The speed with which the reactants

disappear and the products form is called

the rate of the reaction
A study of the rate of reaction can give
detailed information about how reactants
change into products
The series of individual steps that add up to
the overall observed reaction is called the
reaction mechanism

Kinetics
Dr. Saharman Gea

There are five principle factors that
influence reaction rates:
1) Chemical nature of the reactants
2) Ability of the reactants to come in contact
with each other
3) Concentration of the reactants
4) Temperature
5) Availability of of rate-accelerating agents
called catalysts








The progress of the reaction A B. The number of A molecules (in
red) decreases with time while the number of B molecules (in blue)
increases. The steeper the concentration versus time curve, the
faster the reaction rate. The film strip represents the relative number
of A and B molecules at each time.
Chemical nature of the reactants
Bonds break and form during reactions
The most fundamental difference in reaction rates
lie in the reactants themselves
Some reactions are fast by nature and others slow
Ability of the reactants to meet
Most reactions require that particles (atoms,
molecules, or ions) collide before the reaction
can occur
This depends on the phase of the reactants
In a homogeneous reaction the reactants are in
the same phase
For example both reactants in the gas (vapor) phase
In a heterogeneous reaction the reactants are
in different phases
For example one reactant in the liquid and the
second in the solid phase
In heterogeneous reactions the reactants meet
only at the intersection between the phases
Thus the area of contact between the phases
determines the rate of the reaction

Effect of crushing
a solid. When a
single solid is
subdivided into
much smaller
pieces, the total
surface area on all
of the pieces
becomes very
large.
Concentration of the reactants
Both homogeneous and heterogeneous reaction
rates are affected by reactant concentration
For example, red hot steel wool bursts into flames in
the presence of pure oxygen
Temperature of the system
The rates for almost all chemical reactions
increase as the temperature is increased
Cold-blooded creatures, such as insects and reptiles,
become sluggish at lower temperatures as their
metabolism slows down
Presence of a catalyst
A catalysts is a substance that increases the rate
of a chemical reaction without being consumed
Enzymes are biological catalysts that direct our
body chemistry
A rate is always expressed as a ratio
One way to describe a reaction rate is to
select one component of the reaction and
describe the change in concentration per
unit of time



Molarity (mol/L) is normally the
concentration unit and the second (s) is the
most often used unit of time
Typically, the reaction rate has the units
t
X
t t
t X t X
X
A
A
=

=
) of (conc.

) (
) at time of conc. at time of (conc.
respect to with rate
1 2
1 2
1 - 1 -
s L mol or
s
mol/L
By convention, reaction rates are reported
as a positive number even when the
monitored species concentration decreases
with time
If the rate is known with respect to one
species, the coefficients of the balanced
chemical equation can be used to find the
rates with respect to the other species
Consider the combustion of propane:


Compared to the rate with respect to
propane:
Rate with respect to oxygen is five times faster
Rate with respect to carbon dioxide is three
times faster
Rate with respect to water is four times faster
Since the rates are all related any may be
monitored to determine the reaction rate
) ( 4 ) ( 3 ) ( 5 ) (
2 2 2 8 3
g O H g CO g O g H C + +
A reaction rate is generally not constant
throughout the reaction
Since most reactions depend on the
concentration of reactants, the rate changes
as they are used up
The rate at any particular moment is called
the instantaneous rate
It can be calculated from a concentration
versus time plot

A plot of the concentration of HI versus time for the reaction:
2HI(g) H
2
(g) + I
2
(g). The slope is negative because we are
measuring the disappearance of HI. When used to express the
rate it is used as a positive number.
The rate of a homogeneous reaction at any
instant is proportional to the product of the
molar concentrations of the reactants raised
to a power determined from experiment




reaction for the constant rate the
] [ ] [ rate
as expressed be can reaction of rate The
reaction general For the
=
=
+
k
B A k
products B A
n m
Consider the following reaction:

From experiment, the rate law (determined
from initial rates) is

At 0
o
C, k equals 5.0 x 10
5
L
5
mol
-5
s
-1

Thus, at 0
o
C


O H I Se H I SeO H
2 3 3 2
3 2 4 6 + + + +
+
2 3 1
3 2
] [ ] [ ] [ rate
+
= H I SeO H k
2 3
3 2
1 5 5 5
] [ ] ][ [
) s mol L 10 0 . 5 ( rate
+

=
H I SeO H
- -
The exponents in the rate law are generally
unrelated to the chemical equations
coefficients
Never simply assume the exponents and
coefficients are the same
The exponents must be determined from the
results of experiments
The exponent in a rate law is called the
order of reaction with respect to the
corresponding reactant

For the rate law:

We can say
The reaction is first order with respect to
H
2
SeO
3

The reaction is third order with respect to I
-
The reaction is second order with respect to H
+

The reaction order is sixth order overall
Exponents in a rate law can be fractional,
negative, and even zero
2 3 1
3 2
] [ ] [ ] [ rate
+
= H I SeO H k
Looking for patterns in experimental data
provide way to determine the exponents in a
rate law
One of the easiest ways to reveal patterns in
data is to form ratios of results using
different sets of conditions
This technique is generally applicable
Again consider the hypothetical reaction
n m
M A k
products B A
] [ ] [ rate

=
+
Suppose the experimental concentration-
rate data for five experiments is:
5.40 0.30 0.30 5
2.40 0.20 0.30 4
0.60 0.10 0.30 3
0.40 0.10 0.20 2
0.20 0.10 0.10 1
) s L (mol ) L (mol ) L (mol Expt
Rate Initial ] [ ] [
Conc. Inital
1 - 1 - 1 - 1 -
B A
For experiments 1, 2, and 3 [B] is held
constant, so any change in rate must be due
to changes in [A]
The rate law says that at constant [B] the
rate is proportional to [A]
m
m
m m
m
A
A
A
A
2
L mol 10 . 0
L mol 20 . 0
] [
] [
2
s L mol 20 . 0
s L mol 40 . 0
rate
rate
] [
] [
rate
rate
1 -
1 -
1
2
1 - 1 -
1 - 1 -
1
2
1
2
1
2
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
Thus m=1
This means that the reactions is first order
with respect to reactant A
For experiments 3, 4, and 5 [A] is held
constant, so any change must be due to
changes in [B]
The rate law says that at constant [A] the
rate is proportional to [B]
n

Using the results from experiment 3 and 4:







The reaction is second order in B and
rate=k[A][B]
2

n
n n
n
B
B
B
B
2
L mol 10 . 0
L mol 20 . 0
] [
] [
4
s L mol .60 0
s L mol 40 . 2
rate
rate
] [
] [
rate
rate
1 -
1 -
3
4
1 - 1 -
1 - 1 -
3
4
3
4
3
4
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
|
|
.
|

\
|
=
Thus n=2
The rate constant (k) can be determined
using data from any experiment
Using experiment 1:



Using data from a different experiment
might give a slightly different value
1 - 2 - 2 2
2 1 - 1 -
-1 -1
2
s mol L 10 2.0
) L mol )(0.10 L mol (0.10
s L mol 20 . 0
] ][ [
rate
=
= =
B A
k
The relationship between concentration and
time can be derived from the rate law and
calculus
Integration of the rate laws gives the
integrated rate laws
Integrate laws give concentration as a
function of time
Integrated laws can get very complicated, so
only a few simple forms will be considered
First order reactions
Rate law is: rate = k [A]
The integrate rate law can be expressed as:



[A]
0
is [A] at t (time) = 0
[A]
t
is [A] at t = t
e = base of natural logarithms = 2.71828

kt
t
e A A kt
A
A

= =
0 t
0
] [ ] [ or
] [
] [
ln
Graphical methods can be used to determine
the first-order rate constant, note
b mx y
A kt A
kt A A
kt A A
kt
A
A
t
t
t
t


] ln[ ] ln[
] ln[ ] ln[
] ln[ ] ln[

] [
] [
ln
0
0
0
0
+ =
+ =
=
=
=

A plot of ln[A]
t
versus t gives a straight line
with a slope of -k
The decomposition of N
2
O
5
. (a) A graph of concentration versus
time for the decomposition at 45
o
C. (b) A straight line is obtained
from a logarithm versus time plot. The slope is negative the rate
constant.
The simplest second-order rate law has the
form

The integrated form of this equation is
2
] [ rate B k =
t B B
B B
kt
B B
t
t
at time of ion concentrat the ] [
of ion concentrat initial the ] [
] [
1
] [
1
0
0
=
=
=
Graphical methods can also be applied to
second-order reactions
A plot of 1/[B]
t
versus t gives a straight line
with a slope of k
Second-order
kinetics. A plot of
1/[HI] versus
time (using the
data in Table
15.1).
The amount of time required for half of a
reactant to disappear is called the half-life,
t
1/2

The half-life of a first-order reaction is not
affected by the initial concentration
k
t kt
A
A
A A t t
kt
A
A
t
t
2 ln
or
] [
] [
ln
ng substituti , ] [
2
1
] [ , at

] [
] [
ln : law rate order - First
2 / 1 2 / 1
0
2
1
0
0 2 / 1
0
= =
= =
=

First-order radioactive decay of iodine-131. The
initial concentration is represented by [I]
0.

The half-life of a second-order reactions does
depend on the initial concentration
0
2 / 1 2 / 1
0
2 / 1
0 0
2
1
0 2 / 1
0 t
] [
2 ln
or
] [
1
] [
1
] [
1
ng substituti , ] [
2
1
] [ , at

] [
1
] [
1
: law rate order - Second
B k
t kt
B
kt
B B
B B t t
kt
B B
t
= =
=
= =
=
One of the simplest models to explain reactions
rates is collision theory
According to collision theory, the rate of reaction
is proportional to the effective number of
collisions per second among the reacting
molecules
An effective collision is one that actually gives
product molecules
The number of all types of collisions increase with
concentration, including effective collisions
There are a number of reasons why only a
small fraction of all the collisions leads to
the formation of product:
Only a small fraction of the collisions are
energetic enough to lead to products
Molecular orientation is important because a
collision on the wrong side of a reacting
species cannot produce any product
This becomes more important as the complexity of
the reactants increases







The key step in the decomposition of NO
2
Cl to NO
2
and Cl
2
is
the collision of a Cl atom with a NO
2
Cl molecules. (a) A poorly
orientated collision. (b) An effectively orientated collision.
The minimum energy kinetic energy the
colliding particles must have is called the
activation energy, E
a

In a successful collision, the activation energy
changes to potential energy as the bonds
rearrange to for products
Activation energies can be large, so only a
small fraction of the well-orientated, colliding
molecules have it
Temperature increases increase the average
kinetic energy of the reacting particles








Kinetic energy distribution for a reaction at two different
temperatures. At the higher temperature, a larger fraction of the
collisions have sufficient energy for reaction to occur. The shaded
area under the curves represent the reacting fraction of the
collisions.
Transition state theory explains what
happens when reactant particles come
together
Potential-energy diagrams are used to help
visualize the relationship between the
activation energy and the development of
total potential energy
The potential energy is plotted against
reaction coordinate or reaction progress








The potential-energy diagram for an exothermic
reaction. The extent of reaction is represented as the
reaction coordinate.

A successful (a) and unsuccessful (b) collision for
an exothermic reaction.
Activation energies and heats of reactions
can be determined from potential-energy
diagrams
Potential-energy
diagram for an
endothermic
reaction. The
heat of reaction
and activation
energy are
labeled.
Reactions generally have different
activation energies in the forward and
reverse direction
Activation energy barrier for the forward and reverse reactions.
The brief moment during a successful
collision that the reactant bonds are partially
broken and the product bonds are partially
formed is called the transition state
The potential energy of the transition state
is a maximum of the potential-energy
diagram
The unstable chemical species that exists
momentarily is called the activated
complex

Formation of the activated complex in the reaction between
NO
2
Cl and Cl.
NO
2
Cl+ClNO
2
+Cl
2

The activation energy is related to the rate
constant by the Arrhenius equation


k = rate constant
E
a
= activation energy

e = base of the natural logarithm
R = gas constant = 8.314 J mol
-1
K
-1
T = Kelvin temperature
A = frequency factor or pre-exponential factor
RT E
a
Ae k
/
=
The Arrhenius equation can be put in
standard slope-intercept form by taking the
natural logarithm




A plot of ln k versus (1/T) gives a straight
line with slope = -E
a
/RT
x m b y
T R E A k
RT E A k
a
a


) / 1 ( ) / ( ln ln
or / ln ln
+ =
=
=

The activation energy can be related to the
rate constant at two temperatures


The reactions mechanism is the series of
simple reactions called elementary
processes
The rate law of an elementary process can
be written from its chemical equation
|
|
.
|

\
|

=
|
|
.
|

\
|
1 2 1
2
1 1
ln
T T R
E
k
k
a
The overall rate law determined for the
mechanism must agree with the observed
rate law
The exponents in the rate law for an
elementary process are equal to the
coefficients of the reactants in chemical
equation
2
2
3 2
] k[NO rate
NO NO 2NO
: process Elementary
=
+
Multistep reactions are common
The sum of the element processes must give
the overall reaction
The slow set in a multistep reaction limits
how fast the final products can form and is
called the rate-determining or rate-
limiting step
Simultaneous collisions between three or
more particles is extremely rate
A reaction that depended a three-body
collision would be extremely slow
Thus, reaction mechanism seldom include
elementary process that involve more than
two-body or bimolecular collisions
Consider the reaction


The mechanism is thought to be
tal) (experimen ] [H k[NO] rate
O 2H N 2H 2NO
2
2
2 2 2
=
+ +




The second step is the rate-limiting step,
which gives

N
2
O
2
is a reactive intermediate, and can be
eliminated from the expression
(fast) O H N H O N
(slow) O H O N H O N
(fast) O N 2NO
2 2 2 2
2 2 2 2 2
2 2
+ +
+ +

] ][H O N [ rate
2 2 2
k =
The first step is a fast equilibrium
At equilibrium, the rate of the forward and
reverse reaction are equal
2
2 2
2 2
2
2 2
2
NO] [ ] O N [
or ] O N [ NO] [
thus ] O N [ se) rate(rever
NO] [ rd) rate(forwa
r
f
r f
r
f
k
k
k k
k
k
=
=
=
=
Substituting, the rate law becomes





Which is consistent with the experimental
rate law
] H [ NO] [ ' rate
or ] H [ NO] [ rate
] H [ ] O N [ rate
2
2
2
2
2 2 2
k
k
k
k
k
r
f
=
|
|
.
|

\
|
=
=
A catalyst is a substance that changes the
rate of a chemical reaction without itself
being used up
Positive catalysts speed up reactions
Negative catalysts or inhibitors slow reactions
(Positive) catalysts speed reactions by
allowing the rate-limiting step to proceed
with a lower activation energy
Thus a larger fraction of the collisions are
effective

(a) The catalyst provides an alternate, low-energy path from
the reactants to the products. (b) A larger fraction of
molecules have sufficient energy to react when the catalyzed
path is available.
Catalysts can be divided into two groups
Homogeneous catalysts exist in the same phase
as the reactants
Heterogeneous catalysts exist in a separate
phase
NO
2
is a homogeneous catalyst for the
production of sulfuric acid in the lead
chamber process
The mechanism is:




The second step is slow, but is catalyzed by
NO
2
:
4 2 2 3
3 2
2
1
2
2 2
SO H O H SO
SO O SO
SO O S
+
+
+
2 2
2
1
3 2 2
NO O NO
SO NO SO NO
+
+ +
Heterogeneous catalysts are typically solids
Consider the synthesis of ammonia from
hydrogen and nitrogen by the Haber process

The reaction takes place on the surface of
an iron catalyst that contains traces of
aluminum and potassium oxides
The hydrogen and nitrogen binds to the
catalyst lowering the activation energy
3 2 2
2NH N 3H +

The Haber process. Catalytic formation of ammonia molecules
from hydrogen and nitrogen on the surface of a catalyst.