For A B Z C D
r r Cz
where is a frequency
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
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)
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
h= Plancks constant
S o
h
3
exp(
) exp( ) 2
R
kt
2
H E RT
T
E E o C dT
0
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)
(1)
rcoll 2 C AC B
(2)
kT
~ 1013 sec 1
h
kT
S o
o
r
exp(
) exp(
)C ACB
h
R
RT
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
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
H heat of adsorption
(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 cPA
Freundlich 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.