Topic 6.

3
Reversible reactions
and Equilibrium
Reference: Essential chemistry book .
 Chemical
Reaction

One way Two way

Irreversible Reversible
A single-headed arrow
indicates that a reaction is double-headed arrow (⇌) to
not reversible and goes to represent a reversible reaction
completion.

A+B → C+D A+B ⇌ C+D

 Chemical reaction
• One way • Two way
• assumed that chemical reactions go • Chemical reaction that takes place in both
to completion, meaning that almost directions.
all reactants are converted to • Many reactions, however, do not go to
products. completion and are reversible.
• A single-headed arrow (one-way • These reactions reach a point when they
arrow (→)) indicates that a reaction is are said to be at equilibrium.
not reversible and goes to completion. • double-headed arrow (⇌) to represent a
reversible reaction .
• In these reactions, reactants continue
to react give products until all the • In these reactions, reactants start to give
reactants are consumed. products then after a while products will
react again to give reactants back.
CaCO3 (s) +2HCl (aq) → CaCl2 (s) + H2O (l) +CO2 (g)
Mg (s) + 2HCl (aq) → MgCl2 (s) + H2 (g)
The products are not suitable to react with each other
Reactants →Products

NH4Cl (s) ⇌ NH3 (g) +HCl (g)

Ammonium chloride ⇌ammonia + hydrogen chloride
CuSO4.5H2O(s) ⇌ CuSO4(s)+5H2O(l)
The products are suitable to react with each other
Reactants ⇌ Products
 Example
• Ammonium salt
NH3+HCl ⇌ NH4Cl
NH3 react with HCl giving NH4Cl, THEN , after heating NH4Cl gives HCL and NH3.
CuSO4.5H2O (s) → CuSO4 (s) + 5H2O (l)
Observation:
Blue crystals White powder Blue color turns white
Hydrated anhydrous Drops of water will be collected near
the top of the tube.

Heat
Hydrated salt → Anhydrous salt
←
Adding water
Observation:
White powder turns into blue crystals
CuSO4 (s) + 5H2O (l) → CuSO4.5H2O (s)
White powder Blue crystals
Both reactions can be written in one
equation
CuSO4.5H2O(s) ⇌ CuSO4(s)+5H2O(l)
double-headed arrow (⇌) to represent a reversible reaction
Anhydrous cobalt(II) Chloride → Hydrated cobalt chloride
CoCl2 + 6H2O ⇌ CoCl2.6H2O
Blue pink
 Note:
• Forward and backward reactions are opposite to each other in:
• Energy and product
• Forward= right-side
• Backward = left side
 A+B ⇌ C+D
How the reaction reaches dynamic
equilibrium
• At the beginning of the reaction, the concentration of reactants would
be very high so the reaction would go forward to give products ,since still
no products are formed. No backward reaction.
• After a time , the concentration of products increase while the
concentration of the reactants decreases .Products react again to give
reactants.
• After that , the reaction reaches a point Dynamic Equilibrium at which
the rate of the forward reaction equals the rate of backward reaction
and the concentration of the system is kept constant.
Features for Dynamic
equilibrium:
• Many reactions are reversible.
• These reactions reach a point when they are said to be at equilibrium.
• The term dynamic equilibrium means that the reaction has not stopped.
• Features of dynamic equilibrium:
1. The forward and backward reactions occur at the same rate.
2. The concentrations of reactants and products at equilibrium are kept
constant.
3. Equilibrium is achieved in a closed system.
4. There is no change in macroscopic properties at equilibrium.
The forward and reverse reactions occur at the same rate.
• Reactants are continuously being changed to products, and products are continuously
being changed back to reactants.
• This means that, at equilibrium, both reactants and products will be present in the
reaction mixture. When the rates of reaction are equal, the reaction is at equilibrium.
The concentrations of reactants and products at equilibrium are
constant
• At equilibrium, the concentrations of reactants and products are constant , this
does not necessarily mean that they are equal.
Equilibrium requires a closed system.
• Equilibrium can only be achieved in a closed system where the reactants and products
cannot escape.
There is no change in macroscopic properties at equilibrium.
• When a reaction is at equilibrium, there is no change in macroscopic properties such as
colour, pressure, pH.
Graph shows how the rates of reaction change over
time for the forward and reverse reactions.
 Le Châtelier's principle
• Le Châtelier’s principle states that:
• 'When a system at equilibrium is subjected to a change, the system will
respond to minimize the effect of the change.’
• The position of equilibrium change either : shift forward or backward to
achieve equilibrium again.
• When the system at equilibrium and its disturbed by an external factor,
the reaction will shift itself either forward or backward to return back to
equilibrium.
 Le Châtelier's principle
• Factors affecting dynamic equilibrium:
• changes to the concentrations of reactants or products
• changes to the pressure of a system involving gaseous reactants
and products
• changes to the temperature
• These changes can shift the equilibrium position :
• to the right (the products side)
• or to the left (the reactants side);
• or in some cases, they will have no effect on the equilibrium position.
 Changes in temperature
• To determine the effect of a change in temperature on the equilibrium
position the enthalpy change (∆H) for the reaction is used.
• a reaction can be exothermic (−∆H) or endothermic (+∆H).
• If the forward reaction is endothermic, the reverse reaction will be
exothermic and vice versa.
• According to Le Châtelier’s principle:
• Increasing the temperature the equilibrium position will shift to the
endothermic side that absorbs this heat.
• Decreasing the temperature the equilibrium position will shift to the
exothermic reaction that releases this heat.
• The enthalpy value which is written beside the equation for a reversible
reaction , it refers to the value for the forward reaction.
• The decomposition of N2O4 is endothermic with a ∆H value of +57 kJ mol−1.
• This means that the reverse reaction has a ∆H value of −57 kJ mol−1.
• N2O4 (g) ⇌ 2NO2 (g) ∆H = +57 kJ mol−1
Colorless gas red brown gas

• If the temperature of this reaction is increased, the equilibrium position will

shift to the right(forward) , favouring the endothermic reaction. This means
the added heat will be absorbed by the reaction, minimising the change in
temperature.
• if the temperature is decreased, the equilibrium position will shift to the left,
favouring the exothermic reaction , that releases heat and minimising the
change in temperature.
• State and explain the observation if you put the reaction vessel in cold
water?
• Consider the Haber process :
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ∆H = -92 kJ mol−1
• According to Le Châtelier’s principle, if :
• The temperature increases: position of equilibrium shifts backward(favors the endothermic
side)
• The temperature decreases: position of equilibrium shifts forawrd(favors the exothermic side) .
• What will happen to the % yield of ammonia if the temperature is lowered ?
 Changes in pressure
• Changing the pressure in a chemical reaction only has an effect on the
equilibrium position of gaseous molecules.
• Steps to determine the effect of pressure:
• Balance the equation
• Count the number of moles of gases only at each side of the reaction.
• The pressure of gases increases as the number of gas molecules increase.
• The pressure of a system at equilibrium can be changed by either:
• adding or removing a gaseous reactant or product, or
• changing the volume of the reaction vessel.
• Volume and pressure are inversely proportional at constant temperature.
• For example, if the volume of the reaction vessel is increased, the pressure will
decrease and vice versa.
Example on changes in
pressure:
• If pressure increases, the equilibrium position will shift to the side with the lowest
number of gaseous molecules. By responding this way, the pressure of the gaseous
mixture is reduced.
• if the pressure of an equilibrium mixture of gases is decreased, the equilibrium position
will shift to the side with the greatest number of gaseous molecules. This has the effect
of increasing the pressure.
• For reactions that have the same number of gaseous molecules on each side of the
equation, changes in pressure will have no effect on the equilibrium position.
• Consider the following :
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
if pressure changes what happens to the concentration of NH3 and explain it?
The pressure increases:
The pressure decreases:
CaCO3 (s) ⇌ CaO (s) + CO2 (g)
• According to Le Châtelier’s principle, what will happen to the position of
equilibrium if :
The pressure increases:
The pressure decreases:
 Changes in concentration
• A+B ⇌ C+D
• Increasing the concentration of A : position of equilibrium= shift forward
• Increasing the concentration of C : position of equilibrium= shift backward
• Decreasing the concentration of B : position of equilibrium= shift backward
• Decreasing the concentration of D : position of equilibrium= shift forward
 Example on changes in
concentration:
• Consider the Haber process , in which nitrogen (N2) reacts with hydrogen
(H2) to form ammonia (NH3):
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
• if ammonia is removed from the equilibrium mixture:
• more nitrogen and hydrogen will react to replace the ammonia that has
been removed, the equilibrium position will shift to the right (the products
side).
• If nitrogen is removed from the equilibrium mixture, the equilibrium
position will shift to the left (the reactants side), to increase the
concentration of nitrogen.
• Again, the system responds to minimise the effects of the change.
• At equilibrium the color is yellowish-orange.
• What happens if an acid is added? Explain your answer .
• By adding acid (H+ concentration )increases ,so the
reaction shifts forward (to product side) ,the system
responds to minimize the effect of the change.
• Color of the solution changes to orange .

• What happens if an alkali is added? Explain your answer .

By adding alkali (OH hydroxide ion react with H+ ions to form water ) , so the reaction shifts
backward (to reactant side) ,the system responds to minimize the effect of the change.
• Color of the solution changes to yellow.
How indicators work :

Color I Color II
 Effect of adding a catalyst
• If catalyst is added at the beginning ,the advantage of using a catalyst is
that the equilibrium is established more quickly, (less time needed to reach
the equilibrium) which is an economic benefit.
• The presence of a catalyst has no effect on the equilibrium position , if
reaction is at equilibrium because a catalyst increases the rate of both the
forward and reverse reactions by the same amount.
Draw and annotate the graph if a
catalyst is added.
 H2 (g) + I2 (g) ⇌ 2HI (g)
Purple gas colorless gas
Increasing the pressure has no effect on the position of equilibrium why?

The color of the mixture becomes more intense (dark purple) when the pressure increase
why?
Iodine particles get closer to each other so the color seems to be more purple
 H2 (g) + I2 (g) ⇌ 2HI (g)
Purple gas colorless gas
Increasing the pressure has no effect on the position of equilibrium why?

The color of the mixture becomes more intense (dark purple) when the pressure increase why?
Iodine particles get closer to each other so the color seems to be more purple

N2O4 (g) ⇌ 2NO2 (g) ∆H = +57 kJ mol−1

Colorless gas red brown gas

If the pressure increases ?

a) Mixture will gets darker then goes paler

b) Mixture will gets paler then goes darker

c) Mixture will gets paler and stays pale

d) Mixture will gets darker and stay dark