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H2 Chemistry Notes

H2 Chemistry (9729)
Lecture Notes 7
Reaction Kinetics

Assessment Objectives:
Candidates should be able to:
(a) explain and use of terms: rate of reactions, 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, (limiting to simple cases of single-step
reactions and multi-steps processes with a rate-determining step, for which m and n are 0, 1, 2),
including:
(i) deducing the order of a reaction by the initial rate 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 methods
(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 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 engines
(iii) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur dioxide
(iv) catalytic role of Fe3+ in the I-/ S2O82- reaction
(k) Describe enzymes as biological catalysts 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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Lecture Outline:

1. Introduction
2. Simple rate equations; orders of reaction; rate constants
3. Reaction Mechanisms
4. Determination of orders of reaction, rate equation and rate constant from experimental data
5. The Collision Theory
6. Factors that affect rate of reaction

References:
1 Chemistry by Silberberg, 3rd edition.
2 Chemistry by Raymond Chang, 8th edition.
3 Chemistry for Advanced Level by Peter Cann and Peter Hughes
4 Advanced Study Guide Chemistry by C S Toh, published by Step-by-Step International Pte. Ltd.

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1. Introduction

Reaction kinetics is a study of rate of reaction, factors affecting rate of reaction and the study reaction
mechanisms.
Data from the studies of reaction kinetics enable the industrial chemist to know the mechanism of the
reaction so that he could set conditions of temperature, pressure, concentration, use of catalysts, in order
to produce maximum yield at the fastest rate with the minimum cost.

2. Simple rate equations; orders of reaction; rate constants

2.1 REACTION RATES

(a) Rate of a reaction

 Rate of reaction is defined as the change in concentration of reactant consumed or product formed per
unit time.

Change in concentration of a substance

Rate =
time

For a simple reaction: A + B C

[A] [B] [C]

Rate = - = - = +
t t t

d[A] d[B] d[C]

Rate = - = - = +
dt dt dt

- Rate is measured in units of concentration per unit time, mol dm-3 t-1. (e.g. mol dm-3 s-1)
- Rate is a positive quantity
- By plotting a graph of concentration against time, the rate of the reaction at any time t is determined as
the gradient at that time t. This is also known as the instantaneous rate.
- Rate of reaction at time t = Gradient of the graph at time t
- Initial rate is the rate measured at time t= 0, i.e. at the start of the reaction.

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Figure 1(a): Graph of [reactant] against time

[Reactant]

Horizontal line suggests

that gradient is zero.
i.e rate = 0, reaction has stopped.
[reactant]

t
t Time

Figure 1(b): Graph of [product] against time

[Product]

[product] Horizontal line suggests

that gradient is zero.
i.e rate = 0, reaction has stopped.
t

t Time

- The steeper the gradient, the faster is the rate.

- When the gradient is zero, this implies that the rate of reaction is zero,
i.e. the reaction has stopped (as shown by the horizontal portion, in Figure 1(b))
- The gradient of the graph decreases with time, showing that the rate of reaction is inversely proportional
to the time taken for the reaction to complete.
1
Rate 
time

i.e. The faster the rate of reaction, the shorter the time taken for the reaction to complete.

(b) Rate equation and Order of reaction

- Experimental results have shown that rates of reaction are related to the concentrations of the
reactants.

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- The rate equation shows how the rate of reaction depends on the concentration of the various species
involved in the reaction.

Consider a reaction between A and B,

aA + bB cC + dD

Experimentally,
Rate = k [A]m [B]n

- The above equation is known as a rate equation / rate law.

- A rate equation is determined experimentally and it shows the relationship between the rate of reaction
and the concentrations of each reactant raised to a specific power.
- The rate constant, k is the proportionality constant in the experimentally determined rate equation. It
is temperature dependent.
- The order of a reaction with respect to the concentration of a given reactant is the power of that
reactant’s concentration in the experimentally determined rate equation.
m = order of reaction with respect to [A]
n = order of reaction with respect to [B]
The values of m and n must be experimentally determined.
a = m or a  m ; b = n or b  n
- Reaction order can be a whole number or a fraction, positive or negative
- Reaction order can help to work out the reaction mechanism
- The overall order of the reaction is the sum of the powers of the concentration terms in the rate
equation.
Overall order of reaction = m + n
Note:
 Rate equation, rate constant and the order of reaction can only be obtained experimentally. They
cannot be deduced theoretically from the stoichiometric overall equation.
 The rate equation may or may not include any of the reactants in the stoichiometric equation.
 The rate equation may involve catalyst which does not appear in the stoichiometric equation.

Some examples of experimentally-determined rate equations:

Example 1: 2N2O5(g) 4NO2(g) + O2(g)

 Rate equation for this reaction:

Rate = k [N2O5]1 = k [N2O5]
 The reaction is 1st order with respect to [N2O5].

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+
H catalyst
Example 2: CH3COCH3(aq) + I2(aq) CH2ICOCH3(aq) + HI (aq)
 Rate equation for this reaction:
Rate = k [CH3COCH3] [H+]
 The reaction is 1st order with respect to [CH3COCH3] and 1st order with respect to [H+].
 Overall, it is second order reaction.
 The rate equation does not include I2(aq), i.e. [I2] does not affect the rate of reaction. The reaction
rate is independent of the concentration of iodine.
Characteristics of rate constant, k:
 The value of k gives an indication of the rate of reaction.
The larger the value of rate constant k, the faster the rate of the reaction.
 k is a constant for a given reaction at a particular temperature.
 k is dependent on temperature and activation energy.
o As temperature increases, k increases.
o When a catalyst is present at a given temperature and the reaction rate increases, k increases.
 k is independent of the concentration of reactant.
 Units of rate constant depends on the order of reaction and are derived from the rate equation.

Summary of the types of order of reactions and the units of rate constant, k:

Type of reaction General Rate equation Units of rate constant, k

Zero order Rate = k [Reactant]0 = k mol dm-3 t-1
First order Rate = k[Reactant] t-1
Second order Rate = k[Reactant]2 mol dm3 time-1
-1

2.2 Zero, First and Second order reactions

(a) Zero order reaction

 Reaction takes place at constant rate, independent of the concentration of the reactant, R.

Rate = k [R] n
0
When n = 0, Rate = k [R]
Rate = k
Thus, rate is constant, regardless of the concentration of R.
Figure 2(a) Figure 2(b) Figure 2(c)

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[R]/ mol dm-3 Rate / mol dm-3 t-1 [product]/ mol dm-3

[R]/ mol dm-3 time

time
Concentration of R will
decrease as reaction
proceeds.
Gradient of slope = - k
No change in the rate as Gradient of slope = k
concentration of R changes
over time.

Example of a zero order reaction: 2NH3(g) N2(g) + 3H2(g)

Rate = k [NH3]0 ∴ rate = k

This means that changing the concentration of ammonia will not affect the rate of reaction.

(b) First order reaction

Rate = k [R]1

Units of rate constant, k = t-1

 For a first-order reaction, rate is directly proportional to the concentration of the reactant.
Doubling the concentration of the reactant will cause the rate to increase by 2 times.

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Figure 3(a): Graph of rate against [R]

Gradient = rate constant k

[R] / mol dm-3

Rate / mol dm-3 t-1

Half-life of a First Order reaction

0
 Half – life, t1/2 is the time taken for the initial concentration of a reactant to fall to half its original
value.
 For all first order reaction, the half - life is constant at a given temperature. For all other orders of
kinetics, half-life is not constant.
 Half-life is independent of the initial concentration of the reactant.

Figure 3(b): Concentration-time graph for the a first order reaction

Time
t½
t½
[R] / mol dm-3

t½
1.0

0.5

0.25
0.125

From the graph in Figure 3(b),

time taken for the [reactant] to decrease from 1.0 to 0.5 mol dm-3 = t½
time taken for the [reactant] to decrease from 0.5 to 0.25 mol dm-3 = t½
time taken for the [reactant] to decrease from 0.25 to 0.125 mol dm-3 = t½

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 Since all first-order reactions have constant half-lives, one method to determine whether a given
reaction follows first-order kinetics is to plot a graph of concentration of the reactant against time and
check from the graph whether the half-life is constant.
 Relationship between t½ and rate constant, k

In2
t1 =
2
k

 To calculate the number of half-life elapsed

[ R ]t n where n = number of half-lives elapsed

1
( )()
[ R ]0
=
2
[R]t = concentration of R at time t
R]0 = concentration of R at time t= 0
 Examples of 1st order reactions are:

(1) Radioactive decay of an unstable isotope where k is known as decay constant.

The half-life, t½, for the decay of 235U is 7.1 x 108 years. After 710 million years, a 1 kg sample of 235U will
contain 0.5 kg of 235U, and a 1 mg sample of 235U will contain 0.5 mg.
Hence, the time to reach one-half the starting concentration in a 1st order reaction does not depend on
what that starting concentration is.

(2) Decomposition of 1.0 mol dm-3 of aqueous hydrogen peroxide, H2O2

2H2O2(aq) 2H2O(l) + O2(g)

This decomposition follows a first-order kinetics. The rate equation is: Rate = k[H2O2]

Figure 4(a): Figure 4(b):

Concentration of [H2O2] against time Volume of O2 gas collected against time

[H2O2] / mol dm-3

[O2] / mol dm-3
1.0
0.5

0.375
0.5
0.25

0 T1 T2 Time / t
0 T1 T2 Time / t

[H2O2] falls from 1 to 0.5 mol dm-3, time taken = T1 – 0 = t½

[H2O2] falls from 0.5 to 0.25 mol dm-3, time taken = T2 – T1 = t½
 From the data, we deduce that half-life for the decomposition of hydrogen peroxide is constant. This is a
first order reaction.

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Exercise 1
Question 1

H2O2 decomposition is a 1st order reaction. If the initial concentration of H2O2 is

2.3 mol dm-3 and the half-life of this reaction is 14 minutes, how long has the decomposition
occurred if the concentration is now 1.0 mol dm-3?

Answer:
[ R ]t 1 n

( )()
[ R ]0
=
2

[ R]t = 1

[ R]0 = 2.3

1.0
2.3 = ( ½ )n

Solving for n,
n = 1.20 (This means that 1.2 half-lives have elapsed.)

Time taken = 1.20 x 14 min = 16.8 min.

Question 2 [J97/III/10]

Lead is the final product formed by a series of changes in which the rate-determining step is
the radioactive decay of uranium-238. This radioactive decay is a 1st order reaction with a t1/2
of 4.5 x 10 9 years. What would be the age of a rock sample, originally lead-free, in which the
molar proportion of uranium to lead is now 1:3?

A 1.5 x 109 years C 9.0 x 109 years

B 2.25 x 109 years D 13.5 x 109 years

Answer:
[ R ]t 1 n

( )()
[ R ]0
=
2

[ R]t = 1

[ R]0 = 4
n =2
Time taken = 2 x 4.5 x 10 9 years = 9.0 x 109 years

Question 3 [N2000/III/11]
Which graph would confirm that the rate of decomposition of hydrogen peroxide was first
order with respect to the concentration of hydrogen peroxide?

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Answer: (B) because the rate is directly proportional to [H2O2].

(b)(i) Pseudo First Order reactions

 If the concentration of one reactant is very large, the reaction appears to be zero order with respect to
that particular reactant’s concentration.
 If the concentration is very large, then the change in the concentration of the reactant is considered to
be negligible. Hence its concentration can be taken to be constant during the reaction.
 There are 3 situations to consider:
o Presence of a large excess of a reactant
o Reactant is also the solvent
o Presence of a catalyst
Example: Acid-catalysed hydrolysis of methylmethanoate

HCOOCH3 (l) + H2O(l) HCOOH(l) + CH3OH(l)

Rate = k [HCOOCH3] [H2O]

 Since water is present in large excess, [H2O] can be taken to be constant.

The amount of water actually used up in the reaction is comparatively small.

 Rewriting the rate equation, since k and [H2O] are constant,

Rate = k’ [HCOOCH3] where k’ = a first order rate constant

k’ = k [H2O]

The kinetics now appears to be only dependent on the concentration of the ester and appears to be a
first-order reaction.

Example: Acidic Hydrolysis of sucrose into glucose and fructose

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C12H22O11(aq) + H2O(l) C5H12O6(aq) + C6H12O6(aq)

Sucrose glucose fructose

Rate = k [Sucrose] [H+]

 Concentration of the acid is very large, hence [H+] is remains almost unchanged
during the reaction.

 Rewriting the rate equation, since k and [H+] are constant,

Rate = k’ [sucrose] where k’ = k [H+]

(c) Second order reaction

A second-order reaction is one which the reaction rate is proportional to the product of the
concentrations of two reactants (e.g. rate ∝ [A] [B], where A and B are reactants) or to the concentration
of a single reactant raised to the power of two (e.g. rate ∝ [A]2)

Given a reaction: R1 + R2 Products

For a second order reaction:

Rate = k[R1] 2 or Rate = k [R1] [R2]

Units of k = mol-1 dm3 t-1

From the rate equation, this suggests that when the concentration of [R1] increases by 2 times, the rate
increases by 22 = 4 times, i.e. reaction takes places 4 times faster.
For a second-order reaction, the half-life of the reaction is not constant. In fact, the half-life gets larger as
the reaction proceeds.

Figure 5(a): Figure 5(b): Figure 5(c):

Rate against [R1] Rate against [R1]2 [R1] against time
[R1] / mol dm-3

[R1]2 / mol2 dm-6

Time / t
rate constant k
Gradient =
Rate / mol dm-3 t-1
Rate / mol dm-3 t-1

[R1] / mol dm-3

As [R] increases by 2 times, Rate α [R]2 Non-exponential

Rate increases by 22 = 4 times. Linear line passing through the decreasing curve.
origin. t½ is not constant.

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Gradient = rate constant, k

 Examples of experimentally-determined 2nd order reactions

2NO2(g) 2NO(g) + O2(g) Rate = k [NO2]2

2HI(g) H2(g) + I2(g) Rate = k [HI]2

CH3COOCH2CH3(aq) + OH-(aq) Rate = k [CH3COOCH2CH3] [OH]

-
CH3COO (aq) + CH3CH2COOH(aq)

CH3Br(aq) + OH-(aq) CH3OH(aq) + Br-(aq) Rate = k[CH3 Br] [OH-]

Exercise 2
Question 1 [J97/III/11]

In the reaction between aqueous sodium thiosulphate and dilute acid, the reaction is found to be first
order with respect to acid at low concentrations of acid, but zero order with respect to acid when the acid
concentration is high.
Which graph represents the experimental results?
A B

[acid] [acid]

Rate Rate
C D
[acid] [acid]

Rate Rate
Answer: (B)

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SUMMARY OF THE TYPES OF ORDER OF REACTION

Consider the following reaction: R P
the rate equation is given by
Rate = k[R]m
Type of Rate Units of k Rate vs [R] [R] vs time
reaction equation
Zero Rate = k mol dm-3 t-1 Rate / mol dm-3 t-1 [R]/ mol dm-3

[R]/ mol dm-3 time

First Rate = k[R] t-1

Rate / mol dm-3 t-1 [R]/ mol dm-3

time
[R]/ mol dm-3

Second Rate = k[R]2 mol-1 dm3 t-1 Rate / mol dm-3 t-1 [R]/ mol dm-3

[R]/ mol dm-3 time

Rate / mol dm-3 t-1

[R]2/ mol2 dm-6

3. Reaction Mechanisms

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3.1. Elementary and multi-step reactions

 Atoms, ions and molecules rearrange and recombine during chemical reactions.
 The exact pathway by which a chemical reaction occurs is the reaction mechanism.
 Reaction mechanism of a reaction is a collection of elementary steps in the proper sequence
showing how reactant particles are converted into products. It is the explanation of how a reaction takes
place.
 A reaction may occur by a single step, such a reaction is called an elementary reaction.
 An elementary step cannot be broken down into simpler steps.

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

The reaction involves the collision of one H2 molecule with one I2 molecule to form two HI molecules in
a single step.
 Most reactions occur in more than 1 step, i.e. multi-step reactions.
 A multi-step mechanism consists of a sequence of steps. Usually one of the steps is slower than others.
The slow step is the bottleneck and thus controls the overall rate of the reaction.

Traffic jam analogy

 The SLOW step = RATE -DETERMINING STEP (RDS)

 The other elementary steps that are not involved in the RDS are the fast steps.

3.2 Rate equation and Rate-Determining Step

 The molecularity of a reaction is the number of molecules involved in the rate-determining step.
 The rate equation is obtained from the RDS. Hence, particles that collide together in the RDS are the
species that appear in the rate equation.
 Since the fast step is not the RDS, the particles that collide in the fast step do not appear in the rate
equation.

For example, the reaction 2A + C D may proceed via the following mechanism in two steps:
Step 1 2A B
(slow step)
Step 2 B+ C D

Overall 2A + C D

 From the slow step, 2 moles of A are involved. Hence A will appear in the rate equation.

 The rate equation reflects the particles and the number of particles that are involved in the slow step.

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 The order of the reaction with respect to [A] is equal to the stoichiometric coefficient of A in the rate
determining step.

In the above example, Rate = k[A]2

 B is produced in the Step 1 but consumed in Step 2. B also does not appear in the overall equation. B
is known as an intermediate.

 Intermediates do not appear in the stoichiometric / overall equation. A stoichiometric or an overall

equation describe the starting materials and final products but do not give any information on the
individual steps by which the reaction occurs.

3.3 Molecularity of a Reaction

 The molecularity of an elementary step is the number of reacting particles (molecules, atoms or ions)
that take part in that step.
 A unimolecular reaction involves one molecule. The molecule may fragment into two pieces or it may
re-arrange to become a new isomer.
Example: Dissociation of N2O4
Rate-determining step
N2O4(g) 2NO2(g)
Rate = k [N2O4]

From the rate equation, the following information can be deduced:

1. This reaction is 1st order reaction with respect to [N2O4]. It is also overall first order reaction.

It also tells us that 1 mole of N2O4 is involved in the slow step.

 A bimolecular reaction involves the collision of two molecules in the rate-determining step.
Example: Dimerisation of NO2
Rate-determining step
2NO2(g) N2O4(g)
Rate = k [NO2]2

From the rate equation, the following information can be deduced:

1. This reaction is 2nd order reaction with respect to [NO2]. It is overall second order reaction.
2. It also suggests that 2 moles of NO2 are involved in the slow step.
Example: Reaction of O3 with NO
Rate-determining step
O3(g) + NO(g) O2(g) + NO2(g)
Rate = k [O3] [NO]

From the rate equation, the following information can be deduced:

1. This reaction is 1st order reaction with respect to [O3] and 1st order with respect to [NO].
2. It is overall second order reaction.

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3. 1 mole of O3 and 1 mole of NO are involved in the slow step. Overall molecularity for the slow step
is 2.

 In a termolecular reaction, three molecules collide simultaneously to form the products. These
reactions are not common since the collision of 3 particles at the same time is required and in exactly
the right orientation to form products.
Example: Reaction of NO and O2
Rate-determining step
2NO(g) + O2(g) 2NO2(g)

Rate = k [NO]2 [O2] (overall 3rd order reaction)

Summary:
Order of
Rate-determining step Molecularity Rate equation
Reaction
A product Unimolecular 1 rate = k [A]

2A product Bimolecular 2 rate = k [A]2

A + B product Bimolecular 2 rate = k [A][B]

2A + B product Termolecular 3 rate = k [A]2[B]

 Rate equation is determined by the species involved (raised to the stoichiometric

coefficient) in the RDS and this must be found by experiments.
 Order of Reaction is determined by the molecularity in the RDS and this must be
found by experiments.
 Stoichiometric equation (or overall equation) is determined by (RDS + fast steps).

*Take note:
Rate equation may or may not include any of the reactants in the stoichiometric equation.

Exercise 3:

Question 1

The decomposition of nitrous oxide, N2O, is believed to occur via two elementary steps:

Step 1: N2O k1 N2 + O
k2
Step 2: N2O + O N2 + O2

Experimentally the rate equation is found to be: Rate = k[N2O]

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(a) Write the equation for the overall reaction.

(b) Identify the intermediate.
(c) What can you say about the relative rates of steps 1 and 2?

Answer:
(a) Add equations for steps 1 and 2 to give the overall reaction:

2N2O 2N2 + O2 (This is the stoichiometric or overall equation.)

(b) O atom is the intermediate, as it does not appear in the overall equation.
(c) The rate equation: rate = k[N2O] indicates that Step 1 is the RDS
Step 2 must be the fast step since the rate equation suggests only N2O is involved in the slow step.

Question 2

The overall reaction between X and Y in the presence of an acid catalyst is shown:
H+
X + Y Z

The proposed mechanism for the reaction is:

X + H+ XH+ slow
XH+ + Y Z + H+ fast

Which one of the following rate equations would be consistent with the proposed mechanism?
A Rate = k [X][Y] B Rate = k [X]
C Rate = k [X] [H+] D Rate = k [XH+] [Y]

Answer: (C) because this rate equation contains all the species in the slow step.

Question 3

The reaction of acidified, aqueous potassium iodide with aqueous hydrogen peroxide

2I-(aq) + H2O2(aq) + 2H+(aq) I2(aq) + 2H2O(l)

is thought to involve the following steps:

H2O2 + I- H2O + OI - slow

OI - + H+ HOI fast
HOI + H+ + I- I2 + H2O fast

Which one of the following conclusions cannot be drawn from this information?
A The iodide ion is oxidised by the hydrogen peroxide.
B The acid acts as a catalyst.
C The reaction is first order with respect to the concentration of the iodide ion.
D The rate determining step is H2O2 + I- H2O + OI-
E The rate equation for the reaction is: rate = k[H2O2][I-]

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Answer: (B) because H+ is consumed and is not regenerated in the reaction.

[H+ is not a catalyst.]

4 Determination of Orders of reaction, Rate equation and Rate constant from experimental data
 The order of a reaction can be deduced by the initial rates method.
 The initial rates of 2 reactions at known initial concentrations are compared and the order of reaction
with respect to the concentration of each reactant is deduced.
 Typically, experimental data are collected and plotted into graphs. Initial rates are calculated by
determining the gradients of the graphs at time t= 0.
2 methods: By inspection and by mathematical methods
Example 1:
For the reaction: P + Q S the following results were obtained.

Initial concentration / mol dm-3 Initial rate / mol dm-3 s-1

Experiment
[P] [Q]
1 0.01 0.01 0.0001
2 0.01 0.02 0.0002
3 0.02 0.02 0.0008

(a) How does the rate of reaction depend on the concentrations of P and Q?
(b) What is the rate equation for the reaction?
(c) What is the overall order of reaction?
(d) Calculate the rate constant, k, giving the units.

Solution:
(a) Method 1: By inspection
Compare experiments 1 and 2, where [P] = constant,
When [Q] is doubled, the rate also doubles.
 rate  [Q] 1 ⇒ 1st order w.r.t. [Q]
Compare experiments 2 and 3, where [Q] constant,
[P] doubles, rate increases by 4 times.
 rate  [P]2 ⇒ 2nd order w.r.t. [P]

Hence, Rate  [P]2[Q]

Method 2: Mathematical method

Let rate = k [P]m [Q]n

Compare experiments 1 and 2, where [P] = constant

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m n
Rate 2 k [ P ] [ Q ]
=
Rate 1 k [ P ]m [ Q ]n
m n
0. 0002 k (0 . 01) (0 . 02)
=
0. 0001 k (0 . 01)m (0 . 01)n
2=2n
∴n=1
Compare experiments 2 and 3, where [Q] = constant

m 1
Rate 3 k [ P ] [Q ]
=
Rate 2 k [ P ]m [Q ]1
m
0. 0008 k (0 . 02) (0 . 02)
=
0. 0002 k (0 . 01)m (0 . 02)

4=2m
∴ m=2
(b) Rate equation: rate = k [P]2[Q]

(c) 2nd order with respect to [P]; 1st order with respect to [Q].

Overall order = 2 + 1 = 3

(d) To calculate the value of rate constant, k, substutite the values of initial rate, concentration of P and Q
into the rate equation determined in (b).

Using experiment 1,
Rate = k [P]2[Q]
0.0001 = k (0.01)2(0.01)
0.0001
3
k = (0.01 )
k = 1 × 102 mol–2 dm6 s-1

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Example 2: Given the reaction of H2O2 with acidified I- ions, liberating I2.

Experiment Initial concentrations of reactants / mol dm-3 Initial rate of formation

of iodine
/ mol dm-3 s-1
[H2O2] [I-] [H+]
1 0.010 0.010 0.010 2.0 x 10-6
2 0.030 0.010 0.010 6.0 x 10-6
3 0.030 0.020 0.010 1.2 x 10-5
4 0.030 0.020 0.020 1.2 x 10-5

(a) Find the order of the reaction with respect to the concentration of each reactant. Hence, write the rate
equation and calculate the rate constant, k, stating its units clearly.
(b) What would be the initial rate if the volume of solution used for Experiment 1 were suddenly halved
(assuming no change in number of moles)?
Answer:

(a) Comparing experiments 1 and 2, where [I-] and [H+] = constant

When [H2O2] is tripled, initial rate is also tripled.
 Reaction is 1st order w.r.t. [H2O2]

Comparing experiments 2 and 3, where [H2O2] and [H+] = constant

When [I-] is doubled, initial rate is also doubled,
 Reaction is 1st order w.r.t. [I-].

Comparing experiments 3 and 4, where [I-] and [H2O2] = constant

When [H+] is doubled, initial rate is unchanged.
 reaction is zero order w.r.t. [H+]

Rate = k[H2O2] [I-]

Calculating rate constant, k, substitute values of initial rate and concentrations of the reactants from
Experiment 1 into rate equation:

Rate = k[H2O2] [I-]

2.0 x 10-6 = k(0.010)(0.010)

2. 0×10−6
k=
(0 . 010)(0 . 010)
k =2×10−2 mol−1 dm 3 s−1

(b) When volume of vessel is halved, concentration of solution is doubled. Hence the concentrations of
the reactants double.
Since reaction is 2nd order overall,

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initial rate is increased by 22 or 4 times.

Initial rate = 2.0 x 10-6 x 4 = 8.0 x 10-6 mol dm-3 s-1

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Example 3: Determination of Initial rate using Graphical method (Nov 2000/ P1/Q3, modified)

Bromoethane is hydrolysed by aqueous sodium hydroxide according to the following equation:

C2H5Br + OH- C2H5OH + Br-
The following results were obtained from two experiments on such a hydrolysis. In each experiment, the
overall concentration of NaOH (aq) remained virtually constant at the value given at the top of the column.

[C2H5Br] / mol dm-3 when [C2H5Br] / mol dm-3 when

Time /
[OH-] = 0.10 mol dm-3 [OH-] = 0.15 mol dm-3
min
0 0.0100 0.0100
40 0.0079 0.0070
80 0.0062 0.0049
120 0.0049 0.0034
160 0.0038 0.0024
200 0.0030 0.0017
240 0.0024 0.0012

(b) Plot these data on suitable axes and use your graphs to determine the following:
(i) Use the half-life method to deduce the order of reaction with respect to [bromoethane].
(ii) Use the initial rates methods to deduce the order of reaction with respect to [sodium hydroxide].
(b) Write a rate equation for the reaction.
Solution:
(a) Plot the 2 graphs.

0.012

0.01
[Bromoethane]

0.008
[brommethane] when
[hydroxide] = 0.1M
0.006
[bromoethane] when
[hydroxide] =0.15M
0.004

0.002

0
0 40 80 120 160 200 240
Time/ min

(i) Half-life method: Determine the half-life of bromoethane using only one graph. Use either curves to
determine the constant half-life. 2 constant half-lives need to be determined from the graph.

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From the curve when [hydroxide] = 0.1 mol dm-3, half-life of bromoethane is about 120 min.
Or, from the curve when [hydroxide] = 0.15 mol dm-3, half-life of bromoethane is 80 min.
Since half-life is constant, it is first order w.r.t bromoethane.

(ii) Initial rate method: Drawing tangents to BOTH curves at time t= 0 min.
 The initial rate can be determined by drawing as accurately as possible tangents to BOTH curves at
the start. (Recap: Gradient of concentration- time graph would give the rate of the reaction.)
 Once the gradients of each tangent is determined, the ratio of the 2 tangents are compared to the
ratio of concentration of hydroxide ions.
Since concentration of hydroxide increases by 1.5 times, the gradients also increase by 1.5 times,
hence it is a first order reaction w.r.t. [sodium hydroxide].
(b) Rate = k[C2H5Br][OH-]

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Exercise 5
Question 1 [N90/P1/13]

The table shows experimental results obtained for:

2XO + O2 2XO2

Experiment 1 2 3 4
Partial pressure of XO (in arbitrary unit) 100 100 50 50
Partial pressure of O2 (in arbitrary unit) 100 25 100 -
Relative rate 1.0 0.25 0.50 0.125

What is the missing value of the partial pressure of O2 in the table?

A 12.5 B 25 C 40 D 50 E 75

Answer:
From experiment 1 and 2, 1st order with respect to [O2]

From experiment 1 and 3, 1st order with respect to [XO]

Rate  (PXO)(PO2)

From experiment 3 and 4, PXO = constant

Rate  PO2
Since the rate decreased by 4 times, PO2 should also decreased by 4 times.
 PO2 in expt 4 = 100/4
= 25

Answer: (B)

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5. The Collision Theory

The Collision Theory states that

 Chemical reactions take place as a result of particles collisions.
 Not all collisions result in reaction
 Only a small fraction of the collisions that occur actually leads to reaction.
 Reactant particles must collide in a favourable orientation in order to react.
 Only particles which collide with energy greater than or equal to the Activation Energy, EA, (and with the
correct orientation for some reactions) are able to react. These collisions are called effective
collisions.
 Activation energy is the minimum energy required for a reaction to occur.
 The greater the frequency of effective collisions, the greater the rate of reaction.
EA represents the energy barrier that the reactants must overcome in order to become products.
E colliding particles  EA leads to effective collisions Reaction occurs

E colliding particles  EA leads to ineffective collisions NO reaction

(Particles rebound from each other)

 Reactions with high EA are slow because only a small proportion of molecules will have the necessary
activation energy.
 Reactions with stable reactants require large amount of energy to break strong covalent bonds and
hence have high EA and usually require heating.
Example: Combustion of hydrogen in the presence of oxygen gas

2H2(g) + O2(g) 2H2O(g) ΔH = - 484 kJ mol-1

The combustion reaction is spontaneous and exothermic but mixtures of hydrogen and oxygen gases
are stable indefinitely at room temperature.
The reaction does not occur at room temperature because strong covalent bonds must be broken to
transform H2 and O2 into water.
However, a violent spark will provide some of the molecules enough energy to overcome the activation
barrier, and then, the formation of water releases enough energy to drive the reaction to completion
very quickly.

 Reactions with very high EA are very slow and they may be practically no reaction, even though the
reaction is energetically favourable.

Example: Conversion of diamond into graphite

C(diamond) C(graphite) ΔH = -3 kJ mol-1

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Diamond is energetically unstable with respect to graphite, so the conversion should be favourable.
However, the conversion of diamond to graphite occurs immeasurably slow. This is due to the
extremely large activation energy for the conversion to occur.
 Reactions with low EA are fast because a large proportion of molecules will have the necessary
activation energy.
Example: Dimerisation of NO2 molecules into N2O4

O O O O

N + N N N
O O O O

The activation energy,EA, for the dimerisation of NO2 to N2O4 is zero because NO2 is a radical and has an
odd electron is readily available for bond formation.

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6. Factors that affect rate of reaction

6.1 Effect of physical state of reactants

 For a reaction between an aqueous solution and a solid reactant, increase in the surface area of the
solid reactant will increase reaction rate due to increase in effective collisions between the ions and the
solid.
 For a given mass of solid, surface area increases as particle size decreases. Hence reaction rate
increases as a solid becomes more finely divided.
 Three questions to consider:
o Are the reactants in solution present as molecules or ions?
(1) CH3CH2Cl(aq) + NaOH(aq) → CH3CH2OH(aq) + NaCl(aq) slow, requires heating
a. Involves cleavage of the C-Cl bond which requires energy  high activation
energy
b. Hence heating is required to increase the temperature of the reaction mixture so
as to increase the reaction rate.
(2) HCl(aq) + NaOH(aq) → H2O(l) +NaCl(aq) Immediate reaction
a. Both NaOH(aq) and HCl(aq) dissociate completely in aqueous solution
b. The reactants are essentially OH- and H+ ions which being oppositely charged
ions would have a natural tendency to attract each other to form H2O
c. No breaking of covalent bonds low activation energy
d. Hence the reaction occurs instantaneously.
o Are the reactants in solution or in solid form?
(1) NaCl(s) + AgNO3(s) → no reaction
(2) NaCl(aq) + AgNO3(aq) → immediate reaction
o Are the reactants in solid form of a finely divided state?
(1) CaCO3 (marble chips) + 2HCl (aq) → CaCl2 (aq) + H2O (l) + CO2(g) slower
(2) CaCO3 (powder) + 2HCl (aq) → CaCl2 (aq) + H2O (l) + CO2(g) faster

6.2 Effect of concentration (or pressure of a gas)

 When concentration increases, the molecules are closer. Hence effective collisions increase and
reaction rate increases. The degree to which the concentration of a particular reactant affects the rate of
reaction depends on the rate equation.
If rate = k [A][B]2, then changing [B] has a greater impact.
 For a gaseous reaction, increase in pressure brings the particles closer together.
It has the same effect as an increase in concentration. Hence effective collisions increase and reaction
rate increases.
Solids and liquids are not compressible; therefore, pressure has little effect on their reaction rates.

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Note: pV=nRT  p=n/V RT= cRT  p∝c where c =concentration = n/V

6.3 Effect of temperature

 Increasing temperature increases

(i) kinetic energy of particles (due to more energetic movement of particles)
(ii) the number of particles with energy  EA (due to more effective collisions)
 Unlike concentration or pressure changes, which do not affect the rate constant, k, temperature
changes do affect the rate constant, k. Almost always, k increases exponentially with temperature.
 For many reactions, reaction rate is roughly doubled for every 10 K rise in temperature.

(a) Boltzmann distribution curve

 For gaseous molecules at a particular temperature, e.g. 30 0C, their speeds are not uniform. Some may
have very slow speeds hence very low energies and some may have very high speeds hence very high
energies.
 There is a spread or distribution of molecules having energies (or speeds) from very low to very high
with the average value corresponding to 300C.
This distribution of molecular speeds/ energies is shown by a Boltzmann (or Maxwell- Boltzmann)
distribution curve.

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molecules having
energy E ≥ Ea
Figure 10: Boltzmann distribution curve of a sample of gas at T K.

Number of

Energ
y
 The total area under the curve represents the total number of molecules.
 The number of molecules with energy E  EA is the area under the curve, which corresponds to
number of molecules with sufficient energy to react. Hence when these molecules collide, they lead
to effective collisions and reaction occurs.

Ea
 Increasing temperature increases the number of particles with energy E  EA .
of molecules

energy E ≥ Ea at TK

molecules having
energy E ≥ Ea at
Figure 11: Boltzmann distribution curves at different temperatures, T K and
molecules having
energy E

(T+ 10) K
Number of
Fractionof

(T+10)K
TK
Number
having

Energ
y
(T+ 10)K

Ea
Fraction of molecules
having energy E

Explanation of the effect of temperature on reaction rate

TK

 When temperature is increased, the molecules gain kinetic energy and move about faster. This
increases the number of molecules having energy E ≥ EA. As a result, the frequency of effective
collisions increases. Reaction rate thus increases.

Note: EA does not shift as temperature changes

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(b) Relationship between Temperature and Rate constant, k

 An increase in temperature increases the rate of a reaction by increasing the rate constant.

i.e. T  k or k  T

The rate constant is related to temperature by Arrhenius equation (not in syllabus).

EA
(− ) where k = rate constant
RT
k =Ae A = Arrhenius constant
EA = activation energy
T = temperature in K
R = molar gas constant

From the Arrhenius equation, it can be seen that

 Increasing temperature T leads to a larger rate constant k. Hence reaction rate is increased.
 Using a catalyst leads to a smaller activation energy, E A, and hence a larger rate constant, k.
Reaction rate is also increased.

6.4 Effect of light

 Reactions which are light sensitive are called photochemical reactions. Light may thus increase
reaction rates in examples such as photosynthesis and photography.

E.g. H2(g) + Cl2(g) 2HCl(g) slow in the dark

H2(g) + Cl2(g) 2HCl(g) fast above 2000C
H2(g) + Cl2(g) 2HCl(g) Very fast with sunlight at room temperature

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6.5 Catalysis

6.5.1 Definition of a catalyst

 A catalyst/positive catalyst is a substance that increases the rate of a chemical reaction without
being consumed in the reaction.
 A positive catalyst increases the rate of reaction by providing a different mechanism or alternative
reaction pathway with a lower activation energy for the reaction, which in turn make the rate
constant larger and the rate faster.
 A positive catalyst does not increase the yield of products but only increases the rate at which the
products are formed.
 A catalyst is chemically involved in a reaction. It is consumed in one step and regenerated in a
subsequent step. It can thus be used repeatedly without undergoing any permanent change.
 A negative catalyst or an inhibitor decreases the rate of reaction.
 However, a catalyst does not alter the ΔHreaction and does not increase the yield of products in a
given reaction.

Figure 12: Boltzmann distribution curve, showing the effect of catalyst on the distribution of
molecules having
energy E reaction

molecules having
≥ Ea

energies of the molecules

energy E ≥ Ea’
Uncatalysed

Number of

Number of
Catalysed
reaction

Energ
y
Ea
Fraction of molecules

Ea’
having energy E

TK

Explanation of the effect of catalyst on reaction rate

A catalyst lowers the activation energy of a reaction by providing an alternative reaction pathway. The
number of reactant molecules having energy greater than or equals to the activation energy increases,
hence the frequency of effective collisions increases. Rate increases.

Figure13: Energy profile diagrams of the uncatalysed and catalysed pathways

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Energy / kJ

Ea

Ea'

Products
H >0

Reactants

Reaction progress

 Addition of a positive catalyst can decrease the required EA by providing a different mechanism with a
lower Ea so that more particles have energy E  EA, hence the reaction rate increases.

6.5.2 Types of Catalysis

Some related terms:

Inhibitor - An inhibitor is a substance which decreases the rate of a chemical reaction.

- Example: presence of dilute acids or glycerine retards the decomposition of H2O2
Promoter - A promoter is a substance which enhances the efficiency of a catalyst.
- Example: In the Haber process, small amounts of Al2O3 and K2O are added to
promote the efficiency of the iron catalyst.
Catalyst poison - A catalyst poison is a substance which inhibits the effectiveness of a catalyst.
- Example: Lead poisons the platinum-rhodium surface in car exhaust catalytic
converters, hence the need for un-leaded petrol.

(a) Heterogeneous catalysis

 Catalyst and reactants are in the different physical states.

 A heterogeneous catalyst is usually a solid catalyzing reaction between gases or reaction in solution.
The catalysts are usually one or a mixture of transition metals or their compounds (halides or oxides).

 The catalysis at a solid surface can be explained in terms of adsorption theory. A heterogeneous
catalyst works by providing a surface onto which reactants are adsorbed and from which products are
desorbed.

 The availability of 3d and 4s electrons allows the ready exchange of electrons between the transition
metal catalyst and the reactants molecules to form weak bonds. This adsorption weakens the bonds in
reactant molecules, thereby lowering the activation energy, as well as increasing the surface
concentration reactants.

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active sites

Desorption

Adsorption Adsorption Reaction

1. Diffusion Reactant molecules diffuse towards the catalyst surface.
2. Adsorption Reactant molecules become adsorbed onto the active sites of the catalyst surface by
means of van der Waals’ forces. This increases the local concentration of reactants and
also weakens the covalent bonds in the molecules.
3. Reaction Adjacent reactant molecules react to form products. This reaction has lower activation
energy (Ea) than the uncatalysed reaction.
4. Desorption This is the reverse of adsorption. The product molecule eventually breaks free from the
catalyst surface.
5. Diffusion The product molecules diffuse away from the surface. The vacant active sites are now
available for adsorbing other reactant molecules.

 Examples:
(a) Finely divided iron powder with a promoter, alumina, in the Haber process,
Fe(s)
NOTE:
N2(g) + 3 H2(g) 2 NH3(g) What are promoters and
why are they important in
the use of catalyst?
(b) V2O5 in the Contact process,
V2O5(s) What does it mean to
2 SO2(g) + O2(g) 2 SO3(g) “poison the catalyst”?
How can a catalyst be
“poisoned”?
(c) Pt or Ni in the hydrogenation of alkene at 4000C.
Ni(s)/Pt(s)
C2H4(g) + H2(g) C2H6(g)

(d) Catalytic removal of oxides of nitrogen in exhaust gases from car engine
 In many countries, pollution from motorcars is being reduced by fitting a catalytic converter
onto motorcar exhaust system. The exhaust gases (nitrogen oxides, carbon monoxide and
unburnt fuels) react together on the surface of a platinum, Pt or rhodium, Rh catalyst, and
are converted into harmless nitrogen, carbon dioxide and steam.
 Usage of ‘lead-free’ petrol in motorcars prevents “poisoning” of the catalyst.
Catalyst supported on a ceramic block
OUT

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‘honeycomb’ H2O
of small beads CO2, N2
coated with Pt & Rh

IN
CO
CxHy, NOx

(b) Homogeneous catalysis

 Catalyst and reactants are in the same phase.

 A catalyst speeds up a reaction by providing a new lower energy pathway.

 Homogenous catalysts take part in the reaction by being converted into an intermediate species which
is subsequently consumed to form the products.

 By the time the reaction is completed, the catalyst would have been regenerated.

Example: Reaction between peroxodisulfate ions, S2O82- and iodide ions, I-

Uncatalysed reaction: S2O82-(aq) + 2I-(aq) 2SO42-(aq) + I2(aq)

The uncatalysed reaction is slow because it involves the reaction between 2 negatively charged ions. The
repulsion between the 2 negatively charged ions causes the reaction to have high activation energy.
When the reaction is catalysed by aqueous iron(III) ions, Fe3+(aq):
Step 1: 2Fe3+(aq) + 2I-(aq) 2Fe2+(aq) + I2(aq)
Step 2: 2 Fe2+(aq) + S2O82-(aq) 2 Fe3+(aq) + 2 SO42-(aq)

Overall reaction 2I-(aq) + S2O82-(aq) I2(aq) + 2SO42-(aq)

 In the presence of Fe3+, the reaction proceeds via a two-step mechanism, which involves the approach
of oppositely charged species. This lowers the activation energy and enhances the reaction rate.

(c) Autocatalysis

 When a product of a reaction acts as a catalyst in the reaction, it is called an autocatalyst.

Example: Reaction between MnO4- and C2O42- in acidic medium
600C
- 2- +
2MnO (aq) + 5C2O4 (aq) + 16H (aq)
4 2Mn2+(aq) + 10CO2(g) + 8H2O(l)

 Manganese (II) ion, Mn2+ is an autocatalyst.

 At the start, the reaction starts slowly because no Mn2+ ions were produced yet.
 As reaction progress, the rate increases after a small amount of catalyst, Mn2+ ions has been formed.

Graph of [MnO4-] against time Graph of rate against time for an autocatalytic
reaction

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(d) Biological (enzymatic) catalysis

 Enzymes are biological catalysts (proteins) which catalyse biochemical reactions in living systems.
Without them, most biochemical processes would be too slow to sustain life.
 Enzymes are also important in industrial manufacture of food, wine, beer, textile and detergents
(including biological washing powder).

(i) Properties of enzymes

(a) Enzymes are neither homogenous nor heterogenous catalysts are they are colloidal in nature.
(b) Enzymes are highly selective and would only catalyse a specific reaction or type of reaction.
(c) Sensitive to temperature - Most have an optimum temperature of about 380C - 40C,
are destroyed or denatured at higher temperatures.
© Reaction rate

Temperature
37

(d) Sensitive to pH changes.

(e) Sensitive to poisons.
Example: In the fermentation of sugars into ethanol, ethanol poison the enzymes in yeast if the ethanol
concentration is more than 15.5 %. The fermentation thus stops.
(ii) Enzymatic action

 Enzymes catalyse reactions by providing an alternative pathway with a lower activation energy.

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To bring about this about, the enzyme forms a complex with the substrate or substrates (the reactants)
of the reaction. A simple picture of the enzyme action is:

Substrate + Enzyme Substrate/enzyme complex Product + Enzyme

One model to explain the how enzymes work is the lock and key model (not in syllabus).
Do you know?
Lock and key model of enzymatic action
According to this model, the substrate and the enzyme molecules have complementary
shapes, so that they fit together like a lock and its key.
The substrate (reactant) fits the active site on the enzyme (catalyst) the same way a key fits
the lock.
An enzyme-substrate complex is formed and this weakens the covalent bonds within the
substrate, lowering the activation energy.
The substrate-enzyme complex breaks apart as the products formed are no longer of the
right shape to remain in the active site, leaving the enzyme free to catalyse further reactions.

(iii) Relationship between enzyme, substrate concentration and rate of reaction

In an enzyme-catalysed reaction:
For a fixed amount of enzyme, there is limited number of active sites in each enzyme.
When [enzyme] << [substrate]:
The rate of reaction is directly proportional to the [enzyme], i.e. the reaction is first order with
respect to the enzyme.

 At low [substrate], the active sites are not fully filled, and the rate is proportional to [substrate].
 At higher [substrate], the active sites are fully filled, and any increase in substrate concentration will
not have any effect on the reaction rate.

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SUMMARY

Effect on rate of Effect on rate constant,

Change Effect on EA
reaction k
Increase in
Increased No effect No effect
concentration
Increase in pressure
Increased No effect No effect
(gaseous system)
Increase in
Increased Increased No effect
temperature

Use of catalyst Increased Increased Decreased

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