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2.
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
Equilibrium System
Vapour
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
Evaporated
Number Of Particles
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
k1 [Alcohol] * [Acid]
k2 [Ester] * [Water]
[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]
R + 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
Species
Number Of Moles (Initially)
Number Of Moles At
Equilibrium
2HI
H2 (g)
(g)
I2 (g)
2HI
H2
I2
1.0 0.78
0.78
0.11
0.11
= 0.22
0.22 / 2
0.78
1
0.11
1
0.11
1
0.11 For
Each Product
=
[HI (g)]
0.11 * 0.11
=
1
=
(1.78.2
=
0.02
50
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
(Initially)
0.0525
0.0515
0.0314
0.0167
0.0255
0.0245
0.0584
0.0437
[CH3COOC2H5] [H2O]
Kc
=
[CH3COOH] [C2H5OH]
[0.0584] [0.0437]
=
[0.0255] [0.0245]
Kc
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
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) +
COCl2
Cl2 (g)
(g)
0.60
1.10
- 0.10
- 0.10
+ 0.10
0.50
1.00
0.10
PCOCl2 (g)
Kp
=
(PCO2 (g)) (PCl2 (g))
(0.10)
=
(0.50) (1.0)
Kp
0.20 atm-1
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.
Le Chateliers Principle
The principle states that a system in equilibrium that is subjected to stress will react in a way that
counteracts the stress.
+ O2 (g)
The greatest yield of ammonia is obtained at low temperature and high pressure.
200 oC
% Conversion of Ammonia
100
300 oC
80
Figure 1.19
% 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.