Kinetics theory

Arrhenius law
The Arrhenius equation is founded on the empirical
observation, that raising the temperature increases
the rate of reaction
Quantitatively this relationship between the rate a
reaction proceeds and its temperature is determined
by the Arrhenius Equation:



Ea = activation energy
R = 8.314 J mol
-1
K
-1

T = absolute temperature in Kelvin
A = frequency factor/Arrhenius constant/ pre-
exponential factor



The Arrhenius equation is often written in
the logarithmic form:



A plot of ln k versus 1/T produces a straight
line, from which the activation energy, Ea,
can be determined because the slope is
equal to - Ea/ R.

The y-intercept represents the value for ln
A


"Two-Point" Arrhenius Equation
The Arrhenius equations for two temperatures (T
1

and T
1
) give two rate constants (k
1
and k
1
):
at T
1


at T
2
:

Combining the two Arhenieus equations yields

Example

The first order rate constant, k
1
, for thermal
decomposition of nitrogen pentoxide increase with
temperature as shown below. Evaluate the activation
energy, Ea and the Arrhenius pre-exponential factor A
for this reaction



A second order reaction in solution has a rate
constant of 5.7 x 10
-5
dm
3
mol
-1
s
-1
at 25 C and 1.64 x
10
-4
dm
3
mol
-1
s
-1
at 40 C. Calculate the activation
energy and the preexponential factor.

k
1
/10
-5
s
-1
3.4 13.5 76 487
T/K 298 308 323 338
Maxwell-Boltzmann Distribution

Maxwell and Boltzmann discovered that this
distribution may be described by plotting the fraction of
molecules in a container with a given kinetic energy vs
kinetic energy or average speed
As temperature increases, the curve will spread to the
right and the value of the most probable kinetic energy
will decrease.
as T increases, the fraction of molecules with energies
greater than the red line increase

Fraction of activated molecule :

|
.
|

\
|

RT
a
E
e
Example:

The activation energy for the decomposition of
hydrogen iodide is 184 kJ mol
-1
. Calculate the
fraction of activated molecules at 500K and
700K

COLLISION THEORY
Molecule must meet and collide

Molecule must transfer enough energy to
overcome the activation barrier (effective
collision)

They must meet in the right orientation.
Collision :
dwimolecule
Unimolecule
termolecule

DWIMOLECULE IDENTICAL COLLISION

rate of reaction :


Where Z
AA
= frequency of collision
Frequency Collision of n molecule A in 1 m
3
:


Where c = average speed of molecule A
d = collision diameter



1 3 RT
E
AA
s m molecule e Z
a

|
.
|

\
|

= u
2 2
2
1
AA
n c d 2 Z t =
Average speed can be calculated from kinetics
gas theory :


Where: k
B
= Boltzmann constant, 1.38 x 10
-23

J K
-1

m = mass of each molecule A
T = absolute temperature
Then, Frequency of collision, Z
AA
:



m
T k 8
c
B
t
=
m
T k
d n 2 Z
B 2 2
AA
t
=
Rate of reaction :
|
.
|

\
|

=
RT
E
B
2 2
a
e
m
T k
d n 2
t
u
NON-IDENTICAL DWIMOLECULE
COLLISION

Frequency of collision, Z
AB



Where : m
A
= mass of each molecule A
m
B
= mass of each molecule B
d = collision diameter
Rate of reaction :


|
|
.
|

\
| +
t =
B A
B A
B
2
AB B A AB
m m
m m
T k 8 d n n Z
|
|
.
|

\
|
|
|
.
|

\
| +
t = u

RT
a
E
B A
B A
B
2
AB B A
e .
m m
m m
T k 8 d n n
Rate constant:


Multiply with Avogadro number, N
A



|
|
.
|

\
|
|
|
.
|

\
| +
t =

RT
a
E
B A
B A
B
2
AB
e .
m m
m m
T k 8 d k
m
3
molecule
-1
s
-
1

|
|
.
|

\
|
|
|
.
|

\
| +
t =

RT
a
E
B A
B A
B
2
AB A
e .
m m
m m
T k 8 d N k
m
3
mol
-1
s
-1

Comparison with Arrhenius Equation

Pre-exponential factor, A for non-
identical molecule


Identical molecule :


Inserting stearic factor, P



|
|
.
|

\
| +
t =
B A
B A
B
2
AB A
m m
m m
T k 8 d N A
m
3
mol
-1
s
-1


m
T k
d N 2 A
B 2
AA A
t
=
m
3
mol
-1
s
-1

|
.
|

\
|

=
RT
a
E
PZe k
Example :
The collision diameter of hydrogen iodide at
298K calculated from measured viscosity
coefficient is 0.35 nm. Calculate the collision
number Z
AA
for HI (relative molecular mass =
128) at 700 K and 1 atm.

2HI H
2
+ I
2


The dwimolecular reaction has a rate constant
k
exp
= 3.3 x 10
-3
dm
3
mol
-1
s
-1
at 700K and an
activation energy of 170 kJ mol
-1
, calculate the
p factor necessary to give agreement between
the collision theory prediction for this rate
constant and that experimentally observed.