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Rate equation for surface reaction as rate controlling

So S Sa Sb  Sc  Sd1

Assume that the reaction is like

A  g   B  g 

Catalyst
C(g)D(g) 2

 AS
Step1:
k1
 AS )  3
k '1

(BS)  4
k2
Step2: BS
k'2


Step3:(AS)(BS)
k3
(CS)(DS)  5
k '3


Step4: (CS)
k4
CS  6
k '4


Step5:(DS)
k5
D+S-7
k '5

If we consider surface reaction as rate controlling

rk3 (AS)(BS) k'3(CS)(DS)  8

The measurable quantity in these equations are A, B,C and D. Rest of the variables are not
measurable.

Except rate controlling step, all the other steps are considered to be in ‘thermodynamic equilibrium’.

When equation 5 is considered to be the rate controlling step, all the other steps are assumed to be in
equilibrium.

From step 1,

AS k
K1  1  9
A S k '1

Step 2,

BS k
K 2  2  10
BS k '2

Step 4,

CS k
K 4  4  11
CS k '4

Step 5,

DS k
   5  12
DS k '5
Substituting equation 9, 10, 11, 12 in equation 8.

We get,

r k3[K1 .A.S][K
 2 .B.S]k'3[K 4 .C.S][K
 5 .D.S] 13

K 4 .K 5
r [k 3 .K1 .K 2 .A.B C.D]S2  14
K 2.K1.Keq
k3
KeqK 
k '3
So S Sa Sb  Sc  Sd  Su
So S  (AS)  (BS)  (CS)  (DS)  (US)  15
So  S K1 . A.S K 2 .B.S  K 4 .C.S  K 5 D.S  Ku.U .S  16
So
S  17
1  K1 A  K 2 B  K 4C  K 5 D  KuU
Substituting equation17in14,
weget ,
C .D
K 3 .K1.K 2 .So 2 (A.B )
r  Ko  18
(1  K1. A  K 2 .B  K 4 .C  K 5 .D  Ku.U ) 2
Cc  CD
K (C A .C B  )
r  Ko  19
(1  K1C A  K 2 C B  K 4 CC  K 5C D  Ku .U) 2
where,        So 2
P C .PD
k (PA .PB  )
r= Ko  20
(1  K1 .PA  K 2 .PB  K 4 .PC  K 5 .C D  Ku .Pu)2
P
C
RT


C  D
Rate equation when A  B

In catalytic reaction, denominator is inhibiting the reaction.

 The square in the denominator indicates that there are two sites involved in the reaction.
 Similarly, K3 is not a part of the term which indicates that surface reaction is rate controlling.
 Therefore, conduct experiment to find out K values.
Adsorption Control (A)

CR
K [CA  ]
r Ko  21
K3
[1 ( K 3 ) CR KuCu]
K2
Commonterminequation20&21iscalled asdriving force.

CR
If reaction is not reversible will not be there.
Ko