RATES OF REACTION 1

(CHEMICAL KINETICS)
INTRODUCTION
Chemical kinetics deals with the study of rates and mechanisms of chemical reactions and the factors
that affect them. It usually includes the study of the rates of change of concentration of substances
involved in chemical reactions. In chemisty, the rates of a chemical change can be interpreted from
the reaction A ⟶ B in one of two ways
✓ The decrease in reactant’s concentration [A], per unit time.
✓ The icreases in product concentration [B], per unit time, where the square brackets represent
concentration in mole.dm-3.
d dx
The symbol is a useful means of rpresneting rates, where means change of x with respect to
dt dt
time. In chemical reactions, its either change of reactants concentration with time, or change or
product concentration with time.

Definition of rates of reaction

The rate of a chemical reaction is the decrease in concentration of a reactant or the increase in the
concentration of a product with time. That is
𝐝[𝐀] 𝐝[𝐁]
Rates = − =
𝐝𝐭 𝐝𝐭
The negative sign indicates that the concentration of A decreases with time.

MEASURING REACTION RATES

(a) PHYSICAL METHODS
1. Conductimetry (measuring rate by conductivity)
✓ This is the physical methos which makes use of the fact that ions in solution conduct electricity.
✓ The conductivity of the reaction mixture is monitored at regular intervals by connecting the
reaction mixture to a conductivity cell (inert electrode), then to a microammeter.

Conductivity meter

Inert electrode

Reaction mixture

Fig. Measurement of conductivity

of a solution

✓ The conductivity apparatus is calibrated in concentration values, and the readings of electrical
conductivity as the reaction proceeds may be converted to concentration of the ions present.
✓ Take reading of electrical conductivity at equal time intervals. The electrical conductivity of a
solution is proportional to the concentration of the ions and the changes they bear.

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✓ A graph of electrical conductivity against time is plotted. The rate of the reaction at anytime is
the tangent line to the curve at the time.
Electrical
conductivity

time
−
5𝐁𝐫(𝐚𝐪) + 𝐁𝐫𝐎−
𝟑(𝐚𝐪) + 𝟔𝐇+
(𝐚𝐪) ⟶ 3Br2(aq) + 3H2O(l)
In the above reaction, the number of ions reduces from twelve ions as reacts to zero ions as product,
the conductivity therefore decreases with time.
In some cases conductivity measurement can be used even if there if no overall change in the number
of ions. An example is alkaline hydrolysis of an ester.
−
CH3COOC2H5 (aq) + 𝐎𝐇(𝐚𝐪) ⟶ CH3C𝐎𝐎−
(𝒂𝒒) + C2H5OH(aq)

Each time a hydroxide ion is used up, a ethanoate ion is produced. Consequently, there is no change
in the total number of ions. However, ethanoate ions have much smaller conductivities than hydroxide
ions, so that the reactions involves a gradual decreases in conductivity.
2. Colorimetry (colorimetric analysis
This method is convenient for systems in which one of the substances is coloured. The change in the
concentration of the coloured reactant or product is followed using a photoelectric colorimeter.

✓ A coloured reaction mixture is placed before a phtocell.

✓ Light of a fixed wavelength is passsed through a filter. It then shines through coloured
reactiuon mixture onto a photocell.
✓ The phtocell ddvelops an emf which is proportional to the intensity of light.
✓ Since a photocell can be calibrated with solutions of known concentration, it means that emf
values can be converted to concentration values.

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✓ Once the concentrations are got for various time intervals the rate of the reaction can be
determined. This is done by pltting a graph of concentration aginst time. The tangent to the
curve is used to determine the rate of reaction.
Colour Colour
intensity intensity

time/s 0 time/s
Fig. Decrease of colour intensity of
product with time Fig. Increase of colour intensity of
product with time
Examples of reactions that can be followed by this method include
HCOOH(aq) + Br2(aq) ⟶ CO2(g) + 2HBr(aq)
2MnO− 2− + 2+
4(aq) + 5C2O4(aq) + 16H(aq) ⟶ 2Mn(aq) + 10CO2(g) + 8H2O(l)

3. Dilatometry
It involves measuring small volume changes in the reaction mixture for reactions in solution due to a
physical or chemical process. A dilatometer is used which is a scientific instrument that measures
volume changes caused by a physical or chemical process. A familiar application of a dilatometer is
the mercury-in-glass thermometer in which the change in volume of the liquid column is read from
the graduated scale.
Graduated
capillary tube

Bulb

Reaction mixture

Fig. Dilatometer

✓ The reaction mixture is filled in the bulb and part of the capillary tube.
✓ The volume of the solution is measured at regular time intervals.
✓ The volume changes are meausred as a rise or fall in the volume level in the capillart tube.
✓ A graph of volume change against time is plotted. The rate of reaction at any time is the gradient
line to the curve at that time.
✓ An example of a liquid mixture that leads to a rise in volume is ethanol and ethanoic acid.
4. Gas syringe method
✓ It involves measuring the volume of a gas evolved at regular time intervals using a gas syringe
attached to the reaction vessel.
✓ This technique is particularly suitable for reactions leading to the evolution of a gaseous product.

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✓ The volume is plotted against the time taken to give a curve and the slope of the tangent line to
the curve at anytime will give the rate of reaction at that time.
Example: Reacting CaCO3 with HCl acid to give CO2.
CaCO3(s) + 2HCl(aq) ⟶ CaCl2(aq) + H2O(l) + CO2(g)
The rate of the reaction is followed or measured vt recording the volume of CO2 produced at a
number of reaction time interval.
Another example is 2H2O2(aq) ⟶ 2H2O(l) + O2(g)

Fig: Measurement of volume of gas evolved

Volume of
CO2/cm3
dV V2 −V1
V2
Rates = =
dt t2 −t1

Slope = Rates of reaction

with respect to volume of
CO2 at that instant
V1

0 T1 t2 time/s
Fig. Increase of colour intensity of
product with time

5. Pressure measurement
This involves reactions between gases in which there is an increase or decrease in the number of
molecules of gas. The change in pressure is measured using a manometer which records pessure
change in the reaction vessel at time intervals. The slope of the graph of pressure against time
gives the reaction rate.
Examples
2NO2(g) + O2(g) ⟶ 2NO3(g)
2N2O5(g) ⟶ 2N2O4(g) + O2(g)

(b) CHEMICAL METHODS

1. Titrimetry or Titrimetric analysis
✓ This is a chemical and it is suitable for reactions which H + , OH − ,I2(aq) and other suitable ions
that are either consumed or produced in the course of the reaction.

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✓ This can be done by pipetting portions or samples or aliquotes of the reacting mixture at regular
time intervals and titrate with the standard solution in the burette.
✓ The major problem with this method is that the reaction continues in the sample volume after
it has been removed from the reaction mixture.
✓ To overcome this problem, the sample volume is either
❖ Added to a large volume of ice cold water which slows down the reaction considerably
or
❖ A known excess of quenching reagent is added.
A quenching reagent (quencher) is a substance that reacts immediately with one of the reactants
and the reaction stops.
✓ A sample of the mixture is withdrawn with a pipette at time intervals and the reaction is
stopped (“quenched”) by removing one of the reactants by a chemical reaction or slowing down
the reaction by cooling or by dilution. This prevents further changes in concentration before
analysis is done. This is done by pipetting a sample of the mixture into a freezing mixture (ice-
cold water) or into an excess of the solvent. A titration is then performed to find the
concentration of one of the reactants or one of the products.
Examples
(i) Alkaline hydrolysis of an ester
CH3CO2C2H5(aq) + NaOH(aq) ⟶ CH3CO2Na(aq) + C2H5OH(aq)
Indicator: Phenolphthalein
A graph of concentration of the alkaline againsti time is plotted. The rate of reaction at anytime
is the gradient of the tangent line at that time.
(ii) Reaction between acetone and Iodine
CH3COCH3(aq) + I2(aq) ⟶ CH3COCH2I(aq) + HI(aq)
Indicator: Starch solution
✓ Iodine in the quenched mixture is titrated with a standard solution of sodium thiosulphate
using starch indicator. The volume of the thiosulphate solution used in each titration is
proportional to the concentration of iodine.
✓ A graph of the volume of thiosulphate against time is plotted. The rate of reaction at any
instant is the slope of the tangent to the curve at that instant.
RATE EQUATION
Experiments show that the rate of most reactions depends on the concentration of certain
reactants as well as the concentration of the catalyst, if there is any. Consider a hypothetical
solution aB + bB ⟶ cC + dD
The rate of reaction is proportional to the concentration of each of the reactants.
Rate α [A]𝐧 and Rate α [B]𝐦
The two expressions may be combined with a constant of proportionality, K to express the rate of
reaction in terms of the concentration of both reactants.
Rate = k[A]𝐧 [𝐁]𝐦
This is called the rate equation. K is the rate constant, n and m are the order of reaction with
respect to A and B respectively. The rate expression indicates the species which are involved in the
rate determing setp and how many of each species are involved. The rate constant K is dependedt on
1. The nature of the reaction.
Fast reactions typically have larger rate constants. If K is small, the reaction is slow at ordinary
concentration.

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2. Temperature
Ordinarily, K increases with temperature

Rate law
It is a mathematical relationship between the rate of reaction and the concentration of reactants
(determined from experiment) raised to various powers.

FACTORS AFFECTING REACTION RATE

1. Concentration of reactants
An increase in concentration of a reactant (mostly in solution or gas phase) increases the frequency with
which it molecules collide and thus leading to an increase in reaction rate. If the concentration of a
reactant in solution or in a gaseous mixture is increased:
✓ There are more particles prsent per volume.
✓ More collisions occur each second.
✓ More collisions exceed the activation energy per second. Thus the reaction rate increases.
It should be noted that not eevry collision leads to a reaction but the collision has to be effective.
Pressure also affect the rate of geasous reactions. Decrease in volume leads to an increase in pressure.
For example CaCO3(s) + 2HCl(aq) ⟶ CaCl2(aq) + CO2(g) + H2O(l)
In the above example, the rate of reaction increases if the concentration of hydrochloric acid is
increased.
2. Temperature
An increase in temperature of the reactants will lead to an increase in the rate of reaction. The rates of
reaction increases with increase in temperature for two reasons
(i) As temperature increases, the reacting particles gain kinetic energy (their speed increase) leading
to more frequent and effective collision with a coresponding increase in rates of reaction.
(ii)Increase in temperature increases the number of collisions with energy equal to or greater than the
activation energy.
The activation energy (Ea) is the miniumum amount of energy needed by the reacting particles
in order to react. That is, the minimum aount of energy for a collion to be effective.
It has been found that for only 10℃ increase in temperature, the rate of most reactions double. This
is because the number of molecules with energy equal to Ea doubles. This is shown in the figure
below
Number of
molecules

T1
T2 Additional number of particles with energy ≥ Ea as
a result of increase in temperature from T1 to T2

Number of particles with energy ≥ Ea at temperature T1

Ea = activation energy

Ea Kinetic energy

3. Surface area of reactants

For reactions that involve solid reactants, the rate of reaction increases if the solid is in powedered
form than in lumps. This will lead to an increase in the total surface area exposed for the reaction.

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The surface of effective contact between the reactants will increase leading to an increase in the rate
of reaction. For example the reaction between zinc and hydrochloric acid is faster when zinc is in
powdered form than with zinc granules.
Zn(s) + 2HCl(aq) ⟶ ZnCl2(aq) + H2(g)
The rate of reaction of calcium carbonate with hydrochloric acid can be increased if lumps of calcium
carbonate are broken up to powder.
CaCO3(s) + 2HCl(aq) ⟶ CaCl2(aq) + CO2(g) + H2O(l)
The rate of reaction can be determined by measuring the volume of CO2 evolved at regular intervals
using a gas syringe.

4. Catalyst
A catalyst is a substance that increases the rate of a chemical reaction without itself undergoing any
permanenet change. The presence of a catalyst increase the reaction rate by providing an alternative
route with a lower activation energy barrier for the reaction. The new reaction pathway has a larger
rate constant and lower activation energy. Fro example, hydrogen peroxide decomposes very slowly
by itself to form water and oxygen.
2H2O2(aq) ⟶ 2H2O(l) + O2(g)
However, in the presence of manganese (IV) oxide (MnO 2) catalyst, the reaction is rapid.

5. Effect of light
Certain reactions are greatly accelerated by light. They are called photochemical reactions. Light
provides the activation energy for the reaction. The energy is used to break the bods in the
reactants to produce reactive free radicals. For example
✓ The reaction between chlorine and methane using UV light as a photochemical catalyst
✓ Hydrogen peroxide and chlorine react explosively in sunlight.
✓ Reduction of silver salts to silver when exposed to light.

ORDER OF A REACTION
The order of reaction with respect to a reactant is the power of that reactant’s concentration in an
experimentally determined rate equation. The overal order of reaction is the sum of the powers of the
concentration of reactants in experimentally determined rate equation.
✓ The order of reaction gives chemists an idea of how the concentration of a reactant affect the
rate of reaction.
✓ It also permits chemists to predict the mechnism of a reaction
Suppose we take the general case of a reaction xA + yB ⟶ Products. The rate equation can be be
expressed as
Rate = k[A]𝐦 [B]𝐧
The indices m and n are known as the orders of the reaction with respect to A and B respectively.
The overal oder of the reaction is (m + n)
Consdier the following reaction between nitrogen monoxide and hydrogen.
2NO(g) + 2H2(g) ⟶ N2(g) + 2H2O(g)
The experimetally determined rate expression is Rate = k[NO]𝟐 [H2]. This indicates that the reaction
is second order with respect to NO, first order with respect to H2 and third order overal.

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DETERMINATION OF REACTION ORDER
1. Initial rate (or isolation) method
The initail rate method allows one to find the order with respect to any species in the reaction mixture.
The experiments are planned so that only the concentration of one reactant changes between pair of
experiments. This method involves carrting out a number of sperate experiments with different initial
concentrations and measuring the initial rates of reaction. That is, measuring the time taken to
produce a small fixed concentration of product.
(i) If doubling the concentration of a reactant has no effect on the rate, the reaction is zero
order with respect to that reactant.
(ii) If doubling the concentration of a reactant doubles the rate of the rate, then the rate is directly
proportional to the concentration of the reactant. The reaction is first order with respect to the
reactant.
(iii) If doubling the concentration of a reactant increases the rate by a factor of four, that is, the
rate quadruples, then the reaction is second order eith respect to the reactant.
(iv) If doubling the concentration of a reactant increases the rate by a factor of eight, then the
reaction is third order with respect to the reactant.
2. Calculation of order of reaction from data
This can be done by
✓ Comparing the initial rates of two reactions at known initial concentrations, If R1 and R2 are
the initial rates and [Ao]𝟏 and [Ao]𝟐 are the initial concentrations of A for experiments 1 and
2 respectively, then
R1 = k[Ao]𝟏 and R2= k[Ao]𝟐 where n= order with respect to A.
By taking the ratio
R1 [Ao ]n
1
=
R2 [Ao ]n
2
✓ By taking the logarithms on both sides

R1 [Ao ]1
ln = nln( )
R2 [Ao ]2

𝐑
𝐥𝐧 𝟏 𝐥𝐨𝐠(
𝐑𝐚𝐭𝐞 𝟏
)
𝐑𝟐
 n= [𝐀𝐨 ]𝟏 or order, n= 𝐑𝐚𝐭𝐞 𝟐
[𝐀𝐨 ]𝟏
𝐥𝐧( ) 𝐥𝐨𝐠( )
[𝐀𝐨 ]𝟐 [𝐀𝐨 ]𝟐