CHEMICAL KINETICS Rate α

𝛛 [𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬]
… … (𝟐)
𝛛𝐭
REVISISON QUESTIONS
(ii) State what the square brackets represent in the
Instructions. two equations.
 Use the reference books listed at the end of this
(iii) Why is the rate of reaction in the equation (1)
text to read and extract solutions for the following
negative while in equation (2) positive?
items.
 You must be brief. 2. The law of mass action / equilibrium law states
 The solution should be written in the separate work that “the rate of chemical reaction is directly
book (research book) and after discussion shall be
proportion to concentration of each reactant raised to
transferred to your class book as notes for this
chapter. an appropriate power at constant temperature,”
 Experimental details shall be dealt with when school For example, for the reaction
are reopened.
x A + YB Products
1(a) State what is meant by term “Rate of reaction?” Rate α[A]X or Rate = k[A]X
(You can give two statements for reactants and Rate α[B]y or Rate = k[B]y
products respectively).

(b) The following mathematical expression shows the Therefore overall Rate = k[A]X [B]y
rate of reaction with respect to reactants and Write equilibrium law for;
products. a) 2 HI(g) H2(g) + I2(g)

−𝛛 [𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬] b) H2(g) + I2(g) 2 HI(g).

Rate α … … (𝟏)
𝛛𝐭

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3. Definition of terms; N.B: - Molecularity is always a whole number.
i) Rate equation / Rate law; Is an equation of chemical - Molecularity is determined from the reaction
reaction that expresses the rate of reaction as a equation.
simple function of the concentration of the reactants iv) Order of reaction: is the sum of the powers to
in the rate determining (slowest) step, which the molar concentration of the reactants is
raised in the experimentally determined rate equation.
e.g For the reaction: n X + mY Products. E.g For the reaction:
n X + mY Products.
n m
Rate = k[x] [y] is the rate equation for the

reaction where K is called the rate constant.

The rate law: Rate = k[x]n [y]m
n – is order of reaction with respect to (m.r.t) X
ii) Rate Constant, K: is the ratio of the rate of chemical m – is order of reaction m.r.t Y
reaction to product of the concentration of the
reactants raised to the appropriate power as written in overall order of reaction = n + m
the rate equation.
N.B - Order of reaction can be zero, a fraction or a
n m whole number.
E.g Rate = k[x] [y]
- Order of reaction is only determined
experimentally.
𝐑𝐚𝐭𝐞 Questions.
Rate Constant K = 𝑛 𝑚
[x] [y] a) Explain what is meant by the following terms:
iii) Molecularity: is the number of reacting spieces i) Rate equation iii) Rate constant
taking part in the rate determining step of the ii) Molecularity iv) Order of reaction
reaction. (Rate determining step is the slowest step of b) State the difference between molecularity of a
the reaction) reaction and order of a reaction.

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 c) The rate of chemical reaction is given by the concentration of the reactant raised to the
relationship; power 2. For the second order reactions,
Z Products, write, the rate equation fir
Rate =k[A]a [B]b
the reaction.
State what each of the following stands for;
A psendo first order; reaction is one in which one of
i) [A]
the reactant is present in excess so its concentration
ii) a
remains constant and therefore reaction becomes first
iii) b
order with respect to the other reactant. E.g in the
iv) K
hydrolysis of sucrose,
4. A First order reaction is a type of reaction in which
the rate of reaction is directly proportional to the Ht
C12H22O11 + H2O(l) C6H12O6 + C6H12O6
concentration of a reactant raised to the power one.
i) For the first order reaction: A Products,
Water is present in large excess, so its concentration
write the rate equation for the reaction.
remains constant so will not affect the rate of reaction

iii) A zero order reaction is one in which the rate

5. Initial rate method.
of reaction is independent of the concentration
This is a method used to workout orders of reaction
of the reactant i.e However much the
(page 300, 14.14.11 A LEVEL Chemistry by E.N
concentration of the reactant changes, the
RAMSDEN 4TH Edition)
rate of reaction remains constant.
Initial rate is the rate of reaction when just a small
For the zero order reaction ; X products, write
amount or concentration of reactant has reacted.
the rate equation for the reaction.

iv) A second order reaction is one in which the rate

of reaction is directly proportional to the

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OR: Is the slope of tangent to the curve of a Order w.r.t B taking experiment 1 & 2 in which [A] is
concentration – time graph when the time is zero. constant
 In the initial rate method, the order with
respect to given reactant is determined by 𝐈𝐧𝐢𝐭𝐢𝐚𝐥 𝐫𝐚𝐭𝐞 𝐢𝐧 𝟐
=
[A]X [B]y 𝒊𝒏 𝟐
[A]x [B]y 𝑖𝑛 1
comparing the initial rate for two experiments in initial rate in 1

which the concentration of only the reactant

whose order is to be determined is changing 5.6x10−5
= (
0.50 y
while the other reactant concentration is kept −5
)
1.4x10 0.25
constant. 4 = 2y
Example. 22 = 2y
The data below was obtained for the reaction:
Therefore y = 2
2A + B C+D
Experiem [A] moldm-3 [B] moldm-3 Initial rate/
Order m.r.t A taking experiment 1 & 3 in which
ent moldm-3min-1
1 0.150 0.25 1.4x10-5 [B] is constant
𝐈𝐧𝐢𝐭𝐢𝐚𝐥 𝐫𝐚𝐭𝐞 𝐢𝐧 𝟏 [A]x [B]y 𝒊𝒏 𝟏
2 0.150 0.50 5.6x10-5 = [A]x [B]y 𝑖𝑛 3
initial rate in 3
3 0.075 0.50 2.8x10-5
4 0.075 0.25 7.0x10-6 1.4x10−5
= (
0.150 x
)
7.0x10−6 0.075

a) Find the order of reaction with respect to A and 2 = 2x

B and the overall order of reaction; X=1
Solution.
Let order of reaction with respect to A and B be Order of reaction w.r.t A is 1
X and Y Respectively;
Over all order of reaction = 2 + 1 = 3

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 b) Determine the value of the rate constant. a) Determine the order of reaction with
Solution: you can use any set of experimental respect to A, B, and C and hence the overall
value to substitute into the rate equation.
order of reaction.
Rate = K[A] [B]2
b) Write the rate equation for the reaction.
c) Determine the value and the rate constant
Expt 1 1.4x10-5 = K (0.150) ( 0.25)2
and state its units.
K=
1.4x10−5
2. Use the data in the table below to answer
(0.150) ( 0.25)2
the questions that follow:
= 1.4933X10-3 mol-2 dm6min-1
experiment concentration Rate of Loss of
Using the above example and information moldm-3 A(moldm-3

answer the following questions. A B

1. Use the data in the table below to answer 1 0.10 0.10 2.5x10-5
the questions that follow.
2 0.20 0.10 2.5x10-5

concentration Rate of loss of 3 0.30 0.20 5.0x10-5

experiment
moldm-3 A(moldm-3
a) Determine the order of reaction with
A B C 2.0x10-4
respect to A and B
0.1 0.1 0.1 4.0x10-4 b) Write the rate equation.
0.2 0.1 0.2 1.6x10-3 c) Determine the value of the rate
constant and its units.
-4
0.1 0.1 0.2 2.0x10
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  For a First order reaction
Concentration the half life is constant and
Co
is independent of the initial
6. Testing First order reactions. concentration of the
C
2
0 reactant.
The following methods are used to show that a
reaction is first order: C
0
4

a) Half-life: Half-life is the time taken for

t
a reaction to go to half completion ( 1/2)
1 1 1
or any equivalent definition. t
2
2t 3t
2 Time
2
0
The half-life can be measured graphically by
plotting a graph of concentration of a For a 1st order reaction A Product
reactant against time. The graph gives a Rate = K [A]
Where K is the first
smooth curve from which the time taken for order rate constant
= K[A]
−d[A]

the concentration to fall to half of the dt

original is measured. d[A]

= -Kdt
d[A}

If [A]0 is the initial concentration of A,

then integration gives,

[𝐴]0 [𝐴]0
2.303log = kt or In = kt
[𝐴] [𝐴]

At half-life, t = t12 , [A] = [𝐴]2 0

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2.303log
[𝐴]0
= kt ⁄2
1 ii) The total pressure after 75.09hours 85k,
[𝐴]0
2 if the initial pressure was one
atmosphere.
2.303log2= kt ⁄2
1
or In
[𝐴]0
[𝐴]0 =kt ⁄2
1
3. The results below were obtained for the
2
reaction of substance R.
0.693 = kt 1⁄2 In 2 = kt
1
⁄2 0 150 300 450 750 1150 1450 1750
Time(sec)
1.000 0.812 0.659 0.535 0.353 0.202 0.133 0.088
t 1⁄2 =
0.693 0.693 = kt 1⁄2 [R](moldm-3
𝐾

0.693 a) Plot a graph of concentration of R against

t 1⁄2 =
𝐾 time. Use the graph to;
i) Determine the order of reaction
ii) The half life
The above expression can be used to calculate
iii) The value of the rate constant.
the half-life for a first order reaction or rate
b) Graphical method
constant.
The graph can be used to show that a
Question 1. The half-life of dinitrogen oxide reaction is first order.
is 75.09hours. Calculate;

i) The rate constant for decomposition of

i) Graph of rate reaction (𝟏⁄𝒕) against
dinitrogen oxide.
concentration.
 For First order reaction where the rate
of reaction is directly proportional to the
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 concentration of the reactant to power
one, the graph will give a straight line [X](moldm-3 0.100 0.210 0.285 0.420 0.540 0.700
0.0055 0.0116 0.0157 0.0231 0.0297 0.0385
through the original with K as the slope. Rate of
 For a second order reaction a graph of decomposition
(moldm-3)
rate of reaction against (concentration)2
gives straight line. use your graph to determine;

Summary i) The order of decomposition reaction

Rate of
and give a reason for your answer.
reaction ii) The rate constant for the reaction and
state its units.
(𝟏⁄𝒕)
A graph of log[𝑨]𝒕 against Time.

For a first order reaction; A products

= kt
[𝐴]0
2.303log
[𝐴]𝑡
Concentration
Question:

1. The results below are for the

Multiplying through by -1 gives,
decomposition of substance X.
= -kt
[𝐴]𝑡
2.303log
[𝐴]0

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 [𝐴]𝑡 k t Question; A compound B decomposes
log =-
[𝐴]0 2.303
according to the following equation:
k t
log [A]t - log [A]0 = -
2.303 2B Products
k t
log [A]t = - + log [A]0 The table shows the concentration of B at
2.303
various times.
k t
log [A]t = - . 𝑡 + log [A]0
2.303
Plot a graph of Log10 [B] against time and use
Therefore, plotting a graph of log [A]t your graph to determine.
against time gives a straight line with a 2.0 4.0 7.0 10.0 14.0 20.0
Time(minutes)
negative slope. The slope of the graph is equal 0.820 0.670 0.490 0.37 0.240 0.141
k Concentration
to - and intercept on the y – axis = log
2.303 of B (Mol-1)
[A]0
i) The original concentration of B
Therefore [A] 0 = antilog of intercept.
ii) Order of reaction
iii) Rate constant for the reaction
iv) Half-life for the reaction.
log [A]t

k t
Slope = -
2.303

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Time (min)
 7. FACTORS AFFECTING RATE OF REACTION

Explain the effect of the following on the rate

of a chemical reaction (illustrate your answer
with examples)

a) Concentration of reactant
b) Temperature (this should include,
activation energy, activated complex.)
c) Catalyst
d) Surface area.

Reminder: Please refer to any of the following

reference books for clear attractive
presentation, helpful reinforcement and
practice.

 Advanced Level Chemistry 4th Edition by

E.N Ramsden
 Chemistry in context 5th Edition by Hil
and Holman
 Advanced Level physical Chemistry by
J.D.Heys
 Advanced Chemistry by Philip Mathew.
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