Kinetics & Equlibria

2. PRINCIPLES OF CHEMICAL EQUILIBRIA

Chemical reactions moving in opposite directions and balances out are said to be in equilibrium.
When evaporation and condensation are occurring at equal rates, equilibrium is set up and in this
case a dynamic equilibrium.

Figure 1.18
Dynamic Vapour
Equilibrium System

Number Of particles
Evaporated =
Number Of Particles
Condensed.

Liquid

Heat

If the system is disturbed, it tends to respond in such a way as to oppose the disturbance and so
restore equilibrium. If an increase in heat energy increases evaporation, then condensation will
increase and vaporization.

Number of Particles Number Of Particles

Evaporated Condensed

The symbol represents two phases in equilibrium in a closed system. The beaker with water
is covered and heated.

Equilibrium Constant

Take the reaction:

Alcohol + Acid Ester + Water

Forward Reaction ∞ [Alcohol] * [Acid]

= k1 [Alcohol] * [Acid]

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Backward Reaction ∞ [Ester] * [Water]

= k2 [Ester] * [Water]

The two reactions are balanced, so

k [Alcohol] * [Acid] = k [Ester] * [Water]

This gives:

k1 [Ester] * [Water]
=
k2 [Alcohol] * [Acid]

k1 / k2 gives a new constant, Kc, where Kc is called the equilibrium constant and the ‘c’ represents
concentration, i.e.

[Ester] * [Water]
Kc =
[Alcohol] * [Acid]

For any reaction:

aP + bQ cR + dS

[R]c [S]d
Kc =
[P]a [Q]b

The statement is the equilibrium law which states that if a reversible reaction is allowed to reach
equilibrium, the product of the concentrations of the products ‘x’ (raised to the appropriate
powers) divided by the product of concentration of the reactants (raised to the appropriate
powers) has a constant value at a particular temperature.

Example

When one mole of hydrogen iodide is allowed to dissolve in a 1 dm3 vessel at 440oC only 0.78
moles of HI are present at equilibrium. What is the equilibrium constant at this temperature?

Solution

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

Species 2HI H2 I2 For Total Products

Number Of Moles (Initially) 1 0 0 1.0 – 0.78

Number Of Moles At 0.78 0.11 0.11 = 0.22

Equilibrium
0.22 / 2

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= 0.11

Concentration At Equilibrium 0.78 0.11 0.11 0.11 For

(mol dm-3) 1 1 1 Each Product

[H2 (g)] [I2 (g)]

Kc =
[HI (g)]

0.11 * 0.11 1
= = = 0.02
(0.78)2 50

= 2 * 10-2 mol dm-3

Example

A 10 cm3 mixture contains the initial amounts / mole; ethanol – 0.0515, ethanoic acid –
0.0525, water – 0.0167, ester – 0.0314. The equilibrium amount of ethanoic acid is 0.0255 mol.

Solution

The amount of ethanoic acid and ethanol decrease by 0.0270 mol, e.g. (0.0525 – 0.0255) and ester
and water increased by that amount (0.0270 mol).

Species CH3COOH + C2H5OH CH3COOC2H5 + H2O

Number Of Moles 0.0525 0.0515 0.0314 0.0167

(Initially)

Equilibrium Amount / Mole 0.0255 0.0245 0.0584 0.0437

[CH3COOC2H5] [H2O]
Kc =
[CH3COOH] [C2H5OH]

[0.0584] [0.0437]
=
[0.0255] [0.0245]

Kc = 4.1 (no units)

N.B. The amount decreased in the left is increased by the same amount in the left of the equation.
Reactions involving gases have their equilibrium constant being expressed in terms of partial
pressure, P

Kp

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Example & Solution

2NO2 (g) N2O4 (g)

P N2O4
Kp =
(P NO2)2

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

(P NH3 (g))2
Kp =
(P N2 (g)) (P N2 (g))3

Problem

Formation of phosgene COCl2 from CO and Cl2

CO (g) + Cl2 (g) COCl2 (g)

At 600 oC, a gas mixture of CO and Cl2 is prepared that has initial pressures (before reaction) of
0.60 atm. and 1.10 atm for CO and Cl2 respectively. After the reaction mixture has reached
equilibrium, the partial pressure of COCl2 (g) at this temperature is measured to be 0.10 atm.
Calculate the Kp for the reaction.

Species CO2 (g) + Cl2 (g) COCl2 (g)

Initial Partial Pressure 0.60 1.10 0

(atm)

Change In Partial Pressure - 0.10 - 0.10 + 0.10

(atm)

Equilibrium Partial Pressure 0.50 1.00 0.10

(atm)

PCOCl2 (g)
Kp =
(PCO2 (g)) (PCl2 (g))

(0.10)
=
(0.50) (1.0)

Kp = 0.20 atm-1

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N.B: When partial pressure on the right hand – side of the equation increases the partial pressures
on the left decreases by the same value.

Influences on Equilibrium Constants

(a) A change of temperature affects equilibrium constants.

(b) Concentration, pressure and catalyst does not affect equilibrium constant provided the
temperature remains constant.

Determination of Equilibrium Constants

The following points to note:

(a) The Equilibrium Law only applies to systems in equilibrium.

(b) Kc is constant so long as the temperature remains constant.

(c) The numerical value of Kc is unaffected in concentration of either reactants or products.

(d) The magnitude of Kc provides a useful indication of the extent of a chemical reaction. A large
value of Kc indicates a high proportion of products to reactants and vice versa.

(e) The equilibrium constant for a reaction indicates the extent of a reaction. It gives no
information about the rates of reaction. Kc tells how far (how much), not how fast.

Le Chatelier’s Principle

The principle states that a system in equilibrium that is subjected to stress will react in a way that
counteracts the stress.

Contact Process – Manufacture of sulphuric acid.

The method involves the catalytic conversion of sulphur dioxide and oxygen into sulphur
trioxide.

2SO2 (g) + O2 (g) 2SO3 (g) ; ∆Ho = - 197 KJ mol-1

By Le Chatelier’s Principle the production of sulphuric trioxide is favoured by:

1) A Low Temperature

2) High Pressure

Haber Process – Manufacture Of Ammonia

N2 (g) + 3H2 (g) 2NH3 (g) ; ∆Ho = - 92 KJ mol-1

The greatest yield of ammonia is obtained at low temperature and high pressure.

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100 200 oC
Figure 1.19
300 oC
% Conversion of
80 Ammonia
% Conversion of Ammonia

400 oC
60

500 oC

40

600 oC

20

20 40 60 80 100
Pressure / M Pa

Graph shows that the % NH3 (g) in the equilibrium mixture of H2, N2 and NH3 is greatest at low
temperature and high pressure.

Increase in concentration of the reactants and the use of a catalyst also increase production or
shift the equilibrium to the right.

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