1.

The rate law for the hydrolysis o ethyl acetate by aqueous sodium hydroxide at 298 K
𝐾𝑜𝑏𝑠
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 (𝑎𝑞) + 𝑂𝐻 − → 𝐶𝐻3 𝐶𝑂2− (𝑎𝑞) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑎𝑞)
Is
𝑑[𝐶𝐻3 𝐶𝐻2 𝑂𝐻]
= 𝐾𝑜𝑏𝑠 [𝑂𝐻 − ][𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ]
𝑑𝑡
Despite the form of this rate law, this reaction is not an elementary reaction but is believed to occur by the
following mechanism.
− 𝐾1 𝑎𝑛𝑑 𝐾−1
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (𝑎𝑞) + 𝑂𝐻(𝑎𝑞) ↔ 𝐶𝐻3 𝐶𝑂− (𝑂𝐻)𝐶𝐻2 𝐶𝐻3 (𝑎𝑞)
𝐾2 −
𝐶𝐻3 𝐶𝑂− (𝑂𝐻)𝐶𝐻2 𝐶𝐻3 (𝑎𝑞) → 𝐶𝐻3 𝐶𝑂2 𝐻(𝑎𝑞) + 𝐶𝐻3 𝐶𝐻2 𝑂(𝑎𝑞)
− 𝐾3
𝐶𝐻3 𝐶𝑂2 𝐻(𝑎𝑞) + 𝐶𝐻3 𝐶𝐻2 𝐶𝑂(𝑎𝑞) → 𝐶𝐻3 𝐶𝑂2− (𝑎𝑞) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑎𝑞)
For those conditions, express 𝐾𝑜𝑏𝑠 in terms of the rate constants for the individual steps of the reaction
mechanism.
𝐾1 𝑎𝑛𝑑 𝐾−1
𝐴+𝐵↔ 𝐶 𝑣1 = 𝐾1 [𝐴][𝐵] 𝑣−1 = 𝐾−1 [𝐶]
𝐾2
𝐶→ 𝐷+𝐸 𝑣2 = 𝐾2 [𝐶]
𝐾3
𝐷+𝐸→ 𝐹+𝐺 𝑣3 = 𝐾3 [𝐷][𝐸]
𝐾1 [𝐴][𝐵]
𝑆. 1 𝑣1 = 𝑣−1 𝐾1 [𝐴][𝐵] = 𝐾−1 [𝐶] [𝐶] =
𝐾−1
𝑑[𝐶𝐻3 𝐶𝐻2 𝑂𝐻]
= 𝑣3 = 𝐾3 [𝐷][𝐸]
𝑑𝑡
𝐾2 [𝐶] 𝐾1 𝐾2 [𝐴][𝐵]
𝑆. 2 𝑣2 − 𝑣3 = 0 𝐾2 [𝐶] − 𝐾3 [𝐷][𝐸] = 0 [𝐷][𝐸] = =
𝐾3 𝐾3 𝐾−1
𝑑[𝐶𝐻3 𝐶𝐻2 𝑂𝐻] 𝐾1 𝐾2 [𝐴][𝐵] 𝐾1 𝐾2 𝑑[𝐶𝐻3 𝐶𝐻2 𝑂𝐻]
= 𝐾𝑜𝑏𝑠 = = 𝐾𝑜𝑏𝑠 [𝑂𝐻 − ][𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ]
𝑑𝑡 𝐾−1 𝐾−1 𝑑𝑡
2. The rate law for the reaction described by
𝐾𝑜𝑏𝑠
2𝐻2 (𝑔) + 2𝑁𝑂(𝑔) → 𝑁2 (𝑔) + 2𝐻2 𝑂(𝑔)
Is
𝑑[𝑁2 ]
= 𝐾𝑜𝑏𝑠 [𝐻2 ][𝑁𝑂]2
𝑑𝑡
Below is a proposed mechanism for this reaction
𝐾1
𝐻2 (𝑔) + 𝑁𝑂(𝑔) + 𝑁𝑂(𝑔) → 𝑁2 𝑂 + 𝐻2 𝑂(𝑔)
𝐾2
𝐻2 (𝑔) + 𝑁2 𝑂(𝑔) → 𝑁2 (𝑔) + 𝐻2 𝑂(𝑔)
𝐾1
𝐴 + 2𝐵 → 𝐶+𝐷 𝑣1 = 𝐾1 [𝐴][𝐵]2
𝐾2
𝐴+𝐶→ 𝐸+𝐷 𝑣2 = 𝐾2 [𝐴][𝐶]
𝑑[𝐸] 𝐾1 [𝐴][𝐵]2 𝐾1 [𝐵]2
= 𝑣2 = 𝐾2 [𝐴][𝐶] 𝐾1 [𝐴][𝐵]2 − 𝐾2 [𝐴][𝐶] = 0 [𝐶] = =
𝑑𝑡 𝐾2 [𝐴] 𝐾2
𝑑[𝐸] 𝐾1 𝐾2 [𝐴][𝐵]2 𝑑[𝑁 2 ]
= 𝐾2 [𝐴][𝐶] = = 𝐾1 [𝐴][𝐵]2 𝐾𝑜𝑏𝑠 = 𝐾1 = 𝐾𝑜𝑏𝑠 [𝐻2 ][𝑁𝑂2 ]2
𝑑𝑡 𝐾2 𝑑𝑡
3. The decomposition of perbenzoic acid in water
2𝐶𝐻6 𝐻5 𝐶𝑂3 𝐻(𝑎𝑞) ↔ 2𝐶6 𝐻5 𝐶𝑂2 𝐻(𝑎𝑞) + 𝑂2 (𝑔)
Is proposed to occur by the following mechanism
 𝐾1 𝑎𝑛𝑑 𝐾−1 +
𝐶6 𝐻5 𝐶𝑂3 𝐻(𝑎𝑞) ↔ 𝐶6 𝐻5 𝐶𝑂3− (𝑎𝑞) + 𝐻(𝑎𝑞)
𝐾2
𝐶6 𝐻5 𝐶𝑂3 𝐻(𝑎𝑞) + 𝐶6 𝐻5 𝐶𝑂3− (𝑎𝑞) → 𝐶6 𝐻5 𝐶𝑂2 𝐻(𝑎𝑞) + 𝐶6 𝐻5 𝐶𝑂2− (𝑎𝑞) + 𝑂2 (𝑔)
+ 𝐾3
𝐶6 𝐻5 𝐶𝑂2− (𝑎𝑞) + 𝐻(𝑎𝑞) → 𝐶6 𝐻5 𝐶𝑂2 𝐻(𝑎𝑞)
Derive an expression for the rate of formation of 𝑂2 In terms of the reactant concentration and [𝐻 + ]
𝐾1 𝑎𝑛𝑑 𝐾−1
𝐴↔ 𝐵+𝐶
𝐾2
𝐴+𝐵→ 𝐷+𝐸+𝐹
𝐾3
𝐸+𝐶→ 𝐷
4.