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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

Kcequilibrium constant for

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)

=(A + B)/2 mean molecular diameter

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

weak temp, dependence

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.
3. adsorbed species is immobile.
A Aad
dn
rate of adsorption A ads k (1 A ) PA
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
dt ads dt des
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

Adsorption equilibrium constant.

H heat of adsorption
(constant and independent of coverage)

For strong adsorption HA is large, KA is large and A is large

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

for K A PA 1
for K A PA 1

High pressures and


strong adsorption

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.
Adsorption isotherms on Non-uniform surfaces

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.