What do we mean by

kinetics?
Kinetics refers to
the rate at which chemical
reactions occur.
The reaction mechanism or
pathway through which a
reaction proceeds.

2.

Factors That Affect Reaction Rates

The Nature of the Reactants

Chemical compounds vary considerably in their

chemical reactivities.

Concentration of Reactants

As the concentration of reactants increases, so does

the likelihood that reactant molecules will collide.

Temperature

At higher temperatures, reactant molecules have

more kinetic energy, move faster, and collide more
often and with greater energy.

Catalysts

Change the rate of a reaction

by changing the mechanism.

3.

Concentration and Rate

NH4+ (aq) + NO2- (aq) N2 (g) + 2H2O (l)

This equation is called the rate law, and k is the

rate constant.
4.

What are the correct units for a second order

rate constant?
a) mol/L s d) L2/mol2 s
b) 1/s e) mol2/L2 s
c) L/mol s

The Rate Law

A rate law shows the relationship between the
reaction rate and the concentrations of reactants.
For gas-phase reactants use PA instead of [A].
k is a constant that has a specific value for each
reaction.
The value of k is determined experimentally.

Rate = K [NH4+ ][NO2- ]

Constant is relative herethe rate constant k is unique for each reaction
and the value of k changes with temperature
6.

The Rate Law

Exponents tell the order of the reaction
with respect to each reactant.
This reaction is
First-order in [NH4+]
First-order in [NO2]
The overall reaction order can be found
by adding the exponents on the reactants
in the rate law.
This reaction is second-order overall.

Rate = K [NH4+ ]1[NO2- ]1

7.

Order of reaction
The number of reactant
molecules which determine the
rate of reaction and sum of
power of all the concentration
terms in the rate equation of the
reaction is known as Order of
reaction.

According to rate law of

reaction

Reaction order, or overall order = n

+m+p

Unit of Rate constant K for given n

order of reaction
=(conc)1-nx
(Time)-1

Illustrative Example
For a reaction, aA + bB + cC proucts,
rate expression can be expressed as rate
= k[A]1[B]-3/2[c]1/2, Write the order of the
reaction with respect to A , B, and C.
Solution
What
is: the overall order of the reaction?

Order of the reaction w.r.t. A = 1

Order of the reaction w.r.t. B = -3/2

Order of the reaction w.r.t. C = 1/2

Overall order of the reaction = 1 + (-3/2) + 1/2 = 0

Illustrative Example
For a first order reaction, A P,
half life is 69.3 min. Calculate the
time taken to decay the amount
Solution:
of
A to 80%.
t1 / 2 69.3 min or

0.693
t1 / 2

0.693
0.01min1
69.3

2.303
100
log
[Q 80% reaction is complete]
t
20

2.303
10

log5 160.97 min.

A certain first order reaction, A ----> B, when

performed at 25 oC, is 46% complete after 68
min. What is the rate constant of this
reaction?
A
9.06 x 10-3 min-1
)
B
1.14 x 10-2 min-1
)
C
31 min-1
)
D
-1.14 x 10-2 min-1
)
E
51 min-1
)

A reaction and its rate law are given below. When [C4H6] = 2.0 M, the rate is
0.106 M/s.
What is the rate when [C4H6] = 4.0 M?
2 C4H6 C8H12
Rate = k[C4H6]2
a) 0.053 M/s d) 0.424 M/s
b) 0.212 M/s e) 0.022 M/s
c) 0.106 M/s

Illustrative Example
The half-life of a substrate in a certain
enzyme-catalyzed first order reaction is 138
s. How long will it require for the initial
concentration of substrate, which was 1.28
mmol/L,
Solution: to fall to 0.040 mmol/L?
[A]0
2.303
log

k
[A]
t 690 second-1
t

2.303 138
1.28
log

0.693
0.040

Rate constant k for 2 order of

reaction
K for 2 order of reaction 1/(a-x)
=
1
-1/a
t

T1/2=

1/k x a

What is the unit of k for 2 order of reaction=?

Practice
It took 143 s for 50.0% of a particular
substance to decompose. If the initial
concentration was 0.060 M and the
decomposition reaction follows second
order kinetics, what is the value for the
rate constant?

Rate constant k for 3

order of reaction
K= 1
x
21/a2

1/(a-x)2

K=

2 xa2 xT

1/2

hat is the unit of k for 3 order of reaction =?

Initial rates in a series of

experiments for the
reaction
reactant
between O2 andinitial
NO
concentrations (mol/L)

experiment
1
2
3

initial rate
(mol/L.s)

1.10 x 10-

N
O
1.30 x 10-

2.20 x 10-

1.30 x 10-

6.40 x 10-

1.10 x 10-2

2.60 x 10-

12.8 x 10-3

O2

3.21 x 10-3

4
5

3.30 x 10-

1.30 x 10-

9.60 x 10-

1.10 x
10-2

3.90 x 10-

28.8 x 10-

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Manipulating the Data

rate 2
rate 1
rate 2
rate 1

k[O2]2m[NO]2n
=
k[O2]1m[NO]1n
=

[O2]2m
[O2]1

([NO] is held constant)

= ([O2]2 / [O1]1)m

6.40 x 10-3 mol/L/s=

(2.20 x 10-2 mol/L/ 1.10 x 10-2 mol/L)m
3.21 x 10-3 mol/L/s
1.99 = (2.00)m
m=1

Thus, the reaction is first order with respect

to O2.
When [O2] doubles, the rate doubles.

rate 3
rate 1

k[O2]3m[NO]3n
m

k[O2]1 [NO]1

([O2] is held constant)

via same manipulations as before:

3.99 =
(2.00)n
n=2

Thus, the reaction is second order with

respect to NO.
When [NO] doubles, the rate quadruples.
2
The rate law is: rate = k[O2][NO]

The reaction is third order overall.

Determining reaction order from initial

rate
data
PROBLEM Many gaseous reactions occur in a car engine and
:

exhaust system. One such reaction is as follows:

NO2(g) + CO(g)

NO(g) + CO2(g)

rate = k[NO2]m[CO]n

Use the following data to determine the individual and overall

reaction orders.
experiment initial rate
initial [CO]
initial [NO2]
(mol/L)
.s)
(mol/L)
(mol/L
1
0.10
0.005
0.10
0
2
0.10
0.080
0.40
3

0.005
0

0.10

0.20

SOLUTIO
rate = k
N:
[NO2]m[CO]n
First, choose two experiments in which [CO] remains constant and
[NO2] varies.

(continued)
k [NO2]m2[CO]n2 [NO2] 2 m
=
=
m
rate 1
k [NO2] 1
[NO2] 1
[CO]n1 m
0.080
0.40
The reaction is
=
; 16 = 4m and m = 2
2nd order in
0.005
0.10
NO2.
0
rate 3
k [NO2]m3[CO]n3 [CO] 3 n
=
=
m
rate 1
k [NO2] 1
[CO] 1
[CO]n1n
0.005
0.20
The reaction is
n
;
1 = 2 and n = 0 zero order in
=
0
0.005
0.10
CO.
0
rate 2

Rate Law: rate = k [NO2]2[CO]0 = k

[NO2The
]2 reaction is second order overall.

Illustrative Problem
For the reaction

A+B

Products

The following initial rates were obtained at

various given intial concentrations
S. No [A][B]Rate (mol lt1 sec1)
1. 0.1

0.1

0.05

2. 0.2

0.1

0.10

3. 0.1

0.2

0.05

Write rate law and find the rate constant of the

above reaction.

Solution
-

dx
= k[A]'[B]o = k[A]
dt

Rate constant, k =

0.05
= 510-1 s-1
0.1

Exercise
Determine the rate law and the value of the
rate
constant for the following reaction.
2 NO + Br2 2 NOBr
Experiment
[NO]0
[Br2]0
Initial Rate

(mole/L s)

0.1

0.1

4.0x10-4

0.2

0.2

1.6x10-3

0.5

0.1

1.0x10-2

0.5

0.5

1.0x10-2

Temperature and Rate

Generally speaking, the
reaction rate increases
as the temperature
increases.
This is because k is
temperature dependent.
As a rule of thumb a
reaction rate increases
about 10 fold for each
10oC rise in temperature

26.

The Collision Model

In a chemical reaction, bonds
are broken and new bonds are
formed.
Molecules can only react if they
collide with each other.
These collisions must occur with
sufficient energy and at the
appropriate orientation.
27.

The Collision Model

Furthermore, molecules must collide with
the correct orientation and with enough
energy to cause bonds to break and new
bonds to form

28.

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.

29.

Reaction Coordinate
Diagrams
It is helpful to
visualize
energy changes
throughout a
process on a
reaction
coordinate
diagram like
this one for the
rearrangement
of methyl
isonitrile.
30.

Reaction Coordinate Diagrams

It shows the energy of
the reactants and
products (and,
therefore, E).
The high point on the
diagram is the
transition state.

The species present at the transition state is

called the activated complex.
The energy gap between the reactants and
the activated complex is the activation
energy barrier.
31.

MaxwellBoltzmann
Distributions
Temperature is
defined as a
measure of the
average kinetic
energy of the
molecules in a
sample.

At any temperature there is a wide

distribution of kinetic energies.
32.

MaxwellBoltzmann Distributions

As the temperature
increases, the
curve flattens and
broadens.
Thus at higher
temperatures, a
larger population of
molecules has
higher energy.

33.

MaxwellBoltzmann
Distributions
If the dotted line represents the activation energy,
as the temperature increases, so does the fraction
of molecules that can overcome the activation
energy barrier.

As a result, the
reaction rate
increases.

34.

MaxwellBoltzmann
Distributions
This fraction of molecules can be found through the expression:

where R is the gas constant and T is the temperature in Kelvin .

35.

Arrhenius Equation for 2 Temperatures

When measurements are taken for two different
temperatures the Arrhenius equation can be
symplified as follows:

Write the above equation twice, once for each of the two
Temperatures and then subtract the lower temperature
conditions from the higher temperature. The equation then
becomes:

36.

Arrhenius Equation Sample Problem 1

The rate constant for the decomposition of
hydrogen iodide was determined at two different
temperatures
2HI H2 + I2.
At 650 K, k1 = 2.15 x 10-8 dm3 mol-1s-1
At 700 K, k2 = 2.39 x 10-7 dm3 mol-1s-1
Find the activation energy for this reaction.

-7
2.39
x
10
Ln ---------------- = - Ea
------------------------ x
2.15 x 10-8
(8.314 J mol-1 K-1)

1 -- -----1
-----700K 650K

Ea = 180,000 J mol-1 = 180 kJ mol-1

37.