A→P k1 = 4,50 h-1 𝑑

𝐴 = − 𝑘1 + 𝑘2 [𝐴] ln[𝐴] = ln[𝐴]0 − 𝑘1 + 𝑘2 𝑡

𝑑𝑡
A→C k2 = 0,12 h-1 ln 2
P→B k3 = 0,50 h-1 𝑡1/2 =
𝑘1 + 𝑘2
= 0,15 ℎ

𝑑 𝑑
𝑃 = 𝑘1 𝐴 0 𝑒 − 𝑘1+𝑘2 𝑡 − 𝑘3 [𝑃] 𝑃 + 𝑘3 [𝑃] = 𝑘1 𝐴 0 𝑒 − 𝑘1+𝑘2 𝑡
𝑑𝑡 𝑑𝑡
𝑑 𝑘1 𝐴 0
𝑒 𝑘3 𝑡
𝑃 + 𝑒 𝑘3𝑡 𝑘3 [𝑃] = 𝑘1 𝐴 0 𝑒 𝑘3 − 𝑘1 +𝑘2 𝑡 𝑃 = 𝑒− 𝑘1 +𝑘2 𝑡
− 𝑒 −𝑘3𝑡
𝑑𝑡 𝑘3 − 𝑘1 + 𝑘2

Concentração Máxima de P: 𝑑[𝑃] = 𝑘1 𝐴 0

− 𝑘1 + 𝑘2 𝑒 − 𝑘1+𝑘2 𝑡 + 𝑘3 𝑒 −𝑘3𝑡 = 0
𝑑𝑡 𝑘3 − 𝑘1 + 𝑘2

𝑘3
𝑘3 𝑒 −𝑘3 𝑡
= 𝑘1 + 𝑘2 𝑒 − 𝑘1+𝑘2 𝑡
∗
ln = 𝑘3 − 𝑘1 + 𝑘2 𝑡 ∗
𝑘1 + 𝑘2
1 𝑘3
𝑡∗ = ln 𝑡 ∗ = 0,54 ℎ
𝑘3 − 𝑘1 + 𝑘2 𝑘1 + 𝑘2

𝑃 𝑘1
Teor de P em t*: = 𝑒− 𝑘1 +𝑘2 𝑡 − 𝑒 −𝑘3𝑡 = 0,744
𝐴0 𝑘3 − 𝑘1 + 𝑘2
 −108
𝑘 1000 𝐾 = 4,34𝑥1014 exp −3 = 9,91𝑥108 𝑠 −1
8,314𝑥10 𝑥1000

Assumindo o Mecanismo de Lindemann:

HOSO2 + M → HOSO2* + M k1
HOSO2* + M → HOSO2 + M k2 𝑘𝑢𝑛𝑖
HOSO2* → HO + SO2 k3
𝑘1 𝑘3 [𝑀]
A constante de velocidade global será: 𝑘𝑢𝑛𝑖 =
𝑘2 𝑀 + 𝑘3

𝑘1 𝑘3 ]
Os limites de alta e baixa pressão são: 𝑘∞ = 𝑘 0 = 𝑘1 [𝑀]
𝑘2 [𝑀]
𝑑
𝐼 = 𝑘1 𝐴 𝑂𝐻 − 𝑘2 + 𝑘3 + 𝑘4 𝐼1 𝑘1 𝐴 𝑂𝐻
𝑑𝑡 1 𝐼1 =
𝑘2 + 𝑘3 + 𝑘4

𝑑 𝑘5 𝐴 𝑂𝐻
𝐼 = 𝑘5 𝐴 𝑂𝐻 − 𝑘6 + 𝑘7 + 𝑘8 𝐼2 𝐼2 =
𝑑𝑡 2 𝑘6 + 𝑘7 + 𝑘8

𝑑 𝑑 𝑑 𝑑 𝑑
𝑃 = [𝑃11 ] + [𝑃12 ] + [𝑃21 ] + [𝑃22 ]
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡

𝑑
𝑃 = 𝑘3 [𝐼1 ] + 𝑘4 [𝐼1 ] + 𝑘7 [𝐼2 ] + 𝑘8 [𝐼2 ]
𝑑𝑡
𝑑 𝑘1 𝐴 𝑂𝐻 𝑘5 𝐴 𝑂𝐻
𝑃 = 𝑘3 + 𝑘4 + 𝑘7 + 𝑘8
𝑑𝑡 𝑘2 + 𝑘3 + 𝑘4 𝑘6 + 𝑘7 + 𝑘8

𝑑 𝑘1 𝑘3 + 𝑘4 𝑘5 𝑘7 + 𝑘8
𝑃 = + 𝐴 𝑂𝐻
𝑑𝑡 𝑘2 + 𝑘3 + 𝑘4 𝑘6 + 𝑘7 + 𝑘 8
 𝑑[𝐶] 𝑑[𝐼]
[𝐶]0 = 𝐶 + [𝐼] + =0
𝑑𝑡 𝑑𝑡
𝑑[𝐶] 𝑘1 [𝑅1 ][𝐶]0
= −𝑘1 𝑅1 𝐶 + 𝑘2 [𝐼][𝑅2 ] −𝑘1 𝑅1 𝐶 0 − [𝐼] + 𝑘2 𝐼 𝑅2 = 0 𝐼 =
𝑑𝑡 𝑘1 𝑅1 + 𝑘2 [𝑅2 ]

𝑑[𝑅1 ] −𝑘1 𝑘2 [𝐶]0 −𝑘1 𝑘2 [𝐶]0 𝑘1 𝑘2 [𝐶]0

= −𝑘1 𝐶 𝑅1 = 𝑅1 𝑅2 = [𝑅] 𝑅 = [𝑅]0 𝑒 −𝑘𝑅𝑡 𝑘𝑅 =
𝑑𝑡 𝑘1 𝑅1 + 𝑘2 [𝑅2 ] 𝑘1 + 𝑘2 𝑘1 + 𝑘2

𝑑[𝑃] 𝑘2 𝑘1 [𝐶]0 𝑘1 𝑘2 [𝐶]0

= 𝑘2 𝐼 𝑅2 = 𝑅1 𝑅2 = 𝑅 = 𝑘𝑅 [𝑅]0 𝑒 −𝑘𝑅 𝑡 𝑃 = [𝑅]0 1 − 𝑒 −𝑘𝑅𝑡
𝑑𝑡 𝑘1 𝑅1 + 𝑘2 [𝑅2 ] 𝑘1 + 𝑘2