Chemistry Reference
In-Depth Information
equilibrium relation which is presumed to apply when the stage is not rate-
determining.
¨
(
)
HO
-
HO
-
[4.8]
2
2
(
)
-
v
=
k
c
1
-
q
k
q
[4.15]
1
1
-
-
-
1
-
HO
HO
HO
2
2
2
(
)
=
[4.32]
k
c
1
-
q
k
q
1
-
-
-
1
-
HO
HO
HO
2
2
2
¨
(
)
()
+
(
)
HO
-
O
-
OH
∑
[4.9]
2
ads
ads
ads
(
)
(
)
(
)
-
v
2
=
k
q
1
-
q
1
-
q
k
q
q
1
-
q
[4.16]
2
-
-
•
-
2
-
•
-
O
OH
O
OH
HO
HO
2
2
(
)
(
)
(
)
=
k
q
1
-
q
1
-
q
k
q
q
1
-
q
[4.21]
2
-
-
•
-
2
-
•
-
O
OH
O
OH
HO
HO
2
2
¨
(
)
()
+
OH
∑
+
OH
-
O
-
H O
[4.10]
2
ads
ads
(
)
-
(
)
v
=
k
q
c
1
-
q
k
q
1
-
q
[4.17]
3
3
•
-
-
-
3
-
•
OH
OH
O
O
OH
(
)
=
(
)
k
q
c
1
-
q
k
q
1
-
q
[4.22]
3
•
-
-
-
3
-
•
OH
OH
O
O
OH
¨
()
+
(
)
O
-
O O
-
-
+
H
-
[4.13]
2
2
ads
ads
(
)
-
v
¢ =
k
¢
c
q
1
-
q
k
c
q
(
1
-
q
)
[4.41]
4
4
-
-
-
-
4
-
-
-
O
OH
O
HO
O
O
2
2
2
(
)
=
(
)
k
c
q
1
-
q
k
¢
c
q
1
-
q
[4.42]
4
-
-
-
-
4
-
-
-
O
O
OH
O
HO
O
2
2
2
¨
(
)
O
-
O
+
e
-
[4.12]
2
2
ads
(
)
()
()
v
=
k
E
q
-
k
c
1
-
q
[4.19]
5
5
-
-
5
-
O
2
O
O
2
2
(
)
()
()
k
E
q
=
k
E c
2
1
-
q
[4.24]
5
-
-
5
O
-
O
O
2
2
On the basis of Equations 4.15, 4.21, 4.22, 4.42 and 4.24, the rate equation
was calculated with stage 1 of the reaction sequence as RDS:
2
2
kk
k
¢¢
2
cc
c
F
R
1
Ê
Á
ˆ
˜
(
)
-
EE
-
-
O
-
1
ref
v
¢ =
k
c
-
-
5
OH
2
e
T
1
1
-
HO
KKK
¢¢
2
¢¢
2
2
2
[4.43]
23
4
5
-
HO
2
It is clear that the anodic term does not meet the experimental observa-
tions and this over the entire potential area. Through Equations 4.16,
4.32, 4.22, 4.42 and 4.24, the rate equation was calculated with stage 2
of the reaction sequence as RDS under the additional condition that
k
-1
>> k
2
:
