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Transition State Theory

Transition state theory describes the chemical reaction process. It states that reactants form an unstable intermediate activated complex during the reaction, where bonds are breaking and forming to generate products or revert back to reactants. The rate constant of the reaction can be represented by the Eyring equation, which relates the activation enthalpy and entropy to temperature and other constants. A plot of the Eyring equation yields a straight line that can be used to determine the activation enthalpy and entropy of the reaction. The activation energy is similar but slightly greater than the activation enthalpy due to additional temperature-dependent terms.

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Nurshuhada Nordin
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1K views10 pages

Transition State Theory

Transition state theory describes the chemical reaction process. It states that reactants form an unstable intermediate activated complex during the reaction, where bonds are breaking and forming to generate products or revert back to reactants. The rate constant of the reaction can be represented by the Eyring equation, which relates the activation enthalpy and entropy to temperature and other constants. A plot of the Eyring equation yields a straight line that can be used to determine the activation enthalpy and entropy of the reaction. The activation energy is similar but slightly greater than the activation enthalpy due to additional temperature-dependent terms.

Uploaded by

Nurshuhada Nordin
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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TRANSITION STATE THEORY

During a chemical reaction the reactants are getting


over into an unsteady intermediate state:



The activated complex (AB
#
)is formed
an unstable arrangement, in which bonds break and
form to generate the products C or to degenerate back
to the reactants A and B.



The rate constant of the reaction can be represent by the Eyring
equation or Wayne-Eyring-Jones



H is the amount of heat of a system with constant pressure.
AH
#
is the enthalpy difference between the activated complex
and the reactants A and B.
It is called activation enthalpy
S is for the entropy, the extent of randomness or disorder in a
system.
AS
#
is The entropy difference between activated complex and
the reactants
it is called activation entropy.
k
B
= Boltzmann constant
h = planck constant
T= Absolute temperature

Additionally thermodynamics gives a further
representation of the driving power for a reaction, AG
#

(free activation enthalpy).


Reduces of AG
#
, increase the rate of reaction
The sign of AG
#
determines if a reaction is spontaneous or
not.

AG
#
< 0 = reaction is spontaneous
AG
#
= 0 = system at equilibrium, no net change occurs
AG
#
> 0 = reaction is not spontaneous

A linear expression of Eyring equation:



A plot of ln(k/T) versus 1/T will be a straight line (Figure 2)
with a slope of m = - AH
#
/ R
AH
#
can be calculated from the slope of this line.
Multiplying -m by -R (-8.314J/molK) yields AH
#
.
AS
#
can be determined and thus is enabled the calculation
of AG
#
for the appropriate reaction temperatures



The activation energy Ea is not exactly equal to the
activation enthalpy AH
#
, but is greater than it by a
small amount (the difference is RT).

AH
#
= AU
#
+ PAV
#


E
a
= AH
#
- PAV
#
+ RT

Where : AV
#
= changes of volume

Comparison between the Arrhenius law
and the Eyring equation
#
a
U RT E A + =
AV
#
for liquid system are too small and for
unimolecular reaction is zero., PAV
#
= 0
Therefore : E
a
= AH
#
+ RT
Therefore: Eyring equation,



Pre-exponential factor, A
|
.
|

\
|

|
|
.
|

\
|
A
|
.
|

\
|
=
RT
a
E
R
#
S
B
e e
h
T k
e k
|
|
.
|

\
|
A
|
.
|

\
|
=
R
#
S
B
e
h
T k
e A
A linear expression of Eyring equation;



Slope of the graph =

Intercept =
RT
E
h
k
ln
R
S
1
T
k
ln
a B
#
|
.
|

\
|
+
|
|
.
|

\
|
+ =
|
.
|

\
|
A
R
E
a

|
.
|

\
|
+
|
|
.
|

\
|
+
h
k
ln
R
S
1
B
#
A
For an ideal gas in transition state,


An
#
= -1 = 1 molecule (hasil AB
#
) 2 molecule (A and
B)
Then : E
a
= AH
#
+ 2RT
Eyring equation becomes;


Linear expression;


|
.
|

\
|

|
|
.
|

\
|
A
|
.
|

\
|
=
RT
a
E
R
#
S
B 2
e e
h
T k
e k
RT
E
h
k
ln
R
S
2
T
k
ln
a B
#
|
.
|

\
|
+
|
|
.
|

\
|
+ =
|
.
|

\
|
A
Slope of the graph =

Intercept =

Small values of Ea and AH
#
- fast rate
large values of Ea and AH
#
- slow rate
ln A small, corresponding to very negative values of AS
#
-
slow rate
ln A large, corresponding to relatively positive values of
AS
#
- fast rate

R
E
a

|
.
|

\
|
+
|
|
.
|

\
|
+
h
k
ln
R
S
2
B
#
A

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