Pioneer Junior College Reaction Kinetics

Pioneer Junior College

Higher 2 Chemistry (9647)
Reaction Kinetics (Tutor’s Copy)
References
th
1. Chemistry In Context (5 edition) by Hill and Holman
th
2. A level Chemistry (4 edition) by E.N. Ramsden

Syllabus content
 Simple rate equations; orders of reactions; rate constants
 Concept of activation energy
 Effect of concentration, temperature, and catalysts on reaction rate
 Homogeneous and heterogeneous catalysis
 Enzymes as biological catalysts

Assessment objectives
Candidates should be able to:
(a) explain and use the terms: rate of reaction, rate equation, order of reaction, rate constant, half-
life of a reaction, rate-determining step, activation energy, catalysis.
(b) construct and use rate equations of the form rate = k[A]m[B]n (limited to simple cases of single
step reactions and of multi-step processes with a rate-determining step, for which m and n
are 0, 1 or 2), including:
(i) deducing the order of a reaction by the initial rates method;
(ii) justifying, for zero- and first-order reactions, the order of reaction from concentration-time
graphs;
(iii) verifying that a suggested reaction mechanism is consistent with the observed kinetics;
(iv) predicting the order that would result from a given reaction mechanism;
(v) calculating an initial rate using concentration data.
[Integrated forms of rate equations are not required.]
(c) (i) show understanding that the half-life of a first-order reaction is independent of
concentration.
(ii) use the half-life of a first-order reaction in calculations.
(d) calculate a rate constant using the initial rates method.
(e) devise a suitable experimental technique for studying the rate of a reaction, from given
information.
(f) explain qualitatively, in terms of collisions, the effect of concentration changes on the rate of a
reaction.
(g) show understanding, including reference to the Boltzmann distribution, of what is meant by the
term activation energy.
(h) explain qualitatively, in terms both of the Boltzmann distribution and of collision frequency, the
effect of temperature change on a rate constant (and, hence, on the rate) of a reaction.
(i) (i) explain that, in the presence of a catalyst, a reaction has a different mechanism,
i.e. one of lower activation energy, giving a larger rate constant.
(ii) interpret this catalytic effect on a rate constant in terms of the Boltzmann distribution.
(j) outline the different modes of action of homogeneous and heterogeneous catalysis, including :
(i) the Haber Process
(ii) the catalytic removal of oxides of nitrogen in the exhaust gases from car engine
(iii) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric
sulphur dioxide
3+ 2+ - 2-
(iv) catalytic role of Fe (or Fe ) in the I /S2O8 reaction
(k) describe enzymes as biological catalysts (proteins) which may have specific activity.
(l) explain the relationship between substrate concentration and the rate of an enzyme-catalysed
reaction in biochemical systems

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(a) explain and use the terms: rate of reaction, rate equation, order of reaction, rate constant, half-life of a
reaction, rate-determining step, activation energy, catalysis.

1. Introduction

Reaction kinetics is the study of the rates of chemical reactions, the factors that
affect the rates of chemical reactions and the mechanisms (sequence of steps) by
which chemical reactions occur.
2. Rate of a Reaction
2.1 Definition

The rate of a chemical reaction is the change in concentration of a reactant or a

product per unit time and measures how fast a reaction proceeds.

The unit for the rate of reaction is always mol dm-3 t-1 (where time, t, is either in
seconds or minutes).

2.2 Concentration-time graphs for reaction : A  B

i) [Reactant]-Time Graph

[A]
Rate of reaction at time, t
= Rate of disappearance of reactant A at time, t

= - d[A]
dt

gradient (rate) = 0
0 time

ii) [Product]-Time Graph

[B] gradient (rate) = 0

Rate of reaction at time, t

= Rate of formation of reactant B at time, t
d[B]
=
dt

0 time
• magnitude of the slope (gradient) of the curve = rate of the reaction
(slope can be negative but rate is never negative, rate simply decreases or increases.
• slope gets less steep (showing the rate is slowing down) as the reaction proceeds
• slope (rate) becomes zero when reactant A is used up and [B] becomes constant
• slope at the start of the reaction will give the INITIAL RATE
• initial rate is usually the fastest (steepest slope) for most reactions

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Example 1:
Given 2A + B → 3C, write the rate in terms of changes in [A], [B] and [C]

For every mol of B used up, 2 mol of A would have been used and 3 mol of C
would have formed.

Mathematical relationship of the rates of reaction:

𝑑[𝐵] 𝑑[𝐴] 1 𝑑[𝐶] 1
− 𝑑𝑡 = − 𝑑𝑡 2 = 𝑑𝑡 3

(b) construct and use rate equations of the form rate = k[A]m[B]n (limited to simple cases of single step
reactions and of multi-step processes with a rate-determining step, for which m and n are 0, 1 or 2),
including:
(i) deducing the order of a reaction by the initial rates method;
(ii) justifying, for zero- and first-order reactions, the order of reaction from concentration-time
graphs;
(iii) verifying that a suggested reaction mechanism is consistent with the observed kinetics;
(iv) predicting the order that would result from a given reaction mechanism;
(v) calculating an initial rate using concentration data.
[Integrated forms of rate equations are not required.]

3 The Rate Law (Rate Equation)

Definition 1 – Rate Law

The rate law or rate equation of a chemical reaction is a mathematical expression

that defines the rate as the product of a rate constant and the concentration(s) of the
reactant(s) raised to appropriate power(s).

Rate = k[reactant]n k is the rate constant

n is order of reaction with respect to reactant
The rate equation is found by doing experiments and not by looking at the
stoichiometric equation
E.g. The equation 2A + 3B + C ——> D + E , might have:
Rate Equation: Rate = k [A] [B]2

Definition 2 – Rate constant

The rate constant , k, is the constant of proportionality in the rate equation

The rate constant , k,

 is constant for a particular reaction at a given temperature
 is determined experimentally and has no fixed units

NOTE :
𝑢𝑛𝑖𝑡 𝑜𝑓 𝑟𝑎𝑡𝑒
unit of k = , where n = overall order
(𝑢𝑛𝑖𝑡 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)𝑛

 generally increases with (1) increase in temperature and (2) the use of catalyst
 if it is larger, rate of reaction is higher.
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Definition 3 – Order of reaction

The order of reaction with respect to a reactant is the power to which the
concentration of that reactant is raised in the rate equation.

E.g. rate = k[A]1[B]2 then the order of reaction w.r.t A is 1 and the order of reaction
w.r.t B is 2.

Order indicates how a change in concentration of a reactant affects the rate

E.g. Rate = k [A]1[B]2 - Doubling [A], doubles the rate (= 21)
Halving [A], halves the rate (=0.51)

Doubling [B], quadruples the rate (= 22)

1
Halving [B], rate will be 4 of the original rate (= 0.52)

Definition 4 – Overall order

The overall order of the reaction is the sum of all the powers of the concentration
terms in the rate equation. E.g. rate = k [A]1[B]2[C]1 then the overall order is 4.

Example 2: Given BrO3 (aq) + 5 Br (aq) + 6 H+ (aq)  3 Br2 (aq) + 3 H2O (l)

The reaction kinetics of the reaction was studied experimentally using the initial
rates method and the results are:

Initial concentration Relative

Mixtures
[BrO3 ] / mol dm -3
[Br ] / mol dm-3 [H+ ] / mol dm-3 rate
A 0.05 0.25 0.30 1
B 0.10 0.25 0.30 2
C 0.10 0.50 0.30 4
D 0.10 0.50 0.60 16

(a) Find the order of reaction w.r.t each reactant and state the overall order.
(b) Write the rate law for the reaction.
(c) Determine the unit for the rate constant, k, in this case.

Using Inspection method

Compare mixtures A and B in which [Br ] & [H+] are constant,

doubling [BrO3 ] doubles the rate. Therefore, rate  [BrO3 ].

Order of reaction with respect to bromate(V) ion = 1

Compare mixtures B and C in which [BrO3 ] & [H+] are constant,

doubling [Br ] doubles the rate. Therefore, rate  [Br ].

Order of reaction with respect to bromide ion = 1

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Compare mixtures C and D in which [Br ] & [BrO3 ] are constant,

doubling [H+] quadruples the rate. Therefore, rate  [H+]2.

Order of reaction with respect to hydrogen ion = 2

Overall order of reaction = 1 + 1 + 2 = 4

(b) Therefore, rate  [BrO3 ][Br ][H+ ]2 and rate = k[BrO3 ][Br ][H+ ]2.

𝑢𝑛𝑖𝑡 𝑜𝑓 𝑟𝑎𝑡𝑒
(c) Unit of k = (𝑢𝑛𝑖𝑡 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)𝑛 where n = overall order
𝑚𝑜𝑙𝑑𝑚−3 𝑠−1
= (𝑚𝑜𝑙𝑑𝑚−3 )4
, since overall order of reaction is 4
= mol-3 dm9 s-1

3.1 Zero Order Reaction

Consider the reaction A → products where the rate law is rate = k [A]n

If n = 0 (rate of reaction is zero order w.r.t to A), then rate = k [A]0 = k

i.e. the rate of reaction is constant and independent of the [A]

The unit for k is mol dm-3 s-1 or mol dm-3 min-1.

[A]
rate For various [A],
rate of reaction For various [A],
e is constant. gradient (i.e. rate of reaction
is constant.

0 0
[A] t
3.2 First Order Reaction

Consider the reaction A → products where the rate law is rate = k [A]n

If n = 1 (rate of reaction is first order w.r.t to A), then rate = k [A]1

i.e. the rate of reaction is directly proportional to [A].

The unit for k is s-1 or min-1.

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Example 3:
Complete the following table for a reaction where rate = k [A].

Initial [A] Initial Rate

x y
2x 2y
3x 3y
½x ½y

When [A] is high, rate of [A] Start of reaction, [A] is high and
rate reaction) is fast. gradient (i.e. rate of reaction) is
a large.

As reaction proceed, [A] is lower

and gradient (i.e. rate of reaction)
½a is smaller.

When [A] is low, rate of ¼a

reaction) is slow.
¼8a
0 0 t½ t½ t½
[A] t
Half-life, t½, is the time taken for the reactant concentration to decrease to half of its
original value.

For a first order reaction, the half-life is a constant and is independent of

concentration of reactant(s).
ln 2 0.693
t1  =
2
k k

Pseudo first order reactions

E.g. hydrolysis of ester: CH3CO2C2H5(l) + H2O(l)  CH3CO2H(l) + CH3CH2OH(l)
ethyl ethanoate

Rate law is rate = k [CH3CO2C2H5][H2O] from experimental studies.

If water is present in large excess, the amount of water used up would be a small
fraction of the amount of water present initially, that is, [H2O] is essentially constant.

rate = k [CH3CO2C2H5][H2O] = k’[CH3CO2C2H5] where k’ = k[H2O]

The reaction appears to be zero order with respect to water and first order with
respect to the ester, hence a pseudo first-order reaction.

Note : Given rate = k [A][B] for a reaction which is first order w.r.t each of the two
reactants, the reaction will be pseudo first-order if the concentration of one of the
reactants is so large that it is effectively constant or if one of the reactants is a
catalyst.
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3.3 Second Order Reaction

Consider the reaction A → products where the rate law is rate = k [A]n

If n = 2 (order of reaction is two wrt A), then rate = k [A]2

Ie. the rate of reaction is directly proportional to the [A]2

The unit for k is mol-1 dm3 s-1 or mol-1 dm3 min-1.

Example 4:
Complete the following table for a reaction where rate = k [A]2.

Initial [A] Initial Rate

x y
2x 4y
3x 9y
½x ¼y

[A]
rate a
first order second order

½a

¼a
¼8a

0 0 t½ t½ t½
[A]2 t

Note: The half-life of a second order reaction is not constant.

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3.4 Summary
[Reactant] Rate
zero order
a
first order second order
zero order
first order
½a

¼a second order
¼8a
0 t½ t½ t½ 0
t [Reactant]
#
Order is usually 0, 1 or 2 although it can be a negative integer or a fraction

Order of Zero First Second

Reaction# A → products A → products A → products
Rate Law/ Rate = k [A]0 Rate = k [A]1 Rate = k [A]2
Equation Or Rate = k [A][B]
for A + B → products

Unit of k mol dm-3 s-1 s-1 mol-1 dm3 s-1

Graph of [A] [A]
[A]
[reactant]
vs time

t½ t½ t 0 t½ t½ t½ t 0 t½ t½ t
0

Straight line graph with Downward sloping Downward sloping

a negative slope curve with constant t½ curve;t½ ≠ constant
Graph of
Rate Rate Rate
Rate
vs
[reactant]

0 [A] 0 [A] 0 [A]

Horizontal straight line Straight line graph Upward sloping curve

graph passing thru’ origin with
a positive slope k
Half-life, decreases with time ln 2 increases with time
t½ t1 
2
k
is a constant
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(e) devise a suitable experimental technique for studying the rate of a reaction, from given information.

4 Experimental Determination of Reaction Rates

Methods in Kinetics Experiment

Initial Rate Method Continuous Method

With Sampling Without Sampling

4.1 Initial Rate Method

 A few sets of experiments are conducted for a reactant R, varying [R] and
keeping the concentration of all other reactants constant.

 Temperature is kept constant for all experiments.

 Principle of initial rate method with constant volume system:

Keep the total volume of mixture constant by making up the total volume with
water. WHY?

If the total volume of the reaction mixture is kept constant, [reactant]  volume
of the reactant.

 There are two types of measurements can be taken for initial rate method:
1) Time taken for the formation of a fixed [product], or
2) Time taken for reactant to be used up

Time taken for a fixed [product] Time taken for reactant

to be formed to be used up

Colourless reactants form coloured product Coloured reactant forms colourless products.

1 Vcolouredreactant
Rate  Rate 
time time

Examples: Examples: brown

H
1) Na2S2O3 (aq) + 2HCl (aq)  1) CH3COCH3(aq) + I2(aq) 
S (s) + SO2 (g) + 2NaCl (aq)+ H2O (l) CH2ICOCH3(aq) + HI(aq)
yellow ppt
2) CH2=CH2 + Br2  CH2BrCH2Br
2) 2HBr + conc H2SO4  SO2 + Br2 + 2H2O
reddish brown
reddish brown

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Example 5: The reaction between HCl and thiosulfate ions can be investigated by
varying the concentration of the two reactants and measuring the time taken by the
product sulfur to obscure a marked cross placed under the reaction mixture.

S2O32- (aq) + 2H+ (aq) S (s) + SO2 (g) + H2O (l)

colourless colourless yellow ppt gas colourless

Various volumes of water are added to the four mixtures below to ensure that the
total volumes of all four mixtures are the same.

Expt. Vol. of Vol. of S2O32- Vol. of Time taken to obscure

No. HCl/cm3 /cm3 H2O/cm3 ‘cross’/ s
1 25 30 0 8
2 25 10 20 24
3 15 10 30 24
(a) Describe the experimental procedure required to perform the experiment to
obtain the results in the table above.
(b) Determine the rate equation by analysing the data in the table.

Ans:
(a) Experimental Procedure:
(i) Preparation of reaction mixture
Stop-watch started at
the point of mixing
Reactants of known volumes
and concentrations are mixed in
a conical flask

Paper marked with a cross “X”

 Add stated volumes of thiosulfate followed by water and finally HCl into conical flask.
 Add solutions quickly but carefully to avoid any spillage.
 Start the stopwatch simultaneously as the last solution is added, with one hand pouring
the solution and the other, starting the stopwatch.
 Swirl the reaction flask 1-2 times and leave it on top of the “X”. Be consistent in the
number of times you swirl the flask for all the experiments.

(ii) Observation of reaction mixture and time measurement

 Look from the top of the flask to judge the obscurity. Stop the stopwatch when the “X” is
just obscured by the sulfur produced in the reaction.

The sulfur is slowly precipitated and forms a

suspension.

The time taken for a fixed amount of sulfur to be

produced is recorded (this is taken as the time
when the “X” beneath the conical flask can just no
longer be seen from the top of the flask)
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(b) Determine the rate equation by analysing the data in the table.

Since the total volume of mixture is kept constant, [reactant]  volreactant

Initial rate = fixed amount of sulfur__
time taken to obscure ‘X’
1
Thus, Initial rate 
time taken to obscure X

Time taken
Expt. Vol. of Vol. of Vol. of Relative
to obscure 1 / t /s-1
No. HCl/cm3 S2O32-/cm3 H2O/cm3 initial rate
‘cross’/ s
1 25 30 0 8 1⁄ 3
8
2 25 10 20 24 1⁄ 1
24
3 15 10 30 24 1⁄ 1
24
Comparing Expt 2 and 1
[H+] kept constant, when [S2O32-] is increased three times.
Relative initial rate increased three times
Thus, rate  [S2O32-] and reaction is first order w.r.t S2O32-

Comparing Expt 3 and 2

[S2O32-] kept constant, when [HCl] increased 5/3 times,
Relative initial rate is unchanged. (Increased (5/3)0 = 1 time )
Thus, rate  [HCl]0 and reaction is zero order w.r.t HCl.

Overall Rate = k [S2O32-] [HCl]0 = k [S2O32-]

Example 6: The kinetics of the acid-catalysed reaction of propanone with iodine can
be investigated experimentally by varying the concentrations of the three reactants
involved (propanone, acid & iodine) and determining the time for the colour of iodine
to disappear.
H
CH3COCH3(aq) + I2(aq)   CH2ICOCH3(aq) + HI(aq)
colourless brown colourless colourless

The following results were obtained in such an experiment.

Expt Vol. of Vol. of Vol. of Vol.of Relative time for I2 Relative

propanone iodine H2SO4 water colour to rate of
/cm3 /cm3 /cm3 /cm3 disappear reaction
1 8 4 8 0 1 4
2 8 4 4 4 2 2
3 4 4 8 4 2 2
4 8 2 8 2 0.5 4

Complete the initial rate for each experiment and find the rate equation.

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Solution:

Since the total volume of mixture is kept constant, [I2]  Vol of I2

Thus, initial rate  volume of iodine used

time taken for iodine colour to disappear

Comparing Expt 1 and 3,

[I2] & [H+] kept constant, when [CH3COCH3] is halved, rate is halved.
Thus, rate  [CH3COCH3] and reaction is first order w.r.t propanone.

Comparing Expt 1 and 4,

[CH3COCH3] & [H+] kept constant, when [I2] is halved, rate remains unchanged.
Thus, rate  [I2]0 and reaction is zero order w.r.t iodine.

Comparing Expt 1 and 2,

[CH3COCH3] & [I2] kept constant, when [H+] is halved, rate is halved.
Thus, rate  [H+] and reaction is first order w.r.t H+.

Rate = k [CH3COCH3] [H+]

4.2 Continuous Method

 Only one experiment is conducted for a reactant R and the rate is measured by
following changes in [reactant] left or [product] formed or some physical
property that is proportional to the [reactant] left or [product] formed as the
reaction progresses.

 Any physical property (e.g. volume of gas, pressure, colour, electrical

conductivity, mass etc.) can be used to measure rate.

Example: P + Q  R

 If two or more reactants are involved, make the reactant P limiting and the rest
in great excess so that the graph of the measured property plotted against time
reflects the order of reaction w.r.t P. Order of reaction w.r.t other reactants e.g. Q
may then be found by performing an experiment in which Q is limiting.

 Plot a graph of the measured property against time. From the graph, rate of
reaction at various times, order of reaction w.r.t reactant R and the rate constant
may be found.

 Continuous method may be performed with or without sampling.

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4.2.1Continuous Method with Sampling (Titration Method)

Experimental Procedure:
(a) Solutions of reactants of known concentrations are mixed at constant
temperature and a stop watch is started.
(b) After t minutes, a sample of the reaction mixture is pipetted out and the reaction
is stopped by quenching using:
* sudden cooling
* sudden dilution
* adding a quenching agent. e.g. NaHCO3 (e.g. for a reaction that requires an
acidic medium, the quenching reagent can be NaOH or NaHCO 3, provided it
does not catalyse or take part in the reaction.)
Quenching stops the reaction so that the concentration of the substance
under study does not change further.
(c) The quenched mixture is then titrated against a suitable reagent to find the
concentration of the reactant left or the concentration of product formed at the
particular time.
(d) Repeat steps (b) and (c) at regular time intervals of t minutes.
(e) Plot a graph of concentration of reactant (or product) against time. The rate of
reaction at various time intervals can be determined by obtaining the respective
gradients.

Procedure Schematics:
(a) Preparation of reaction mixture (b) Withdrawal of samples for analysis

Reactants of known volumes

and concentrations

Stop-watch started at At regular time intervals (eg, 5

3
the point of mixing min), samples (eg, 10.0 cm )
are withdrawn from the
reaction mixture using a pipette

The reaction vessel should be kept in a constant-

temperature water bath
(c) Quenching of reaction in sample (d) Analysis of quenched sample mixture

Titration with a standard solution to

Addition of ‘quenching’ reagent determine concentration of
Withdrawn ‘quenched’ sample at different time.

sample Standard solution with known

concentration.
placed in
conical flask.
“Quenched” sample

The exact time at which the reaction is quenched is

noted.

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Example 7: Iodination of propanone

H
CH3COCH3(aq) + I2(aq)  CH3COCH2I(aq) +HI(aq)
Propanone

Reaction takes place slowly at room temperature and is catalysed by H + ions. The
course of the reaction can be followed by measuring the [I2] left at regular time
intervals.

Note:
1. Since the reaction is catalysed by acid, the withdrawn sample is quenched by
adding sodium hydrogencarbonate to remove the acid catalyst.

NaHCO3 + H+ → Na+ + H2O + CO2

2. The concentration of iodine left at the various time intervals is determined by

titrating with aqueous sodium thiosulfate.

2S2O32-(aq) + I2(aq) → S4O62-(aq) + 2I-(aq)

3. Volume of thiosulfate  [I2]

4. A graph of iodine concentration (vol of S2O32-) against time is plotted.

5. From the graph, rate of reaction at various times, order of reaction wrt reactant
I2 and the rate constant may be found.

4.2.2 Continuous Method Without Sampling (Physical Method)

 Method is preferred over titration as the physical property can be monitored

continuously without disturbing the reaction mixture.

(a) Volume Measurement

 This method is suitable for reactions which produce gaseous product(s).

 Examples of reactions:
 Action of dilute acid on a carbonate (e.g. CaCO3)
 Action of dilute acid on reactive metals
 Catalytic decomposition of H2O2

Experimental procedures: Catalytic decomposition of hydrogen peroxide.

2H2O2(aq) → 2H2O(l) + O2(g)

1. Set up the apparatus as shown setting the syringe to zero.

2. Hydrogen peroxide of known concentration is added to the catalyst (MnO 2) and
a stop watch is started.
3. Volume of gas collected in the syringe is measured at regular intervals

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4. Plot volume collected against time. From the graph, rate of reaction at various
times, order of reaction w.r.t reactant H2O2 and the rate constant may be found.

(b) Changes in Gas Pressure

 This method is suitable for reactions whereby the no. of moles of gaseous
product is different from the no. of moles of gaseous reactants.
 Pressure  number of moles of gaseous molecules at constant
temperature and volume. Hence reaction rate can be followed by measuring the
change in total pressure at regular time intervals.

Examples of reactions:
 2N2O5(g) → 4NO2(g) + O2(g) ∆n = 5 - 2 = 3
 N2(g) + 3H2(g) → 2NH3(g) ∆n = 2 - 4 = -2

Can this method be used with following reaction:

SO2(g) + NO2(g) → SO3(g) + NO(g)?
Ans: No. ∆n = 0

(c) Colorimetric method

 This method is suitable for reactions with coloured reactants and/or products.
 The rate of reaction is followed by measuring the amount of light transmitted
through the solution at regular time intervals during the course of the reaction.
 Colour intensity of a chemical species is directly proportional to its
concentration.

Examples of reactions:
 2HI(aq) + H2O2(aq) → I2(aq) + 2H2O(l)
brown
(The intensity of brown colour increases with time)
 BrO3 (aq) + 5 Br (aq) + 6 H+ (aq)  3 Br2 (aq) + 3 H2O (l)
Reddish brown
(The intensity of reddish brown colour increases with time)
H
 CH3COCH3(aq) + I2(aq)   CH2ICOCH3(aq) +HI(aq)
brown
(The intensity of brown colour decreases with time)

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(d) Conductometric method

 This method is suitable for reactions involving ions in which there is a change in
the number of ions as the reaction proceeds.
eg. BrO3 (aq) + 5 Br (aq) + 6 H+ (aq)  3 Br2 (aq) + 3 H2O (l)

 The rate of reaction is followed by measuring the electrical conductivity with time
since conductivity  [ions]

4.3 Further Examples

Example 8: The reaction kinetics of the decomposition of hydrogen peroxide was

studied experimentally and the results are shown below:

Experiment Initial [H2O2] / mol dm-3 Initial rate / mol dm-3 s-1
1 0.0600 0.350 x 10-3
2 0.120 0.700 x 10-3
3 0.180 1.05 x 10-3
4 0.300 1.75 x 10-3

Find the rate law for the reaction and the rate constant.

Ans:

Inspection method:

Comparing experiments 1 & 2, when the initial concentration of hydrogen peroxide is

doubled, the rate of reaction is doubled.

Therefore, rate  [H2O2]

The reaction is first order with respect to hydrogen peroxide.

Therefore, the rate law is rate = k[H2O2]

OR

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Substitution method:
Let the rate law be rate = k [H2O2]m, substituting rate and [H2O2] into rate equation,

Results of expt 1: 0.350 x 10-3 = k (0.0600)m ……... (1)

Results of expt 2: 0.700 x 10-3 = k (0.120)m ……... (2)

 0.120 
m
 0.700  10 3 
(2)  (1)   =  3

 0.0600   0.350  10 
 (2)m = 2.00
 m=1
To find the rate constant, choose any set of experimental data and substitute
into the previously determined rate equation, rate = k [H2O2]
E.g. Using data of experiment 1:
0.350 x 10-3 mol dm-3 s-1 = k (0.0600 mol dm-3)  k = 5.83 x 10-3 s-1

Example 9: For a reaction A → B, the following results were obtained

Time / s 0 20 40 60 80 100 120 140 160

[A] / 0.800 0.606 0.459 0.348 0.264 0.200 0.152 0.115 0.087
mol dm-3

Find the rate constant.

Ans:

From the graph, half-life = t½ = 50 s.

The half-lives are constant.

Reaction is first order with respect to A.

For 1st order reaction, the rate constant, k = ln2/ t½ = 0.0139 s-1.
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Qn : How to find t½ from a [product] – time graph for a first order reaction?

E.g. For reaction: 1 Reactant  1 Product

[Product] [Reactant]

a a

a
¾a

½a ½a

¼a

0 1/8 a

t½ t½ t½ time t½ t½ t½ time

1st half-life: Total [product] = ½ a 1st half-life: Increase in [product] = ½ a

2nd half-life: Total [product] = ½ a + ¼ a 2nd half-life: Increase in [product] = ¼ a
3rd half-life: Total [product] = ½ a + ¼ a + ⅛ a 3rd half-life: Increase in [product] = ⅛ a

5 Reaction Mechanism

The reaction mechanism of a chemical reaction is a sequence of steps by which

the reaction occurs.

The molecularity of each step is the number of reactant particles (molecules,

atoms or ions) taking part.

 A unimolecular step involves one reactant species.

 A bimolecular step involves two reactant species.
 A termolecular step involves three reactant species.

Consider the reaction: 2A + B → C + D

It could occur in one step and is then known as an elementary reaction

It could occur through a sequence of steps as shown below:

Step 1 A + B → C + X (slow)
Step 2 A + X → D (fast)
--------------------------------
Overall equation: 2A + B → C + D

(Sum of all the steps in the mechanism gives the overall equation)

The slow step is called the rate-determining step (rds).

Overall rate of reaction = rate of the slow step (rds)

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Note:
1. X does not appear in the overall equation. X is known as an intermediate.
2. The rate-determining step is the slowest step in a reaction mechanism.
3. The rate equation for a reaction is obtained from the stoichiometry of the
rate-determining step (rds). Thus, the rate law for the reaction is rate = k [A][B].
4. The overall order of the reaction = 2 (equals the molecularity in the rds)

Example 10: Decomposition of hydrogen peroxide catalysed by iodide ions

2H O (aq)  I- 2H O(l) + O (g)
2 2 2 2

Step 1 H2O2(aq) + I-(aq) → H2O(l) + IO-(aq) (slow)*

Step 2 IO-(aq) + H2O2(aq) → H2O(l) + O2(g) + I-(aq) (fast)
Overall 2H2O2(aq) → 2H2O(l) + O2(g)

The rate-determining step (step 1) shows that rate = k [H2O2][I-]

*
Note: The rate-determining step is not necessarily always step 1 (see E.g. 11)

Example 11: 2 A(aq) + B(aq)  C(aq)

Step 1 A(aq) + B(aq) ⇌ W(aq) (fast)

Step 2 A(aq) + W(aq) → C(aq) (slow)
Overall 2 A(aq) + B(aq) → C(aq)

Determine the rate equation for this reaction.

Ans:
From the slow step, rate = k [A][W]

However, rate equation cannot be expressed in terms of intermediate (e.g. W).

The value of [W] needs to be substituted by another value.

[𝑾]
Since Kc = [𝑨][𝑩], [𝑾] = 𝐾𝑐 [𝑨][𝑩] ---------- (1)

Substitute (1) into rate equation,

𝑟𝑎𝑡𝑒 = 𝑘 [𝑨] (𝐾𝐶 [𝑨][𝑩])
= [(𝑘)𝐾𝑐 ] [𝑨]2 [𝑩]
= 𝑘 ′ [𝑨]2 [𝑩], where 𝑘 ′ = [(𝑘)(𝐾𝑐 )]

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5.1 Relating order of reaction to mechanism

Example 12:
Given rate = k[H2O2][I ] for the reaction between H2O2 & hydrogen iodide :
H2O2 (aq) + 2 H+ (aq) + 2 I (aq)  2 H2O (l) + I2 (aq)

Is the following mechanism consistent with the given rate law?

step 1 H2O2 + I  H2O + IO (slow)

step 2 H+ + IO  HIO (fast)

step 3 HIO + H+ + I  H2O + I2 (fast)

Overall H2O2 + 2 H+ + 2 I  2 H2O + I2

Answer:

Yes, since the slow (rate-determining) step involves one molecule of H2O2
colliding with one I ion.

Example 13

NO2(g) + CO(g) → CO2(g) + NO(g) rate = k[NO2]2

Which of the following mechanisms best agrees with the experimentally determined
rate law?

Mechanism 1: NO2 + CO → CO2 + NO

Mechanism 2: NO2 + NO2 → NO3 + NO (slow)

NO3 + CO → NO2 + CO2 (fast)

Mechanism 3: NO2 → NO + O (slow)

CO + O → CO2 (fast)

Mechanism 4: NO2 + NO2 → N2O3 + O (slow)

N2O3 + CO → 2NO + CO2 (fast)

Ans: Mechanism 2

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6 Theories of Reaction Rates

6.1 Collision Theory

In order to react, reactant particles must collide:

1) with the correct orientation to each other

Collision of incorrect orientation

bounce apart

Collision of sufficient energy and correct orientation

new bonds form

Collision of insufficient energy

bounce apart

2) with a certain minimum amount of (kinetic) energy, known as activation energy,

Ea
Maxwell-Boltzmann Distribution Curve showing distribution of KE
amongst the molecules of a gas.

Area shaded under the curve

= number of molecules having
energy  Ea

Note: It is INCORRECT to draw a symmetrical Maxwell-Boltzman Distribution Curve.

The curve must tail off on the right.
This is because at any temperature, there are more molecules with extremely
low energy than molecules with extremely high energy level.

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Definition

Activation energy, Ea, is the minimum amount of kinetic energy required for an
effective collision* resulting in a reaction.

*An effective collision is a collision with BOTH sufficient energy and correct
orientation.
Hence, it is statistically unlikely for an elementary reaction to be termolecular (difficult
for 3 reactant molecules to collide with BOTH sufficient energy and correct
orientation.

Reactions with low Ea are fast at room temperature as a large proportion of

molecules will have energy  Ea.

Reactions with high E’a are slow and need higher temperature to react as a small
proportion of molecules will have energy  E’a at room temperature.

At the same temperature, reaction with higher E’a thus proceeds at a slower
rate than one with lower Ea.

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6.2 Transition State Theory

Reacting molecules with enough energy will form a transition state or activated
complex which can then decompose to form products.

A–B + X → [A---B---X] ‡ → A + B–X

Energy profile for a single-step reaction

E.g. CH3Br + OH- → CH3OH + Br- (∆H = –ve)

Activated Complex

For information only:

 Reactant molecules approach each other and begin to slow down, due to
mutual repulsion in their electron clouds. Kinetic energy is converted to
potential energy.
 Potential energy increases until a maximum when an activated complex is
formed.
 In the activated complex, the old bonds are partially broken and the new
bonds are partially formed.
-
CH3OH Br
CH3Br

Br
Br

-
OH

 The energy required to form the activated complex is the activation energy,
Ea. Ea thus represents an energy barrier that the reactants must overcome to
become products.
 Heat released in bond formation greater than heat absorbed in bond breaking.
This results in exothermic reaction (∆H –ve)
 The activated complex
 has the maximum energy
 is very unstable
 is a transient state - it cannot be isolated as a compound

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Example 14: Sketch the energy profile for a single-step endothermic reaction.

activated complex
Enthalpy

Ea
products

reactants ∆H

Progress of reaction

Energy profile for a reaction with multiple step reaction mechanism

E.g. 2NO2Cl (g) → 2NO2(g) + Cl2(g)

Mechanism: Step 1 NO2Cl → NO2 + Cl (slow)

Step 2 Cl + NO2Cl → NO2 + Cl2 (fast)
Overall 2NO2Cl (g) → 2NO2(g) + Cl2(g)

The decomposition reaction of NO2Cl in which rate = k[NO2Cl]

Note: Cl is known as a reactive intermediate.

 The (reactive) intermediate

 although a short-lived species, is stable enough to be isolated.
 is not found in the overall reaction
 is formed in one step and then consumed in a subsequent step

 2 steps reaction – 2 Ea
n steps reaction – n Ea

 Activation energy for the slow step is the highest amongst all the steps

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(f) explain qualitatively, in terms of collisions, the effect of concentration changes on the rate of a reaction.

7 Factors Affecting the Rate of a Chemical Reaction

1. Concentration of reactants
2. Temperature
3. Catalyst
4. Nature of Reactants (ions or molecules)
5. Light (photochemical reaction)

7.1 Effect of Concentration on Rate of Reaction

An increase in the concentration of the reactants (or pressure if the reactants are
gaseous) will increase the rate of a reaction. (Exception: zero order reaction)
Rate = k[reactant]n
An increase in concentration leads to:
 increase in number of reacting particles per unit volume
 an increase in the number of reacting particles having energy  Ea
 an increase in the frequency of collisions between reacting particles
 resulting in a greater number of effective collisions per unit time
 an increase in rate of reaction

7.2 Effect of Temperature on Rate of Reaction

The rate of a reaction increases exponentially with increase in temperature.
Rate of reaction approximately doubles for a 10K rise in temperature.
When temperature is increased, there is:
 an increase in the average kinetic energy of the particles, resulting in,
 an increase in the number of reacting particles with energy  Ea
 an increase in the frequency of collisions between reacting particles
 resulting in a greater number of effective collisions per unit time
 an increase in rate of reaction

Note: At higher temperature T2, the curve shifts right with a lower peak since
average kinetic energy of particles increase. The total number of particles
(area under the curve) remains the same.

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(g) show understanding, including reference to the Boltzmann distribution, of what is meant by the term
activation energy.

7.3 Effect of Catalyst on Rate of Reaction

Definition 6 – Catalyst

A catalyst is a substance which alters (generally increases) the rate of a chemical

reaction while remaining chemically unchanged at the end of the reaction. Hence, it
is not consumed in the reaction and only a small amount is needed.

A catalyst:
 increases the rate of a chemical reaction (positive catalyst).
 provides an alternative reaction pathway with a lower activation energy.

Hence, when a catalyst is used in a reaction, it:

 increases the rate of the reaction by providing an alternative reaction pathway
with lower activation energy
 increases the number of reacting particles with energy  Ea
 (there is NO increase in frequency of collisions between reacting particles!)
 increases the number of effective collisions per unit time
 increases the rate of reaction

Note: The enthalpy change of reaction, ∆H, is not affected by the presence of a
catalyst.

(j) outline the different modes of action of homogeneous and heterogeneous catalysis, including :
(i) the Haber Process
(ii) the catalytic removal of oxides of nitrogen in the exhaust gases from car engine
(iii) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulphur
dioxide
(iv) catalytic role of Fe3+ (or Fe2+) in the I-/S2O82- reaction

7.3.1 Homogeneous Catalyst (Covered in greater detail in Transition

Elements)

A homogeneous catalyst is in the same phase as the reactants.

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Examples:
2SO2(g) + O2(g) → 2SO3(g) Catalyst : NO(g)
CH3COCH3(aq) + I2(aq) → CH2ICOCH3(aq) +HI(aq) Catalyst : H+(aq)

Fe3+(aq)
S2O82-(aq) + 2I-(aq)  2-
 2SO4 (aq) + I2(aq) Catalyst: Fe3+ (aq)

Mechanism:
Homogeneous catalyst is converted into an intermediate and is then
regenerated at the end of the reaction

Consider the elementary reaction X + Y → products

Using a catalyst : X + catalyst → X-catalyst ( intermediate )

X-catalyst + Y → products + catalyst
Overall reaction X + Y → products

Note:
The catalysed reaction has an alternative reaction mechanism from that of the
uncatalysed reaction.
The catalysed reaction can have 2 or more steps. The activation energy of each of
these steps is lower than that of the uncatalysed reaction.

Examples:
Oxidation of I- by S2O82- catalysed by Fe3+

Fe3+(aq)
S2O82-(aq) + 2I-(aq)  2-
 2SO4 (aq) + I2(aq)

Step 1 2Fe3+(aq) + 2I-(aq) → 2Fe2+(aq) + I2(aq)

Step 2 2Fe2+(aq) + S2O82-(aq) → 2Fe3+(aq) + 2SO42-(aq)
Overall S2O82-(aq) + 2I-(aq) → 2SO42-(aq) + I2(aq)

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Oxidation of I- by S2O82- catalysed by Fe2+

Fe2+
S2O82-(aq) + 2I-(aq)  2-
 2SO4 (aq) + I2(aq)

Step 1 2Fe2+(aq) + S2O82-(aq) → 2Fe3+(aq)+ 2SO42-(aq)

Step 2 2Fe3+(aq) + 2I-(aq) → 2Fe2+(aq) + I2(aq)
Overall S2O82-(aq) + 2I-(aq) → 2SO42-(aq) + I2(aq)

7.3.2 Heterogeneous Catalyst (Covered in greater detail in Transition

Elements)

A heterogeneous catalyst is in a different phase from the reactants.

Examples:
Haber Process: N2(g) + 3H2(g) → 2NH3(g) Catalyst : Fe (s)
Contact Process: 2SO2(g) + O2(g) → 2SO3(g) Catalyst : V2O5 (s)
2H2O2(aq) → 2H2O(l) + O2(g) Catalyst : MnO2 (s)

Heterogeneous catalysts
 normally transition metals or their compounds
 provide a surface area for the adsorption* of reactant molecules.

 *Adsorption: The reactants are first adsorbed onto the surface of the catalyst,
the metal chosen must adsorb the reactants easily but not so strongly that the
products do not come off again.
 Reaction: the reactants are held on the surface in such a position that they
can readily react together.
 Desorption: the products leave the surface.

Catalytic removal of pollutant gases in exhaust gas of cars

Unburnt hydrocarbons, carbon monoxide and oxides of nitrogen are present in
exhaust gases, causing environmental pollution. Catalytic converters are fitted in
cars to convert these gases into carbon dioxide, water and nitrogen.

CxHy(g) + (x + y/4)O2 → xCO2(g) + y/2H2O(g)

2NO(g) → N2(g) + O2(g)

2CO(g) + O2(g) → 2CO2(g) } 2CO(g) + 2NO(g) → 2CO2(g) + N2(g)

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Lead, if present, in petrol is adsorbed on the catalytic surface containing Pt and Pd

and decreases the number of active sites for the adsorption of reactant molecules.
The catalyst is said to be poisoned and no longer functions as a catalyst.

Cars fitted with catalytic converters must use lead-free petrol.

7.3.3 Autocatalysis

Autocatalysis is a type of catalysis whereby one of the products of the reaction

catalyses the reaction.

E.g. Reaction between managanate(VII) ions and acidified ethanedioate ions:

2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O(l)

The Mn2+ ions formed acts as a catalyst for the reaction.

1. The rate of reaction is slow at the beginning of the reaction.

2. As the reaction proceeds, [Mn2+] increases. The rate of reaction increases.

3. The rate of reaction will eventually decrease as [reactants] decreases to very

low levels despite the increasing concentration of the Mn2+ catalyst.
Concentration of MnO4 / mol dm-3

Rate 3
-

3
1
0 time

(k) describe enzymes as biological catalysts (proteins) which may have specific activity.

7.3.4 Biological Catalysts (Enzymes)

Enzymes are:

 essentially proteins which catalyse reactions in living organisms

 highly specific as each enzyme has an active site which only one type of
substrate of matching shape and size can fit into
 regenerated during their catalytic activities and are highly efficient

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Mechanism (Lock and key):

An enzyme-substrate complex is formed and this weakens the intramolecular

bonding within the substrate, lowering the activation energy. The products are no
longer of the right shape to remain in the active site and the complex breaks up,
releasing the products and freeing the enzyme for further catalytic reaction.

(l) explain the relationship between substrate concentration and the rate of an enzyme-catalysed reaction in
biochemical systems

Factors affecting enzymic activities:

(a) Substrate (reactant) concentration

 The rate of enzyme-catalysed reaction increases with substrate concentration

(reaction is first order with respect to the substrate) until a maximum when all
the active sites of the enzyme molecules are occupied.

 Further increase in substrate concentration does not increase the rate of

reaction and the reaction becomes zero order with respect to the substrate.

Enzyme
E.g. Sucrose(aq) + H2O(l)  glucose(aq) + fructose(aq)

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Rate of reaction
Zero order:
Rate = k [substrate]0 = k

All active sites of the enzyme molecules are

First Order: occupied.
Rate = k [substrate] Any increase in [substrate] beyond [substrate]max
will have no effect on the rate of reaction.
So, rate of reaction becomes zero order w.r.t.
substrate for [substrate] > [substrate]max

[substrate]
(b)0 [substrate]max

Temperature

 Enzymes work well over a narrow temperature range (about 25 0C – 400C).

 At a higher temperature, the protein structure of the enzyme is denatured

and the enzyme loses its catalytic property.
Rate of reaction

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(c) pH

 Enzymes work well over a narrow pH range (about 5 – 8).

 The rate of an enzyme-catalysed reaction reaches a maximum value at a

particular pH (optimum pH) which is characteristic of that enzyme.

Rate of reaction

1 2 3 4 5 6 7 8 9 10

7.4 Effect of Physical Nature of Reactants on Rate of Reaction

 Generally, reactions involving oppositely charged ions can proceed at a

high rate:
e.g. Ag+(aq) + Cl-(aq) → AgCl(s)
 For reactions involving solids, the larger the total surface area, the greater
will be the number of effective collisions per unit time (i.e. faster rate of
reaction).
E.g. powdered CaCO3 reacts much faster with acid than lumps of it.
 Many organic reactions are generally slow as covalent bonds need to be
broken and rearranged to form products. E.g. esterification reaction.
7.5 Effect of Light on Rate of Reaction

 Light increases the rate of photochemical reactions (reactions that absorb

light).

 Such reactions are slow in the dark but the rate can be increased by raising
the temperature or by illumination with visible light or ultra-violet and usually
involve radicals (species with unpaired electron(s)).

 Reaction becomes fast once it is initiated leading to a chain reaction.

Examples:
uv
 CH4(g) + Cl2(g)  CHCl3(l) + HCl(g)

 Destruction of ozone by CFCs (CFC molecules broken up by uv to form Cl)

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