Free Radical Chain Mechanism

k
1
1. Br
2
2 Br inititation
k
2
2. Br + H
2
HBr + H propagation
k
3
3. H + Br
2
HBr + Br propagation
k
4
4. H + HBr H
2
+ Br inhibition
k
5
5. 2 Br Br
2
breaking
experimental rate law:
d[HBr]
dt
=
k
a
[H
2
][Br
2
]
1
/
2
k
b
+k
c
[HBr]
[Br
2
]
I.
d[HBr]
dt
= k
2
[Br][H
2
] + k
3
[H][Br
2
] k
4
[H][HBr]

II.
d[Br]
dt
= 0 = 2 k
1
[Br
2
] k
2
[Br][H
2
] + k
3
[H][Br
2
] + k
4
[H][HBr] 2 k
5
[Br]
2

III.
d[H]
dt
= 0 = k
2
[Br][H
2
] k
3
[H][Br
2
] k
4
[H][HBr]

IV. add II + III : 0 = 2 k
1
[Br
2
] 2 k
5
[Br]
2
[Br] =

k
1
k
5
[Br
2
]
1
/
2

V. solve III for [H] : [H] =
k
2
[Br][H
2
]
k
3
[Br
2
]+k
4
[HBr]
=
k
2

k
1
k
5

1
/
2
[H
2
][Br
2
]
1
/
2
k
3
[Br
2
]+k
4
[HBr]

VI. subtract III from I:
d[HBr]
dt
= 2 k
3
[H][Br
2
]

substitute V into VI:
d[HBr]
dt
=
2k
3
k
2
k
1
1
/
2k
5
-1
/
2[H
2
][Br
2
]
1
/
2[Br
2
]
k
3
[Br
2
]+k
4
[HBr]


d[HBr]
dt
=
2k
3
k
2
k
1
1
/
2k
5
-1
/
2[H
2
][Br
2
]
1
/
2
k
3
+k
4
[HBr]
[Br
2
]
Explosions: 2 H
2
+ O
2
2 H
2
O
H
2
+ (O
2
) 2 OH initiation
H
2
+ OH H + H
2
O propagation
(O
2
) + H O + OH branching
O + H
2
OH + H branching