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# Thermodynamic Formulation of Rates

For A B Z C D

## at equilibrium, r r and concentration Cz transition state rate

of reaction is equal to the number of molecules per unit volume
crossing the barrier per unit time.

r r Cz

where is a frequency

## The fundamental assumption of the transition-state theory is that if

now the products are removed form the system at equilibrium, that
rate of the reaction in one direction.

A B Z C D
is still given by the expression prevailing at equilibrium

r r Cz
when Cz is the con conentration of transition state in equilibrium with
reactants A and B.
Assumption believed to be generally valid.

Kc

CZ
C AC B

## usual thermodynamic relation

RT ln Kc= -Go= -Ho+TSo
R= gas constant
Go= change in standard Gibbs free energy
Ho= change in standard enthalpy
So=change in standard entropy

## denotes transition state

denotes standard states

A B Z

r C 2
C2 C AC B K C
r K c C AC B
S o
H o
K exp(
) exp(
)
R
RT
S o
H o
r exp(
) exp(
)C AC B
R
RT

(1)

need to determine
from gas kinetic theory, the rate of collision between two hard sphere
A and B of diameters A and B and masses mA and mB

rcoll 2 v CA CB

(2)

## v=(8kT/)mean molecular velocity

=

m A mB
m A mB

reduced mass

k= Boltzman constant
Can determinefrom expression (1) and (2) can calculated
Soand Ho terms from statistical mechanics
S o S to, AB S r , AB S to, A S to, B
S to 5
kt 1
3 ln( )
R
2
h
4
SR
kt 1
1 2 ln( ) ln( 4 2 )
R
h
4

rearranging terms

## (AB is missing vibrational model )

h= Plancks constant

S o
h
3
exp(
) exp( ) 2
R
kt
2

H E RT
T

E E o C dT
0

## Eo= 0 since there is no energy of interaction at 0 K

C is difference in molar heat capacities at constant volume
between transition state and reactants
C,A=C,B=3/2 R
C,AB=3/2R + R
C=- R/2
T

R
R
dT T
2
2

H E RT

RT
3
RT RT
2
2

H
3
exp(
) exp( )
RT
2

S o
o
r exp(
) exp(
)C A C B
R
RT

(1)

## substitute So and Ho terms

h
r 2 C A C B
kt
compare to equation (2)

(1)

rcoll 2 C AC B

(2)

kT
~ 1013 sec 1
h

kT
S o
o
r
exp(
) exp(
)C ACB
h
R
RT

## In order to have reaction, it is necessany not to surmount just an

energy barrier but a free energy barrier reaction requires a favorable
configuration, entropy, as well

## Transition state theory and the equation of Arrhenius

for unimolecular gas phase reaction while only one reactant is
involved in the elementary step and transition state

kT
S o
o
r
exp(
) exp(
)C A
h
R
RT
k
where k is first order rate constant
in Arrhenius expression

k A exp( E

RT

there

kT
S o
A
exp(
)
h
R

## thus, both A and E can be considered as independent of the

temperature. The temperature dependence is negligible
unless the temperature range becomes too wide .

LANGMUIR ISOTHERM
ASSUMPTIONS:
1. each surface site can accommodate only one adsorbed
species.
2. all surface sites identical and coverage effects are
negligible.
dn
dt
Fraction of unoccupied
surface sites

Gas phase
pressure of A

dn
rate of desorption A k ' A
dt des
Fraction of occupied
surface sites

at equilibriu m

dn A
dn

A
k (1 A ) PA k ' A
kPA (k ' k ' PA ) A

A
KA k

k'

K Ae H / RT

kPA
K A PA

k ' kPA 1 K A PA

(constant and independent of coverage)

A K A PA
A PA
A 1
f ( PA )

for K A PA 1
for K A PA 1

## A major objection of the Langmuir model is that for most

systems -H, heat of adsorption, is coverage dependent and
decreases with coverage. Nevertheless, this approach is
frequently made because of its simplicity and surprisingly it
yields sometimes even a reasonable modeling of the actual
situationprobably because several effects are able to
compensate each other.

A cPA

Freundlich Isotherm

## distribution of energies among the surface sites

-H decreases logarithmically with coverage
n related to mutual interaction of th adsorbed species
n >1 means adsorbed molecules repulse one another
Temkin Isotherm

RT
ln A0 PA
q0
heat decreases linearly with coverage.

H q q0 (1 )

q0 heat of ads., at 0 A0 a0 e q0 / RT

a0, constants.