William L Masterton

Cecile N. Hurley
http://academic.cengage.com/chemistry/masterton
Edward J. Neth University of Connecticut
PHYSICAL
CHEMISTRY
Nor Azira Irma Muhammad
UiTM Perlis

azira_irma@perlis.uitm.edu.my
3.1 Rates of reaction

3.2 Factors affecting rates of reaction

3.3 Rate Law and order of reaction

3.4 Methods to determine order of reactions



2
Chemical kinetics- a branch of chemistry that deals with the rate
of chemical reaction
Many chemical reactions are fast reactions, especially those
involved reactions between oppositely charged ions in aqueous
solution (e.g, neutralisation, precipitation reaction)
Reaction involving organic compounds are usually slow reactions
because they involved breaking and making covalent bonds

Reaction rate:
Rate of reaction the change in concentration of a reactant with
time (M/s)
Consider the following reaction:
C
4
H
9
Cl + H
2
O C
4
H
9
OH + HCl

The above reaction was conducted using 0.1 M butyl chloride
aqueous solution and its concentration was determined as a function
of time
3
Graph of concentration C
4
H
9
Cl vs time was plotted



4
[C
4
H
9
Cl]
Time (s)
Rate of reaction = concentration
time.

= decrease in concentration of butyl chloride
time taken
= - d [C
4
H
9
Cl]
dt


The average rate = concentration
(of the first 50 s) 50 s
(value taken from table / expt)
The instantaneous rate is a rate of change at particular instant in
time
The instantaneous rate at time t = gradient (slope) of the tangent to
the curve at time, t (specific time)






The instantaneous rate at the start of the reaction (t = o) is called
the initial rate
Initial rate = gradient (slope) of the tangent to the curve at time = 0
5
concentration
time
t
Instantaneous
rate
initial rate
time
concentration
example;

the instantaneous rate at t
= y
2
- y
1
mol dm
-3
s
-1
x
2
- x
1
x
2
x
1
y
1
y
2
example;

the initial rate
= y
2
- y
1
mol dm
-3
s
-1
x
2
- 0

y
1
y
2
0
x
2
(1) Collision theory
(2) Transition state theory
1) Collision theory

Three ideas;
i. Molecules must collide to react
ii. Molecules must posses a certain minimum kinetic energy,
called the activation energy, E
a
to initiate the chemical
reaction. (otherwise they are unable to react)
iii. Molecules must collide in the right orientation

The basis concept of collision is that, for the reaction between
two particles to occur, an effective collision must take place
Not all collision are effective in producing reaction, but only
small proportion of the molecules react after collision
Collision frequency of reaction = total number of collision
between molecules per unit time at specific T


6
The effect of concentration on the rate of reaction
the reaction rate will increase if the concentration of one or
more reactant increase
[ ] high, frequency of collision high, because more particles
present in the same volume and more likely to collide - probability
of collision with sufficient energy for reaction to occur. So, rate
of reaction increase.

The effect of temperature
Rate of chemical reaction increase with T increase
At higher T, Arhenius suggested colliding molecules can react only
if they have total kinetic energy equal or greater than Ea
(activation energy)
Ea (activation energy) is a minimum amount of energy required to
initiate a chemical reaction, which means that Ea is a minimum
kinetic energy that molecules must possess in order for a
chemical reaction to occur
Ea is shown on diagram called reaction profiles /energy profile
- Energy versus progress of reaction
7
8
H
reactant
H
product
Ea
energy
energy
Progress of reaction
Progress of reaction
Ea
reactants
reactants poducts
poducts
H = - ve
H = +

ve
a) Reaction profile of an exothermic reaction b) Reaction profile of an endothermic reaction
Ea = activation energy

H = difference in energies between reactant and product/ heat of reactions
= H product H reactants
2) The transition state theory

This theory focus on what happens to the reactant molecules as
they change into products
The presence of a transitory intermediate stage (that lies
between the reactants and the products) which is called the
transition state, which involved hypothetical species is
activated complex

e.g : H-H + Cl [H----H---Cl] H. + HCl
reactants activated complex products

The complex does not always changed to product. (if it does, it
means that the reaction is occuring / proceed to give the
product)
The reaction progress on x- axis for diagram of reaction
profile represents the extent of the reaction.
The reaction starts with the reactants on the left, progress
through an activated complex (transition state), and ends with
the products on the right.
The activated complex is very unstable. The energy gap
between energies of the reactants and the activated complex is
called the Ea.



9
The rate law is an equation that relates the rate of reaction to the
concentration of the reactants. This rate law can only be
determined by experiment

Example: aA + bB cC + dD

If the rate is to the concentration of A only and not B, then
Rate of reaction [A] [B]
0
Rate of reaction = k [A][B]
0

= k [A]
The reaction is said to be first order with respect to A and zero
order with respect to B
The overall order is 1 + 0 = 1, that is first order

10
Rate = k [A]
m
[B]
n

(the expression is called rate law / rate equation)
m = order of reaction with respect to A
n = order of reaction with respect to B
Overall order of reaction = m + n

The proportionality constant, k is called the rate constant.

k value depends on the specific reaction, the temperature of
the reaction and the presence of a catalyst (if any).

The larger value of k, the faster a reaction proceeds. Once the
k and order of reaction are known, the reaction rate can be
predicted for any concentration of A and B

11
The order of reaction (m + n) and the rate constant
(k) can be determined by using:

I. The reaction rate method

II. The linear plots

III.The half-life method, t
1/2

IV. Initial rate method




12
The order of reaction can be found by plotting a reaction
rate against the concentration

13
k
rate rate rate
[A] [A] [A]
First order Zero order Second order
y= kx y= kx
2
y= k

Example:
Bromine reacts with methanoic acid according to the equation:


The table below shows the rates of reactions at specific concentrations

) ( 2 ) ( 2 ) ( ) (
2
aq H aq Br aq HCOOH aq Br
+
+ +
14
[Br
2
] mol dm
-3
Rate (10
-5
mol dm
-3
s
-1
)
8.0 2.75
7.0 2.40
5.0 1.70
4.0 1.35
2.0 0.70
Show that the reaction between bromine and methanoic acid is a
first order by
a) calculation
b) A graphical method
Solution:
a) Calculation (Refer to the table)
when the concentration of bromine is doubled, the rate of reaction is doubled.
Thus, the reaction is first order with respect bromine. so, rate [Br
2
].

b) By graph


0
0.5
1
1.5
2
2.5
3
0 2 4 6 8 10
[Br2]
R
a
t
e

o
f

r
e
a
c
t
i
o
n
15
A sloping straight line graph is obtained, when the graph of rate against
concentration is plotted. This shows that the reaction is first order with
respect to bromine
Rate [Br
2
]
The order of reaction can be found by plotting a linear plots
with respect to a given reactant

16
ln [A]
t
time
y
x
time time
x
y
x
y
[A]
t
1/ [A]
t
Slope = y / x
= - k /2.303
First order Zero order second order
Slope = y / x
= k
Slope = y / x
= - k
A first order reaction with respect to a reactant A, is a reaction in
which the rate of reaction is directly proportional to the
concentration of A.
If the concentration of a reactant is doubled, the rate of reaction
is also doubled.
The rate equation for a first order reaction is,
rate reactions = k [A]
where, k = rate constant
[A] = concentration in mol dm
-3
the unit of k is time
-1
(that is s
-1
, min
-1
, h
-1
)
Examples of first order reactions:
i. Radioactive decay


ii. Catalytic decomposition of hydrogen peroxide

iii. Thermal decomposition of dinitrogen pentoxide
| | U k e radioactiv of rate
He Th U
238
92
4
2
234
90
238
92
=
+
) ( ) ( 2 ) ( 2
2 2 2
gas O liq O H aq O H +
17
2 4 2 5 2
2 2 O O N O N +
For the reaction:
A products
Having the rate law :
where [A]
t
= concentration of A at time t

Rearrange the expression:


| |
| | A k
dt
A d
reaction of rate = =
18
| |
| |
| |
| |
| |
| |
| | | |
| | | |
o t
o t
t
o
A
A
A n l kt A n l
kt A n l A n l
dt k
A
A d
tegrate in
dt k
A
A d
t
O
+ =
=
=
=
} }
:
ln [A]
t
t
A straight line with -ve slope
19
Rate = - d [A] = k[A]
1
dt

d[A] = - k[A]
1
dt
Integrate:

} 1 d[A] = }- k dt
[A]

ln [A]
t
= - kt + c , t = 0 c = ln [A]
0


ln [A]
t
= - kt + ln [A]
0







ln [A]
t
t
A straight line with -ve slope
A B
(reactant) (product)
y -mx
c

CH
3
CO-C
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH

For example, the hydrolysis of ethyl ethanoate is first order
respect to the ester and first order with respect to the water and
acid.
In the presence of excess H
2
O and H
+
,

only a small fraction of acid
or water used in reaction
The constant of acid and water hardly alter during the course of
the reaction
So, the reaction appear to be zero order with respect to the acid
and water and the rate of hydrolysis is depend only on the
concentration of ester

Rate of hydrolysis = k [ ester]
Thus, acid hydrolysis of ester is first order
The order of reaction which sometimes altered by the conditions
20
O
[H
+
]
A second order reaction is a reaction in which the reaction
rate is proportional to the product of the concentrations two
reactants
The rate equation for a second order reaction is,
rate = k [A] [B] or rate= k [A]
2
where, k = rate constant
[A] = concentration in mol dm
-3
the unit of k is dm
3
mol
-1
time
-1

Examples of second order reactions:
i. The hydrolysis of iodomethane is second order


i. The thermal decomposition of hydrogen iodide is second
order

] [ ] [
) ( ) ( ) ( ) (
3
3 3
NaOH I CH k hydrolysis of rate
aq NaI liq OH CH aq NaOH liq I CH
=
+ +
21
2
2 2
] [
) ( ) ( ) ( 2
HI k ion decomposit of rate
gas I gas H gas HI
=
+
Rate of reaction = - (rate of disappearance of A) = k [A]
2

| |
| |
| |
| |
| |
| |
| | | |
| | | |
o t
o t
o
t
A
kt
A
A
kt
A
A
C t
c kt
A
dt k
A
A d
kdt
A
A d
A k
dt
A d
1 1
1 1
1
, 0
] [
1
] [
2
2
2
+ =
+ =
= =
+ =
=
=
=
} }
22
A straight line graph with a + ve slope
1/[A]
t
y mx c
The rate of zero order reaction does not depend on the
concentration of the reactants
For zero order reaction, the rate law is
rate = k [A]
0
= k
where, k = rate constant
[A] = concentration in mol dm
-3
the unit of k is mol dm
-3
time
-1

Examples of zero order reactions:
i. Reaction between iodine and propanone


The reaction is slow, even at high temperature. However,
addition of dilute acid provides H
+
ion which catalyze the
reaction. The graph of the reaction rate against the iodine
concentration is a straight line parallel to the horizontal
axis. This means reaction rate remains constant even
though the reactant, iodine is being used. Thus, the
reaction is zero order with respect to iodine


) ( ) ( ) ( ) (
2 3 2 3
aq HI aq I COCH CH aq I aq COOH CH + +
23
| |
| |
| |
| |
| |
| | | |
| |
| | | |
o
o
o
o
A kt A
A C
A A o t at
C kt A
dt k A d
kdt A d
kdt A d
k A k
dt
A d
+ =
=
= =
+ =
=
=
=
= =
} }
,
] [
24
[A]
t
A straight line graph with -ve slope
y c mx
t
t
The half-life, t
1/2,
of a reaction is the time required for the
concentration of a reactant to decrease to half-life of its initial
concentration
i. For the first order reaction the half life is independent
of the initial concentration
Thus first half-life (t
1/2
) = Second half-life (t
1/2
)

2
1
2
1
693 . 0
2
t
k
or
t
n l
k
=
=
25
[A], concentration
Times (minutes)
12

10

8

6

4

2


t
1/2
t
1/2
t
1/2
0 2 4 6
First order reaction
3

1.5 -
-
-
-
-
-
ii. For the second order reaction, the half life is inversely
proportional to the initial concentration. Thus, second half
life (t1/2) =2t1/2

| |
2
1
1
0
t A
k

=
26
t
1/2
Second order reaction
[A]
times
2t
1/2













5
2.5
10
-
-
-
-
-
iii. For the zero order reaction, a sloping straight line is
obtained
2
0
1
2
] [
t
A
k =
27
Zero order reaction
[A]
times
n
A
A
r
r
|
|
.
|

\
|
=
2
1
2
1
28
Where:
r
1
and r
2
= initial rates of experiment 1 and 2 respectively

A
1
,A
2
, B
1
& B
2
= initial concentration of A and B for experiment 1
and 2 respectively

m = order of reaction with respect to A
n = order of reaction with respect to B



r
1
= k [A]
1
[B]
1
r
2
= k [A]
2
[B]
2




m n
m n
m
Example;

Reaction A + 2B C have been studying at 25C and the result
are shown below.














Determine the

a) rate law or rate of equation
b) order of reaction
c) rate constant, k
d) write the rate equation for the reaction





Exp [A]
(mol dm
-3
)
[B]
(mol dm
-3
)
Initial reaction rate
(mol dm
-3
s
-1
)
1 0.1 0.1 5.5 x 10
-6
2 0.2 0.1 2.2 x 10
-5
3 0.4 0.1 8.8 x 10
-5
4 0.1 0.3 1.65 x 10
-5
5 0.1 0.6 3.3 x 10
-5
29
30
To find order of reaction for A
consider exp. 1 and 2, where [B] is
keep constant that is [B] = 0.1

So, we have r
1
=5.5 x 10
-6
,
r
2
= 2.2 x 10
-5

A
1
=0.1
A
2
=0.2

To find order of reaction for B
consider exp. 4 and 5, where [A] is
keep constant that is [A] = 0.1

So, we have r
1
=1.65 x 10
-5
,
r
2
= 3.3 x 10
-5

B
1
=0.3
B
2
=0.6

A respect to with
order second is reaction the Thus,
2
5 . 0 25 . 0
5 . 0 25 . 0
1 . 0
1 . 0
2 . 0
1 . 0
10 2 . 2
10 5 . 5
5
6
2
1
2
1
2
1
=
=
=
|
.
|

\
|
|
.
|

\
|
=
|
|
.
|

\
|
|
|
.
|

\
|
=

m
g l m g l
x
x
B
B
A
A
r
r
m
n m
n m
a) So, rate of reaction or rate law = k [A]
m
[B]
n
=

k [A]
2
[B]
1

b) And order of reaction = m+ n = 2 +1 =3

B respect to with
order first is reaction the Thus,
1
5 . 0 5 . 0
5 . 0 5 . 0
6 . 0
3 . 0
1 . 0
1 . 0
10 3 . 3
10 65 . 1
5
5
2
1
2
1
2
1
=
=
=
|
.
|

\
|
|
.
|

\
|
=
|
|
.
|

\
|
|
|
.
|

\
|
=

n
g l n g l
x
x
B
B
A
A
r
r
n
n m
n m
( ) ( )
1 6 2 3
3
2
3
1 3 6
2
10 5 . 5
1 . 0 1 . 0
10 5 . 5
] [ ] [
] [ ] [
2



=
=
=
=
s dm mol x
moldm moldm
s moldm x
B A
reaction of rate
k
B A k reaction of rate
31
c) Rate constant, k
- can use exp 1, 2, 3,4 & 5 for calculation because the value of k
is same for all experiments
d) Write the rate equation
Rate = k [A]
2
[B]
= 5.5 x 10
-3
[A]
2
[B]
1. Titration method
2. Colour changes by visual inspection or by using colorimeter
3. Gas syringe for measuring the volume of gas released
4. Pressure changes
5. Conductivity changes for reactions in which the number of
ions in solution changes
6. Monitoring the rotation of plane polarised light

Example: Titration method

H
2
O
2
+ 2H
+
+ 2I
-
I
2
+ 2H
2
O

Measuring the concentration of I
2
using standard S
2
O
3
-

(thiosulphate). At measured time interval, samples of the
reaction mixture are removed using pipette and titrated with
S
2
O
3
-
32
Is a series of simple steps that lead from the initial reactants to the
final products of a reaction

An elementary reaction represent, at the molecular level, a single
stage in the progress of the overall reaction

One of the main reasons for determining the order of a reaction is to
see whether the experimentally determined overall order sheds any
light on the detailed mechanism by which the reaction occurs

By knowing the reaction mechanism, a chemist can more effectively
control the reaction or predict new reaction

Two requirements must be met:
1) The mechanism must account for the experimentally determined
rate
2) The mechanism must be consistent with the stoichiometry of the
overall/net reaction
33
The exponent in the rate law for an elementary reaction are the same
as the stoichiometric coefficients in the chemical equation for the
reaction (this is not usually the case with the rate law of the overall
reaction)
Reversible reaction
One elementary reaction may be much slower than all the others
the rate determining step

(1) A mechanism with a slow step followed by a fast step.

Example: decomposition of hydrogen peroxide, H
2
O
2

2H
2
O
2
(aq) 2H
2
0 (liq) + O
2
(gas)

In the decomposition of H
2
0
2
, the facts (determined by the
experiment) are:
i. The rate of decomposition of H
2
O
2
is first order in both H
2
O
2

and I
-
(second order overall)
ii. The reactant I
-
(iodide) is unchanged during the reaction (acts as
a catalyst) and therefore does not appear in the equation for the
net reaction.(overall becomes first order)
34
I
-
The mechanism suggested,

Slow step: H
2
O
2
+ I
-
H
2
0 + OI
-
Fast step: H
2
O
2
+ OI
-
H
2
O + O
2
+ I
-

overall/net: 2H
2
O
2
2H
2
0 + O
2


I
-
= is a catalyst (recovered at the end of the reaction)
OI
-
= is an intermediate
The slow step determines the rate of the overall rate
So, the slow step is the rate determining step
We set the reaction rate to that of the slow step;
rate = rate of the slow step = k [H
2
O
2
][I
-
]
rate = k [H
2
O
2
]
where k = k [I
-
] = constant
(the [I
-
] remains constant through out the reaction)

35
(2) A mechanism with a fast reversible step followed by a slow step
The smog forming reaction:
2NO (gas) + O
2
(gas) 2NO
2
(gas)

The rate law investigated experimentally:
rate = k [NO]
2
[O
2
]

Suggested mechanism:
fast step :

slow step : N
2
O
2
+ O
2
2NO
2

overall : 2NO + O
2
2NO
2


The rate equation based on the rate determining step (slow step)
rate = k
2
[N
2
O
2
] [O
2
]

We can state the experimentally determined rate law only in terms of
substances in the net equation. So, we must cancell out/ eliminate N
2
O
2

2NO
k
1
N
2
O
2
k
-1
36
k
2

Fast step:

Forward rate = reverse rate equilibrium
Rate formation of N
2
O
2
= rate of disappearance of N
2
O
2
k
1
[NO]
2
= k
-1
[N
2
O
2
]
[N
2
O
2
] = k
1
[NO]
2

k
-1

Substitute [N
2
O
2
] in the rate- law for the rate-determining
step
rate = k
2
[N
2
O
2
] [O
2
]
= k
2
( k
1
[NO]
2
) [O
2
]
k
-1

= k
2
k
1
[NO]
2
[O
2
]
k
-1

rate = k [NO]
2
[O
2
]

So, the proposed mechanism is consistent with the observed
rate law


2NO
k
1
N
2
O
2
k
-1
37
Example of Question;

For the reaction: H
2
(gas) + I
2
(gas) 2HI (gas)


A proposed mechanism is

fast step :


slow step : 2I
-
+ H
2
2HI
What is
a) The net equation based on this mechanism
b) The order of reaction according to this mechanism

Answer:
a) Net equation: I
2
+ H
2
2HI
b) Rate law for the rate determining step:
rate = k
2
[I
-
]
2
[H
2
] 1
to eliminate I
-
, we assume rapid equilibrium in the first step
rate forward = rate of the reverse reaction
k
1
[I
2
] = k
-1
[I
-
]
2
[I
-
]
2
= k
1
[I
2
]
k
-1

substitute in equation 1
rate = k
2
k
1
[I
2
] [H
2
] = k [I
2
] [H
2
]

k
-1
I
2
k
1
2I
-
k
-1
38
k
2
Arrhenius conducted research on the effects of temperature
on reaction rates
For most reactions, the increase in rate with increasing
temperature is not linear but exponential









Arrhenius equation is useful
in analysing the effect of temperature on the rate constant and
the reaction rate
it allow us to determine the activation energy, Ea, if the value of
the rate constants are known at different temperatures



nt consta rate k
(K) e temperatur T
) Jmol (8.31 nt consta gas R
energy activation Ea
collision) of (frequency nt consta Arrhenius A : where
Ae k
1 1
RT
Ea
=
=
=
=
=
=

K
39
2.303RT
Ea
A g l k g l
RT
Ea
A ln k n l
Ae k
RT
Ea
=
=
=

40
k
T (k)
lg k
1/ T
Gradient = -Ea / 2.303 R
At the temperature high, the rate constant k also high and therefore
the reaction rate also increases

Example:
in the presence of platinum as a catalyst, hydrogen iodide
decomposes to form hydrogen and iodine. The activation
energy for this reaction is 58 KJmol
-1
. Calculate the ratio of
the rate constant at 30C and 20C. Comment on your answer.

Answer:
Let the rate constants at 30C and 20C be represented by k
1

and k
2
, respectively
( )
( )
2 . 2
0 . 1
2 . 2
10 52 . 4
10 9.9
11
11
2
1
20 273 31 . 8
1000 58
30 273 31 . 8
1000 58
2
1
1 1
1
1 1
1
=

= =
=

+

+

k
k
k
k
K K Jmol
Jmol
K K Jmol
Jmol
e
e
41
The calculation shows that for an increase
of 10
o
C, the initial reaction rate increases
by approximately twofold
42
Exercise:
Calculate activation energy, E
a
for the reaction:

2HI H
2
+ I
2
from the k at
(i) 25
0
C = 2.5 x 10
-5
s
-1
(ii) 55
0
C = 1.0 x 10
-3
s
-1
R = 8.314 Jmol
-1
K
-1




Answer:
9.99 x 10
4
J/mol

43
ln k1 = ln A1 - Ea 1 - 1
k2 A2 8.314 T
1
T
2


ln 2.5 x 10
-5
s
-1
= ln A1 - Ea 1 - 1

1.0 x 10
-3
s
-1
A2 8.314 298 328

-3.688 = -Ea (3.069 x 10
-4
)
8.314

Ea = - 3.688 x 8.314
- 3.069 x 10
-4
= 9.99 x10
4
J/mol


44





Answer:
9.99 x 10
4
J/mol

45
A catalyst is a a substance that alters the rate of chemical
reaction without itself being chemically changed at the end of
the reaction
Catalyst (positive catalyst)- speed up the reaction
Inhibitor (negative catalyst)- slow down the reaction
Only a small amount of catalyst is needed to achieve a large/big
increase in reaction rate
Catalyst lower the activation energy of the reaction
46
Ea
catalysed
uncatalysed
energy
Progress of reaction
Catalyst are often highly specific a catalyst for one reaction is
not necessarily a catalyst for another reaction

Catalyst may be poisoned/ becomes ineffective by small amounts
of substances such as lead, As or CN
-

Homogenous catalyst is a catalyst that exists in the same phase
as the reactants. e.g acid catalyst of ester

CH
3
COOCH
3
+ H
2
O
+
CH
3
COOH + CH
3
OH

Heterogenous catalysis occurs when the catalyst and the
reactants are in different phases. e.g. the transition metals,
Al
2
O
3
, SiO
3
, V
2
O
5

Autocatalysis occurs when one of the products of the reaction
is a catalyst for the reaction
47
H
+