CHEMICAL

CHEMICAL
EQUILIBRIUM
EQUILIBRIUM
PHYSICAL CHEMISTRY
Chemical Equilibrium
1. Neuralization produces salt and water. However, salt and water
does not react to produce acid and alkali.
2. NaOH(aq) + HCl (aq)  NaCl (aq) + H2O (l)
3. The above reaction proceeds in one direction: ~ Irreversible
Reaction

H2 (g) + I2 (g) H-I(g)

4. Hydrogen gas and iodine vapor reacts to form hydrogen iodide, at

the same time, HI can dissociate to form hydrogen gas and iodine
vapor.
5. Both forward and reverse (backward) reaction are called
Reversible Reaction
6. When the rates of the forward and reverse reaction are equal,
the concentration of reactants and products remain constant.
[Chemical Equilibrium]
Concept of Dynamic Equilibrium
1. Consider a non reversible reaction: A  B
concentration
[B]

[A]
T1 time

2. Consider a reversible[Y]
concentration reaction: X Y

[X]

T1 time
Concept of Dynamic Equilibrium
1. When we plot the rate of reaction, both the forward
reaction and reverse reaction:
rate Forward reaction

Reverse reaction

T1 time

2. At time T1, the rate of the forward reaction becomes equal

to the rate of the reverse reaction.
3. Thereafter, the concentration of X and Y does not change.
4. We say the system has achieved dynamic equilibrium.
5. The concentration of X and Y at dynamic equilibrium is
called equilibrium concentration.
Equilibrium Constant
1. Consider the decomposition of N2O4 to NO2…
N2O4  2NO2

Initial [ ] Initial [ ] Equal. [ ] Equal. [ ] Equilibrium Equilibrium

Constant Constant
[N2O4]o [NO2]o [N2O4] [NO2] [NO2]/ [NO2]^2/
[N2O4] [N2O4]
0.670 0.000 0.643 0.055 0.085 0.00465
0.000 0.200 0.089 0.021 0.227 0.00463

2. For a general reaction:

aA + bB cC + dD

3. At equlibrium: [C]c[D]d = Equilibrium Constant [Kc]

[A]a[B]b
Equilibrium Constant For Homogeneous System
1. Write the general formula of equilibrium constant for the
following reaction and state its unit.
a) CH3COOH + C2H5OH  CH3COOC2H5 + H2O
b) PCl5  PCl3 + Cl2
c) N2 + 3H2  2NH3

2. Practice:
Consider the following reaction:
2A + B  2C
An equilibrium mixture was found to contain 0.25 moldm-3
of A, 0.56 moldm-3 of B and 1.24 moldm-3 of C at 450 K.
Calculate the equilibrium constant, Kc.
[43.93 mol-1dm3]
Dependence of Kc on Chemical Equation
1. Consider the following reaction:
2SO3 (g) 2SO2 (g) + O2(g)
2. Kc = [SO2]2[O2]/ [SO3]2 = 400
3. If we were interested in the formation of SO 3:
2SO2 (g) + O2(g) 2SO3 (g)
K1 = [SO3]2 / [SO2]2[O2] @ 1/([SO2]2[O2]/ [SO3]2 ) = 1/Kc = 1/400

K1
4. In short, 2SO3 (g) 2SO2 (g) + O2(g)
K-1

5. K1 x K-1 = 1
6. If the equation is written in the following way:
SO3 (g) SO2 (g) + ½ O2(g)
K = [SO2][O2]½ / [SO3] = [[SO2]2[O2]/ [SO3]2 ]½ = [Kc]½ = (400)1/2
Equilibrium Constant For Homogeneous System
1. For a gas, the concentration is directly proportional to its
pressure (partial pressure).
2. N2 (g) + 3H2(g) 2NH3 (g)

Kp = p2NH3/(pN2 x p3H2)

3. Practice
Phosgene (COCl2) dissociate according to the equation:
COCl2 (g)  CO (g) + Cl2 (g)
The equilibrium pressure of COCl2, CO and Cl2 at 360 K are 0.67,
0.45 and 1.60 atm. Calculate the equilibrium constant Kpat the
same temperature.
[1.07 atm]
Adding Chemical Equation
1. If a reaction can be expressed as the sum of two or more
reaction, K for the overall reaction is the product of the
equilibrium constants of the individual reaction.

K (overall reaction) = K 1 x K2

For example:
SO2 (g) + ½ O2 (g) SO3 (g) K1 = 2.2
NO2 (g) NO(g) + ½ O 2 (g) K2= 4.0

Adding the equations eliminates ½ O2, the result is:

SO2 (g) + NO2 (g) SO3 (g) + NO (g)

K = 2.2 x 4.0 = 8.8

Adding Chemical Equation: PRACTICE
1. Consider the reaction by which the air pollutant, NO is
made from the elements in a automobile engine:
N2 (g) + O2(g) 2NO (g)

a) Write the equilibrium constant expression for the

reaction.
b) At 25oC, K for this reaction is 4.2 x 10-31. Calculate the K
for the reaction
½ N2 (g) + ½ O2(g) NO (g) (6.5x 10-16)
c) At 25oC, K for this reaction
N2 (g) + 2O2(g) 2NO2 (g)
is 1.0 x 10-18. Calculate K at 25oC for the reaction:
2NO (g) + O2 (g) 2NO2 (g)
(2.4x1012)
Heterogeneous System
1. Consider the following equilibrium in a closed system:
CaCO3 (s)  CaO(s) + CO2 (g)
2. The concentration of a solid like its density, is a constant.
In heterogeneous system, solids, pure liquids and solvents
can be omitted from the equilibrium constant expression.
3. Thus, the equilibrium constant:
Kp = PCO2

Let’s try to write the equilibrium constant:

(NH4)2S (s) 2NH3 (g) + H2S (g)

The Relationship between Kc and Kp
1. Kp = Kc (RT)∆ n

2. Consider the following general equation:

aA + bB cC + dD

∆n = (c+d) – (a+b)

Practice:
The equilibrium constant, Kp for the following reaction is 3.00 x
104 Pa at 450 K.
PCl5(g)  PCl3 (g) + Cl2 (g)

Calculate Kc for the reaction at the same temperature.

0.125
PRACTICE
1. Kc of the following reaction is 4.0 at 298 K.
CH3COOH (l) + C2H5OH (l)  CH3COOC2H5 (l) + H2O (l)

A mixture containing 2 mol of CH3COOH and 2 mol of

C2H5OH were allowed to come to equilibrium at 298 K.

a) Calculate the number of moles of ester produced.

b) Sketch a concentration/time graph for the system.

2. N2(g) + 3H2(g)  2NH3(g)

A mixture containing 1 mol of N2 and 3 mol of hydrogen are
left to attain equilibrium at 650oC and a total pressure of
200 atm. The equilibrium mixture was found to contain
20% ammonia. Calculate the equilibrium constant Kp.
Reaction Quotient and Direction of Reaction
1. The reaction quotient (Q) is obtained by substituting the
initial concentrations into the expression for Kc.
Q > Kc There is too much product. A net reverse reaction
( from right to left) will happen to decrease Q.
Q < Kc There is too little product. A net forward reaction
( from left to right) will happen to increase Q.
Q = Kc The system is in equilibrium. No net reaction
occur

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

The Kc for the above reaction at 200oC is 25.
A mixture containing 1 M of H2 and I2 and 1.2 M of HI was
left standing at 200oC. Determine the net direaction of
reaction.
 Le Chatelier’s Principle

When a system at equilibrium is subjected to a change in

temperature, pressure or concentration of a reactant or
product, the system will, if possible, shift its equilibrium
position so as to partially counteract the effect of the
change.
Factors that affect equilibrium system
1. The equilibrium constant of reversible reaction is only dependent
on temperature. It does not depend on changes in concentration
of the reactants or products, pressure or the use of catalyst.

Change Rate Rate constant Equilibrium constant Equilibrium

composition
Conc. Change Unchanged Unchanged Change

Pressure Change Unchanged Unchanged Changed

Temperature Change Change Change Change

Catalyst Change Change Unchanged Unchanged
Effect of Concentration and concentration
A B

[B]

[B]
[A]

[A]

Addition of A

New equilibrium
Effect of Concentration and concentration

Conc.

[B]
[B]

[A]
[A]

Addition of B
time
New equilibrium
Effect of Temperature
1. Low temperature would favor exothermic reaction, while
high temperature would favor endothermic reaction.

Decreasing Temperature
∆H = -ve A+B C + D ∆ H = + ve
Increasing Temperature

Kc Kc
Exothermic Endothermic

temperature temperature
Relationship between Kc and Temperature
1. Van’t Hoff Equation: ln K = -∆H/RT + C
where K = equilibrium constant
H = enthalpy change of reaction
R = gas constant
T = temperature in (K)
C = constant

2. For endothermic reaction, where ∆H = positive, a plot of ln k

against 1/T would give a straight line with a negative slope:

3. For exothermic reaction, where ∆H = negative, a plot of ln k

against 1/T would give a straight line with a positive slope:
 Relationship between Kc and Temperature
Practice

• Ammonium hydrogen sulphide dissociates according to the

equation:
NH4HS (s) H2S (g) + NH3 (g)

At 9.5 oC, the total pressure at equilibrium is 23.4 kPa.

When the temperature is raised to 25.5 oC, the total
pressure is 67.8 kPa. Calculate the value of ∆H for this
reaction.

+92.6 kJ
Effect of Catalyst

1. Catalyst does not affect systems that are ready

in equilibrium.
2. For system that have not reached equilibrium, it
merely speeds up the rate of the forward and
reverse reaction by the same factor, so that
equilibrium is reached in a shorter time.
3. A catalysts does not affect the yield of a
reaction. The same amount is obtained
regardless of whether a catalyst is present or
not.
The effect of a Noble Gas on an Equilibrium

At constant Pressure

• If a noble gas such as argon or neon is added to a gaseous

equilibrium mixture at constant pressure, the partial
pressure for the gases in the system is lowered.
• Thus, according to Le Chatelier’s Principle, the presence of a
noble gas favors the direction that increases the number of
moles of gas.

PCl3 (g) + Cl2 (g) PCl5 (g)

2H2O (g) 2H2 (g) + O2 (g)
H2 (g) + I2(g) 2HI (g)
 The effect of a Noble Gas on an Equilibrium
At constant Volumes

• If a noble gas such as argon or neon is added to a gaseous

equilibrium mixture at constant volume, no effect on the
position and composition of the mixture
Equilibrium and Industrial Process
Haber Process
• N2 (g) + 3H2 (g) 2NH3 (g) ∆H = -92 kJ/mol
• According to the Le Chatelier’s Principle, the forward
reaction would be favored by high pressure as it is
accompanied by a decrease in the number of moles of gas.
The pressure normally used is 200 – 1000 atm.
• The forward reaction is exothermic. Hence, it is favored by
low temperature. However, a low temperature will slow down
the rate of reaction. A compromise temperature would be
450 -500o C.
• Fine divided iron is added as catalyst to increase the rate of
reaction and shorten the time required to reach equilibrium.
Equilibrium and Industrial Process
Contact Process
• 2SO2 (g) + O2 (g) 2SO3 (g) ∆H = -197 kJ/mol
• Vanadium (V) oxide
• The rate of production of SO 3 is greatly improved by:
a) increasing the concentration (Pressure) of SO 2 and O2
b) increasing the temperature
c) Using catalyst
3. Because of exothermic, low temperature and high pressure is
needed.
4. At low temperature, rate of reaction become slow. (450 C)
5. In theory, application of higher pressures will give a higher
yield of sulphur trioxide. However, in practice, it only has small
effect on the yield of SO3. (1atm)
Equilibrium and Industrial Process
Practice
The oxidation of sulphur dioxide to sulphur trioxide is reversible
reaction.
The table below shows the equilibrium partial pressure of SO2,
O2, SO3 at 700o C.
Gas SO2 O2 SO3
Partial Pressure atm 0.27 0.40 0.32

a) Calculate the Kp.

b) What are the initial partial pressure of SO2 and O2?

3.51, 0.59, 0.56