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International Journal of Chemical Engineering
/
2011
/
Article
/
Sch 4
/
Review Article
Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen
Scheme 4
Nonbranched-chain oxidation of hydrogen and changes in enthalpy (
Δ
𝐻
∘
2
9
8
, kJ mol
−1
) for elementary reactions.
9
Chain initiation:
(1)
H
2
ℎ
𝜈
,
𝛾
−
−
−
→
2
H
•
,
Δ
H
∘
2
9
8
=
4
3
6
.
0
±
0
.
0
.
Chain propagation:
(2)
H
•
+
O
2
𝑘
2
−
→
H
O
•
2
,
Δ
H
∘
2
9
8
=
−
2
0
5
.
4
±
1
.
7
;
(3)
H
O
•
2
+
H
2
𝑘
3
−
→
H
2
O
+
H
O
•
,
Δ
H
∘
2
9
8
=
−
2
1
5
.
4
±
2
.
9
;
(
o
r
H
2
O
2
+
H
•
)
,
Δ
H
∘
2
9
8
=
6
9
.
4
±
1
.
7
;
(3′)
H
O
•
+
H
2
𝑘
3
′
−
−
→
H
2
O
+
H
•
,
Δ
H
∘
2
9
8
=
−
6
2
.
8
±
1
.
2
.
Inhibition:
(4)
H
O
•
2
+
O
2
𝑘
4
−
→
H
O
•
4
,
Δ
H
∘
2
9
8
=
1
1
0
.
0
±
1
5
.
4
.
Chain termination:
(5)
2
H
•
(
+
M
)
2
𝑘
5
−
−
→
H
2
(
+
M
)
,
Δ
H
∘
2
9
8
=
−
4
3
6
.
0
±
0
.
0
;
(6)
H
•
+
H
O
•
4
𝑘
6
−
→
H
2
O
2
+
O
2
,
Δ
H
∘
2
9
8
=
−
4
7
6
.
6
±
1
3
.
7
,
(
o
r
∶
H
2
O
+
O
3
,
Δ
H
∘
2
9
8
=
−
4
3
9
.
3
±
1
5
.
4
,
H
2
+
2
O
2
)
,
Δ
H
∘
2
9
8
=
−
3
4
0
.
6
±
1
3
.
7
;
(7)
2
H
O
•
4
2
𝑘
7
−
−
→
H
2
O
2
+
3
O
2
,
Δ
H
∘
2
9
8
=
−
3
8
1
.
2
±
2
7
.
4
,
(
o
r
:
H
2
O
+
O
3
+
2
O
2
,
Δ
H
∘
2
9
8
=
−
3
4
3
.
9
±
2
9
.
1
,
H
2
O
2
+
2
O
3
,
Δ
H
∘
2
9
8
=
−
9
5
.
0
±
3
0
.
8
,
H
2
+
4
O
2
)
,
Δ
H
∘
2
9
8
=
−
2
4
5
.
2
±
2
7
.
4