Lecture 27

Ki ti Kinetics
The Arrhenius rate constant
Transition state rate constant
The Arrhenius equation The Arrhenius equation
The empirical observation is that: The empirical observation is that:
ln k =ln A
E
a
RT
for many reactions. This means that a plot of
ln(k) vs. 1/T gives a straight line.
RT
( ) g g
A is the pre-exponential or frequency factor.
E i th ti ti Al E
a
is the activation energy. Also:
k =Ae
E
a
/RT
k Ae
Experimental determination of
A h i t Arrhenius parameters
We can plot ln(k) vs. 1/T to determine the
activation energy activation energy.
E = R
d ln k
E
a
= R
d(1/T)
A plot of ln k vs. 1/T yields a
slope of -E /R and an intercept of ln A slope of -E
a
/R and an intercept of ln A.
A ti t d l th Activated complex theory
H

H
The diagramdepicts a reaction coordinate The diagram depicts a reaction coordinate.
The intermediate is the activated complex.
Th t iti t t The transition state
The activated complex is a distorted structure
that is intermediate between the structure that is intermediate between the structure
the reactants and that of the products.
At the peak of the potential energy surface
between the reactants and products lies the
transition state. The fundamental assumption
of acti ated comple theo is that the t ansition of activated complex theory is that the transition
state Is in equilibium with the reactants
and products and products.
A + B C

The assumption of equilibrium between

the reactants and the transition state
Since the formation of the activated complex C

occurs in equilibriumwith the reactants we can occurs in equilibrium with the reactants we can
express the equilibrium constant as
[C

]
K

[C]
[A][B]
K

=
and the rate constant is given by the product of
a frequency factor k
B
T/h for the formation of the q y
B
/
complex times the equilibrium constant.
H
f
*
H
r
*
K =
k
f
kk
r
H
o
H
rxn
The relationship of kinetics
d th d i and thermodynamics
The principle of microscopic reversibility requires p p p y q
that:
K =
k
f
k
Using definitions from thermodynamics and from
transition state theory:
k
r
transition state theory:
e
G
o
RT
=
e
G
f
*
/RT
e =
e
G
r
*
/RT
Note that at constant temperature the prefactor
k
B
T/h is the same for each of the rate constants.
The math behind the
i comparison
Using the definition of free energy: Using the definition of free energy:
G = H TS
for each free energy gives: for each free energy gives:
e
S
o
/R
e
H
o
/RT
=
e
S
f
*
/R
e
H
f
*
/RT
S
*
/R H
*
/RT
which can be separated into:
e
S
r
/R
e
H
r
/RT
and
e
H
o
/RT
=
e
H
f
*
/RT
e
H
r
*
/RT
e
S
o
/R
=
e
S
f
*
/R
e
S
r
*
/R
e
H
r
/RT
e
S
r
/R
The connection of entropy and
th l enthalpy
These equations imply simply that: These equations imply simply that:
S
o
=S
f
*
S
r
*
H
o
=H
f
*
H
r
*
Note that the relationship between the enthalpies
can be seen graphically in the energy diagram
th t t t d ith that we started with.
Note: and* have the same meaning Note: and* have the same meaning.
Relationship to the Arrhenius
parameters
The transition state rate constant
k = (k
B
T/h)e
-G

/RT
is
k = (k
B
T/h)e
S

/R
e
-H

/RT
and the Arrhenius rate constant is
k = Ae
-Ea/RT
which leads to the identification
A = (k
B
T/h)e
S

/R
The frequency factor depends
th ti l f th ti ti t on the exponential of the activation entropy.
E
a
= H

where E
a
is the activation enthalpy.