Chapter 21

Reversible Reactions and Equilibria

• A reversible reaction is a reaction in which the conversion of reactants to products and the conversion of
products to reactants occur simultaneously.

• A and B can react to form C and D or, in the reverse reaction, C and D can react to form A and B. This is
distinct from a reversible process in thermodynamics.
 Reversibility and dynamic equilibrium
Two reversible reactions
1. Dehydration of copper (II) sulfate crystals
• On heating blue copper (II) sulfate crystals, water is driven off and change blue to white coloured
powder .
CuSO4.5H2O (s) → CuSO4(s) + 5H2O(l) ( Heat is needed for this reaction to occur )
blue white
• If you add water to the white solid , it turns blue again. ( Heat is released from this reaction)
CuSO4(s) + 5H2O → CuSO4.5H2O (s)
white blue
• This is called a reversible reaction and is indicated by a special arrow.
Dehydration of copper (II) sulfate crystals
 Two reversible reactions
2. Heating ammonium chloride
• Heating ammonium chloride splits it into the colourless gases ( ammonia and hydrogen chloride)
NH4Cl(s) → NH3(g) + HCl(g) (heat is needed)
white solid colourless gases
• These gases recombine further up the tube , where it is cooler , to form a white solid.
NH3(g) + HCl(g) →NH4Cl(s) (heat is released)
colourless gases white solid
• This is called a reversible reaction and indicated by a special arrow.
 Reversible reaction in a sealed container

• A sealed container means that no substances are added to the reaction mixture and no substances
escaped from it.
• Only heat is given off or absorbed .
• Substance of reversible reaction exists in two forms ( blue and yellows) .

• Rate of change ( blue to yellow ) → high at beginning and decrease gradually

• Rate of change ( yellow to blue ) → low at beginning and increase gradually
• Soon , the rates become equal when equilibrium is reached.
 Dynamic equilibrium
• Although the reaction is still happening, the total numbers of reactants (blue squares) and of
product( yellow squares) remain constant .
• In this situation , rate of forward reaction is equal to rate of reverse reaction but total amount or
concentration of reactants and products are not same but remain constant.
• Dynamic equilibrium occurs only in closed system ( nothing except heat in or out)..
• For example ,

• If the reaction is in opened system , the carbon dioxide gas will escape and cannot be formed back
to reactant.
 The position of equilibrium
• Forward reaction ( A to B) and backward reaction ( B to A) .
• A 2B
• Equilibrium = the concentrations of A and B stay constant at equilibrium ( doesn’t mean 50% of
reactants and products)
• Position of equilibrium lies to the left ( A 2B)
• 90% 10%
• Position of equilibrium can be shifted to the right by changing conditions such as
o Temperature
o Pressure
o Adding a catalyst ( no effect )
For example , A 2B
80% 20%
 The effect of changing conditions on the position of
equilibrium
Changing the pressure
• Pressure is caused by molecules hitting the walls of their container .
• It affects to the reaction in which
 At least one of the reactants or products is a gas
 The total numbers of gases molecules on both sides of the equation must be different
• If you increase pressure , the equilibrium will shift to the side which has fewer gas molecules.
• If you decrease pressure , the equilibrium will shift to the side which has more gas molecules.
• If there is same number of gases molecules on both sides of the equation , changing the pressure
will make no difference to the position of the equilibrium.
• For example ,
 Changing the temperature
• ∆ H always shows the enthalpy change for the forward reaction.
• The value of ∆ H is given as if the reaction was a one-way process.
A + 2B C +D ∆ H = -100 kj per mol
• If ∆ H being negative , the forward reaction is exothermic . The reverse reaction will be
endothermic.
• If you increase the temperature , the position will shift in the endothermic direction.
• If you decrease the temperature , the position will shift to the exothermic direction.

A + 2B C +D
Equilibrium at 500˚C 80% 20%
Equilibrium at 100˚C 60% 40%
 Adding a catalyst
• Adding a catalyst speeds up both forward and reverse reaction by the same proportion.
• There is no net effect on the equilibrium so that there will be no changes on the position of the
equilibrium.
• For example,
2NO2(g) N2O4(g) ∆H = -57 kj per mol
brown colourless
• Effect of pressure change, ↑ → more N2O4
↓ →more NO2
• Effect of temperature change, ↑ →endothermic direction → more NO2( the colour darker)
• Effect of temperature change, ↓ → exothermic direction → more N2O4(the color will fade)
 Effect of changing concentration
• Adding more amount of A → reaction removes the extra A by turning it into C and D .
• Removing the amount of C → more A and B react to replace the C removed .
• If the concentration of a substance is increased, the reaction that consumes that substance is
favored, and the equilibrium shifts away from that substance.
• If the concentration of a substance is decreased, the reaction that produces that substance is
favored, and the equilibrium shifts toward that substance.

Add more A remove C

↓ ↓
A + 2B C + D A + 2B C + D

Reaction goes to right (products) Reaction goes to left ( reactants)

 Chapter Questions
1.(a) The reversible symbol ‘⇌’ shows that the reaction can go both ways. The reactants can form
products and the products can react to form the reactants.
(b) White solid decomposes to form colourless gases. c Ammonium chloride, ammonia and hydrogen
chloride

2.(a) Right (b) Left (c) Left (d) No change (e) No change

3.(a) ‘Dynamic’ means that the reactions are still happening and the rate of the forward reaction is
equal to the rate of the reverse reaction. ‘Equilibrium’ means that the concentrations of the reactants
and the products remain constant.

(b) The proportion of sulfur trioxide will increase. An increase in pressure shifts the position of
equilibrium to the right because this side has fewer moles of moles of gas molecules.

(c) The position of equilibrium shifts to the right. A decrease in temperature favours the forward
exothermic reaction.
4.(a) Less carbon monoxide and hydrogen would be produced. (A high pressure favours the reverse
reaction, as the left hand side of the reaction has fewer number of moles of gas molecules.)

(b) A high temperature favours the endothermic forward reaction and shifts the position of
equilibrium to the right hand side of the reaction.

(c) Using a catalyst increases the rate of the reaction, as it provides an alternative pathway for the
reaction with lower activation energy.
More particles will have energy greater than or equal to the activation energy so there will be more
successful collisions per unit time.
More products will be made quickly and relatively low temperature and pressure can be used in the
presence of a catalyst. This saves energy and money.
Adding a catalyst has no effect on the position of equilibrium, as the rate of the forward reaction and
the rate of the reverse reaction are increased by an equal amount.
 5.(a)A high pressure favours the reaction producing fewer moles of gas, shifting the position of
equilibrium to the right hand side.

(b) Very high pressures are expensive to produce for two reasons: all the reaction vessels and
pipework have to be built much more strongly, and it takes a lot more energy to drive the
compressors producing the very high pressures.
The extra ammonia produced isn’t worth the extra cost, so a compromise of 200 atmospheres
pressure is used.

(c) At a low temperature. Lower temperature favours the forward exothermic reaction, shifting the
position of equilibrium to the right hand side to produce more ammonia.

(d) At low temperatures the reaction is extremely slow even in the presence of a catalyst. 450°C is
chosen because it gives a compromise between the rate and the yield of the reaction.