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CHAPTER 2

Chemical Kinetics
NURUL AIN BINTI JAMION
1

CHAPTER 2
Rates of Reaction
Factors affecting rates of
reaction
Rates law and order of
reaction
Methods to determine order
of reaction
Relation between rate and
temperature
Reaction Mechanism
Catalytic kinetics

INTRODUCTION
Chemical

kinetics - is the study of chemical

rxns/processes with respect to reaction rates,


effect of various variables

INTRODUCTION

RATEs of REACTION
Definition:
A measure of the change in the concentration of
a reactant or product in a given time.

[ x]
rate
t
Unit
= mole / liter =
mol / L
second
s
= Mol L-1 s-1

Reaction Rates(cont.)
depending on the experimental conditions :
average rate: rate measured between long time
interval
instantaneous rate: rate measured between
very short interval
initial rate: instantaneous rate at the beginning
of an experiment

12

RATEs of REACTION
Reactant

Product

When the reactants change into products


the

concentration of reactants decreases

the

concentration of products increases

with time.

[A]
rate = t
[B]
rate =
t
13

Measuring Reaction Rate


To

measure a reaction rate, we usually monitor


either a product or a reactant for its change.
Some of the characteristics to be monitored
are:
-changes in pressure
-changes in color (use spectrofotometer )
-temperature for exothermic or
endothermic reaction, and
-presence of certain key substance

Reaction Rates and


Stoichiometry
2A
B
Two moles of A disappear for each mole of B that is
formed.

1 [A]
rate = 2
t
aA + bB

rate =

[B]
t

cC + dD

1 [A]
1 [B]
1 [C]
1 [D]
rate = ==
=
a t
b t
c t
d t

Reaction Rates and


Stoichiometry
Example : Write the rate expression for the following reaction:
CH4 (g) + 2O2 (g)

CO2 (g) + 2H2O (g)

[CH4]
1 [O2]
rate = =
=t
2 t

[CO2]
1 [H2O]
=
t
t
2

16

17

TRY
2N2O 5(g) 4NO2(g) O 2(g)
Write the Differential rate equation for
above equation.
Solution

1 d[N 2 O 5 ]
1 d[NO 2 ]
d[O 2 ]
Rate

2
dt
4
dt
dt

18

TRY
2O3 ( g ) 3O2 ( g )
1 d [O3 ]
1 d [O2 ]
rate

2 dt
3 dt

TRY

TRY
Consider the reaction for the combustion
of methane, CH4 ,
CH4(g) + 2O2(g) CO2(g)+ 2H2O(g)
If the methane is burning at a rate of 0.16 molL-1s1 , at what rates are CO and H O being formed?
2
2

Solution
CH4(g) + 2O2(g) CO2(g)+ 2H2O(g)
Given d[CH4] = - 0.16 molL-1s-1
dt
so; -d[CH4] = d[CO2] = d[H2O]
dt
dt
2 dt

Solution
To calculate rate of N2;
d[CO2] = - d[CH4]
dt
dt
= -(-0.16 molL-1s-1 )
= 0.16 molL-1s-1

Solution
To calculate rate of H2O;
d[H2O] = 2x -d[CH4]
dt
dt
= 2 x (-0.16 molL-1s-1 )
= 0.32 molL-1s-1

24

TRY : Calculate the rate of reaction of C2H4 converted to C4H8


from t=0 to t=40s

2C2H4 (g)

C4H8(g)

Time(s)

10

20

40

60

[C2H4]/mol L-1

0.884

0.621

0.479

0.328

0.169

Answer :
At t = 0s, [C2H4] = 0.884 M
At t = 40s, [C2H4] = 0.328 M
Rate = (0.884 0.328)M
40s
= 0.0139 Ms-1
= 0.014 Ms-1 so, the rate of reactions at 40s is 0.014 Ms-1

The Rate Law


THE RATE LAW Expresses the relationship of the rate of a
reaction to the rate constant and the concentration of the
reactants raised to some powers.

aA + bB

cC + dD

Rate = k [A]a[B]b

k
= rate constant
a & b = reaction order with
respect to A & B
a + b = overall reaction
order
13.2

Rate laws are always determined experimentally unless


you have been told a rate-limiting or slow step.

Reaction order is always defined in terms of reactant


(not product) concentrations.

The order of a reactant is not related to the


stoichiometric coefficient of the reactant in the balanced
chemical equation.
F2 (g) + 2ClO2 (g)

2FClO2 (g)

rate = k [F2][ClO2] 1
13.2

27

THE ORDER OF REACTION

The number of concentration factors in


the rate equation.
Can only be determined experimentally.
It shows the exact dependence of rate on
concentration.
not from the number of moles as written
in the stoichiometric equation.
The units of the rate constant depend
on the overall reaction order.

28

First order reaction:


- A reaction with a single reactant A
- Rate is directly proportional to [A]

rate= k[A]
Second order reaction:
- Rate is directly proportional to the square of [A]

rate= k[A]2
Zero order reaction:
- the rate is not dependent on [A]

rate= k[A]0 = k (1) = k

29

THE OVERALL REACTION


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

The overall order of reaction = sum of


the individual orders = m+n.

with respect to each reactant in the rate


law.

Rates as Functions of Reactant


Concentrations
In a general reaction,
a A + b B + products
Rate = k[A]x[B]y
If concentrations of B is kept
constant, you can measure the reaction
rate of A at various concentrations.

33

DETERMINING REACTION
ORDER

Initial
rate
Integrated Rate
Law
Half
life

34

1. Initial Rate Method


To find the reaction orders by initial
rate method,
Run a series of experiments,
Each of the experiments have a
different set of reactant
concentration,
From each experiments, obtain an
initial rate.

35

Example 1
The results shown below are obtained for
the reaction between A and B. Determine
the rate equation for the reaction between
A and B.
Experiment

1
2
3

Concentration
(mol L-1)

[A]

[B]

0.0575
0.0713
0.0575

0.0216
0.0216
0.0333

Initial rate
(mol L-1 s-1)

8.21x10-3
1.26x10-2
1.26x10-2

36

Calculating m in [A]m; we take the ratio of


the rate laws for two experiment 1 and 2,
in which [A] varies but [B] is constant:

rate1 k [A] [B]


m
n
rate2 k [A] [B]
m

8.2110
0.0575

2
1.2610
0.0713

That is, 0.652 = 0.806m


log 0.652 = m x log 0.806
m
= 1.98 2
Thus, the reaction is
second order with respect to A

37
Calculating n in [B]n; we
take the ratio of the
rate laws for two experiment 1 and 3, in
which [B] varies but [A] is constant

rate1 k [A] [B]


m
n
rate 3 k [A] [B]
m

8.21 10
0.0216

2
1.26 10
0.0333

That is,

0.652 = 0.649n
log 0.652 = n x log 0.649
n 1
Hence, the reaction is first order with respect
to B.
The rate equation is

rate k[A]2[B]

38

Example 2
The reaction between C and D is represented as
follows :

C D E

The experiment results are shown in the table


below. Determine the rate equation for the
reaction between C and D.
Experimen
t

1
2

Initial concentration
(M)

[C]

[D]

0.05
0.05

1.0
2.0

Time
interval
(minutes)

The change in
concentration
of C (M)

30
30

2.5 x 10-3
1.0 x 10-2
-3

39

rate1 k [C] [D]


m
n
rate 2 k [C] [D]
m

2.5 10
1.0

2
1.0 10
2.0

That is, 0.25 = (0.5)n


log 0.25 = m x log 0.5
n=2
Thus, the reaction is second order
with respect to D

Example :
Derive the rate law for the reaction
A + B + C products
from the following data :

[A]0

1
0.100

2
0.200

3
0.200

4
0.100

[B]0

0.100

0.100

0.300

0.100

[C]0

0.100

0.100

0.100

0.400

rate

0.100

0.800

7.200

0.400

Expriment

solution
Assume:
rate = k [A]x [B]y [C]z
From experiment 1 and 2, we have:
0.800 k [0.2]x [0.1]y [ 0.1]z
----- = -----------------------0.100 k [0.1]x [0.1]y [0.1]z
Thus, 8 = 2x; and x = ln8 / ln2 = 3
By similar procedures, we get y = 2 and z = 1.
Thus, the rate law is: rate = k [A]3 [B]2 [C]
overall order = 3+2+1 = 6

42

rate1 k [C]m [D]n


m
n
rate 3 k [C] [D]

2.510
0.05

3
5.010
0.1

That is, 0.5 = (0.5)m


log 0.5 = m x log 0.5
m=1
Thus, the reaction is first order
with respect to C
The rate equation is

rate k [C][D]2

TRY
The following data refers to the following
reaction:
CH3COCH3 + I2 + H+ CH3COCH2I + HI
Expt.

[CH3COCH3],

3.0

M [H+],
M

Initial rate,
Ms-1

0.2

[I2],
M
0.02

3.0

0.4

0.02

12.0 x 10-6

4.0

0.4

0.02

16.0 x 10-6

4.0

0.2

0.04

8.0 x 10-6

6.0 x 10-6

Based on the above information,

Calculate the order with respect to


CH3COCH3 , I2 and H+.
Write the rate law for the reaction.
What is the overall order of the reaction?
Determine the rate constant,k with the
correct unit.
Calculate the rate of reaction if the
concentration of propanone, iodine and
hydrogen ion are each 0.5 mol dm-3.

zero order reaction


you will get a horizontalline,
because rate = k[A]0
rate = k (a horizontal line)

rate

k
independent to [reactant]

[A]
45

first order reaction


For

first order, rate = k[A]

rate

the plot is a straight line (linear)

[A]
46

second order reaction

the plot is a branch of a prabola, because


rate = k [A]2

Rate

[A]
47

The Rate Law &


Order Of Reaction
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Order Rate Law

Unit

Integrated rate
law
[A] = [A]0 - kt

rate = k

Ms

rate = k [A]

s-1

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

rate = k [A]

M s

1
1
=
+ kt
[A]
[A]0

-1

-1 -1

Half-Life
[A]0
t =
2k
t = ln 2
k
1
t =
k[A]0

Exercise 1 - Initial rate


The reaction of nitric oxide with hydrogen at 1280 C is
method
o

2NO(g) + 2H2(g)

N2(g)

2H2O(g)

From the following data collected at this temperature, determine :


a) The rate law
b) The rate constant
c) The rate of the reaction when [NO] = 1.2 x 10-3M and [H2] = 6.0 x 10-3 M
experiment

[NO] (M)

[H2] (M)

Initial
rate(M/s)

5.0 x 10-3

2.0 x 10-3

1.3 x 10-5

10.0 x 10-3

2.0 x 10-3

5.0 x 10-5

10.0 x 10-3

4.0 x 10-3

10.0 x 10-5

Exercise 2 - Half - Life


.
Method

What is the half-life of N2O5 if it decomposes with a rate


constant of 5.7 x 10-4 s-1?
0.693
t = ln 2 =
= 1200 s = 20 minutes
-4 -1
k
5.7 x 10 s
How do you know decomposition is first order?
units of k (s-1)

Exercise 3 Integrated rate -law


The reaction 2A
B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?
[A]0 = 0.88 M

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

[A] = 0.14 M

kt = ln[A]0 ln[A]f
ln[A]0 ln[A]t
=
t=
k

ln

[A]0
[A]t
k

ln
=

0.88 M
0.14 M

2.8 x 10 s
-2

-1

= 66 s

TRY
1. The rate constant for the decomposition of
N2O5 to NO2 and O2 at 70C is 6.82 x 10-3 s-1.
Suppose we start with 0.300 mol of N2O5(g) in
a 0.500 L container.
How many moles of N2O5 will remain after 1.5
min?
How many minutes will it take for the quantity
of N2O5 to drop to 0.030 mol?
What is the half-life of N2O5 at 70C ?

The Collision Theory


In

a chemical reaction, bonds are


broken and new bonds are formed.
Molecules can only react if they
collide with each other.
Furthermore, molecules must collide
with the correct orientation and with
enough energy to cause bond
breakage and formation.

The Collision Theory


Effective
collision

Ineffective
collision

..but how do we define it as an effective??

The Collision Theory


EFFECTIVE COLLISION - Collision with
sufficient amount of energy for reactant
molecules to form products.
Collision theory:
I. Molecules must collides
II. Right orientation
III. Collision Energy > Ea

The Collision Theory :


Activation Energy
In other words, there is a minimum amount
of energy required for reaction: the
activation energy, Ea.
Just as a ball cannot get over a hill if it does not
roll up the hill with enough energy, a reaction
cannot occur unless the molecules possess
sufficient energy to get over the activation
energy barrier.
The activation energy (Ea ) is the
minimum amount of energy required to
initiate a chemical reaction.

Activation energy (cont.)


The activation energy
is represented on a
reaction profile
(reaction energy
diagram) as the
energy barrier
between reactants
and products.

Activation energy(cont.)
The height of the activation barrier influences the
rate:
If

Ea is large, then few molecules possess


enough energy to get over the barrier; few
products are formed and the rate is slow.

If

Ea is small, then many molecules possess


enough energy to get over the barrier; more
products are formed and the rate is faster.

What factors affect the rate of


reactions?
increased concentration of
dissolved reactants
increased pressure of gaseous
reactants
increased temperature
use of a catalyst
increased surface area of solid
reactants

Effect of temperature on rate


The higher the temperature, the faster the rate of a reaction.
In many reactions, a rise in temperature of 10 C causes the
rate of reaction to approximately double.
Why does increased temperature
increase the rate of reaction?
At a higher temperature, particles
have more energy. This means
they move faster and are more
likely to collide with other particles.
When the particles collide, they
do so with more energy, and so
the number of successful
collisions increases.

Effect of concentration on rate of


reaction
The higher the concentration of a dissolved reactant, the
faster the rate of a reaction.
Why does increased concentration increase the rate of
reaction?
At a higher concentration, there are more particles in the
same amount of space. This means that the particles are
more likely to collide and more effective collision will
happen.

lower concentration

higher concentration

Slower and slower!


Reactions do not proceed at a steady rate. They start off at
a certain speed, then get slower and slower until they stop.
As the reaction progresses, the concentration of reactants
decreases.
This reduces the frequency of collisions between particles
and so the reaction slows down.

0%

25%
reactants
product

50%

75%

100%

percentage completion of reaction

Effect of pressure on rate of reaction


Why does increasing the pressure of gaseous reactants
increase the rate of reaction?
As the pressure increases, the space in which the gas
particles are moving becomes smaller.
The gas particles become closer together, increasing the
frequency of collisions. This means that the particles are more
likely to react each other thus increase rate of reaction.

lower pressure

higher pressure

Effect of surface area on rate of reaction


Any reaction involving a solid can only take place at the
surface of the solid.
If the solid is split into several pieces, the surface area
increases. What effect will this have on rate of reaction?

low surface area

high surface area

This means that there is an increased area for the


reactant particles to collide with.
The smaller the pieces, the larger the surface area. This
means more collisions and a greater chance of reaction.

How catalysts increase rate of rxn?

energy (kJ)

Speeds up a reaction but is chemically unchanged at the


end of the reaction.
Adding a catalyst has exactly effect on EA.
provides an alternative route for the reaction with
lower activation energy.
Ea without
catalyst

Different catalysts work in


different ways, but most
lower the reactions
activation energy (Ea).

Ea with
catalyst
reaction (time)

Type of catalysis
a) Homogeneous

The catalyst is in the same phase


as the reactants.
b) Heterogeneous

The catalyst is in a different phase


than the reactants often a solid
catalyst and liquid or gaseous
reactants.
67

How temperature and Catalysts Affect Reaction Rates

The Arrhenius Equation


k= A e-Ea/RT
Frequency
of collisions

Temperature in K

Activation
energy

Gas constant
8.314 J/mol K

Determination of the values of


A and Ea
linearizing the Arrhenius equation;

Determination of the values of


A and Ea
A plot of ln k versus 1/T will have a slope of
-Ea/R and an intercept of ln A.

70

Example:
A plot of ln(k) vs. 1/T(K)
Rate vs. Temperature
2

y = -7330.4x + 25.417

ln rate

1.6
1.2
0.8
0.4
0
3.1E-03

3.2E-03

3.3E-03

3.4E-03

3.5E-03

3.6E-03

1/T, Kelvin
71

Example: (cont.)
Q1Calculate the activation energy for this
reaction?
Q2 Calculate rate would be expected for this
reaction at 30C?
Q3 Determine temperature is needed to
double this rate?

Solution for Q1:


First, correlate the actual equation of the
line with the Arrhenius Equation:
ln k = - Ea/R(1/T) + ln A
y = mx
+
c
y = -7330.4x + 25.417

73

Solution for Q1:


Slope =

Ea

Ea = - (Slope) x (R)
Ea = - (-7330.4 K) x (8.314 J/molK)
Ea = 60.9 kJ/mol
So the activation energy for this reaction
is 60.9 kJ/mol

74

Solution for Q2:


The rate at 30C is
( 30 + 273 = 303K)
ln(k) = -7330.4(1/T) + 25.417 (given)
ln(k) = -7330.4(1/303K) + 25.417
ln(k) = 1.22
k = e 1.22
k = 3.40 Ms-1

75

Solution for Q3:


The temperature needed to double this
rate.( 3.4 x 2 = 6.8)
ln(rate) = -7330.4(1/T) + 25.417 (given)
ln(6.8) = -7330.4(1/T) + 25.417
1.91 = -7330.4(1/T) + 25.417
-23.50 = -7330.4(1/T)
T = 312K
= 312 273 = 39C

76

If we have two different k values at different


temperatures, you can combine the two
reactions to give:
ln k2 = Ea 1
k1 R T1

1
T2

Where T1 < T2

Example
The rate constant for the formation of HI at 600K and 650K
are measured and found to be 2.7x10-4 M-1s-1 and 3.5x10-3
M-1s-1, respectively. Determine the activation energy and
the rate constant at 800 K.
H2+I2 2HI
Solution

ln k2 = Ea 1
k1 R T1
ln (3.5x10-3 ) = Ea
(2.7x10-4 ) 8.314 Jmol-1
ln (13.0 )
Ea

= Ea
8.314 Jmol-1
=

1
T2
1

1
600K
650K

(1.28x10-4)

2.56 x 8.314 Jmol-1 = 1.66x105 Jmol-1


(1.28x10-4)
= 166 kJmol-1

Example
Solution
To determine rate constant at 800K.
ln k2
= Ea
(3.5x10-3 )
R

1 650

1
800

= 1.66 x 105 Jmol-1 (2.88 X 10-4 K-1)


8.314 Jmol-1
= 5.75
Taking the anti ln:
k2
= 314
3.5x10-3
The rate constant at 800 K, k2 = 314 (3.5x10-3 ) = 1.10 M-1s-1

81

TRY
The

rate constant of a reaction is 1.2 x 10 3


sec-1at 300C and 2.1 x 10-3sec-1at 400C.
Calculate the energy of activation of the
reaction.

ln k2 = Ea 1
k1 R T1
Answer:

1
T2

Ea= 44.168 kJ mol-1

Reaction Mechanism
Elementary reactions

+
Elementary reactions

Elementary reactions
Unimolecular

Bimolecular

Trimolecular

REACTION
MECHANISM
Reaction
intermediate
Fast
Slow

Rate determining step

Reaction Mechanisms
The overall progress of a chemical reaction can be represented
at the molecular level by a series of simple elementary steps
or elementary reactions.
The sequence of elementary steps that leads to product
formation is the reaction mechanism.
2NO (g) + O2 (g)

2NO2 (g)

Elementary step:

NO + NO

N 2 O2

+ Elementary step:

N2O2 + O2

2NO2

Overall reaction:

2NO + O2

2NO2

84
Intermediates are species that appear
in a reaction
mechanism but not in the overall balanced equation.

An intermediate is always formed in an early elementary step


and consumed in a later elementary step.
Elementary step:

NO + NO

N 2 O2

+ Elementary step:

N2O2 + O2

2NO2

Overall reaction:

2NO + O2

2NO2

The molecularity of a reaction is the number of molecules


reacting in an elementary step.

Unimolecular reaction elementary step with 1 molecule

Bimolecular reaction elementary step with 2 molecules

Termolecular reaction elementary step with 3 molecules

Rate Laws and Elementary Steps


85

Writing reaction mechanisms:

The sum of the elementary steps must give the overall


balanced equation for the reaction.

The rate-determining step should predict the same rate


law that is determined experimentally.

The rate-determining step is the slowest step in the


sequence of steps leading to product formation.

The experimental rate law for the reaction between NO 2


and CO to produce NO and CO2 is rate = k[NO2]2. The
reaction is believed to occur via two steps:
Step 1:
NO2 + NO2
NO + NO3
Step 2:

NO3 + CO

NO2 + CO2

What is the equation for the overall reaction?


NO2+ CO

NO + CO2

What is the intermediate?


NO3
What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 must be slower than step 2
13.5

Thank you!

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