CHEM 43044

Chemical Kinetics

Textbooks
P. W. Atkins
The Elements of Physical Chemistry (Third Ed., Ch. 10)

P. W. Atkins
Physical Chemistry
Any Physical Chemistry Text Book; Levine, Daniel &
Alberty, Barrow.
Michael J. Pilling & Paul W. Seakins
Reaction Kinetics
K.J. Laidler
Chemical Kinetics

Chemical reaction
bonds break - this requires energy
bonds form - this releases energy
overall for the reaction
exothermic reaction - releases energy
endothermic reaction - absorbs energy

Will the reaction occur?

How far ?
How fast ?
How?

Chemical kinetics

"Everyone has Problems but Chemists have Solutions"

Will the reaction occur?

How far ?
How fast ?
How?

Chemical kinetics

Outline
Basic kinetics
Theories of reaction rates
- Collision theory
- Activated complex theory

Theories of unimolecular reactions

Liquid phase reactions

Kinetics
studies the rates at which chemical reactions
occur.
gives information about how the reaction
occur, that is, the reaction mechanism

Rate of reaction
Rate change in some variable per unit time

1
rate
time
reaction rate: change in concentration of a
product or a reactant per unit time.

change in concentration, c, in t
t

reactant

in [products]
in [reactants]
Rate = ______________
= ______________
change in time
change in time
rate = + d[product] = - d[reactant]
dt

dt

c
t

The rate is the instantaneous slope, and this varies

with time

d[concentration ]
rate =
dt

HUnits

ratio of concentration upon time,

i.e.
[(amount of material)(volume)-1] [time]-1
common units:

mol dm-3 s-1

Reaction Rates and Stoichiometry

O2 + 2H2 2 H2O
The molar ratios between reactants and products
correspond to the rates of reaction.
Relative rates relationship between rates of
reactant disappearance and product appearance at a
given time.
d[H 2 O]
d[O 2 ]
= 2
dt
dt

Or, equivalently

1 d[H 2 O] d[O 2 ]

=
2 dt
dt

1 d[A ]
r=
A dt
Where vA is the stoichiometric coefficient of
species A

RATE LAW
aA + bB products
Rate of reaction changes as concentration of
reactants change at constant temperature
RATE LAW:
equation describing the relationship between
concentration of a reactant and the rate

Rate = k[A]m[B]n

the rate equation

For the general reaction:
aA + bB + cC mM + nN .
-d[A]
= k [A]x [B]y [C]z
dt
the rate law can only be determined by experiment,
not from the stoichiometric equation
x is the order of the reaction with respect to A,
y is the order of the reaction with respect to B
the overall order of the reaction is given by x + y + z
there is no relationship between a and x, b and y .

THE RATE CONSTANT

1. The units of k depends on the overall order of
reaction
2. The value of k is independent of concentration
and time
3. The value refers to a specific temperature
and changes if we change temperature
4. Its value is for a specific reaction

Units

Types of Rate Laws

1. Differential rate law or rate law

Shows how the reaction rate changes

with concentration
2. Integrated rate law

Shows how concentration changes

with time
Graphical determination of the order

Deriving the Integrated Rate

Expressions
First-order reactions

B, then the rate of disappearance of A is:

d [ A]
R=
= k [ A]
dt
Rearranging gives:

d[ A]
= kdt
[ A]
At time t = 0, [A] = [A]0
And when t = t, [A] = [A]

Integrating:

d[A ]
= k
[A ]

Re call

that

dt

ln[ A ] = kt + const .

1
x dx = ln x

at t = 0 , [ A ] = [ A ] 0
ln[ A ] 0 = const .

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

= c

+ mx

Integrated form of the

1st order rate expression

Intercept = ln[A]0

slope = -k
ln[A]

t/s

Recall ln[A] = ln[A]o - kt

Antilog gives:

[A] = [A]0 e-kt

Intercept = [A]0

 Second-order reactions
Two possible cases:

Case I : A

Products

Case II : A + B

Products

d[ A ]
r=
= k[ A ]2
dt
Rearranging gives:

At time t = 0, [A] = [A]0

And when t = t, [A] = [A]

d[A ]
= kdt
2
[A ]

Integrating:

1
d [ A ] = k dt
2
[A ]

1
dx =
2
x

x 2 +1
1
1
dx =
= x =
2 +1
x

= kt + const .
[A ]
at t = 0 , [ A ] = [ A ] 0
1
1
= kt +
[A ]
[ A ]0

= const .
[ A ]0
Integrated form of the
2nd order rate expression

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

mx

slope = k
(1/[A]) / dm3 mol-1
Intercept = 1/[A]0
t/s

Case II :

A+B

Products

d[ A ]
r=
= k [ A ][ B ]
dt
If t=0, [A] = [B]

d[ A ]
r=
= k[ A ]2
dt

 Zero-order reactions
A

Products

d[ A ]
r=
= k [ A ]0
dt

1 d[A ] =

d[ A ]

=k
dt

k dt

[ A ] = kt + const

at t = 0 , [ A ] = [ A ] 0
[ A ] 0 = const .

[ A ] = kt + [ A ] 0
Plotting [A] versus t will give a straight line with slope -k.

Order

Rate law
Integrated
rate law
Straightline plot
Slope
Half-life
(t1/2)

zero

1st

2nd

rate = k

rate = k[A]

rate = k[A]2

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

[A] vs. t

ln[A] vs. t

1/[A] vs. t

[A]o/2k

0.693/k

1/k[A]0

Zero order:

1st order:

2nd order:

d[ A ]
= k[ A ]2
dt

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

Half life:

The half-life, t1/2, is defined as the time it takes for

the reactant concentration to drop to half its initial
value
It is a useful indication of the rate of a chemical reaction.

[ A]0
[ A]t 1
[ A]t =

= @ t1/ 2
2
[ A]0 2

 First-order reactions
Remember that for a 1st order reaction: ln[A]t = ln[A]0 - kt
At time t = 0, [A] = [A]0
Then at time t = t (half-life), [A]t = [A]0/2
Substituting into above equation,
ln([A]0/2) = ln[A]o kt
ln([A]0/2) ln[A]0 = -kt

[ A]0 / 2
= kt 1 / 2
ln
[ A]0
1
ln = kt 1 / 2
2
ln 1 ln 2 = -kt, where ln 1 = 0
Therefore, ln 2 = kt

Hence,

t1 / 2

ln 2
=
k

t1 / 2

or

0.693
=
k

What is/are the main point(s) to note from this expression??

For a 1st order reaction, the half-life is independent of reactant
concentration but dependent on k.
The half-life is constant for a 1st order reaction
[A]0

concentration
[A]0/2
[A]0/4
[A]0/8

Recall: [A]t = [A]0e-kt

t1/2
t1/2

t1/2

time

Note: Radioactive decay

follows 1st order kinetics.

 Zeroth-order reactions
Dependent on initial concentration

t1/ 2

[A]0
=
2k

 Second-order reactions
1
1
=
+ kt
[A]t [A]0
At time t = 0, [A] = [A]0
And when t = t, [A]t = [A]0/2

1
1
=
+ kt
[A ]0
[A ]0
2

2
1
=
+ kt
[ A ]0
[ A ]0

1/2

1/ 2

1
= kt 1 / 2
[ A ]0
1
t1/2 =
k [ A ]0

So t1/2 for 2nd order reactions

depends on initial concentration

Therefore, larger initial concentrations imply shorter half-lives

(so faster the reaction).

[A]0

concentration
[A]0/2
[A]0/4

t1/2

t1/2

[A]0/8

time

t1/2

Arrhenius Equation
Arrhenius developed an equation for the mathematical
relationship between k and Ea.
E
k = A exp a
RT

Ea = activation energy (kJ mol-1), and is the

minimum kinetic energy required to allow reaction to occur

A = the frequency factor or pre-exponential factor (same units as k),

is the fraction of sufficiently energetic collisions that actually
lead to reaction.

T = Kelvin temperature
R = ideal gas constant (8.314 J mol-1 K-1)
k is the rate constant

 Ea
k = A exp

RT

 Ea
k = A exp

RT

Arrhenius Equation
k = Ae

Ea
RT

Ea
ln k = ln A
RT
E a 1
ln k = + ln A
R T
y

Ea
m=
Ea = m R
R

R = 8.3145 molJ K
T in K