as indicated by the

positive value for H°. Energy can be viewed as a reactant
and K increases as the temperature increases.

• b. This is an exothermic reaction. Energy can be viewed as

a product and K decreases with temperature increase.
Exercise : Predict whether the following reaction is
exothermic or endothermic

N2O4 (g) 2NO2 (g)

Endothermic
Transparent gas Brown gas

Cooled container Heated container

 Real life example of equilibrium
Hemoglobin in our body combines with oxygen to form oxyhemoglobin according to
the following equation:
Hb (aq) + O2 (aq) HbO2 (aq)
Oxyhemoglobin is responsible
for transporting oxygen to
tissues.

 At high altitudes, the level of oxygen drops.

So the equilibrium will be shifted to the left, which
decreases the supply of oxyhemoglobin, causing hypoxia.
 That is why mountain climbers always carry with them
oxygen tanks when they climb summits.
References
• Chemistry, 10th ed., Chang, Chapter 14.
• Lecture 11 by Prof. Rasha Elnashar, GUC, WS 2014.

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