RATE OF REACTION AND REVERSIBLE REACTIONS

Rate of reaction
Some reactions proceed very fast. For example, when aqueous ammonia is added to a solution of lead
(II) salts, a white precipitate forms immediately. Some reactions proceed at moderate speed. For
example, it takes some time for the reaction between calcium carbonate and dilute hydrochloric
acid to come to completion. Other reactions are slow. For example, it takes iron a few days to rust in
moist air. The above mentioned reactions proceed at different rates.
The rate of a chemical reaction is the speed at which products are formed or the speed at
which reactants are used up in the reaction.
Rate of reaction = concentration in moles per litre

Time in seconds

Units for the rate of reaction are moles/litre/second (i.e mol/l/s).

Determination of rate of reaction
Let us consider the reaction between magnesium and dilute hydrochloric acid.
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
The determination of the rate of this reaction can be done by either measuring the volume of
hydrogen evolved with time or by measuring the time a given length of magnesium ribbon
takes to dissolve in varying concentrations of the acid.
Determination of rates of reaction by measuring the volume of the gas evolved with time
A known mass of magnesium and a known volume of dilute hydrochloric acid in a test- tube tied
with a thread, are placed in a conical flask and the experiment is set up as shown in the figure
below. The stopper is opened for a moment so that thread is free. The test- tube drops pouring
hydrochloric acid into the conical flask. At the same time, the clock is started. The volume of
hydrogen in the syringe is recorded at regular intervals until the reaction is complete
A graph of volume of hydrogen evolved against time is plotted. A typical graph has the
form below.

To determine the rate of reaction at a given time, say t1, the tangent to the curve is drawn at
that time as shown in the figure below. The gradient of the tangent is the rate of reaction at that time
that is y/x. the units are cm3/s.

Factors affecting the rate of chemical reactions

Factors which affect the rate of a chemical reaction are;
 Concentration
 Temperature
 Catalyst
 Surface area (particle size),
 Light
 Pressure
Effect of concentration of reactants on the rate of reaction
The higher the concentration, the higher the rate of reaction and the lower the concentration,
the lower the rate of reaction. This is because increase in concentration brings the reactant
particles close to one another hence increasing the chances of the reactant particle to collide
and react with one another.
Experiment to investigate the effect of concentration on the rate of the reaction
Make a mark with blue or black ink on a piece of paper. Place 50 cm3of 0.05 M sodium thiosulphate
solution into a beaker. Add 10 cm3of 1 M hydrochloric acid to the sodium thiosulphate and at the
same time start the stop clock. Gently shake the mixture to mix the solution well and place
the beaker onthe paper over the mark. Watch the mark through the solution from above the
beaker. Stop the clock when the mark just disappears. Vary the concentration of the thiosulphate
solution by taking 40, 30, 20 and 10cm3 each time by adding distilled water. Tabulate your results
including 1/time. Plot graphs of volume of sodium thiosulphate solution against1/time (time-1) and
against time. The rate of reaction is proportional to the reciprocal of time (time-1). Your graphs
should appear as shown in figure 11.4a and11.4b.
The mark disappears because the reaction between hydrochloric acid and sodium thiosulphate
forms a precipitate of sulphur which renders the mixture opaque.
NaS2O3(aq) + 2HCl(aq) → 2NaCl(aq) + S(s) + H2O(l) + SO2(g)
Figure 11.4a shows that the higher the volume of the sodium thiosulphate, the less the time taken to
form a precipitate. Figure 11.4b shows that the rate of the reaction increases with increase in
volume of sodium thiosulphate solution.
Effects of temperature on the rate of reaction
The higher the temperature, the higher the rate of reaction and the lower the temperature the lower
the rate of reaction. This is because increase in temperature increases the kinetic energy of the
reactant particles which increases their speed of movement. The frequency at which the reacting
particles collide increases and thus the rate of the reaction increases.

Experiment to investigate the effect of temperature on the rate of reaction

The previous experiment can be repeated by reacting sodium thiosulphate solution and hydrochloric
acid at varying temperatures, using the same concentration of the thiosulphate. Put a test- tube
o
containing 1 M hydrochloric acid into a beaker of water maintained at 30 C. After sometime,
add at the same time start of 0.05 M sodium thiosulphate solution in a beaker and at the same time
start mark. Note the time taken for the mark to disappear. The experiment is repeated using
different temperatures. Tabulate your results including 1/time. Plot graphs of temperature against
1/time. The shapes of typical graphs are shown in figure 11.5a and 11.5b.

Figure 11.5a shows that the higher the temperature the less the time taken to form a precipitate.
Figure 11.5b shows that the rate of the reaction increases with increase in temperature.
Effect of a catalyst on the rate of reaction
A catalyst is a substance which changes the rate of chemical reactions without undergoing any
overall chemical change itself. Most catalysts speed up the rate of reaction. The greater the amount
of the catalyst but within the limits, the higher the rate of reaction. Powdered catalysts offer a larger
surface area over which the reaction takes place and therefore are more effective than one in lump
form. Catalysts remain unchanged chemically after a reaction has taken place. Catalysts are very
specific to a particular chemical reaction. A catalyst which slows down a reaction is called a
negative catalyst.
Experiment to investigate the effect of catalyst on the rate of reaction
Place 100 cm3 of 0.1M hydrogen peroxide in a conical flask. Add 0.5g of manganese (IV) oxide to
the hydrogen peroxide in a test tube. Then set up the experiment as shown in figure below.

Manganes (iv) oxide

Hydrogen peroxide

Record the volume of oxygen in the syringe at regular intervals until the reaction is complete.
Repeat the experiment using 1g of manganese (IV) oxide. When the graphs of volume of oxygen
against time are plotted using the same axes, they appear as shown in figure below.

Effect of surface area on the rate of reaction

Increase in surface area increases the rate of reaction and reduction in surface area reduces the rate of
reaction. This is because increase in surface area exposes the reactant molecules to be able to react
with one another. Solids react much more rapidly when powdered than when in large lumps. This is
because reactions with solids take place at the surface. Powdered solids present a large surface area
over which the reaction occurs than solids in lump form.
Experiment to investigate the effect of surface area on the rate of reaction
Pour 20 cm3of 1 M hydrochloric acid in a test- tube. To the conical flask add 10 g of calcium
carbonate lumps and then set up the experiment as shown in figure below.
Record the volume of carbon dioxide in the syringe at regular intervals until the reaction is complete.
Repeat the experiment using the same mass of powdered calcium carbonate. When the graphs of
volume of carbon dioxide against time for both powdered calcium carbonate and calcium carbonate
lumps, are plotted using the same axes, they appear as shown in figure below.

Effect of light on the rate of reaction

For reactions which are photosensitive, increase in light intensity increases the rate of reaction
and reduction in light intensity reduces the rate of reaction. This is because light is a source of
energy and can therefore influence some chemical reactions considerably by providing energy
to the reactant molecules. For example the reaction between chlorine and hydrogen is very
slow in darkness but very fast in sunlight.
Investigation of the effect of light on the rate of reaction
Add 1 cm3of sodium chloride solution to two test- tubes. To each test- tube add a few drops of
silver nitrate solution. Immediately, a white precipitate forms. Put one test- tube in a dark cup
board and the other in sunlight for about 4 minutes. Record your observations.
Sodium chloride solution forms a white precipitate with silver nitrate solution according
to the equation.
Ag+(aq) + Cl-(aq) → AgCl(s)

In presence of light, the precipitate darkens because of the decomposition of silver chloride to
solver and chlorine. In absence of light, the precipitate remains white.
2AgCl(s) → 2Ag(s) + Cl2(g)
The effects of light on hydrogen peroxide and concentrated nitric acid explain why they are
stored in dark- glass bottles.
Effect of pressure on the rate of reaction
Pressure only affects reactions which occur in the gaseous phase. When pressure of a gaseous
mixture is increased, the gases are compressed. This brings the reacting particles together and
thus increases the frequency at which the reacting particles collide hence increased rate of
reaction.
Reversible reactions
Reversible reactions are reactions that can be made to go forward and backward by changing the
conditions.
For example when copper (II) sulphate-5-water crystals are heated, they turn from blue to white as
they lose water of crystallization.
CuSO4.5H2O(s) CuSO4 (s) + 5H2O(l)
If water is added to the white solid, it turns blue again.
CuSO4(s) + 5H2O(s) CuSO4.5H2O(s)
The two equations can be combined into one equation by introducing a double arrow ( )
CuSO4.5H2O(s) CuSO4 (s) + 5H2O(l)
This equation indicates a reversible reaction.
In reversible reactions, it is possible to have both reactants and products present. If the forward
and backward rates are equal, there is a state of balance.
Applications of reversible reaction

1) Haber process
This is the process in which ammonia is manufactured on large scale. The equation for the
reaction is as shown below.
3H2(g) + N2(g) 2NH3(g) ∆H = - ve
If we need to yield high amount of ammonia, the optimum conditions are;
 High pressure of 200 – 300 atmospheres
 Low temperature of 450oC
 Iron catalyst (finely divided)
2) Contact process
This is the process in which sulphuric acid is manufactured on large scale.
The main reaction is:
2SO2(g) + O2(g) 2SO3(g) ∆H = - ve
The optimum conditions for this reaction are;
 Pressure of about 1 – 2 atmospheres
 Temperature of 450oC
 Vanadium (V) oxide catalyst