Reversible Reactions

Most chemical reactions only proceed in one direction. They cannot be reversed.

Reactant → Products

Some reactions can be reversed. In some reactions, the products of the reaction can react to reform the
original reactants. Such reactions are reversible.
They proceed in both directions i.e in forward direction as well as in backward direction. Reversible
reactions are denoted by the sign “⇌” where the arrow denotes forward reaction, where reactants
react to form products, and the arrow denotes backward reaction where products react to reform
reactants. The reactions occur at the same time.

Reactant Products

for example: NH4Cl NH3 + HCl

(white solid) (colourless gases)

Hydrated salts contain water of crystallisation which affects their molecular shape and colour.
Water of crystallisation is the water that is stoichiometrically included in the structure of some salts during
the crystallisation process. Water of crystallisation is indicated with a dot written in between the salt
formula and the surrounding water molecules
Anhydrous salts are those that have lost their water of crystallisation, usually by heating.

When hydrated copper (II) sulfate crystals are heated in a test tube, the blue crystals turn into a white
powder and a clear, colourless liquid (water) collects at the top of the test tube.
When anhydrous copper (II) sulfate crystals are added to water they turn blue and heat is given off.
This reaction is reversible.

CuSO4.5H2O CuSO4 + 5H2O

(blue) (white)

Similarly when hydrated cobalt (II) chloride crystals are heated in a test tube, the pink crystals turn into a
blue powder and a clear, colourless liquid (water) collects at the top of the test tube.
When anhydrous copper (II) sulfate crystals are added to water they turn pink and heat is given off.

CoCl2.6H2O (s) CoCl2 (s) + 6H2O (l)

(pink) (blue)

The percentage yield of products is never 100% in reversible reactions.

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Dynamic equilibrium
Dynamic Equilibrium is the state when the rate of forward reaction is the same as the rate of backward
reaction. Hence, there is no overall change in the amounts of reactants and products.
For example; formation of ammonia from nitrogen and hydrogen.

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

When only nitrogen and hydrogen are present at the beginning of the reaction, the rate of the forward
reaction is at its highest, since the concentrations of hydrogen and nitrogen are at their highest.
As the reaction proceeds, the concentrations of hydrogen and nitrogen gradually decrease, so the rate of
the forward reaction will decrease.
However, the concentration of ammonia is gradually increasing and so the rate of the backward reaction
will increase. Since the two reactions are interlinked and none of the gas can escape.
The rate of the forward reaction and the rate of the backward reaction will eventually become equal and
equilibrium is reached.

How the concentrations of H2, N2, and NH3 vary with time is shown in graph below. Notice that an
equilibrium mixture is obtained regardless of whether we begin with N2 and H2 or with NH3.
The equilibrium condition is reached from either direction.

The graphs have the following features:

 When the graphs become horizontal, equilibrium is reached. This is when the concentration of all
H2, N2, and NH3 become constant.
 The concentration of reactants in the forward direction does not become zero when the graph
becomes horizontal.
The equilibrium position is achieved only in a closed system.
A system in which matter neither enters into nor leaves the system is called closed system.

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Factors Affecting Equilibrium
The composition of an equilibrium mixture in a reversible reaction can be affected by changes in
 Concentration
 Temperature
 Pressure

The best way to predict the effect of a change in conditions is to use Le Chatelier’s principle. This says:
If an equilibrium mixture is disturbed by changing the conditions, then the composition of the equilibrium
mixture will change to try to remove the disturbance.
OR
If one or more factors that affects equilibrium are changed then the position of equilibrium shifts in the
direction which reduces the change.

Equilibrium position refers to the relationship between the concentration of reactants and products at the
equilibrium state.

What does shift mean?

If a system in equilibrium is disturbed by changing concentration, temperature or pressure then the
position of equilibrium will shift.
 When the position of equilibrium shifts to the left, it means the concentration of reactant increases.
 When the position of equilibrium shifts to right, this means the concentration of product increases.
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Concentration: adding or removing a reactant or product

If a substance is added to a system at equilibrium, the system reacts to consume some of the substance. If a
substance is removed from a system, the system reacts to produce more of substance.

As an example, consider our familiar equilibrium mixture of N2, H2, and NH3:

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

Adding H2 causes the system to shift so as to reduce the increased concentration of H2. This change can
occur only if the reaction consumes H2 and simultaneously consumes N2 to form more NH3.

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Adding N2 to the equilibrium mixture likewise causes the reaction to shift toward forming more NH3.
Removing NH3 also causes a shift toward producing more NH3, whereas adding NH3 to the system at
equilibrium causes the reaction to shift in the direction that reduces the increased NH3 concentration:
Some of the added ammonia decomposes to form N2 and H2.
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Temperature

If the temperature is raised at equilibrium then the reaction mixture gains heat energy. The reaction
mixture will try to get rid of the extra heat energy. It can do this by consuming the heat energy and thus the
temperature of equilibrium mixture decreases. This happens in endothermic reaction. Thus equilibrium
position shifts in the direction of endothermic reaction. So
 If the temperature is increased, the equilibrium will move to reduce the increased temperature.
It does this by moving in the direction of the endothermic reaction.
 If the temperature is reduced, the equilibrium will move to increase the reduced temperature.
It does this by moving in the direction of the exothermic reaction.

OR

Endothermic: Reactants + heat products

Exothermic: Reactants products + heat

When the temperature of a system at equilibrium is increased, the system reacts as if we added a reactant
to an endothermic reaction or a product to an exothermic reaction.
The equilibrium shifts in the direction that consumes the excess reactant (or product), namely heat.

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Pressure: changing the pressure by changing the volume

Changing pressure can effect gas reactions.

If the number of gaseous moles in reactants and the products are equal then pressure has no effect on
equilibrium position. For example;

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

If the pressure of the equilibrium mixture is increased, the reaction mixture will try to get rid of extra
pressure. It can do this by decreasing the number of gaseous moles. Thus the position of equilibrium shifts
in the direction of lesser number of gaseous moles. The opposite happens if the pressure is decreased. So
 If the pressure is increased, the equilibrium will move to reduce the increased pressure. It does this by
moving to the side with less gas molecules.
 If the pressure is reduced, the equilibrium will move to increase the reduced pressure. It does this by
moving to the side with more gas molecules.

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The Effect of Catalyst

What happens if we add a catalyst to a chemical system that is at equilibrium?
A catalyst lowers the activation barrier between reactants and products. The activation energies for both
the forward and reverse reactions are lowered. The catalyst thereby increases the rates of both forward
and reverse reactions. As a result, a catalyst increases the rate at which equilibrium is achieved but does
not change the composition of the equilibrium mixture.
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Consider the equilibrium
N2O4 2 NO2 ∆H = +58.0 kJ
In which direction will the equilibrium shift when
(a) N2O4 is added,
(b) NO2 is removed,
(c) the pressure is increased by addition of N2(g),
(d) the volume is increased,
(e) the temperature is decreased?
Solve
(a) The system will adjust to decrease the concentration of the added N2O4, so the equilibrium shifts to the
right, in the direction of product.
(b) The system will adjust to the removal of NO2 by shifting to the side that produces more NO2; thus the
equilibrium shifts to the right.
(c) Adding N2 will increase the total pressure of the system, but N2 is not involved in the reaction.
Thus there is no shift in the position of the equilibrium.
(d) If the volume is increased, the system will shift in the direction that occupies a larger volume or more
gas molecules; thus, the equilibrium shifts to the right.
(e) The reaction is endothermic, so decreasing the temperature will shift the equilibrium in the direction
that produces heat, so the equilibrium shifts to the left, toward the formation of more N2O4.
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Haber’s Process
This process is used in industry to make ammonia. Ammonia is a poisonous gas with formula NH3.
Ammonia is colourless gas and has a characteristic pungent smell. It is lighter than air.
It is highly soluble in water and makes an alkaline solution.

Raw Material:
Nitrogen: It is obtained from air by its fractional distillation.
Hydrogen: It is obtained from cracking of hydrocarbons or from water.

Nitrogen and hydrogen are mixed together in ratio 1:3 and passed over iron catalyst at 450oC temperature
and 200 atm or 20000 kPa pressure through a reaction chamber.

N2(g) + 3H2(g) ⇌ 2NH3(g) ∆H = − ve

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A mixture of nitrogen, hydrogen and ammonia is obtained after the reaction since the reaction is
reversible. The gases are cooled and ammonia is separated by liquefying it. The unreacted nitrogen and
hydrogen are recycled to produce ammonia again.

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Le Chatelier’s principle is used to get the best yield of ammonia.

Pressure
A lower pressure would decrease the percentage of ammonia in the equilibrium position.
This is because equilibrium shifting in the direction of the greater number of gaseous moles. However, low
pressure makes the reaction too slow to be economic. A higher pressure would increase the percentage of
ammonia in the equilibrium position. This is because equilibrium shifting in the direction of the lesser
number of gaseous moles. High pressure makes the reaction to becomes fast but it is also not economical.
A high pressure is expensive to produce and maintain (extra thick pipes and reactor walls would be
needed) and make for a less safe process. This is why a compromise pressure of 200 atm is used.
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Temperature
A lower temperature would increase the percentage of ammonia in the equilibrium position. This is
because equilibrium shifting in the forward direction as reaction is exothermic. Low temperature makes
the reaction too slow to be economic. A higher temperature would decrease the percentage of ammonia in
the equilibrium position. This is because equilibrium shifting in the backward direction as reaction is
exothermic. High temperature makes the reaction becomes fast but it is also not economical. This is why a
compromise temperature of 450 oC is used.

A heat exchanger warms the incoming gas mixture to give molecules more kinetic energy such that the
gas molecules collide more frequently increasing the likelihood of a reaction.

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Removing ammonia
Removing ammonia by condensing it to a liquid causes the equilibrium position to shift to the right to
replace the ammonia causing more ammonia to be formed from hydrogen and nitrogen.
The removed ammonia is stored at very low temperatures and there is no catalyst present with the stored
ammonia so the decomposition reaction of ammonia to decompose back into hydrogen and nitrogen will
be too slow.

Catalysts
In the absence of a catalyst the reaction is so slow that hardly anything happens in a reasonable time!
Adding an iron catalyst speeds up the rate of reaction.
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Contact Process
This process used in industry to make sulfuric acid. Sulfuric acid is a colourless oily liquid with density
slightly higher than water and high boiling point of 338oC.
It’s soluble in water and emits heat when dissolved.

Sulfuric acid is manufactured from the raw materials

 Sulfur
 Air
 Water

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1. Preparation of Sulfur Dioxide, SO2
It is prepared by the burning of sulfur or metal sulfide in combustion chamber.

S(g) + O2(g) → SO2(g)

OR PbS(s) + O2(g) → PbO(s) + SO2(g)

2. Purification
SO2 gas is purified from impurities by passing it through dust settlers and washed with water then dried
with concentrated H2SO4.
If there are impurities then the catalyst will be “poisoned” and the reaction will be less effective.

3. Oxidation of Sulfur Dioxide

Sulfur dioxide is mixed with air and the mixture passed over a catalyst of vanadium (V) oxide (V2O5) at a
high temperature of 450°C and at a pressure of 1 atm or 200 kPa. The reaction is exothermic.

2SO2(g) + O2(g) ⇌ 2SO3(g) ∆H = − ve

This is a reversible reaction and percentage yield of sulfur trioxide is about 97%.
The equilibrium is very much to the right hand side despite the reaction being exothermic and a high
temperature used. The reaction is favoured by high pressure but only a small increase in pressure is used
to give high yields of sulfur trioxide, because the right hand side is energetically very favourable.
The use of a catalyst ensures a fast reaction without having to use too much higher temperature which would
favour the left hand side reaction.

4. Formation of Oleum
Sulfur trioxide is cooled and is dissolved in concentrated sulfuric acid to produce oleum, H2S2O7.

SO3 + H2SO4 → H2S2O7

Sulfur trioxide is not dissolved in water as it is highly exothermic process and makes a mist of sulfuric acid
in that region which is toxic and dangerous.

5. Dilution of Oleum
Oleum is diluted with distilled water to produce sulfuric acid.

H2S2O7 + H2O → 2H2SO4

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Le Chatelier’s principle is used to get the best yield of sulfuric acid.

Pressure
A lower pressure would decrease the percentage of sulfur trioxide in the equilibrium position.
This is because equilibrium shifting in the direction of the greater number of gaseous moles. However, low
pressure makes the reaction too slow to be economic. A higher pressure would increase the percentage of
sulfur trioxide in the equilibrium position. This is because equilibrium shifting in the direction of the lesser
number of gaseous moles. High pressure makes the reaction to becomes fast but it is also not economical.
A high pressure is expensive to produce and maintain (extra thick pipes and reactor walls would be
needed) and make for a less safe process. This is why a compromise pressure of 1 atm is used.

Temperature
A lower temperature would increase the percentage of sulfur trioxide in the equilibrium position.
This is because equilibrium shifting in the forward direction as reaction is exothermic. Low temperature
makes the reaction too slow to be economic. A higher temperature would decrease the percentage of sulfur
trioxide in the equilibrium position. This is because equilibrium shifting in the backward direction as
reaction is exothermic. High temperature makes the reaction becomes fast but it is also not economical.
This is why a compromise temperature of 450 oC is used.

Removing sulfur Trioxide

SO3 is removed by absorbing it in 98% sulfuric acid.
The SO3 reacts with the solution and more H2SO4 is formed.

Catalysts
The Contact process uses vanadium (V) oxide as a catalyst to increase the rate of reaction.
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