CHEMICAL KINETICS

The Rate of a chemical Reaction

RATE OF A REACTION
 The rate of a reaction is defined as the decrease in the
concentration of reactant per unit time, or the increase in the
concentration of product per unit time.

 Alternatively, the rate of a reaction may be defined as the change

in the concentration of a reactant or product per unit time.

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Change in rate with concentration
 As a reaction takes place the concentration of reactants decrease
while that of products increase.This can be represented
graphically as shown below:

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Average rate of a reaction
 In general the rate of a reaction is not constant. At the beginning
of products decrease and hence the rate falls.The averagof the
reaction the rate is very fast due to the high concentration of
reactants. However, as the reaction goes on the concentration e
rate of a reaction is a measure of the rate of the reaction over a
certain period of time.The average rate is defined by the
equation:

 Rate(av)= Total change in concentration of reactant or product

Total change in time

 The change in concentration is final concentration minus initial

concentration. When rate is defined in terms of reactants a
negative sign is added to make the rate positive
 Rate = -  Final concentration  Initial concentration 
 Final time  Initial time 

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 Rate at an Instant
(Instantaneous Rate)
 The average rate of a reaction only gives the rate measured over
a period of time.The rate at a particular time or concentration is
known as the instantaneous rate.The rate at an instant is defined
as an infinitesimal change in concentration per unit time.

ΔC
Rate(Inst)
=
Δt

 The instantaneous rate is obtained from the gradient of

concentration-time curve.
 The instantaneous rate at t=0 is known as the initial rate. It is the
rate when the concentration is at is highest, and hence is the
fastest rate.

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CH4H9Cl + H2O →CH4OH + HCl

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Relative Rates of Reactions
 When two reactants A and B are put in a reaction vessel, the rate
at which A reacts may be different from the rate at which B
reacts.The rate of reaction of B compared to A is known as the
relative rate of reaction of B to A.The rate at which one
substance reacts relative to another can be obtained from the
balanced equation for the reaction.
 E.g. 2NO2 → 2NO + O2

 The NO2 is consumed twice the rate at which oxygen is

produced.The relative rate of consumption of NO2 to production
of O2 is 2:1. Similarly, the NO is produced at twice the rate that
oxygen is produced.Thus the relative rate of production of NO to
oxygen is 2:1

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Graphical representation of relative
rates
 Note how the concentration of NO at the end of the reaction is
twice that of O2.
Concentration vs Time

0.012

0.01
[NO2]

0.008
Conc.,mol/L

[NO]

0.006

0.004 [O2]

0.002

0
0 50 100 150 200 250 300 350 400 450

Time, sec

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Sample questions
 1. For the reaction A + B  D, 1.6mols each of A and B were
introduced into a 1dm3 reaction vessel. After a period of
40minutes the concentration of D was found to be 0.6mols.
Calculate the average rate of formation of D in moldm-3min-1.

 2. For a reaction A products, the initial concentration of A in

moldm-3 was 2.4. After 120 seconds the concentration of A was
found to be 0.12moldm-3. Calculate the average rate of reaction
of A.
 3. Consider the reaction
 N2 + 3H2 = 2NH3

 The rate of consumption of Nitrogen was found to be 1.2moldm-3

at 200oC. Calculate the rates of consumption of hydrogen, and
 production of ammonia
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Calculation of rate at an instant
 Calculate the initial rate and the rate at 600s for the hydrolysis of
chlorobutane:
 CH4Cl + H2O → CH4OH + HCl

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THE COLLISION THEORY OF
REACTION RATES
This states that chemical reactions occur
 when particles collide with each other.
 The greater the frequency of collisions, the faster the rate of the
reaction.
 These particles must have the right amount of energy equal to or
greater than the activation energy for the reaction
 And be properly oriented in space.

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The Transition State
 During collision of particles only those with energy equal to or
above the activation energy of the reaction actually react.
 These particles form an unstable intermediate called a transition
state or activated complex, which then breaks down to form the
products or to reform the reactants.
 E.g. H2 + F2 → [H2F2]activated complex → 2HF

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Factors affecting rates of reactions
 The following factors affect the rate of a reaction
 Concentration of reactants
 Temperature
 Nature of reactants
 Catalyst
 Pressure (for gaseous reactions).
 Light (for light sensitive reactions).

 1. Concentration: increase in the concentration of a reactant

generally increases the rate of a chemical reaction.
 Explanation:This is because the particles become more crowded
in the same volume and this brings about an increase in the
number of effective collisions between them resulting in an
increase the rate of the reaction.

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 2.Temperature: increase in temperature brings about an increase
in the rate of reaction.
Explanation:
 Increase in temperature results in an increase in the average
kinetic energy of the particles hence the frequency of collisions
between the particles increase resulting in an increase in the
number of effective collisions.

 Secondly more particles have energy greater than the activation

energy of the reaction hence more particles are able to react.
These two effects result in an increase in the rate of the reaction.


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Maxwell-Boltzmann distribution
curves for molecular velocities
 These are graphs used to explain the effect of increase in
temperature on the rate of a reaction. At a temperature T1 fewer
particles have energy greater than the activation energy Ea as
shown by the area ‘a’. When the temperature is increased to T2,
the number of particles with energy greater than the activation
energy Ea increases to ‘a’ + ‘b’ and hence the reaction is faster at
the higher temperature.

 The rate is approximately doubled for a 10o rise in temperature

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 3. Pressure:This applies to only gaseous reactions.
 Increase in the pressure of gaseous reactants is equivalent to an
increase in concentration.
 This is because increase in pressure results in the particles being
more crowded. Hence the frequency of effective collisions
increase and the rate of the reaction increase.
 Decrease in volume has the same effect as increase in pressure.

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Surface Area
 Finely powdered solids react faster than lump form.
 This is because the powdered form exposes a larger surface area
for collision with the other reactant.
 Thus powder CaCO3 reacts faster with HCl(aq) than lump CaCO3.

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Light catalyzed reactions
 Certain reactions are speeded up by light for example,
photosynthesis.

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Effect of a catalyst
 Catalyst: a catalyst speeds up a reaction by providing an
alternative pathway with lower activation energy.
 Hence more molecules are able to overcome the energy barrier
and react.

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TYPES of CATALYSIS
 Homogenous Catalysis:This is a type of catalysis in which the
reactants and products are in the same phase. For example, in the
reaction of ethanol with ethanoic acid to form ethyl ethanoate,
H2SO4 is used as a catalyst.The reactants and catalyst are all
liquids.
 CH3COOH(l) + C2H5OH(l) → CH3COOC2H5(l) + H2O(l)

 Heterogeneous catalysis: This is a type of catalysis in which the

reactants and catalysts are in different phases. For example, in the
production of ammonia from nitrogen and hydrogen, finely
divided iron which is a solid is used as a catalyst.
Ni
 N2(g) + 3H2(g) 2NH3(g)

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Catalyst in catalytic converters
 Rhodium, catalyses the reaction between carbon monoxide and
nitric oxide to form carbon dioxide and nitrogen gas
 2CO + 2NO → 2CO2 + N2
 Another metal, platinum, catalyses the reactions of carbon
monoxide and unburnt hydrocarbon to carbon dioxide.
 2CO + O2 → 2CO2
 These reactions remove three most harmful pollutants from the
exhaust gas: carbon monoxide, unreacted hydrocarbons and nitric
oxide.

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Autocatalysis
 During the course of some reactions, species are produced that
act as catalyst to speed up the reaction.
 For example, in the reaction of permanganate with oxalate,
manganese(II) ions are produced and these in turn catalyses the
reaction.
 2MnO4-(aq) + 16H+ (aq) + 5C2O42-(aq) → Mn2+(aq) + 8H2O + 10CO2

 Enzyme catalysis: Enzymes are biological catalysts that speed up

many biochemical processes.
 enzymes are proteins and hence are easily destroyed by heat.
When this happens we say the enzyme has been denatured.This
means that the enzyme loses its enzymatic ability.
 Example of enzyme catalysis-Maltase converts maltose to glucose
units in the body.

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MEASUREMENT OF RATES

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Measurement
 The volume of hydrogen gas released from reacting magnesium
with hydrochloric acid can be used to measure rate.

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Measuring the change in mass of a
reaction mixture
 E.g. the reaction between CaCO3 and HCl. The reaction flask and
content is placed on a digital balance. As reaction proceeds, gas
escape resulting in a decrease in mass with time.

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Sulphur-Clock reaction
 Sodium thiosulfate reacts with hydrochloric acid to produce
sodium chloride, sulfur, sulfur dioxide and water.
 Na2S2O3 + 2HCl → 2NaCl + S + SO2 + H2O
 An ‘X’ is placed on a piece of paper under the reaction flask. The time for
the reaction will be measured by recording the time from when the
solutions are mixed until the ‘X’ can no longer be seen from above the
flask.

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The Iodine Clock reaction
 Iodide ions react with peroxydisulphate ions to produce iodine
according to the equation:
 2I-(aq) + S2O82-(aq) → I2(aq) + SO42-(aq)

 If the reaction mixture contains a small amount of thiosulphate and

starch, the iodine produced initially reacts with the thiosulphate:
 2S2O32-(aq) + I2(aq) → 2I-(aq) + S4O62-(aq)

 When all the thiosulphate has been consumed, the iodine

produced now reacts with the starch present in the mixture to
form a deep blue starch-iodine complex.
 The rate can be monitored by measuring the time taken for the
blue colour to appear.
 A similar experiment can be performed using

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Other reactions suitable for rates
1. Hydrogen peroxide reacts with an acidified solution of iodide ions
to produce iodine according to the following equation:
H2O2(aq) + 2I−(aq) + 2H+(aq) → I2(aq) + 2H2O(l)

2. The reaction between acidified potassium permanganate (a

purple solution and oxalic acid (H2C2O4)
2MnO4−(aq) + 5H2C2O4(aq) + 6H+(aq) →2Mn2+(aq) + 10CO2(g) + 8H2O(l)

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