Derivation of equation E a U o RT

H o S o
k BT RT
Transition state theory k [e e R ]
h
k T S o
H o
ln k ln B (1)
h R RT
For ideal gas behavior H o U o PV o
U RTn ( 2 )
o

Where n# = No. of moles of activated complex- No. of moles of

reactant = 1-m (3)

From ( 2 ) H o
U o
( 1 m )RT ( 4 )
Not for ideal gas behavior : U o & S o are R independent of T
 o
K BT S H o
ln k ln (1)
h R RT

Differentiate equation (1) w.r.t. T

d d K BT d So d H o
(ln k ) ln
dT dT h dT R dT RT
h K B
0
1 o 1 d
H Uo
(1 m)RT
K BT h RT RT dT
2

From ( 2 ) H o U o ( 1 m )RT ( 4 )

1 1 o 1
2
H (1 m)R
T RT RT

1
RT H o
(1 m ) RT
1

RT
2 RT H o
RT mRT
RT
2

d 1 o
(ln k ) 2
( H mRT) (5)
dT RT
 Starting with Arrhenius Equation

1
ln k ln A Ea
RT
Differentiate w.r.t. T

1 1
d
ln k 0 2 Ea 2 Ea (6 )
dT RT RT
d 1
Compare eq ( 5 ) with ( 6 ) (ln k ) 2
( H o
mRT ) ( 5 )
dT RT
Ea H o mRT ( 6 A )

From ( 2 ) H o U o ( 1 m )RT ( 4 )
Ea U o ( 1 m )RT mRT
Ea U o RT mRT mRT

Ea U o RT