Topic 2:

Chemical
Kinetics
Part I:
Rate Law: Differential Law
Integrated Law
Reaction Mechanism

1
 2

Recall
3H2(g) + N2(g) 2NH3 (g)
Reaction is spontaneous at

298K as G =33.1 kJ.

But why we do not get NH3?
 3

Reaction rate is influenced by

Concentration of reactants
Pressure
Surface area
Temperature
Catalyst
 4

Learning Objectives:
Express the relationship between reaction
rate and concentration in an experimentally
determined rate law.
Determine order of reaction and deduce rate
law using initial rate data.
Calculate rate constant and concentration of
reactants using integrated rate law.
Deduce rate law from reaction mechanism.
 5

Reaction Rate:
Thechange in concentration of a
reactant or product per unit time,
expressed as mol L-1s-1

[ R ] [ P]
Rate = or
time time
 6

Reaction Rate
There are three ways to express the
reaction rate:

Slope of
Slope of
tangent at tangent
certain time. at time=0

Average Instantaneous Initial

 7

Find average rate of reaction

Average rate of reaction
= [ NO2 ]t =50 [ NO2 ]t =0
50 0
0.0079mol / L 0.0100mol / L
=
50 0
= 4.2 10 5 mol / L.s
8
 9

Find instantaneous rate

Instantaneous rate at t= 100s
= slope of the tangent line
=
[ NO2 ]
t
0.005 0.0075
=
160 50
0.0026
=
110
= 2.4 10 5 mol / L.s
 10

Rate Law:
Itis experimentally determined
relationship between the rate of a
reaction and concentrations of the
reactants.
 11

Rate Law: Differentiated Law

aA + bB + cC xX + yY

Rate = k[A] [B] [C]

where
k = specific rate constant
, , = order of reaction
 12

Order of reaction
experimentallydetermined power defining the
dependence of the reaction rate on the
concentration of a reactant
 13

Rate constant, k
proportionality constant that relates the rate of
a reaction to the concentrations of reactants.
Higher value of rate constant, higher rate of
reaction.
 14

First Order of Reaction

Rate

Rate [A]
Rate = k[A]1

Concentration of reactant A
 15

What does this mean?

Rate = k [A]

Double [A]

rate =21

rate is doubled.

Quadruple [A]

rate= 41

Rate is quadrupled.

Halved [A]
rate = (1/2)1

Rate is halved.
 16

Second order of reaction

Rate

Rate [B]2
Rate = k[B]2

Concentration of reactant B
 17

What does this mean?

Rate = k [B]2

Double [B]

rate =22

rate increases 4 times.

Quadruple [B]

rate= 42

Rate increases 16 times.

Halved [B]
rate = (1/2)2

Rate decreases times.
 18

Zeroth Order of Reaction

Rate
Rate = k[C]0

[C] increases,
Rate is constant.

Concentration of reactant C
 19

What does this mean?

Rate = k [C]o
no
Doubl rate
chan
e [C] =20
ge
no
Quadru rate=
chan
ple [C] 40
ge
Halve rate = no
d [C] (1/2) chan
0 ge
 20

Effect of [reactant] on rate

Order of Double [R] Quadruple [R] Halve [R]
reaction
0th No change No change No change
Rate =k

1st Increase by 21 Increase by 41 Decrease by

Rate = k[A]1

2nd Increase by 22 = 4 Increase by 42 = 16 Decrease by ()2

Rate = k[A]2 = 1/4
 21

How to determine order of

reaction?
By performing experiment.
Initial Rate method
Graphical method
Reaction mechanism
 22

Initial rate method

Initial rates from three experiments for the
reaction 2NO(g) + 2H2(g) N2(g) + 2H2O(g) at
300K.
Trial Initial [NO] Initial [H2] Initial rate
(M) (M) (mol.L-1s-1)
1 0.100 0.100 8.00x10-4
X2 X2
X2
2 0.100 0.200 X 4 1.6x10-3

3 0.200 0.100 3.2x10-3

 23

Finding reaction order

Rate Rate = k[H2]
= k[NO]
Trial 1: Trial 1:
8.0x10-4=k(0.100) 8.0x10-4=k(0.100)
Trial 3: Trial 2:

3.2x10-3 = k(0.200) 1.6x10-3 = k(0.200)

Trial 3/Trial 1: Trial 2/Trial 1:

3
3.2 10 . k (0.200) 1.6 10 3. k (0.200)
= =
8.0 10 4
k (0.100) 8.0 10 4
k (0.100)
4 = 2 2 = 2
=2 =1
 24

Write Rate Law:

2NO(g) + 2H2(g) N2(g) + 2H2O(g)
Rate Law:

rate = k[NO]2[H2]
Second order in NO and first order
in H2.
Overall order of reaction = 2+1 = 3
 25

Find the rate constant, k

Rate = k[NO2]2[H2]
What is the value of k?
Take trial 1:

8.0x10-4 = k(0.100)2(0.100)
k = 0.8
Unit of k =
mol / L.s
(mol / L) 3
= mol 2 L2 s 1
 Integrated
Rate Law
(1st Order of Reaction)

26
 27

The Integrated Rate Law

We will proceed by first looking at reactions
involving a single reactant:
aA products

all of which have a rate law of the form

d[A]
rate = = k[A] n

dt
 28

First-Order Rate Laws

For the case n = 1 (first order),
d[A]
rate = = k[A]
dt
the integrated first-order rate law is

ln [A] = -k t + ln [A]0 How to

integrate?
y= mx+ c
 29

First-Order Rate Laws

d[A]
rate = = k[A]
dt
1
d[A] = k dt
[A]
1
d[A] = k dt
[A]
A
ln [A] A = k t
0
t
t0
 30

First-Order Rate Laws

A
ln [A] A = k t 0
t
t0

( ln [A]) ( ln [A]0 ) = k (t - t 0 )
ln [A] + ln [A]0 = k t
ln [A] = k t + ln [A]0
y= mx+ c
 31

Example 1:
2N2O5(g) 4NO2(g) + O2(g)
[N2O5] Time
(mol L-1) (s)
0.1000 0
0.0707 50
Use data provided, verify that the rate law is first
0.0500 100

order in [N2O5] and calculate the rate constant.

0.0250 200
0.0125 300
0.00625 400
 32

Plot [N2O5] versus time graph

This is not a linear plot.

 33

2N2O5(g) 4NO2(g) + O2(g)

[N2O5] In [N2O5] Time
(mol L-1) (s)

0.1000 -2.303 0

0.0707 -2.649 50

0.0500 -2.996 100

0.0250 -3.689 200

0.0125 -4.382 300

0.00625 -5.075 400

 34

2N2O5(g) 4NO2(g) + O2(g)

 35

Solution:
The fact that the In[N2O5] versus time plot is a
straight line confirms that the reaction is first order in
N2O5 since it follows the equation:

ln [N2O5 ] = k t + ln [N2O5 ]0
 36

Solution:
Sincethe reaction is first order, the slope of the line
equals to k, where

5.075 (2.303)
slope =
400.0 0.00 s
= 6.93 10 3 s 1
k = 6.93 10 3 s 1
 37

Summary: First order of reaction

ln [A] = k t + ln [A]0
 Integrated
Rate Law
(2nd Order of Reaction)

38
 39

Second-Order Rate Laws

For the case n = 2 (second order),

[A]
rate = = k[A] 2

t
the integrated second-order rate law is

1 1
=k t +
[A] [A]0
y=mx+ c
 40

Example 2:
2C4H6(g) C8H12(g)
[C4H6] Time (a) What is the order
(mol/L) (s) of reaction with
0.01000 0 respect to C4H6?
(b) Calculate the
0.00625 1000
concentration of
0.00476 1800 C4H6 at 3000s.

0.00370 2800

0.00313 3600

0.00270 4400
 41

It is not a straight line,

so it is not zeroth order
in [C4H6].
 42

2C4H6(g) C8H12(g)

[C4H6] In [C4H6] Time

(mol/L) (s)
0.01000 -4.605 0

0.00625 -5.075 1000

0.00476 -5.348 1800

0.00370 -5.599 2800

0.00313 -5.767 3600

0.00270 -5.915 4400

43

It is not a straight line,

so it is not first order in
[C4H6].
 44

2C4H6(g) C8H12(g)
[C4H6] In [C4H6] 1 Time
(mol/L) [C 4 H 6 ] (s)
0.01000 -4.605 100 0

0.00625 -5.075 160 1000

0.00476 -5.348 210 1800

0.00370 -5.599 270 2800

0.00313 -5.767 320 3600

0.00270 -5.915 370 4400

45

Solution: (a)
1
[C 4 H 6 ] vs time is a
straight line.
So, it is second order
with respect to C4H6.
Rate = k[C4H6]2
k = slope
 46

Solution: (b)
Calculate the concentration of C4H6 after 1300 seconds.
1 1
= kt +
[ A] [ A]0
1 1
= ( slope )(1300) +
[ A] (0.0100)
= 6.14 10 2 (1300) + 100
1
= 179.82
[ A]
[ A] = 0.00556
 47

Summary: Second order of reaction

1 1
=k t +
[A] [A] 0
 Integrated
Rate Law
(0th Order of Reaction)

48
 49

Zero-Order Rate Laws

For the case n = 0 (zero order),
[A]
rate = = k[A] = k
0

t
the integrated zero-order rate law is

[A] = - k t + [A]0
y=mx+ c
 50

[Reactant] vs time graph:

Zero order reactions can
Example 3: be indicated by a linear
plot, with a descending
gradient k

Examples:
Catalytic degradation of ammonia:
Pt catalyst
2NH3(g) N2(g) +
3H2(g)

Photochemical synthesis of
hydrogen chloride:
UV
H2(g) + Cl2(g)
2HCl(g)
 51

Summary: Zero order of reaction

[A] = - k t + [A]0
 52

Summary:
 53

Decomposition of NO2

What is the order of reaction in [NO2]?

 54

Reaction Mechanism
A series of individual steps by means of which reactants
are converted to products.
 55

Reaction Mechanism
Reaction often occurs in several steps. The
rates of individual reactions involved in a
multi-step reaction determine the overall rate
expression of the overall reaction.
 56

Elementary Step
Each of these steps in the reaction mechanism
is called an elementary step.
The reaction order of an elementary step is the
same as its molecularity.
 57

Molecularity of the reaction

The number of species (molecules, atoms,
free radical, or ions) that collide in elementary
step is called the molecularity of the
reaction.
If
1 particle : Unimolecular
2 particles : Bimolecular
3 particles : Termolecular
 58

Molecularity of the Reaction

No reactions involve more than 3 particles

colliding simultaneously are known.
 59

Determine the rate law

Therate law of an overall reaction can be
determined from the molecularity of the rate
determining step.
The order of reaction with respect to each
reactant is determined by the number of
molecules appear in the rate determining step
and all steps before that.
 60

Example
Step 1:
NO2(g) + NO2(g) NO3(g) + NO(g) slow
Step 2:
NO3(g) + CO(g) NO2(g) + CO2(g) fast
_____________________________________
Overall reaction:
NO2(g) + CO(g) NO(g) + CO2(g)
 61

Rate Determining Step

The slowest step (with the highest activation
energy) in a series of individual steps is called
the rate determining step.
For instance,

NO2(g) + NO2(g) NO3(g) + NO(g) slow

is the rate determining step.
 62

Determine the order of reaction

NO2(g) +NO2(g)NO3(g)+NO(g)slow

There are 2 molecules of NO2 appear

in rate determining step,
So, Rate = k[NO2]2
 63

Reaction Intermediate
Reaction intermediate is product produced in
one step but consumed in the following step.
It appears in both side of reaction mechanism
but do not appear in the overall equation.
NO3 is an example of reaction mechanism in
the reaction shown.
 64

Reaction Intermediate
Step 1:
NO2(g) + NO2(g) NO3(g) + NO(g) slow
Step 2:
NO3(g) + CO(g) NO2(g) + CO2(g) fast
_____________________________________________________________
_____
Overall Equation:
NO2(g) + CO(g) NO(g) + CO2(g)

Intermediate: NO3
product of step 1 but consume in step 2 and do not
appear in overall equation.
 65

Catalyst
Step 1:
NO2(g) + NO2(g) NO3(g) + NO(g) slow
Step 2:
NO3(g) + CO(g) NO2(g) + CO2(g) fast
_____________________________________________________________
_____
Overall Equation:
NO2(g) + CO(g) NO(g) + CO2(g)
Catalyst : NO2
Reactant in step 1 but reappear as product in step 2
Substance that increase rate of reaction without being
consume in the reaction.
 66

Advance technique: Mechanisms with

a fast initial step(s)
Initialrate determining step means products
produced will be consumed instantaneously
by the consequence reaction steps.
If the rate determining step (slow step) is the
second or a subsequent step, there is a
tendency for its reactant to break apart in a
reversible reaction.
 67

For example:
Consider the reaction A + 2B E
For which the accepted mechanism is:

A + B C (Fast step)
B + C E (slow step/ RDS)
Because the second step is slow, C produced
can often break apart in reverse step as
depicted:
k1
A + B C (Fast step)
k-1
k2
B + C E (Slow step)
 68

Think..
1. Concentration of C in RDS will be lower than
expected.
2. At equilibrium, rate of forward reaction is
equals to the rate of reverse reaction.
.Step 1: Calculate [C] at equilibrium:

Forward step: RateFwd = k1[A][B]

Reverse step: RateRev = k-1[C]
At equilibrium: RateFwd = RateRev

k1[A][B] = k-1[C]

[C] =(k1/k-1)[A][B]-----(Eq 1)
 69

Step 2: Construct rate law based on the rate

determining step:
Slow step (RDS) rate law: Rate = k2[B][C]-----(Eq. 2)

By substituting (Eq. 1) into (Eq. 2):

k1 k 2
Rate = [ A][ B ]2
k 1
Use k to represent (k1k2)/k-1:
Rate = k[A][B]2
(k is a constant value at constant Temperature)
 70

Summary
A mechanism needs to satisfies both the
requirements from overall balance equation
and experimentally determined rate law.
The molecularity of rate determining step is the
same as reaction order displayed in rate law of
the overall reaction.
Rate = k [species in slow step]n

where n = number of particles

 71

Kinetics

Part I Part II

Rate Law Collision Theory

Transition
State Theory

Differential Integrated
Activation energy
Initial Rate Graphical
Frequency of collision
Method Method
rate = k Zero order [ A] = kt + [ A]0 Orientation
rate = k[ A] First order In[ A] = kt + In[ A]0
1 1
rate = k[ A]2 Second order = kt +
[ A] [ A]0
 72

Reference:
http://www.wwnorton.com/college/chemistry/gi
lbert/overview/ch14.htm
 73

Half lifes
The time required for a reactant to reach half its original
concentration is called the half-life of a reactant, t1/2.
 74

First-Order Reaction
First order of reaction has a
constant half life.
A general formula for t1/2 of a
first-order reaction can be
derived from the integrated
rate law:
0.693
t1/2 =
k
(independent on [A]0)
 75

Example:

Find the order of reaction and rate constant for

decomposition of N2O5.
 76

Solution:
From the concentration versus time graph, the
half lifes, t1/2 are constant.
First order of reaction has constant half life, so it
is first order in N2O5.
0.693
t1/ 2 =
k
0.693
k=
100
3
k = 6.93 10
 77

Second-Order Reaction
Half life increases in
second order reaction.
A general formula for
t1/2 of a second-order
reaction is:

1
t1/2 =
k[A] 0
(knowledge of [A]0 is needed)
 78

Zeroth-Order Reaction
Half life decreases in
zeroth order
reaction.
A general formula for
t1/2 of a zeroth-order
reaction is:

[A]0
t1/2 =
2k
(knowledge of [A]0 is needed)