Department of Chemistry/Biochemistry/Molecular Biology

CHM 002 - Physical Chemistry

Topic: Chemical Equilibrium

Reversible Reaction
Not all chemical reactions proceed to completion. In most reactions two or more chemical
substances react to form products which themselves react to give back the original substances.
Thus A and B may react to form C and D which react together to reform A and B.

A+B C+D (Forward reaction)

C+D A+B (Reverse reaction)

A reversible reaction is a reaction which can go in the forward and backward reactions
simultaneously. Such reacts are represented by writing a pair of arrows between the reactants and
products.

A + B C + D

Examples of reversible reactions are:

2NO2 N2O4(g)

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

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

Chemical equilibrium
Chemical equilibrium may be defined as the state of a reversible reaction when the forward and
reverse reactions occur at the same rate and the concentrations of reactants and products do not
change with time.

Chemical equilibrium is dynamic equilibrium. This means that, the forward and reverse reactions
are taking place at equilibrium but the concentrations remain unchanged.

Characteristics of chemical equilibrium

(1) Constancy of concentrations
(2) Equilibrium can be initiated from either side
(3) Equilibrium cannot be attained in an open vessel

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 (4) A catalyst cannot change the equilibrium point
(5) Value of equilibrium constant does not depend upon the initial concentration of reactants
(6) At equilibrium, ∆G = 0

Law of Mass Action

The law of mass action states that the rate of a chemical reaction is proportional to the active
masses of the reactants. The term ‘active mass’ is equal to molar concentration.

Let us consider the reaction

aA + bB cC + dD
Where a, b, c and d are numerical quotients of the substances A, B, C and D respectively.
According to Law of Mass Action,

Rate of forward reaction =k1[A]a[B]b

Rate of reverse reaction = k2[C]c[D]d

At equilibrium, k1[A]a[B]b = k2[C]c[D]d

K1 [C]c[D]d
K2 = [A]a[B]b
Kc = [C]c[D]d
[A]a[B]b

Kc is the equilibrium constant in terms of molar concentration. k1and k2 are velocity constants for
forward and reverse reactions respectively.

Solved problem 1: Write the equilibrium constant expression of the following reactions

i. 2N2O5 4NO2(g + O2(g)

)
ii. N2(g) + 3H2(g) 2NH3(g)
Solution

i) Kc = [NO2]4[O2]
[N2O5]2

ii) Kc = [NH3]2
[N2][H2]3

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Relationship between Kc and Kp
As we mentioned earlier, Kc is equilibrium constant in terms of molar concentration while Kp is
the equilibrium constant in terms of partial pressure. Kc and Kp are not numerically equal, the
relationship can be derived as follow:

For an ideal gases,

Recall that

Where ∆n is the differences in the sums of the coefficients for the gaseous products and
reactants, R is the gas constant and T is the temperature in Kelvin.

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Solved Problem 2: At 500oC, the reaction between N2 and H2 to form ammonia has Kc = 6.0x10-
2
. What is the numerical value of Kp for the reaction.

Solution

N2(g) + 3H2(g) 2NH3(g)

From the reaction, ∆n = 2-4 = -2

Kc = 6.0x10-2

T = 500 + 273 = 773K

R = 0.0821

Kp =Kc (RT)∆n

Kp = (6.0x10-2) (0.0821 x 773)-2

= 1.5 x 10-5

Solved problem 3: for the following reactions

2SO2(g) + O2(g) 2SO3 (g)

the equilibrium concentrations at 727 oC were found to be SO2 = 0.27mol dm-3, O2 = 0.40mol
dm-3 and SO3 = 0.33 mol dm-3. What is the value of the equilibrium constant, Kc and Kp at this
temperature.

Solution
[SO3]2
Kc =
[SO2]2 [O2]

(0.33)2
Kc = 2
= 3.7mol-1 dm3
(0.27) (0.40)
Kp =Kc (RT)∆n

Kc= 3.7mol-1 dm3

T = 727 + 273 = 1000K

R = 0.0821

∆n = 2-3 = -1
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Kp= 3.7 (0.0821 x 1000)-1

= 0.0451

Relationship Between ∆G and the Equilibrium Constant

Thermodynamically, equilibrium constant is related to Gibb’s free energy by equation (3). The
equation is also known as van’t Hoff Isotherm.

∆Go= -RT In k ……………………………………………………………………… (3)

The sign of ∆Go indicates whether the forward or reverse reaction is spontaneous

1) If ∆Go is negative, the reaction proceeds spontaneously in the forward reaction

2) If ∆Go is positive, the reverse reaction is spontaneous
3) If ∆Go = 0, the reaction is in equilibrium

Solved problem 4: the equilibrium constant, Kp, for the following reaction is 5.04 x 1017 atm-1 at
25oC. Calculate ∆Go and from the value of ∆Go, what can you infer about the reaction.

C2H4 (g) + H2(g) C2H6 (g)

Solution

∆Go = -RT In k

R = 8.314; T = 25 + 273 = 298K, Kp= 5.04 x 1017atm-1

∆Go = -8.314 x 298 (In 5.04 x 1017)

∆Go = -101KJ

From the result, the reaction proceeds spontaneously in the forward reaction because ∆G o is
negative.

Assignment

1) The Kp for this equilibrium reaction: NH4Cl( s) NH3(g) + HCl(g) is 0.11 at 25oC,
calculate Kc at this temperature.

Homogeneous and Heterogeneous Equilibria

A homogeneous equilibrium is an equilibrium that involves reactants and products in a single

phase. Catalytic methanation is an example of a homogeneous equilibrium; it involves only
gaseous reactants and products. On the other hand, a heterogeneous equilibrium is an

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equilibrium involving reactants and products in more than one phase. For example, the reaction
of iron metal filings with steam to produce iron oxide, Fe3O4, and hydrogen involves solid
phases, Fe and Fe3O4, in addition to a gaseous phase.

3Fe(s) + 4H2 O ↔ Fe3 O4 (s) + 4H2 (g)

In writing the equilibrium-constant expression for a heterogeneous equilibrium, you omit

concentration terms for pure solids and liquids. For the reaction of iron with steam, you would
write:
[H2 ]4
Kc =
[H2 O]4

Factors Affecting Chemical Equilibrium

In 1884 a French Chemist called Henry Le Chatelier proposed a principle which is applicable to
all system in equilibrium.

Le Chatelier’s principle may be stated as: if a change in concentration, pressure or temperature is

caused to a chemical reaction in equilibrium, the equilibrium will shift to the right or the left so
as to minimize the change. Therefore, factor affecting chemical equilibrium include:
temperature, concentration and pressure of the reactants and products, catalyst.

N.B: catalyst does not change the position of equilibrium, but affects the rate of attainment of
equilibrium.

Effect of Change in Concentration on Equilibrium Mixture

When concentration of any of the reactant or products is changed, the equilibrium shifts in the
direction so as to reduce the change in concentration that was made. A change in the
concentration of reactant or product can be affected by the addition or removal of that species.
For instance, when the concentration of reactant is increased for a reaction in equilibrium, the
forward reaction alone occurs momentarily to consume more of the reactant until a new
equilibrium is established.

Effect of a Change in Pressure on Equilibrium Mixture

The pressure of a gaseous reaction at equilibrium is determined by the total number of molecules
it contains. Generally, if the pressure of system in equilibrium is increased, the equilibrium shifts
to the side with less number of gaseous molecules. When the total number of gaseous molecules
of reactants and products are the same, change in pressure has no effect on the equilibrium.
i) 2SO2(g) + O2(g) 2SO3 (g)
ii) PCl5 PCl3 + Cl2

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If the pressure is increased, the equilibrium will shift to the right for reaction (i) favouring
formation of more SO3. However, increase in pressure will shift equilibrium to left for reaction
(ii) favouring formation of PCl5 and vice-versa.

Effect of change of concentration on Equilibrium Mixture

In general, increase in temperature favours the reverse reaction in an exothermic reaction but
favours forward reaction in an endothermic reaction.

Consider contact process for manufacturing of sulphuric acid:

2SO2(g) + O2(g) 2SO3 (g) + 42 kcal

The reaction is endothermic. Increase in temperature will shift equilibrium position to right,
favouring the formation of SO3

Effect of Catalyst on Equilibrium Mixture

Addition of catalyst to a reaction mixture does not affect the equilibrium; catalyst only quickens
the attainment of equilibrium by the reaction. The value of the equilibrium constant is not
affected.

Solubility
When a solid is placed in a solvent, molecules or ions, as the case may be, break away from the
surface and pass into the solution (dissolution).At the same time, some of the dissolved solute
particles are ‘redeposited’ or recrystallized out of the solution (recrystallization or
precipitation). At a point, the rate of dissolution of the solute is equal to the rate of precipitation;
dynamic equilibrium is achieved. The solution at this state is said to be saturated.

Solubility of a substance in a solvent is the concentration in the saturated solution.

Solubility products
Solubility product is a special type of equilibrium constant. When a sparingly soluble salt e.g.
AgCl dissolves in water at a given temperature, a stage will be reached when it will not dissolve
further and both the solid and solution will co-exist in equilibrium.

AgCl(s) Ag+(aq) + Cl-(aq)

At equilibrium, the rate at which AgCl(s) dissociate becomes equal to the rate at which Ag+ and
Cl-recombines to form back AgCl(s). This equilibrium is referred to as ionic equilibrium.

Applying the Law of Mass action for dissolution of AgCl, we have

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 [Ag+] [Cl-]
K =
[AgCl]
The amount of AgCl in contact with saturated solution does not change with time and the factor
[AgCl] remains same. Thus the equilibrium expression becomes

Ksp = [Ag+] [Cl-] ………………………………………………………………….. (4)

Kspis solubility product, [Ag+] and [Cl-] are expressed in mol/L.

[Ag+] [Cl-] in equation (4) is called the ionic product or ion product.

Solved problem 5: calculate the solubility product of Bismuth sulphide, Bi 2S3 if the solubility of
the salt in water is 1.0 x10-15mol/L at 25oC

Solution
3+ 2-
Bi2S3(aq) 2Bi (aq)
+ 3S (aq)
3+ 2- -15
1 mole of Bi2S3 gives 2 moles of Bi and 3 moles of S . Therefore, 1.0 x10 mol/L will give
3+ -15
[Bi ] = 2 x 1.0 x10 mol/L
2- -15
[S ]= 3 x 10 mol/L
3+ 2 2- 3
Ksp = [Bi ] [S ]
-15 2 -15 3
Ksp = (2 x 10 ) (3 x 10 )
-73
= 1.08 x 10

The Common-ion Effect

When a soluble salt (say, A+C-) is added to a solution of another salt (A+B-) containing a
common ion (A+),the dissociation of AB will be suppressed.

AB(s) A+(aq) + B-(aq)

For instance, a saturated solution of silver chloride, equilibrium is established

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AgCl(s) Ag+(aq) + Cl-(aq)

When NaCl is added to the solution, the concentration of Cl- ion will increase. The equilibrium
will be shifted to the left to form more of solid AgCl. Thus, the solubility of AgCl will decrease.

Thus, the reduction of the degree of dissociation of a salt by the addition of a common-ion is
called the common-ion effect.

Solved problem 6: If solid NH4Cl is added to a saturated aqueous solution of ammonia,

(1) where will the equilibrium shift to

(2) what will happens to the equilibrium concentration of OH-

Solution

NH4OH NH4+ + OH-

(i) The equilibrium will shift to left, favouring precipitation of NH4OH

(ii) The equilibrium concentration of OH- will decrease

Assignment

2. The solubility of CuBr is found to be 2.0 x 10-4mol/L at 25oC, calculate Ksp value for CuBr.

3. The solubility of Mg(OH)2 at 25oC is 0.00764g/L, what is the value of Ksp for Mg(OH)2?