Free Radical Chain Mechanism

k1
1. Br2 → 2 Br inititation experimental rate law:
k2
2. Br + H2 → HBr + H propagation
k3 d[HBr] ka [H2][Br2]1/2
3. H + Br2 → HBr + Br propagation dt = [HBr]
k4 kb + kc
4. H + HBr → H2 + Br inhibition [Br2]
k5
5. 2 Br → Br 2 breaking

d[HBr]
I. dt = k2 [Br][H2] + k 3 [H][Br2] – k4 [H][HBr]
d[Br]
II. dt = 0 = 2 k1[Br2] – k2 [Br][H2] + k 3 [H][Br2] + k 4 [H][HBr] – 2 k5[Br]2

d[H]
III. dt = 0 = k2 [Br][H2] – k3 [H][Br2] – k4 [H][HBr]
1
 k1  /2
IV. add II + III : 0 = 2 k1[Br2] – 2 k5 [Br]2 ⇒ [Br] = k [Br2]
 5 

k1 1/2
k2 k  [H2][Br2]1/2
k2[Br][H2]  5
V. solve III for [H] : [H] = k [Br ] + k [HBr] =
3 2 4 k3[Br2] + k 4[HBr]
d[HBr]
VI. subtract III from I: dt = 2 k3 [H][Br2]
-
d[HBr] 2 k 3 k 2 k 11/2 k5 1/2 [H2][Br2]1/2 [Br2]
substitute V into VI: dt = k3[Br2] + k 4[HBr]
-
d[HBr] 2 k 3 k 2 k 11/2 k5 1/2 [H2][Br2]1/2
dt = [HBr]
k3 + k4
[Br2]
Explosions: 2 H2 + O2 → 2 H2O

H2 + •(O2)• → 2 •OH initiation

H2 + •OH → •H + H2O propagation
•(O2)• + •H → •O• + •OH branching
•O• + H2 → •OH + •H branching