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CHAPTER 5 :
KINETIC CHEMISTRY Past Year Questions Analysis
CHAPTER 5 : KINETIC CHEMISTRY
5.1
Rate of reaction
5.2
Rate law, Order of reactions and rate constants
5.3
The effect of temperature on reaction kinetics
5 4
.
The role of catal sts in reactions
y
2013
2014
2007
2008
2009 2010
2011 2012
Sem 1
Sem 1
Topic
B,
B,
P1
P2
P1
P2
P1
P2
P1
P2
P1
P2
P1
P2
A
A
C
C
5. Kinetic
Chemistry
1b
1
5b
1
3
3
3
6
3
1
2
17
2c 5.1 Rate of reaction
1. Chemical kinetics is the area of chemistry concerned with the
speeds, or rates, at which a chemical reaction occurs.
Kinetics, in this case is referring to the rate of a reaction,
which is the change in the concentration of a reactant or a
product with time. Generally, rate of reaction is inversely
proportional with time, therefore, longer the time taken for a
reaction to occur, lower the rate of reaction
1
rate ∝
time
2. Generally in chemical reaction
Reactants
Products
For example, when
A
(Concentration decrease)
B
(Concentration increase)  b) Consider the following chemical equations :
a A (aq)
+
b B (aq)
c C (aq)
+
d D
(g)
Rate of reaction can also be expressed base on the stoichiometry
coefficient, where it can be written as
Rate of reaction based on A
Rate of reaction based on B
1 d [A]
1
d [B]
Rate =
Rate =
a d t
b
d t
R
ate o react on
f
i
b
ase
d
on
C
R
ate o react on
f
i
b
ase
d
on
D
1
d [C]
1
d [D]
Rate =
Rate =
c
d t
d
d t
As a conclusion,
1 d [A]
1
d [B]
1
d [C]
1
d [D]
Rate =
= −
=
=
a d t
b
d t
c
d t
d
d t For example, in a chemical reaction of Ostwald Process, where
4 NH 3 (g)
+
5 O 2 (g)
4 NO (g)
+
6 H 2 O (g)
Rate of reaction based on A
Rate of reaction based on B
1
d [NH ]
1
d [O
]
3
2
Rate
= −
Rate
= −
4
d t
5
d t
Rate of reaction based on C
Rate of reaction based on D
1
d [NO]
1
d [H O]
Rate =
2
Rate
=
4
d t
6
d t
As a conclusion,
1
d [NH ]
1
d [O
]
1
d [NO]
1
d [H O]
3
2
2
Rate
= −
= −
=
=
4
d t
5
d t
4
d t
5
d t 5.1.1 Theory of Reaction Rates
Collision Theory – use to explain the effects of
concentration and temperature on rate of
reaction.
Base on 3 main ideas
Molecules must collide to react
Molecules must collide at the right orientation
Molecules must collide at the minimum amount of
energy called activation energy. Molecule must collide to react
Theory
use
to
explain
the
effects
of
concentration
and
temperature on rate of reaction.
Molecule must collide to react
In order for a reaction to occur, there must be physical interactions
that take place, where the molecules are able to collide with each
other and form a chemical reaction. Rate of collision is directly
influenced by the following factors :
Concentration : As the concentration of particles increased,
frequency of collision occur more rapidly. This will increase the
chances of effective collision and hence increase the rate of
reaction. From the diagram below, we can see that, as the number
of particles increase with concentration hence increase the
frequency of collision between particles. the frequency of collision
increase significantly from (a) < (b) < (c) as the number of particles
increase  Temperature : When temperature
increase, particles absorbed the
energy supplied and stored in the
form of kinetic energy. Particles
with higher kinetic energy can
move faster, and hence has a
higher frequency of collision
between particles. Furthermore
higher kinetic energy allows more
particles to have energy higher
than the activation energy, hence
increase the rate of reaction. Molecule must collide in the right orientation in
order to form the right product.
Consider the following reaction occurs.
2 AB
+
2 B.
A 2
For the reaction to take place, when the molecules
collide, it must collide under the correct way, in
order for that particular reaction to happen
Diagram of collision with the correct
orientation. Note that, the position
of the 2 molecules must be in the
correct position. If not, the reaction
will not take place, such as the
diagram below If the molecules collide at a wrong orientation
or position is not correct, the reaction will not
occur, as illustrated in the 2 diagrams below Molecule must possessed certain amount of
kinetic energy called activation energy
Even if the 2 conditions above is fulfilled – the
molecules collide as in (a) ; it is collided in the
right orientation as in (b), does it mean, the
reaction will occur?
Note the diagram below
Diagram of collision with the
correct orientation. Note that,
even though it collides with the
right orientation, the reaction
does not occur. This is due to
the collision is too gently, and
does not have the enough
energy to react. So, this
minimum required for the
reaction to happened is called
activation energy Activation energy is defined as …… ………………………… minimum amount of
energy ……………………………………………………………………. required to initiate a chemical reaction
So, in order for a reaction to take place, there must
be a certain amount of energy absorbed in order for
the molecules which collide at the right orientation
to happen.
As discussed during Maxwell-Boltzmann distribution
graph, when temperature increase, more particles
has energy higher than activation energy, and this
will increase the rate of reaction.
Activation is always endothermic, as heat is
required in order for molecule to collide effectively
and form a new compound.
The energy profile bellow shows the reaction
of both endothermic and exothermic reaction Endothermic process
Exothermic process
E a
E a Theory of transition state
Theory of transition state explained the process that take
place during a chemical reaction.
Supposedly the reaction of
B–C
+
A
C
+
A–B is a one
step reaction where it can be described as
A +
B – C
[A---B---C] A–B
+
C
The height of the "barrier" in the
beginning of the graph is called the
activation energy, and the
configuration of atoms at the
maximum in the potential energy
profile is called the transition state,
or the activated complex. In another
words, A--B--C formed is an activated
complex where it usually exist as an
intermediate of a chemical reaction, a
substance that appear during a
reaction but will not form as products Hydrolysis in 3 o haloalkane
Hydrolysis in 1 o haloalkane
C(CH 3 ) 3 Br +
OH - →
CH 3 CH 2 Br +
Equation
OH - →
CH 3 CH 2 OH +
C(CH 3 ) 3 OH +
Br -
Br -
Occur in 2 steps
Occur only in 1 step
Step
1
:
Formation
of
carbocation
Step 2 : Nucleophilic attack
Process Energy
Energy / kJ
Energ
y
profile
Reaction coordinate
Reaction coordinate
Rate
equati
Rate = k [C(CH 3 ) 3 Br]
Rate = k [CH 3 CH 2 Br][OH-]
on 5.2
Rate law, Order of reactions and rate constants
1. From what we had learn so far, we know that concentration is
directly proportional to rate of reaction where
rate ∝ [concentration]
;
rate = k [concentration]
The equation bolded is also known as rate equation, (also known
as rate law) a way to expresses the relationship of the rate of a
reaction to the rate constant and the concentrations of the
reactants raised to some powers. Rate constant, k, in the other
hand, is the proportionality constant of a given chemical reaction.
2. Supposedly if a chemical reaction take placed as shown in the
equation below
a A (aq)
+
b B (aq)
c C (aq)
+
d D (g)
The rate equation for the reaction is expressed by
k
=
rate constant
[A] and [B]
=
concentration of A and B
rate = k [A] x [B] y
x and y
= order of reaction with
respect to concentration of A and B rate = k [A] x [B] y
a) Only the concentration of reactants is taken into consideration
of rate of reaction, as the speed of the reaction largely depend
on the amount and concentration of reactants used in the
process. Generally, greater the amount (concentration) of
reactant used, greater the rate of reaction
b) Rate constant, k, is the proportionality constant of the
reaction, in which the value remain constant under constant
temperature, regardless of the changes in concentration of
the reactants take place. However, rate constant changes
with temperature of the reaction rate = k [A] x [B] y
c) order of reaction, x and y, is the power to which the
concentration of the reactants (in this case, [A] and [B]
respectively) is raised to in the rate equation.
i. Note that the order of reaction has no relationship with the
stoichiometry coefficient of the chemical equation. Therefore,
x ≠ a
;
y ≠ b .
ii. Order of reaction can only be determined from series of
experiments carried out under different concentration.
iii. The overall order of reaction can be calculated by summing
up the order of reaction for each reactant involved. In this
case.
Overall order
=
x
+
y d) Once the overall order of reaction is known, the rate constant
can be calculated accordingly by substituting the concentration
and order of reaction towards the rate of each experiment. Unit
of rate constant depend largely on the overall order of reaction.
Overall reaction
order
Example
Unit of rate constant, k
(mol dm -3 s -1 ) = k (mol dm -3 ) 0
Zero order
rate = k [A] 0
k =
mol dm -3 s -1
First order
rate = k [A]
(mol dm -3 s -1 ) = k (mol dm -3 ) 1
k = s -1
(mol dm -3 s -1 ) = k (mol dm -3 ) 2
Second order
rate = k [A][B]
k =
mol -1 dm 3 s -1
(mol dm -3 s -1 ) = k (mol dm -3 ) 3
Third order
Rate = k [A][B] 2
k = mol -2 dm 6 s -1
Fifth order
Rate = k [A][B] 2 [C] 2
(mol dm -3 s -1 ) = k (mol dm -3 ) 5
k = mol -4 dm 12 s -1 5.2.1
First order of reaction
1. A first-order reaction is a reaction whose rate depends on the
reactant concentration raised to the first power. Supposedly in a
chemical reaction, where
Integration of the equation
A
products
Therefore, for this reaction, rate of reaction can be expressed
d [ A ]
rate
= −
or it can be written as rate
=
k [A]
dt
When the rate is substituted between each other, it can be expressed
d[A]
d [A]
k [A] =−
which can be rearrange as
k dt
=
dt
[A]
d[A]
= −
k
d t
ln [A ]
= −
kt
+
c
Integration of the equation
[A]
c is a constant which can be determined when time, t = 0 (initial
time), c = ln [A]. Usually, it is indicated as ln [A] 0 , since it is the initial
concentration of the reaction. As a result, the equation that can be
applied to a first order reaction is :
ln [A] t
=
- kt
+
ln [A] 0 Graph in first order reaction -3
Half life in first order of reaction
3. Order of a reaction can also be determined by using half-life
method. Half life, t 1/2 is defined as the time required for the
concentration of a reactant to decrease to half of its initial
concentration, [A] 0 /2. Flow below shows the decreased of
concentration of reactant for each half-life take place
0.
st
[A]
nd
[A]
rd
[A]
1
t
2
t
3
t
1/ 2
0
0
0
[A] 0 →
→
1/ 2
→
1/ 2
2
4
8
Initial concentration of a reactant is 1.00 mol dm -3
st
nd
1
t
2
t
1.00 mol dm -3
→
1/ 2
0.50 mol dm -3
→
1/ 2
rd
3
t
1/2
0.25 mol dm -3
→
0.125 mol dm -3 Half life in first order of reaction (graph) Equation of Half life in first order of reaction
c) Using the equation of the first order of reaction, we can also
calculate the half-life of the reaction, and also rate constant, k,
if either one of these information is given. Derived from the
equation of first order of reaction :
Since after t 1/2 ; concentration of the initial reactant decreased
[A]
by half. Therefore,
0
[A] t =
2
[A]
0
substituting into the equation,
ln
= −
kt
+
ln [A]
1/ 2
0
2
[A] 0
[A]
0
Rearranging equation
ln [A]
0 − ln
=
kt
or
ln
= kt
1/ 2
[A]
1/ 2
2
0
2
0.693
or simply
ln 2 = k t 1/2
or
t 1/2 =
k 5.2.2
Second order of reaction
1. A second-order reaction is a reaction whose rate depends on the
concentration of one reactant raised to the second power or on the
concentrations of two different reactants, each raised to the first power.
A
+
B
→ products
Rate equation for a second order reaction can be either :
rate =
k [A] 2
or
rate =
k [B] 2
or
rate = k [A][B]
d[A]
rate =
dt
or it can be written as
rate =
k [A]
2
When the rate is substituted between each other, it can be expressed as
d[A]
d [A]
2
k [A]
= −
which can be rearrange as
k
dt
= −
2
dt
[A]
d[A]
1
Integration of the equation
=
k
d t
=
kt
+
c
2
[A]
[A]
c is a constant which can be determined when time, t = 0, c = 1/[A]. Usually,
it is indicated as 1/[A] 0 , since it is the initial concentration of the reaction:
1
1
=
kt
+
[A]
[A]
t
0 Graph in second order reaction Graph of half life in second order reaction The graph above clearly shows how does the half life occur for a
second order of reaction, where times taken for each stage of
half life :
1
1
1
[A] → [A] → [A] → [A]
0
0
1 min
2
2 min
4
0
8
0
4 min
For a second order of reaction : Since
1 st
=
1 min
t 1/2
=
=
2 (1 min) = 2 min
2 x 1 st t 1/2
2 nd t 1/2
3 rd
=
2 x 2 nd t 1/2 = 2 (2 min) = 4 min
t 1/2
As for 4 th
=
=
2 (4 min) =
8 min
2 x 3 rd t 1/2
t 1/2
b)
Similar to first order of reaction, the equation of the half life in
second order of reaction can be derived from the second
[
A
]
order equation. At t 1/2 ;
0
[
A
]
t =
2
1
1 = kt
1
1/ 2
[
A
]
1 kt
=
t
=
[
A ]
0
1/ 2
1/ 2
0
[
A ]
k A
[
]
0
o
2 Zero order reaction
1. First- and second-order reactions are the most common
reaction types. Reactions whose order is zero are rare. For a
zero-order reaction, where
A
products
rate equation : rate = k [A] 0
rate of reaction can be expressed using the equations below,
d[A]
rate =
or it can be written as
rate
=
k
dt
When the rate is substituted between each other, it can be
expressed as
d[A]
k = −
which can be rearrange as
k t
=
d[A]
dt
Integration of equation
d [A]= − k
d t
[A]
= − kt + c
[A] t
=
- kt
+
[A] 0 Graph Zero order reaction 3. For a zero order of reaction, since the graph of concentration
against time is linear, therefore, it is impractical to determine
the half-life of zero order using practical methods. In fact, the
linear shape of the graph itself has proven that the reaction is
zero order with respect to the reactant involved.
a) Though, the half-life of zero order reaction can be calculated
using equation method, where the equation is derived from the
zero order equation
[
A
]
During half life, t 1/2 , occur ;
0
[
A
]
t =
2
when [A] t is substitute in equation
[A]
[A]
0
0
[A] 0 −
=
k t
t
=
1/ 2
1/ 2
2
2k

1.

A

+

B

C

The reaction above is first order

with respect to A and zero order with respect to B. the initial concentration of A and B are 1.50 mol dm -3 and 2.00 mol dm -3 respectively & the initial reaction rate is 6.70 x 10 -5 mol dm -3 s -1 .

a) rate = k [A] 1 [B] 0

b) rate constant, k = rate / [A] k = 6.70 x 10 -5 mol dm -3 s -1 / 1.50 mol dm -3

@

rate = k [A]

k = 4.47 x 10 -5 s -1

c) Using 1 st order equation, [A] t at 1 hour is calculated ln [A] t = – k t + ln [A] 0

=>

ln [A] t = - 4.47 x 10 -5 x [A] t = 1.28 mol dm -3 Then use rate = k [A]

3600 + ln 1.50

; rate = 4.47 x 10 -5 x 1.28

rate = 5.71 x 10 -5 mol dm -3

2. A dilute solution of hydrogen peroxide can be used to bleach hair. It decomposes slowly in aqueous solution according to the following equation:

2 H 2 O 2 (aq) 2 H 2 O (l) + O 2 (g) A solution with an original concentration of 3.0 mol dm -3 was placed in a bottle contaminated with transition metal ions, which act as catalysts for the decomposition. The rate of decomposition was measured by withdrawing 10 cm 3 portions at various times and titrating with acidified 0.10 mol dm -3 KMnO 4 (aq). (5 mol of peroxide react with 2 moles of KMnO 4 .) The following results were obtained:

 Time / min 0 5 10 15 20 25 30 V of 0.10 mol dm -3 KMnO 4 / cm 3 30 23.4 18.3 14.2 11.1 8.7 6.8

Plot a graph of volume of KMnO 4 against time. Based on the graph sketch, determine the order of reaction with respect to H 2 O 2 , express the rate equation for the reaction and calculate the rate constant of the reaction. 30
25
20
15
10
5
0
0
5
10
15
20
25
30

From the graph, since first t 1/2 is 13.5 min, while second t 1/2 is also 13.5 min, therefore, the reaction is first order with respect to H 2 O 2 .

The rate equation can be expressed as :

rate constant can be calculated using

t

1/ 2

0.693

=

k

;

k

0.693

=

13.5

:

rate =

k [H 2 O 2 ]

k

=

0.0513 min

1

3. Substance B decomposed according to the following equation 2 B → C + 2 D The concentrations of B were determined at certain interval time and the graph of 1/[B] against time was obtained 8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0
50
100
150
200
250
300
 a) Determine the order of reaction with respect to B. Second order of reaction b) From the graph, determine i. the initial concentration At t = 0 ; 1/[B] = 1.0 ; [B] = 1.0 mol dm -3 ii. rate constant of reaction Using any two point to form tangent . R t t t k = 5 6 3 2 / 200 . a e cons an , – – 100 = 0.024 mol -1 dm 3 s -1 c) Write the rate equation for the reaction

Rate = k [B] 2

4. Trichloromethane, CHCl 3 reacts with sodium hydroxide solution as represented by the following equation:

→ CO

The reaction is first order with respect to each reactant.

2 CHCl 3 +

7 OH

+

HCOO +

6 Cl +

4 H 2 O

a) Write the rate equation for the reaction above.

Rate = k [CHCl 3 ] [OH ]

b) Determine the rate of production of chloride ions at 28 °C when the

rate of loss of trichloromethane is 2 0 x 10 5 mol s 1

rate

 1 = − 2 rate =

d[CHCl ]

3

1

dt

d[Cl ]

6

dt

;

;

.

1

so, rate =−

rate

=

2

1.0

so,

1.0

×

10

5

d[Cl ]

dt

×

2.0

×

×

10

5

1

=− ×

6

=

6.0

×

.

10

5

d[Cl ]

10

dt

5

c) If the rate of reaction is r when the concentrations of both trichloromethane and sodium hydroxide are both 2.0 mol dm 3 , what is the rate of reaction in terms of r when half of the hydroxide ion is reacted?

d)

2 CHCl 3

+

7 OH - products

Initial conc. Final conc.

Rate, r = k [CHCl 3 ][OH ] ;

2

2 – (2/7 x 1) = 12 /7

2

2 – (2 x ½) = 1

r = k [12/7 CHCl 3 ] [1 OH ] r = 12 / 7 k [CHCl 3 ] [OH ]

So, rate is

12 / 7 r

Sketch a graph of the rate of reaction against the concentration of trichloromethane if sodium hydroxide is in excess such that the hydroxide ion concentration remains practically constant in the reaction mixture. rate [CHCl 3 ] 5.2.4 Determination of order of reaction via experiment
1. Consider the reaction between oxygen and nitrogen
monoxide, a key step in the formation of acid rain and in the
industrial production of nitric acid .
O 2 (g)
+
2 NO (g)
2 NO 2 (g)
The rate equation, expressed in general form, is
rate =
k [O 2 ] x [NO] y
Note that the order of reaction cannot be determined directly
from the stoichiometry of the reaction. To find out the orders
of reactant with respect to each O 2 and NO, we run series of
experiments, starting each one with a different set of reactant
concentrations and obtaining an initial rate in each case. Initial concentration of reactant
Exp
O 2 / mol dm -3
NO / mol dm -3
Initial rate
(mol dm -3 s -1 )
1
1.10
x 10 -2
2.50
x 10 -2
2.40
x 10 -3
2
2.20
x 10 -2
2.50
x 10 -2
4.80
x 10 -3
3
1.10
x 10 -2
5.00
x 10 -2
9.60
x 10 -3
4
3.30
x 10 -2
7.50
x 10 -2
x
From each experiment, the rate equations are expressed individually,
where
Experiment 1 :
2.40 x 10 -3 = k (1.10 x 10 -2 ) x (2.50 x 10 -2 ) y
Experiment 2 :
4.80 x 10 -3 = k
Experiment 3 :
9.60 x 10 -3
x
=
k
Experiment 4 :
=
k
(2.20 x 10 -2 ) x (2.50 x 10 -2 ) y
(1.10 x 10 -2 ) x (5.00 x 10 -2 ) y
(3.30 x 10 -2 ) x (7.50 x 10 -2 ) y Comparing Experiment 2 to Experiment 1 :
4.80
x 10 -3
=
k (2.20 x 10 -2 ) x (2.50 x 10 -2 ) y
2.40
x 10 -3
=
2
=
k (1.10 x 10 -2 ) x (2.50 x 10 -2 ) y
(2) x
Order of reaction with respect to O 2
;
x
=
1
Comparing Experiment 3 to Experiment 1 :
9.60
x 10 -3
=
k (1.10 x 10 -2 ) x (5.00 x 10 -2 ) y
2.40
x 10 -3
=
4
=
k (1.10 x 10 -2 ) x (2.50 x 10 -2 ) y
(2) y
Order of reaction with respect to NO ;
y =
2
From the order of reaction deduced, the rate equation is
rate = k [O 2 ][NO] 2 .
The overall order of reaction = 1 +
2
=
3 Using any experiment, rate constant can be calculated. For
example, in experiment 1
2.40 x 10 -3
k
=
=
k (1.10 x 10 -2 ) (2.50 x 10 -2 ) 2
349 mol -2 dm 6 s -1 .
Once the order of reaction and the rate constant were
determined, we can predict the rate of reaction under any
concentration of reactants used. For example, in Experiment
4, where
rate
= k [O 2 ][NO] 2 ;
rate = 349 (3.30 x 10 -2 ) (7.50 x 10 -2 ) 2
rate = 6.48 x 10 -2 mol dm -3 s -1 2. Sometimes, using a combination of graphical methods and
initial rate methods, the order of reaction can be found
individually. For example, in hydrolysis of bromoethane with
potassium hydroxide at different concentrations.
CH 3 CH 2 Br (l)
+ KOH (aq)
CH 3 CH 2 OH (l) +
KBr (aq)
The following results were obtained from two experiments
on such a hydrolysis. In each experiment, the overall
[KOH(aq)] remained virtually constant at the value given at
the top of the column.
time /min
[CH 3 CH 2 Br] / mol dm -3 when
[KOH] = 0.10 mol dm -3
[CH 3 CH 2 Br]/mol dm -3 when
[KOH-] = 0.15 mol dm -3
0
0.0100
0.0100
40
0.0079
0.0070
80
0.0062
0.0050
120
0.0049
0.0034
160
0.0038
0.0025
200
0.0030
0.0017
240
0.0024
0.0012 0.01
0.008
0.006
0.004
0.002
0
0
50
100
150
200
250 a) From the reaction, the rate equation can be written as
rate = k [CH 3 CH 2 Br] x [KOH] y
Therefore, to determine the order of reaction with respect to
CH 3 CH 2 Br, the half-life method is applied, since the graph of
concentration of CH 3 CH 2 Br against time are plotted
accordingly, while the order of reaction with respect to KOH
can be obtained using initial rate methods, where the initial
rate for both [CH 3 CH 2 Br] under different concentration of KOH
can be found hence calculated.
b) By the mean of half-life method, the first t 1/2 , second t 1/2 and
third t 1/2 of the concentration of CH 3 CH 2 Br under the
concentration of KOH 0.15 mol dm -3 occurred at 80 s, 160 s
and 240 s. Since the 1 st t 1/2 = 2 nd t 1/2 = 3 rd t 1/2 = 80 s, therefore
the order of reaction with respect to CH 3 CH 2 Br is first order of
reaction.  d) From both methods applied, the rate equation can be written
as
rate = k [CH 3 CH 2 Br] [KOH]
The overall order of reaction is 1 + 1 = 2
e) Using any experiment above, rate constant of the reaction
can be calculated.
In experiment 2
:
1.00 x 10 -4 = k (0.0100) (0.15)
k = 0.0667 mol -1 dm 3 s -1 5.2.5
Reaction Mechanisms
1. Chemical reactions may occur in one way reaction or a
reversible reaction. Example of a one way reaction, is the
formation of nitrogen dioxide via the reaction of nitrogen
monoxide and oxygen gas
2 NO (g)
+
O 2 (g)
2 NO 2 (g)
(symbolised one way reaction)
While the example of a reversible reaction as in production of
ammonia from nitrogen gas and hydrogen gas, which is
largely used in industrial process via Haber process.
N 2 (g)
+
3 H 2 (g)
2 NH 3 (g)
(symbolised reversible reaction) 2. In a one way reaction, process may be taken in multiple steps,
and therefore irreversible back to the reactants, as they might
involve in steps that required higher activation energies. For
example, in the reaction stated above where
2 NO (g)
+
O 2 (g)
2 NO 2 (g)
The steps (or simply mechanism) for the reaction of nitrogen
monoxide and oxygen to form nitrogen dioxide can be
described below.
slow
Step 1
:
2 NO → N O
2
2
fast
Step 2
:
N
O
+
O
→ 2 NO
2
2
2
2
Overall
:
2
NO
+
2 NO 2
O 2 a) In the process of the formation of nitrogen dioxide, N 2 O 2 is formed
temporary, but it will not exist as a product in the end of reaction.
Therefore, N 2 O 2 is also known as intermediate, a substance that
appear in the mechanism of the reaction but not in the overall
balanced equation.
b) For each step of reaction, the rate equation can be described
accordingly
M
ec an sm
h
i
R
eac on
ti
E
qua on
ti
R
a e equa on
t
ti
slow
Step 1
2 NO → N O
rate = k [NO] 2
2
2
fast
Step 2
N
O
+ O → 2 NO
2 rate = k [N 2 O 2 ] [O 2 ]
2
2
2
From the rate equation proposed for each step in the series of
mechanism proposed the order of reaction can be determined
straight forward by the stoichiometry coefficient. From the
mechanism equation in step 1, order of reaction is second order
with respect to NO, while in step 2, order of reaction is first order
with respect to each N 2 O 2 and O 2 respectively. c) Note that in the series of step, above the arrow is written with
the word "slow" and "fast", which can be interpreted as a slow
step of reaction, and a fast step of reaction. In determining the
order with respect of each reactant involved, we can make use
the mechanism to determine the order of each reactant, since
slow step is the rate determining step. Therefore, the rate
equation that can represent the overall equation
2 NO
+
2 NO 2
rate =
k [NO] 2 .
O 2  5.3 The effect of temperature on reaction kinetics
1. Temperature often has a major effect on reaction rate. In
general, increasing the temperature of a reaction increases
the average speed of particles and therefore their frequency
of collisions.
a) Arrhenius proposed that every reaction has an energy
threshold that the colliding molecules must exceed in order to
react. This minimum collision energy is the activation energy
(E A ), the energy required to activate the molecules into a state
from which reactant bonds can change into product bonds.
b) Many of the chemical reactions near room temperature
approximately double their rates with a 10 0 C rise in
temperature. 2. The effect of temperature towards the rate of reaction can be
further explained using Maxwell-Boltzmann distribution graph.
From the graph obtained, particles at 800 K have move collision
energy compared to particles at 300 K. This is due to, as the
kinetic energy increased, particles moved faster and more
particles collides more frequently hence increased the collision
energy. Therefore, more particles have energy greater than
activation energy, and results higher rate of reaction. 3. Generally, the rate of reaction increased with temperature as it
affect the rate by increased the rate constant of the reaction. The
dependence of the rate constant of a reaction on temperature can
be expressed by using Arrhenius equation.
k = rate constant
E A
A
= Arrhenius constant
T
= temperature
k = Ae
RT
E A = activation energy
R = gas constant (8.31 J mol -1 K -1 )
Arrhenius equation shows that the rate constant is directly
proportional to A and, therefore, to the collision frequency. In
addition, because of the minus sign associated with the exponent
E A /RT, the rate constant decreases with increasing activation
energy and increases with increasing temperature Derivation of Arrhenius Equation.
a)
Arrhenius equation – expressed as natural logarithm of both
sides, where the equation can be expressed as :-
E
E
1
A
A
ln k
=
ln A
;
rearrange : ln k
=−
+ ln A
RT
R
T
From the rearranged equation, if a graph of ln k against 1/T is
plotted, a negative gradient linear line may be obtained,
where the gradient, m = EA / R. Therefore, using this
method, the activation energy of a reaction can be calculated Example : The table below shows how the rate constant, k, varies
with the temperature for the reaction between H 2 (g) and I 2 (g)
H 2 (g)
+
I 2 (g)
2 HI (g)
Temperature (K)
556
575 647
700
791
Rate constant,
k (mol -1 dm 3 s -1 )
3.52 x 10 -7
1.22 x 10 -6
8.59 x 10 -5
1.16 x 10 -3
3.90 x 10 -2
By plotting a suitable graph, determine the activation energy for
the reaction.
Solution : A table of 1/T and ln k is first calculated and placed
accordingly.
1 / T (K -1 )
0.00180
0.00174
0.00155 0.00143
0.00126
ln k
-14.9
-13.6
-9.36
-6.76
-3.24
− 13.6
− −
( 9.36)
=− 22316
0.00174
− 0.00155
E
A
22316 = −
8.31
− 1
E
A =+
185, 444 @
+
185 kJ mol 0.0
0.00100 0.00110 0.00120 0.00130 0.00140 0.00150 0.00160 0.00170 0.00180 0.00190
-2.0
-4.0
-6.0
-8.0
-10.0
-12.0
-14.0
-16.0 b)
An equation relating the rate constants k 1 and k 2 at temperatures
T 1 and T 2 can be used to calculate the activation energy or to
find the rate constant at another temperature if the activation
energy is known.
E
E
A
A
At T
ln k 1
= −
+
ln A
;
At T
ln k
= −
+
ln A
1
2
2
RT
RT
1
2
Subtracting both equation at two different temperatures above
E
E
A
A
ln k
ln k
= −
+ ln A −  −
+
ln A 
1
2
RT
RT
1
2
k
E
 1
1 
1
A
ln
=
k
R
T
T
2
2
1 ;
Example 2 : The rate constant of a first-order reaction is 3.46 x
10 -2 s -1 at 298 K. What is the rate constant at 350 K if the
activation energy for the reaction is 50.2 kJ/mol?
Solution :
k
E
 1
1 
1
A
ln
=
k
R
T
T
2
2
1
2
3
3.46
×
10
50.2
×
10
1
1
ln
=
k
8.31
350
298
2
=
0.703 s -1
k 2 5.4 The role of catalysts in reactions
1. A catalyst is a substance which alter the rate of reaction
without changing its chemical composition. Therefore the
chemical formula will remain the same after the reaction
occur. In most of the chemical reactions, a catalyst is usually
added to speed up the reaction (increase the rate of
reaction), however, the quantity of catalyst used was only in
a small amount, since large amount of catalyst does not
significantly increase the rate of reaction.
2. A catalyst works by providing an alternative pathway for a
chemical reaction to take place, which required a lower
activation energy. However, it will not affect the enthalpy
change (∆H) of a chemical reaction. Endothermic process
Exothermic process
Energy / kJ
Energy / kJ
Reaction coordinate
Reaction coordinate 3. As proposed by Arrhenius' equation,
E A
k
= Ae
RT
when the activation energy, E A , of a chemical reaction
decreased, the rate constant of the reaction increased,
therefore increased the rate of reaction. However a catalyst
do not initiate the reaction, rather it accelerate the reaction 5.4.1
Autocatalysis
1. If the product of a reaction itself acts as a catalyst for the reaction,
the product is also known as autocatalyst. For example, the
reaction between manganate (VII) ions, MnO 4 - and ethanedioate
ions, C 2 O 4 2- in the presence of sulphuric acid, H 2 SO 4 :
2 MnO 4 - + 5 C 2 O 4 2-
+
16 H + →
2 Mn 2+ +
10 CO 2 +
8
H 2 O
Table below shows the observation from the first drop of KMnO 4 is
added slowly to until the end of reaction
No of drop of
KMnO 4
Observation
First two drops
Purple colour of KMnO 4 decolourised slowly
Following drops
Purple colour of KMnO 4 decolourised more rapidly.
Last few drops
before reaction
end
Purple colour of KMnO 4 decoloursied less rapidly
and eventually become slower until it no longer
decolourised. 5.8

Application of catalysis in industries

Catalysis can be categorised into 2 types, namely

heterogeneous catalyst

homogeneous catalyst

5.8.1 Heterogeneous catalyst

A heterogeneous catalyst is a catalyst which has different phase with reactants. Usually it was between a solid catalyst that is used to catalyse between a gaseous or liquid reactants. We shall stu dy 4 specific examples of heterogeneous catalyst, which are Haber Process, Ostwald Process, Contact Process and Catalytic converter use in automobile exhaust.

5.8.1.1

Haber Process

Ammonia is an extremely valuable inorganic substance used in the fertilizer industry, the manufacture of explosives, and many other applications The main ingredients use to synthesis ammonia are nitrogen (which can be obtained through fractional distillation of liquefied air) and hydrogen (which can be obtained either from syn gas [C + H 2 O] or petroleum refining process)         In heterogeneous catalysis, the surface of the solid catalyst is usually the site of the reaction.The initial step in the Haber process involves the dissociation of N 2 and H 2 on the metal surface. Although the dissociated species are not truly free atoms because they are bonded to the metal surface, they are highly reactive. The highly reactive N and H atoms combine rapidly at high temperatures to produce NH 3 molecules   5.8.1.2

Ostwald Process

Nitric acid is one of the most important inorganic acids. It is used in the production of fertilizers, dyes, drugs, and explosives.The major industrial method of producing nitric acid is the Ostwald process.The starting materials, ammonia and molecular oxygen, are heated in the presence of a platinum-rhodium catalyst to 850 0 C Step 1 This step is the crucial step as it will determine the yield of nitric acid formed.The rest of the steps do not require catalysis and will occur at high temperature Step 2 :The nitric oxide readily oxidizes (without catalysis) to nitrogen dioxide:

2 NO(g)

+

O 2 (g)

2 NO 2 (g)

Step 3 :When dissolved in water, NO 2 forms both nitrous acid and nitric acid:

2 NO 2 (g)

+

H 2 O (l)

HNO 2 (aq) + HNO 3 (aq)

On heating, nitrous acid (HNO 2 ) is converted to nitric acid as follows:

3 HNO 2 (aq) HNO 3 (aq) +

H 2 O (l)

+

2 NO (g)

The NO generated can be recycled to produce NO 2 in the second step

5.8.1.3

Contact Process

Sulphuric acid is one of the most widely use inorganic acids. Contact process is still preferable, even today, to synthesise high concentration of sulphuric acid.The following are steps in manufacturing sulphuric acid, starting from heating sulphur with oxygen.

Step

After sulphur dioxide is formed and filtered, it was further oxidised to form

sulphur trioxide, using vanadium (V) oxide,V 2 O 5 , as catalyst.This step is crucial as it will influence the amount of H 2 SO 4 formed. Step 2

1

S

(g)

+

O 2

(g)

SO 2

(g)

:      V 2 O 5 catalyst serve as the active site and provide an alternative solution for the formation of SO 3 . Alternative Step 1 : 2 SO 2 + 4V 5+ + 2 O 2- 2 SO 3 + 4V 4+ (Oxidation of SO 2 into SO 3 by V 5+ ) Alternative Step 2 : 4V 4+ + O 2 4V 5+ + 2 O 2- (Oxidation of V 4+ back intoV 5+ by oxygen - catalyst regenerate)

Hot sulphur trioxide passes through the heat exchanger and is dissolved in concentrated H 2 SO 4 to form oleum Step 3 : H 2 SO 4 (l) + SO 3 (g) H 2 S 2 O 7 (l) Oleum is reacted with water to form concentrated H 2 SO 4 Step 4 : H 2 S 2 O 7 (l) + H 2 O (l) 2 H 2 SO 4 (l) The yield of sulphuric acid solution formed is around 30 - 40%.The unreacted suphur dioxide and sulphur trioxide is then further treated in another recycle chamber named as DCDA (Double Contact Double Absorption) Chamber.Through this method, the yield will be maximised to nearly 99.8% of H 2 SO 4

5.8.1.4

Catalytic converter

At high temperatures inside a running car’s engine, nitrogen and oxygen gases react to form nitric oxide

N 2 (g)

+

O 2 (g)

2 NO (g)

*Note that this reaction occur only when the engine is very hot. This is due to nitrogen gas, NΞN has a short and strong triple bond, with a high bond energy. So, high amount of heat is required to break the bond. Another phenomenon which caused the same reaction are when air is surrounded by lightning. When released into the atmosphere, NO rapidly combines with O 2 to form NO 2 . Nitrogen dioxide and other gases emitted by an automobile, such as carbon monoxide (CO) and various unburned hydrocarbons (C x H y ), make automobile exhaust a major source of air pollution To overcome these problem, most of cars nowadays are equipped with catalytic converter, which contain platinum-rhodium catalyst and copper (II) oxide + chromium (III) oxide as co-catalyst An efficient catalytic converter serves two purposes: It oxidizes CO and d

unburned hydrocarbons to CO and O 2 .

2 an

d H O

2

, an

d i

t re uces

NO

d NO

an

2 to

Oxidation : CO (g) + 1/2 O 2 (g)

Oxidation

Reduction :

The suitable catalyst use is platinum / rhodium (use to oxidise CO and

CO 2 (g) x CO 2 (g)

+

C x H y +

(x + y/4) O 2 (g)

1/2 N 2 (g)

+

y/2 H 2 O (g)

:

NO x (g)

x/2 O 2 (g)

N

2

C x H y ) based catalyst doped with copper (II) oxide or chromium (III) oxide

(use to reduce NOx). Because the catalyst serve these 3 purposes, sometime

it is also referred as three-way catalyst 5.8.2

Homogeneous catalyst.

In homogeneous catalysis the reactants and catalyst are dispersed in a single phase. Acid and base catalyses are the most important types of homogeneous catalysis in liquid solutions For example, in the hydrolysis of ester      The rate equation of the reaction above is written as However, this reaction can be catalysed by the addition of hydrogen ion (H + ) from an acidic substance for example, hydrochloric acid or sulphuric acid, where now, the rate equation can be written as rate = k [CH 3 COOCH 2 CH 3 ] [H + ] By this, the rate of hydrolysis of ester can be increased by the addition of acidic substance, which may caused faster reaction, without increasing the concentration of ester. Other than this, homogeneous catalyst can also be exemplified by the reaction between disulphate ion, (S 2 O 8 2- ) and iodide ion, (I - ) where iron (III) ion here can be added as catalyst to increase the rate of reaction. Equation : S 2 O 8 2- (aq) + 2 I - (aq) I 2 (aq) + 2 SO 4 2- (aq) The reaction can be catalysed using aqueous iron (III) ion. Step 1 : oxidation of iodide ion by iron (III) ion [catalysed]

3+

2 Fe

(aq)

+

-

2 I

(aq)

2+

2 Fe

(aq)

+

I 2 (aq)

Step 2 : Oxidation of iron (II) ion back to iron (III) ion by persulphate ion.

2 Fe 2+ (aq) + S 2 O 8 2- (aq)

2 Fe 3+ (aq)

+ 2 SO 4 2- (aq)

Homogeneous catalysis can also take place in the gas phase.This can be exemplified by the reaction from SO 2 to SO 3 , which is one of the major pollutant in air. SO 2 in the air are mainly released by the fumes of volcanic activities. However, recent papers had reported that SO 2 emission could also be mainly contributed by the combustion of diesel oil, mining activities (sulphide based ores), and through various chemical industries processes such as Contact Process.

SO 2 can be oxidised in air under the presence of nitrogen dioxide according to the equation below

 2 SO 2 (g) + 2 NO 2 (g) → 2 SO 3 (g) + 2 NO (g) 2 NO (g) + O 2 (g) → 2 NO 2 (g)

Overall :

SO 3 produced are hygroscopic, hence they react easily with water droplet or rain to form corrosive acidic rain.

2 SO 2 (g)

+

O 2 (g)

2 SO 3 (g)

5.9

Enzymes as Biological Catalysts

Chemical reactions that occur in our bodies are speeded up by enzymes, which act as biological cataysts. Enzymes are the largest and most highly specialised class of proteins and are produced by living cells from amino acids. Its molecular weight varies from 12,000 to over 1 million. Enzymes work under mild conditions and often give 100% yields and may speed a reaction by 106 or 1012 times.

Some enzymes require the presence of metal ions as cofactors, and these are called metalloenzymes. Many but not all metalloenzymes contain a transition element

 Type of Enzyme Metalloenzyme Function Arginase Mn 2+ Urea formation Carboxypeptidase Zn 2+ Digestion of proteins Ferredoxin Fe 2+ or Fe 3+ Photosynthesis Glutamic mutase Co Metabolism of amino acids Nitrogenase Fe and Mo Nitrogen fixation Tyrosinase Cu + or Cu 2+ Skin pigmentation

Compared to inorganic catalysts, enzymes are specific'in their actions. Each enzyme catalyses only one type of reaction whereas platinum catalyses several reactions. In the lock-and-key theory, the active site of the enzyme conforms exactly to the substance molecule.This specificity results from the fact that enzymes are formed from L-amino acids and therefore the active sites are asymmetrical. Factors affecting enzyme activity:

Temperature - Most enzymes have their highest activity at temperatures from 35°C to 45°C. Above this range, the enzymes start to denature and the reaction rate decreases. Above 80°C, enzymes are permanently denatured. pH -The structure and geometry of an enzyme's active site changes when the pH of the surrounding medium changes. For example, trypsin (which is active in the small intestine) has its maximum activity at pH 8 whereas pepsin (which is active in the stomach) has an optimum pH of 1.5.

Solvents and salt concentrations can also change the structure of a protein and the activity levels of enzymes. The activity of enzymes can be inhibited by heavy metals as mercury, lead and silver.These metals are toxic because they bind irreversibly with free sulphydryl (-SH) functional groups on enzymes, which are then not available to bind with the necessary cofactor. Compounds in nerve gases combine with the hydroxyl (-OH) functional group on enzymes and cause the enzymes to lose their ability to catalyse a reaction.This is why animals poisoned by nerve gas become paralysed.