Reaction Kinetics Lecture Notes PDF

Teacher’s Copy
YISHUN JUNIOR COLLEGE

H2 CHEMISTRY 9729
Reaction Kinetics
Article I.
Content
1. Basic concepts & definitions
2. Methods of determining the rates of reactions
3. Factors affecting rates of reactions
4. Reaction mechanism
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 frequency 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 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 (proteins) which may have specific activity
(l) explain the relationship between substrate concentration and the rate of an enzyme-catalysed
reaction in biochemical systems
Reference Texts
1. Chemistry – The Central Science, Brown
2. Chemistry in Context, Hill & Holman
3. Longman A-Level Course in Chemistry, JGR Briggs
Notes
JC1 Chemistry: Reaction Kinetics
(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
DEFINITIONS OF REACTION RATE
Rate of reaction (or reaction rate) is defined as the increase in concentration Rate of
reaction is
of products per unit time or the decrease in concentration of reactants per always a
positive
 [reactant]  [product] value.
unit time. i.e. Rate = − or Rate = +
t t Since the
[reactant] is
decreasing,
[reactant] is a
Graph of [reactant]remaining against time Graph of [product] against time negative value.
-3 The minus sign
[reactant] / mol dm
[product] / mol dm-3 ensures that
rate of
reaction is a
positive value.
The steeper
the gradient,
the faster the
reaction
t time / s
t time / s
As reaction proceeds, [reactant] decreases.
As reaction proceeds, [product] increases.
Types of Rates
 Initial rate is the rate of reaction at time, t = 0.
 Instantaneous rate is the rate of reaction at any given time.
 Average rate is the total concentration of reactant used or total concentration
of product formed over total time.
 Common units for rate: mol dm− 3 s−1, mol dm−3 min−1 and mol dm−3 h−1
Chung LS / YJC / 2018 / Teacher’s Copy Page 2 of 38

Notes
Initial rate
Graph of [reactant]remaining against time Graph of [product] against time
[reactant] / mol dm-3 [product] / mol dm-3
d [product]
d [reactant] Initial rate =
Initial rate = dt
dt
time / s time / s
Average rate

change of [product]
Average rate =
change of [reactant] change in time
Average rate =
change in time [product]final  [product]initial
=
 [reactant]final  [reactant]initial 
t final  tinitial
= 
 t final  t initial 
time / s time / s
Instantaneous rate

Instantaneous rate =
+ d[product] at time t
Instantaneous rate = dt
d [reactant]
at time t
dt
t time / s t time/s

Notes
(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
v) calculating an initial rate using concentration data
[integrated forms of rate equations are not required]
Rate Equation
The equation that describes the mathematical relationship between the rate of
a reaction and the concentration of the reactants in a reaction is called the rate
law or rate equation. Consider a reaction between A and B:
A + B  Products
m and n are not
necessary the
The rate equation is: stoichiometric
coefficients.
Rate = k [A]m [B]n
The relationship
between the rate
where k is the rate constant of reaction and
m is the order of reaction with respect to reactant A the concentration
of reactants can
n is the order of reaction with respect to reactant B only be
determined
(m + n) is the overall order of the reaction experimentally.
Incorrect ways of writing rate equation: (by students)

m n
X (1) Rate equation
X = k[A] [B]
m n
X (2) k[A] [B]  Does not show the relation between rate and concentration
of reactants
Example: Decomposition of dinitrogen pentoxide (N2O5) The unit for k

depends on the
2N2O5  4NO2 + O2 form of the rate
equation and
The rate law for this reaction has been experimentally determined to be may be different
for each
Rate = k [N2O5]1 reaction and
hence need to
be worked out.
The order of reaction with respect to N2O5 is 1.
It is not related to the stoichiometric coefficient of 2.

Notes
Order of reaction
The order of reaction with respect to a particular reactant is the power to which
the concentration of that reactant is raised in an experimentally
determined rate equation.
Consider a reaction,
aA  products
where it’s rate equation is given by
Rate = k[A]n
Order of reaction with respect to reactant A is n, where n can be positive,
negative or fractional. A detailed study is found in the following section, where
n is restricted to 0, 1 and 2.
Zero Order
If n = 0,
Rate = k
Here, the [A] term does not appear in the rate equation. It implies that the rate
of reaction is independent of [A], i.e., the concentration of A will have no
influence in the rate as long as some of this reactant is present.
Graphs for a zero order reaction

Do you know?
Metabolism of
ethanol in the
rate [A]
human body
is a zeroth
[A]o order
k reaction.
Gradient = k
0 [A] 0 t
Gradient of the graph = rate

Rate = k[A]0
Since the gradient is constant,
( y = k) it implies that the rate is not
affected as concentration of A
decreases.

Notes
First Order
If n = 1,
Rate = k [A]
The reaction is said to be first order with respect to A, where the rate of
reaction is directly proportional to the concentration of A, i.e. doubling [A] will
double the rate of reaction.
Graphs of a first order reaction
rate [A]
[A]o
Half-life constant
(to be covered later)
Gradient = k
[A]
0 0 t
Rate = k[A]
( y = kx)
Second Order
If n = 2,
Rate = k[A]2
The reaction is said to be second order with respect to A, where the rate of
reaction is directly proportional to the [A]2, i.e. doubling [A] will increase the rate
of reaction by four times.
Graphs of a second order reaction
rate rate [A]
[A]o Half-life NOT constant

(to be covered later)
Gradient = k
0 [A] 0 [A]2 0 time

2 2
Rate = k[A] Rate = k[A]
( y = k x2 ) ( y = kx)

Notes
Overall Order
The overall order of the reaction is the sum of the powers of the concentration
terms in the experimentally determined rate equation.
aA + bB  products
Rate = k[A]m[B]n
Overall order of the above reaction = m + n
Example
Consider the following reaction:
BrO3−(aq) + 5Br−(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l)
Given that the experimentally determined is
rate = k[BrO3−][Br−][H+]2
Order of reaction with respect to BrO3− = 1
Order of reaction with respect to Br− =1
Order of reaction with respect to H+ =2
Overall order of reaction = 4
Rate Constant
 The rate constant, k, is the constant of proportionally in the

experimentally determined rate equation that relates the reaction rate to
the product of the concentrations of the reactants.
 It is characteristic of a particular reaction. For example,
2N2O5(g)  4NO2(g) + O2(g)
Rate = k1[N2O5]
CO(g) + NO2(g)  CO2(g) + NO(g)
Rate = k2[CO][NO2] (k1 is not equal to k2)
 Rate constant is dependent on temperature and the presence of k is a constant

catalyst. This is illustrated through the Arrhenius equation: at constant
temperature.
A A is the pre-exponential factor that
k  Ea encompasses the orientation factor and
e RT collision frequency, while Ea is the activation
energy, R is molar gas constant and T is
temperature.
 The larger the value of k, the faster the rate of the reaction.
 The units of k depend on the overall order of reaction and need to be
worked out.

Notes
Example
The decomposition of H2O2 is a first order with respect to H2O2.
When [H2O2] = 0.780 mol dm3, the rate of the reaction is 57.0 mol dm3 s−1.
What is the value of k in this reaction?
Solution
Rate = k[H2O2]
Rate 57.0 mol dm 3 s 1
k= = = 73.1 s−1
[H 2O 2 ] 0.780 mol dm 3
The units of rate constants
Overall Order General

Units of k
of Reaction Expression
0 Rate = k[R]0 = k mol dm−3 time−1
1 Rate = k[R]1 time−1
2 Rate = k[R]2 mol−1 dm3 time−1
3 Rate = k[R]3 mol−2 dm6 time−1
In general, units of k is (mol dm−3)1−n time−1 , where n is the overall order of the
reaction.

Notes
Concept of Half – life

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
The half-life ( t 1 2 ) of a reaction is the time taken for the concentration of a
reactant to fall to half its initial value. It is constant only for a first order
reaction.
[reactant] mol dm-3 [product] mol dm-3
[reactant]o
7 [product]o
8
3 [product]o
4
[reactant]o 1
2 [product]o
[reactant]o
[reactant]o
time time
t1 t2 t3
Example:
Taking consecutive half-lives ( )
–3 For first order
[Reactant] / moldm t½ (1) = 10 – 0 = 10 mins reaction,
when the
t½ (2) = 20 – 10 = 10 mins concentration
1.00 of the
t½ (1) = t½ (2) reactant is
halved, time
Half lives are constant, reaction is taken for the
0.80 first order with respect to reactant concentration
of reactant to
be halved is
Taking non-consecutive half-lives ( ) constant.
t½ (1) = 10 – 0 = 10 mins
0.50 At the same
t½ (3) = 12 – 3 = 9 mins time, the rate
0.40 t (1)  t (3) of reaction is
½ ½ also halved
Half lives are constant, reaction is (gradient of the
0.25 first order with respect to reactant tangent to the
curve at that
point)
0 3 10 12 20 Time/min
t (1) t (3) t (2)

½ ½ ½

Notes
Determination of half – life of a reactant from a product

concentration – time curve
[product] reactant product

start x 0
y
¾y first half life : ½x ½y
½y
2nd half life : ¼x ¾y
0 time
t1 t2 end 0 y
t ½ (1) = t1
t ½ (2) = t2 - t1
When first half life is reached, half the amount of
reactant is used up, it’s logical that half of the amount of
product (y) will be formed.
When the second half life is reached, half the remaining

amount is used up : ½ ( ½ x) = ¼ x ,
Amount of product formed = ½ y + ½(½ y ) = ¾ y
Calculate rate constant,k using half – life
t½ =
ln 2
k
For 1st order only :
rate constant, k , can be calculated.
Determine number of half – lives, n
1 n Final concentration of reactant

=
2 Initial concentration of reactant

Notes
Example
The decomposition of hydrogen peroxide is a first order reaction with a half-life
In general,
of 20 days. What will be the concentration of a 0.100 mol dm-3 solution after the fraction
of sample
100 days? remaining
after n half-
Solution
lives = ( 1 2 )n
After 100 days, 5 half-lives have passed.
1 5
= Final concentration of reactant
2 0.100
Therefore, [H2O2] after 100 days = ( ½ )5 x 0.100
= 3.13 x 10 3 mol dm  3
Pseudo First Order Reactions
If the concentration of one reactant is very large (at least 20 times more than
that of the other reactant), its overall concentration remains virtually constant.
Reason: The change in concentration of this reactant in large excess can
be treated as negligible and its concentration can be regarded to
be constant.
Determining half – life of a pseudo first order reaction :

Rate = k [ A ]n [ B ] ; t ½ (with respect to B) = 10 mins
By making [ A ] >> [ B ],
Rate = k’ [ B ]  This is a pseudo first order rxn, (where k’ = k [ A ]n )
ln 2 ln 2
t½ = k’ = k [ A ]n
ln2
If n= 1, t½ = 10 mins
= k [ A ]1
when [A] is doubled, t ½ (wrt B) will be halved ( = 5 min ) .
ln2 1 ln2 1
t ½ (new) = k2[A] = 2 k[ A ] = 2 10 mins = 5 mins
ln2
If n = 2, t½ = k [ A ]2 = 10 mins
when [A] is doubled, t ½ (wrt B) will be decreased by ¼ times (= 2.5 min) .
ln2 1 ln2 1
t ½ (new) = k (2[ A ])2 = 4 k[ A ]2 = 4 10 mins = 2.5 mins

Notes
Methods for Determining Order of Reaction

The order of reaction can only be determined experimentally. There are two
commonly used methods for the determination of the order of reaction.
Graphical Method
Using the chemical and physical methods discussed in Sections 2.2 and 2.3,
we can obtain the concentration vs time graph for a particular reactant in a
reaction. Based on the graphs obtained, we can deduce the order of reaction
with respect to the particular reactant.
At a glance,
aA  products
Order of Reaction Zero One Two

Rate Equation Rate = k Rate = k[A]1 Rate = k[A]2
Units of rate
constant (k) mol dm−3 time−1 time−1 mol−1 dm3 time−1
[A] [A] [A]
Half-life not
Concentration time Half-life constant
graph constant
[A] vs t
time time time

The rate of
rate rate rate reaction at various
times can be
determined by
drawing tangents
to the [reactant]
k Rate = k
vs time graph and
obtaining the
gradient = k gradients
Rate concentration
graph [A] [A] [A]
Rate vs [A] rate
[A]2

Notes
Initial Rate Method

In this method, we observe how the initial rate of the reaction is affected by
changing the initial concentrations of the reactants. This technique utilises
several experiments in which the initial concentration of the reactant of
interest is varied while keeping the concentrations of the rest of the
reactants constant.
Example
The initial rate of reaction aA + bB + cC  products was measured for several
different initial concentrations of A and B, and the results are as follows:
Experiment [A] [B] [C] Initial Rates
No. (mol dm−3) (mol dm−3) (mol dm−3) (mol dm−3 s−1)
1 0.100 0.100 0.100 4.0 x 10−5
2 0.100 0.200 0.100 4.0 x 10−5
3 0.100 0.200 0.200 8.0 x 10−5
4 0.200 0.100 0.100 16.0 x 10−5
Using these data, determine
(a) the rate law for the reaction,
(b) the magnitude of the rate constant and its unit, and
(c) the rate of the reaction when [A] = 0.0500 mol dm−3, [B] = 0.100 mol dm−3
and [C] = 0.200 mol dm−3
Solution
(a) The general form of rate law for the above reaction is
Rate = k [A]x[B]y[C]z
To determine x, the order of reaction with respect to reactant A:

Comparing experiments 1 and 4, where [A] is varied while [B] and [C] are kept
constant.
rate 4 k(0.200) x (0.100) y (0.100) z

rate1 k(0.100) x (0.100) y (0.100) z
16.0 x 10 5
x
 0.200 
 
4.0 x 10 5  0.100 
4  2x
x 2
When [A] is doubled, the initial rate increases by four times.

This result indicate that the rate is proportional to [A]2, i.e., the
reaction is second order with respect to reactant A. Hence x = 2

Notes
To determine y, the order of reaction with respect to reactant B:

Comparing experiments 1 and 2, where [B] is varied while [A] and [C] are kept
constant
rate 2 k(0.100) x (0.200) y (0.100) z

rate1 k(0.100) x (0.100) y (0.100) z
4.0 x 10 5
y
 0.200 
 
4.0 x 10 5  0.100 
1  2y
y 0
When [B] is doubled, the initial rate remains the same.
This result indicates that the rate is independent of [B], i.e., the
reaction is zero order with respect to reactant B. Hence y = 0
Alternatively,
any 2 sets of
To determine z, the order of reaction with respect to reactant C: experimental
data with
Comparing experiments 2 and 3, where [C] is varied while [A] and [B] are kept different [C]
can be used
constant to compute z
rate 3 k(0.100) x (0.200) y (0.200) z as x and y
 have been
rate 2 k(0.100) x (0.200) y (0.100) z
determined.
8.0 x 10 5
z
 0.200 
 
4.0 x 10 5  0.100 
2  2z
z 1
When [C] is doubled, the initial rate doubles.
This result indicates that the rate is proportional to [B], i.e., the reaction
is first order with respect to reactant C. Hence z = 1
Rate = k [A]2[B]0[C]1
Rate = k [A]2[C]
(b) Using the rate law and the data from experiment 1,
Rate = k [A]2[C]
Substituting the values,
4.0 x 10-5 = k(0.100)2(0.100)
k = 0.0400 mol– 2 dm6 s– 1
(c) Rate = k [A]2[C]

= (0.0400)(0.050)2(0.200)
= 2.00 x 10 – 5 moldm– 3 s– 1

Notes
Example:
Bromoethane, CH3CH2Br, can be hydrolysed by heating with aqueous sodium

hydroxide to form ethanol, CH3CH2OH, as illustrated by the following equation.
CH3CH2Br(aq) + NaOH(aq)  CH3CH2OH(aq) + NaBr(aq)
The following results were obtained from two experiments on such a hydrolysis.
In each experiment, the overall [NaOH(aq)] remained virtually constant at the
value given at the top of the column.
[CH3CH2Br]/mol dm3 [CH3CH2Br]/mol dm3

time/min when [OH] = 0.10 mol when [OH] = 0.15 mol
dm3 dm3
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
(a) Explain why the overall [NaOH(aq)] remained virtually constant at the
given value for each experiment.
(b) Plot these values on the same axes and use it to determine the following.
I Use the half-life method to verify that the reaction is first order with
respect to CH3CH2Br.
II Use the initial rates method to deduce the order of reaction with respect
to NaOH.
III Construct a rate equation for the reaction and use it to determine the
value of the rate constant, giving its unit.

Notes
Solution:
(a) [NaOH(aq)] is in large excess, as compared to [CH3CH2Br].
Hence, any changes in [NaOH] can be regarded as negligible and its
concentration remains vitually constant at the given values.
[CH3CH2Br]
/mol dm3
t1 = 116 min [OH] = 0.10 mol dm3
[OH] = 0.15 mol dm3
t2 = 200 – 84 = 116 min
84 116
time / min
I Using the graph at [OH ] = 0.10 moldm – 3 (keeping [OH – ] constant)
–
Halving [CH3CH2Br] from 0.01 to 0.005, t ½ (1st) = 116 – 0 = 116 mins
Halving [CH3CH2Br] from 0.0006 to 0.003, t ½ (2nd) = 200 – 84 = 116 mins
t ½ ( 1st)  t ½ ( 2nd ) , the half-life of the reaction is constant.
Hence, the reaction is first order with respect to CH3CH2Br.
II Initial rate =  gradient of the graph at t = 0 min

When [OH] = 0.10 mol dm3,
0.00  0.0100
initial rate =  = 5.83 x 10 – 5 mol dm– 3 min– 1
160  0
When [OH] = 0.15 mol dm3,
0.00  0.0100
initial rate =  = 9.00 x 10 – 5 mol dm– 3 min– 1
108  0

Notes
Now, rate = k[CH3CH2Br][OH]n
Comparing both experiments at t = 0 min,

9.26  10 5 k (0.0100)(0.15) n

6.25  10 5 k (0.0100)(0.10) n
1.4816  1.5
n
lg (1.4816) = lg (1.5)n
lg (1.4816) = n lg (1.5)
lg 1.4816
n = lg 1.50
n = 1
So, the reaction is first order with respect to NaOH.
III Rate = k[CH3CH2Br][NaOH]
rate
Now, k=
[CH 3 CH 2 Br][NaOH]
9.0 10 5
=
(0.0100)(0.15)
= 0.0600 mol1dm3 min– 1
Example : GCE A level Paper

The kinetics of the acid-catalysed reaction of propanone with iodine
H+
CH3COCH3 (aq) + I2(aq) CH2ICOCH3(aq) + HI (aq)
can be investigated experimentally by varying the concentrations of the three

substances involved and determing the time for the colour of iodine to
disappear. The following results were obtained.
experiment Volume of Volume Volume of Volume Time for
number propanone of I2 sulfuric of water colour of
/cm3 /cm3 acid /cm3 iodine to
/cm3 disappear /s
1 8 4 8 0 25
2 8 4 4 4 50
3 4 4 8 4 50
4 8 2 8 2 12.5
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑖𝑜𝑑𝑖𝑛𝑒
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ∝
𝑡𝑖𝑚𝑒 𝑓𝑜𝑟 𝑐𝑜𝑙𝑜𝑢𝑟 𝑜𝑓 𝑖𝑜𝑑𝑖𝑛𝑒 𝑡𝑜 𝑑𝑖𝑠𝑎𝑝𝑝𝑒𝑎𝑟
a. Calculate the initial rate for each of these four experiments and use the
results to deduce the order of reaction with respect to each of the three
reactants in the reaction.
b. Sketch a graph for (i) concentration vs time (ii) rate vs concentration

Notes
for iodine.
c. Write an overall rate equation, stating the units of the rate constant.
Solution:
1
a. ( concepts used : 𝑅𝑎𝑡𝑒 ∝ 𝑡𝑖𝑚𝑒 and 𝐶𝑜𝑛𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 ∝ 𝑣𝑜𝑙𝑢𝑚𝑒 )
To calculate rate, since time is measured with respect to iodine whose volumes
for all experiments are not the same.
experiment Volume Time for colour of iodine to Rate  VI
2 /t
number of I2 /cm3 disappear /s
1 4 25 4/ 25 = 0.16
2 4 50 4/ 50 = 0.08
3 4 50 4/ 50 = 0.08
4 2 12.5 2/ 12.5 = 0.16
Rate = k [ propanone]x [ I 2 ]y [ H + ]z
Using expt 1 & 2

4 / 25 8 z
4/ 50 = 4
(2) = (2)z
 z = 1
Reaction is first order with respect to sulfuric acid .
Using expt 1 & 3
4 / 25 8 x
4/ 50 = 4
(2) = (2)x
 x = 1
Reaction is first order with respect to propanone .
Using expt 1 & 3
4 / 25 4 y
2/ 12.5 = 2
(1) = (2)y
 y = 0,
Reaction is zero order with respect to I2 .
b. Rate
[I2]remaining
time [I2]
c. Rate = k [ propanone] [ H + ]
Unit for rate constant = mol1 dm3 s1

Notes
Basic Knowledge #1: The Collision Theory

(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
 The Collision Theory states that reactant particles must undergo

a successful collision for a reaction to occur.
 Two conditions of a successful collision:

1. Reactant particles must collide in the correct orientation.
2. Reactant particles must collide with sufficient energy to
break the existing bonds.
The minimum energy which colliding molecules must possess to

react is called the activation energy, Ea.
1. Collision of correct orientation and sufficient energy
2. Collision of correct orientation but insufficient energy
3. Collision of incorrect orientation

Notes
Basic Knowledge #2: Activation Energy

 Definition: Activation energy is the minimum amount of energy that
reactant particles must possess in order to undergo a
successful collision.
 Energy Profile Diagram:
energy
Ea Ea = activation energy
reactants
products
progress of reaction
 Activation energy is used to:
1. overcome repulsive forces between reactant particles in close
proximity.
2. break existing bonds within reactant particles.
 Relationship between activation energy Ea and rate constant k:

The smaller the value of Ea, the larger the value of k.
Basic Knowledge #3: Maxwell-Boltzmann Distribution Curve
 The Maxwell-Boltzmann Distribution Curve shows how the kinetic

energy of the particles of a sample of gas varies at a given temperature.
Note:
The graph
fraction of applies only
particles to gaseous
reactions,
but the
Ea = activation energy conclusions
that we
draw from it
can also be
applied to
reactions
involving
energy liquids.
Ea
 The area under the curve represents the total number of gaseous
particles present.
 Only the particles represented by the shaded region have the minimum
amount of energy for reaction to occur. The rest of the particles will not
participate in the reaction.

Notes
Temperature Increase rate

constant
 increases the average kinetic
energy of particles
increases molecular  increases number of particles
speed of particles with energy greater or equal to
activation energy
Increase in frequency Increase in frequency of Increase in rate

of collisions effective collisions
 provide an alterative path of

increases increases number lower activation energy
sites of of particles per  increases number of particles
collision unit volume with energy greater or equal to
activation energy
Particle size 1. Pressure increase  rate constant also increases.
decreases 2. Concentration increase
Catalyst Increase rate
(Surface Area constant
Increase)
Frequency of Effectiveness of Frequency of

collisions collisions(%) effective
collisions
1000 1% 10
10,000 1% 100
100,000 1% 1000
Factors Increases frequency of collisions

1. Concentration
2.  Pressure
3.  Surface Area Increases frequency of effective collisions
4. Temperature
( molecular speed) Increases rate
Frequency of Effectiveness of Frequency of

collisions collisions(%) effective collisions
1000 1% 10
1000 10% 100
1000 50% 500
Factors Increases frequency of effective

1. Temperature collisions
(average kinetic energy)
2. Catalyst Increases rate
(lowers activation energy)

Notes
Factor #1: Concentrations of Solutions
 The rate of reaction increases when the concentration of reactant is

increased.
Reason: When concentration increases, the number of reactant particles per

unit volume increases, frequency of collisions increases.
Hence, the frequency of effective collisions between reactant
particles also increases.
Factor #2: Pressures of Gases
 The rate of reaction increases when the pressure exerted on the

gaseous reactants increases.
Reason: When pressure increases, the number of gaseous reactant particles

per unit volume increases, frequency of collisions increases.
Hence, the frequency of effective collisions between reactant
particles also increases.
Factor #3: Particle size (solids)
 The rate of reaction increases when particle size of solid reactants

decreases.
eg, the reaction between Mg and HCl(aq) is faster, when powdered Mg
is used rather than Mg strip.
Reason: When particle size of a solid decreases, number of sites of collisions
increases, frequency of collisions increases. Hence, the frequency
of effective collisions between reactant particles also increases.

Notes
Factor #4: Temperature
 The rate of reaction increases when the temperature increases.

Reaction rate
 Reasons: is roughly
doubled by a
1. When temperature increases, the reactant particles have 10 K rise in
temperature
higher average kinetic energies, a greater fraction of the particles
will have energy greater than or equal to the activation energy required
for reaction. Hence, there will be a higher frequency of collisions
resulting in higher frequency of effective collisions.
fraction of particles with

fraction of E > Ea at T1
T1
particles
fraction of particles with
T2 E > Ea at T2
T2 > T1
energy
Ea
Note :
At higher temperature:
The peak of the graph is lower and shifts to the right.

The tail end of the graph is higher.
2. The rate constant k increases as the temperature increases.

Reason: Rate = k[reactant]n
When temperature increases, the rate of reaction also
increases. Since [reactant] remains constant, there must
be an increase in the rate constant, k.

Notes
Factor #5: Use of Catalysts
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
 A catalyst is a substance which increases the rate of a reaction by

providing an alternate reaction pathway of lower activation energy.
energy
II
progress of reaction
 A catalyst remains chemically unchanged at the end of the reaction.
 The use of a catalyst increases the rate of a reaction.

Reasons:
 A catalyst provides an alternate reaction pathway of lower activation
energy. Hence, a greater fraction of the reactant particles will have
energy greater than the reduced or lowered activation energy
required for reaction. Hence, the frequency of effective collisions
increases.
 The rate constant k increases when a catalyst is used.

Reason: Rate = k[reactant]n
When a catalyst is used, the rate of reaction increases. Since [reactant]
remains constant, there must be an increase in the rate constant k.

Notes
Features of a catalyst
 A catalyst is usually unchanged in quantity but may change physically
at the end of reaction. For example, pellets may become powder.
 A small amount of catalyst is usually sufficient to bring about a rapid
increase in reaction rate. Increasing the amount of catalyst indefinitely
does not mean that the rate will keep increasing indefinitely.
 Each catalyst is specific in character. One may catalyse a class of
reactions but not for all other reactions.
 A catalyst generally increases the rate constant, k, for a reaction.
 A catalyst alters the reaction mechanism and hence the order and rate
equation (covered in the next section).
Types of 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
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
There are two types of catalyst

 Homogeneous catalyst – catalyst in the same physical state as the
reactants
Example : reaction between peroxodisulphate ions and iodide ions (I(aq))
catalysed by Fe2+(aq) or Fe3+(aq).
 Heterogeneous catalyst – catalyst in a different physical state from the

reactants
Example: Haber Process, an important industrial reaction to produce
ammonia, uses a solid iron catalyst to speed up the reaction.
Fe(s)
N2(g) + 3H2(g)  2NH3(g)

Notes
Enzymes
(k) describe enzymes as biological catalysts (proteins) which may have specific Hydrogen
activity peroxide,
which is
(l) explain the relationship between substrate concentration and the rate of an
strongly
enzyme-catalysed reaction in biochemical systems oxidising, is
physiologically
harmful. For
Enzymes are complex proteins which catalyse biochemical reactions. Most are this reason,
the blood and
very selective in the reactions that they catalyse, and some are absolutely livers of
mammals
specific, operating for only one substance in only one reaction. contains an
enzyme,
Title: “Key-and-lock” model of enzymatic catalysis. catalase,
which
catalyzes the
decomposition
of hydrogen
peroxide into
water and
oxygen.
1. Within the structure of the enzyme, there is an active site with a specific
shape. Only a substrate (reactant) with the correct shape can fit into it.
2. The enzyme and substrate slot together to form a complex. In this complex,
the bonds within the substrate are usually weakened, enabling it to react
with a lower activation energy.
3. Products are formed having a different shape as the reactants. They could
not stay in the active site and thus the complex breaks up.
4. Products leave the enzyme and the enzyme is free for further catalytic
action.
The rate of an enzyme-catalysed reaction depends on [enzyme], [substrate],

pH, and temperature.
In an enzyme-catalysed reaction,
 [enzyme] is usually very small compared to [substrate]
 the rate of reaction is directly proportional to [enzyme]; i.e. reaction is first
order w.r.t. enzyme).
This is because the active sites on the enzyme are saturated with the
substrate molecules; i.e. all the active sites on the enzyme has a substrate
bound to it – and any increase in [enzyme] would lead to an increase in the
rate of reaction.

Notes
Relationship between substrate concentration and the rate of an

enzyme-catalysed reaction in biochemical systems
For a fixed amount of enzyme, there is a finite number of active sites in the
enzyme.
 At low [substrate], the active sites are not filled and rate = k[substrate];
i.e. rate is proportional to [substrate] and the reaction is first order w.r.t.
the substrate (region A).
 When [substrate] increases, more of the active sites on the enzymes are
occupied, rate of reaction increases.
rate
 At high [substrate], increasing its
concentration has no effect at all on the rate
Region Region
of reaction; A B
i.e. reaction is zero order with respect to

the substrate (region B).
At this point, all the active sites of the [substrate]

enzyme is saturated with substrate. Each
enzyme binding site / active site has a substrate bound to it, and all the
enzyme molecules are continuously catalysing the conversion of substrate
to product (i.e. no change in the rate of reaction).
rate
profit
Legends :
[Substrate] = Customers
Region Region
[Enzymes] = Tables A B
Rate = Profit
= $10 per customer
Region A Region B [substrate]

customers
table table table table table table table table table table
table table table table table table table table table table
Profit
Profit===$$$100
Profit 20
40
60
80 No table
Profit = $ 100

Notes
Denaturation
Enzymes are denatured by high temperatures and extremes pH.
The 3-D structure of enzymes is altered and its catalytic
rate of reaction
activity is destroyed.
 Enzymes only work well over a narrow pH range Region Region
A
(about 5 – 8) and over a narrow temperature range B
(about 20 – 50 °C).
 With increasing temperature, the rate of enzyme-
catalysed reaction increases at first (due to the
temperature
increase in temperature – increase in effective
collisions), and then decreases as temperature increases (as the enzyme
starts to denature).
 Denaturation destroys an enzyme activity irreversibly.
The role of catalysts in our daily lives (Self-read)
 Cataytic converters in vehicles to convert harmful emissions (NO, CO

and unburnt hydrocarbons) to less harmful products, N2, CO2 and H2O.
In Singapore,all petrol-driven vehicles are fitted with three-way catalytic
converters to meet Euro II exhaust emission standard, which was effective as of
1st Jan 2001.
1. Reduction of nitrogen oxides to nitrogen and oxygen: 2NOx → xO2 + N2

2. Oxidation of carbon monoxide to carbon dioxide: 2CO + O2 → 2CO2
3. Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water:
CxH2x+2 + [(3x+1)/2]O2 → xCO2 + (x+1)H2O..
 Catalytic role of oxides of nitrogen in the formation of acid rain

The main cause of acid rain is sulfur dioxide. It is oxidised to give sulfur trioxide
which reacts with rain water to give very dilute sulfuric acid.
Nitrogen dioxide acts as a homogenous catalyst in the conversion of sulfur

dioxide into sulfur trioxide.
The nitrogen dioxide first oxidises sulfur dioxide to sulfur trioxide. In the process,
the nitrogen dioxide is reduced to nitrogen monoxide.

Notes
Now the nitrogen monoxide is converted back to nitrogen dioxide again by

reaction with oxygen.
So, the nitrogen dioxide is regenerated at the end of the reaction, and can go on
to do the same thing again.
Various countries reduces the production of oxides of nitrogen and sulfur dioxide
by capping emissions from power plants or vehicles, reducing the use of fossil
fuels or using alternative sources of energy. For example, in Singapore, cleaner
petrol for motor vehicles with less than 0.005% sulfur content was enforced in
October 2013 to align to the Euro IV emission standards.
Autocatalyst (Self – Read)
When a product of a chemical reaction acts as a catalyst in the reaction,

the catalyst is said to be an autocatalyst.
An autocatalysed reaction is slow initially and then becomes more rapid as
the catalyst is produced in the reaction.
[reactant] [product]
time time
An example of an autocatalysed reaction

2MnO4− + 5C2O42− + 16H+  2Mn2+ + 10CO2 + 8H2O
Mn2+ is the autocatalyst in this reaction. Once it is formed, the reaction
rate will increase rapidly and will slow down only when concentration of
the reactants becomes low.

Notes
REACTION MECHANISM
(b) iii) verifying that a suggested reaction mechanism is consistent with the
observed kinetics
A balanced equation for a chemical reaction indicates the substances present

at the start of the reaction and those produced as the reaction proceeds. It does
not provide information on how the reaction occurs. The process or the steps
by which a reaction occurs is called the reaction mechanism. Reaction kinetics
can provide details of this aspect of a reaction.
Elementary Reaction
We have seen that reactions take place as a result of collisions between reacting
molecules. For example, the reaction of NO and O3 appears to occur as a result
of a single collision involving suitably oriented and sufficiently energetic NO and
O3 molecules:
Overall equation: NO(g) + O3(g)  NO2(g) + O2(g)
This process occurs in a single step and is called an elementary reaction.
Rate = k [NO][O3]
transition state
Energy
Ea
NO + O3
Enthalpy change of reaction
NO2 + O2
Reaction coordinates
Notes
Reaction involving multistep mechanism

NO2 can react with CO to form CO2 and NO.
Overall equation: NO2 + CO → NO + CO2
The mechanism of the reaction is as follows:

Step 1 NO2 + NO2 → NO3 + NO slow
Step 2 NO3 + CO → CO2 + NO2 fast
The slowest step in the reaction mechanism determines the rate of the
overall reaction, and is called the rate determining step.
Rate = k [NO2]2
Energy
Ea2
Ea1
AB + B
A + 2B AB2
Reaction coordinate
Energy profile diagram of a Reaction Mechanism
Mechanism Correspond Energy profile diagram

to
Number of steps in Number of peaks

mechanism
Slowest step in mechanism Peak with the largest Ea
Important Points to note:

 For each step in the mechanism, a rate equation can be written.
 The rate equation for the overall reaction is the one with the slowest
step. In an elementary reaction, the overall reaction is also the slowest step
since it’s a one step process.
Reactants of the slow step = reactants in the rate equation
Coefficients of the reactants in the slowest step = orders of reaction
 It is incorrect to assume a process is an elementary process unless this is
specified in the question.

Notes
Writing a proposed multistep mechanism
Step 1
Using the rate equation, construct the rate determining step (slow step),
propose a suitable intermediate formed from the reactant.
Step 2
Use the overall equation, subtract the equation for the rate determining step.
( Overall equation ) – ( Equation for rate determining step )

= ( Overall equation ) + ( Reversing equation for rate determining
step)
Consider the hypothetic reaction:

Overall equation : A + 2B  AB2
Rate = k [A] [B]
The mechanism is proposed as follows: Overall : A + 2B  AB2

+
Step 1: A + B  AB (slow) Reverse : AB  A+B
equation A
for r.d.s AB + B  AB2
Step 2: AB + B  AB2 (fast)
Overall: A + 2B  AB2
Note : All the steps of the mechanism adds up will give the overall
equation
Example
Overall equation : 2NO + Cl2  2NOCl
The rate law is thought to proceed via the following two step mechanism :
NO + Cl2  NOCl2 (fast)
NO + NOCl2  2NOCl (slow)
Determine the rate law.
Solution:
Rate = k[NO][NOCl2]
Example
Propose a mechanism consistent with the observed rate equation for
2H2O2(aq)  2H2O(l) + O2(g)
Rate = k [H2O2]
Solution:
Step 1: H2O2  H2O + O (slow)
Step 2: H2O2 + O  H2O + O2 (fast)

Notes
devise a suitable experimental technique for studying the rate of a reaction, from
given information
INTRODUCTION
Reaction rates can be determined by monitoring the change in concentration of

any one of the substances in the reaction mixture during the course of the
reaction. There are generally two methods of doing so, namely the chemical
method and the physical method.
CHEMICAL METHOD (Continuous Rate Method)

In this method, the concentration of any one of the substances is monitored via Quenching:
slowing the
volumetric analysis. reaction
abruptly at the
The steps of the general procedure are as follows: measured time
to prevent
1. The reaction is carried out in a thermostatically controlled water bath. further
changes in
2. Reactant solutions of known concentrations are mixed and a stop-watch is concentration
before
started. analysis.
3. A sample of the reacting mixture is withdrawn at a suitable time interval with

A quenching
a pipette and the reaction in the sample is quenched by either: agent reacts
immediately
 sudden cooling by adding large amount of ice water, with one of the
reactants and
 or removing a reactant by pipetting into an excess of a quenching reagent. so, stops the
reaction.
4. A titration is then performed to determine the concentration of any one of the
species in the quenched sample.

Notes
Case Study: Alkaline hydrolysis of an ester
CH3CO2C2H5(aq) + NaOH(aq)  CH3CO2Na(aq) + C2H5OH(aq)
Procedure:
1. Separate solutions of the ester and alkali solution of known concentrations
are allowed to reach the temperature of a thermostat bath.
2. The solutions are mixed and the time of mixing is noted.
3. After a suitable time interval, a sample of the reaction mixture is withdrawn

by a pipette and run into a large volume of ice cold water. This dilution and
sudden cooling reduce the reaction rate to almost zero.
4. The remaining alkali in this sample is titrated against standard acid using
phenolphthalein as the indicator, hence determining its concentration.
5. The analysis (step 3 and 4) is repeated at various intervals of time after the
start of the reaction.
6. A graph of concentration of alkali against time can be plotted. Its gradient

corresponds to the rate of the reaction.
d[CH3CO2C2H5 ] d[NaOH]
Rate =  
dt dt
7. Since the volume of acid used in the titration is directly proportional to the
concentration of the remaining alkali, the rate may also be found by plotting
a graph of volume of acid used against time.
[NaOH] / Volume of
mol dm-3 acid / cm3
time / s time / s

Notes
PHYSICAL METHOD
The rate of reaction can be determined by monitoring an appropriate physical
property which will alter during the course of the reaction. The property chosen
must be in some way proportional to the concentration of any one of the
species in the reaction mixture.
Volume measurement of gas

The progress of a reaction which produces a gas can be followed by measuring
the volume of the gas produced at regular intervals. Some examples of such
reactions include the action of acid on carbonates, the action of acid on metals
and the decomposition of H2O2.
Case Study: Reaction between CaCO3 and HCl
CaCO3(s) + 2HCl(aq)  CaCl2(aq) + CO2(g)
Procedure:
Carbon dioxide collects in

the syringe. The volume can
be read
tangent
volume of gas
x
Hydrochloric acid
O t1
Calcium carbonate time / s
1. The apparatus above is set up to monitor the volume of CO2 gas produced.
2. Hydrochloric acid of known concentration is added to the CaCO3 in a flask and
a stop watch is started.
3. Volume of CO2 gas collected in the gas syringe is recorded at regular time
interval.
4. A graph of volume of O2 gas produced against time can be plotted. The rates
at the various times may be determined from the gradients of the tangents at
the respective times.

Notes
The order of reaction may be found by plotting (Vn – V t) against time
where Vt = volume of gas at time t

Vn = volume of gas at the end of the reaction
(Vn – Vt)  concentration of reactant remaining at time t.
reactant product
start x 0
At time = t Vt
V reactant remaining V – V t
end 0 V
Change in pressure of gas

The progress of a reaction between gases can be followed by measuring
Pressure 
changes in pressure at regular intervals. However, it must be ensured that the number of moles
of gas at
reaction is performed in a constant volume closed system. This method works constant V and T
only for gas reactions in which there is a change in the number of moles of
gas. The rate of the reaction can then be determined by plotting the pressure
against time.
Example:
For which of the following reactions can the rate of reaction be monitored via
changes in pressure?
(i) 2N2O5(g)  4NO2(g) + O2(g)
(ii) 2H2(g) + O2(g)  2H2O(g)
(iii) N2(g) + 3H2(g)  2NH3(g)
(iv) SO2(g) + NO2(g)  SO3(g) + NO(g)

Notes
Change in intensity of coloured reaction mixtures

Since the colour intensity of a substance varies with its concentration, the This is also
known as the
progress of the reaction may be followed by measuring the colour intensity at colorimeter
regular intervals using a colorimeter. This method is useful when one of the method
species in the reaction mixture is coloured. The rate of the reaction can then be
determined by plotting the colour intensity against time.
Beer’s law:
Narrow beam of filtered light of A = bc
appropriate wavelength
A = absorbance
C = concentration
Photo-cell Meter
Solution under test
Examples of such reaction include:
(i) Oxidation of HI by H2O2
2HI(aq) + H2O2(aq)  I2(aq) + 2H2O(l)

colourless brown
(ii) Reaction between Br2 and HCOOH
HCOOH(aq) + Br2(aq)  2HBr(aq) + CO2(g)

red-brown colourless
Change in conductivity
The progress of a reaction between gases can be followed if there is a change in

number of moles of ions by measuring changes in electrical conductivity
at regular intervals.
Example : BrO3  + 5 Br  + 6 H +  3 Br2 + 3 H2O

Notes
Discontinuous method (encountered in practical : Self – Read)
Objective: To investigate the effect of [S2O32−] on reaction rate for:
S2O32−(aq) + 2H+(aq)  H2O(l) + SO2(g) + S(s)
1. Five samples of Na2S2O3 solution are prepared in similar beakers which are
placed over a piece of white paper marked clearly with a cross.
2. 10 cm3 of 1.0 moldm−3 HCl is added to each individual sample and the time
taken for the cross to become obscured by the sulfur suspension is
recorded.
Results:
Sample Composition / cm3 Time VNa2S2O3 x t
taken for
Sample Volume of cross to V 2Na2S 2O3 x t
Volume of
0.150 moldm−3 vanish
water constant
Na2S2O3 /s
1 50 0 28.6 1430 71500
2 40 10 35.1 1404 56160
3 30 20 45.6 1368 41040
4 20 30 69.0 1380 27600
5 10 40 154.0 1540 15400
Note:
 Volume of HCl is kept constant  [HCl] is kept constant
 Total volume of reaction mixture for all experiments must be constant.
 Volume of Na2S2O3 solution used is proportional to its concentration.
Evaluation:
If we assume rate of reaction is 1st order w.r.t. Na2S2O3
Hence rate = k [S2O32−]
Since rate  1/t and [S2O32−]  Volume of S2O32−
 1/t = k (Volume of S2O32−)
Implies that V Na 2S2O3 x t = constant
If we assume rate of reaction is 2nd order wrt Na2S2O3

Hence rate = k [S2O32−]2
 1/t = k (Volume of S2O32−)2
Implies that V2 Na 2S2O3 x t = constant

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Teacher’s Copy

YISHUN JUNIOR COLLEGE

DEFINITIONS OF REACTION RATE

 Initial rate is the rate of reaction at time, t = 0.

 Instantaneous rate is the rate of reaction at any given time.

 Average rate is the total concentration of reactant used or total concentration

of product formed over total time.

Chung LS / YJC / 2018 / Teacher’s Copy Page 2 of 38

Graph of [reactant]remaining against time Graph of [product] against time

[reactant] / mol dm-3 [product] / mol dm-3

[reactant] / mol dm-3 [product] / mol dm-3

[reactant] / mol dm-3 [product] / mol dm-3

Chung LS / YJC / 2018 / Teacher’s Copy Page 3 of 38

Incorrect ways of writing rate equation: (by students)

Example: Decomposition of dinitrogen pentoxide (N2O5) The unit for k

Chung LS / YJC / 2018 / Teacher’s Copy Page 4 of 38

Graphs for a zero order reaction

Gradient of the graph = rate

Chung LS / YJC / 2018 / Teacher’s Copy Page 5 of 38

Graphs of a first order reaction

Graphs of a second order reaction

rate rate [A]

[A]o Half-life NOT constant

0 [A] 0 [A]2 0 time

Chung LS / YJC / 2018 / Teacher’s Copy Page 6 of 38

 The rate constant, k, is the constant of proportionally in the

 Rate constant is dependent on temperature and the presence of k is a constant

Chung LS / YJC / 2018 / Teacher’s Copy Page 7 of 38

The units of rate constants

Overall Order General

Chung LS / YJC / 2018 / Teacher’s Copy Page 8 of 38

Concept of Half – life

The half-life ( t 1 2 ) of a reaction is the time taken for the concentration of a

[reactant] mol dm-3 [product] mol dm-3

t (1) t (3) t (2)

Chung LS / YJC / 2018 / Teacher’s Copy Page 9 of 38

Determination of half – life of a reactant from a product

[product] reactant product

When the second half life is reached, half the remaining

Calculate rate constant,k using half – life

For 1st order only :

rate constant, k , can be calculated.

Determine number of half – lives, n

1 n Final concentration of reactant

Chung LS / YJC / 2018 / Teacher’s Copy Page 10 of 38

Therefore, [H2O2] after 100 days = ( ½ )5 x 0.100

Pseudo First Order Reactions

Determining half – life of a pseudo first order reaction :

Chung LS / YJC / 2018 / Teacher’s Copy Page 11 of 38

Methods for Determining Order of Reaction

Order of Reaction Zero One Two

time time time

Chung LS / YJC / 2018 / Teacher’s Copy Page 12 of 38

Initial Rate Method

To determine x, the order of reaction with respect to reactant A:

When [A] is doubled, the initial rate increases by four times.

Chung LS / YJC / 2018 / Teacher’s Copy Page 13 of 38

To determine y, the order of reaction with respect to reactant B:

(c) Rate = k [A]2[C]

Chung LS / YJC / 2018 / Teacher’s Copy Page 14 of 38

Bromoethane, CH3CH2Br, can be hydrolysed by heating with aqueous sodium

CH3CH2Br(aq) + NaOH(aq)  CH3CH2OH(aq) + NaBr(aq)

[CH3CH2Br]/mol dm3 [CH3CH2Br]/mol dm3