Chapter 14, Problem 110
The following mechanism has been proposed for the gasphase reaction of chloroform 1CHCl32 and chlorine: Step 1: Cl21g2 Δ k1 k - 1 2 Cl1g2 1fast2 Step 2: Cl1g2 + CHCl31g2 ¡k2 HCl1g2 + CCl31g2 1slow2 Step 3: Cl1g2 + CCl31g2 ¡k3 CCl4 1fast2 (a) What is the overall reaction?
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Ozone in the upper atmosphere can be destroyed by the following two-step mechanism: Cl1g2 + O31g2¡ClO1g2 + O21g2 ClO1g2 + O1g2¡Cl1g2 + O21g2 (b) What is the catalyst in the reaction?
The gas-phase decomposition of ozone is thought to occur by the following two-step mechanism.
Step 1: O3(g) ⇌ O2(g) + O(g) (fast)
Step 2: O(g) + O3(g) → 2 O2 (slow)
(b) Derive the rate law that is consistent with this mechanism. (Hint: The product appears in the rate law.)
The gas-phase decomposition of ozone is thought to occur by the following two-step mechanism.
Step 1: O3(g) ⇌ O2(g) + O(g) (fast)
Step 2: O(g) + O3(g) → 2 O2 (slow)
(d) If instead the reaction occurred in a single step, would the rate law change? If so, what would it be?
In a hydrocarbon solution, the gold compound (CH3)3AuPH3 decomposes into ethane (C2H6) and a different gold compound, (CH3)AuPH3. The following mechanism has been proposed for the decomposition of (CH3)3AuPH3:
Step 1: (CH3)3AuPH3 k1 k -1 (CH3)3Au + PH3 (fast)
Step 2: (CH3)3Au k2 C2H6 + (CH3)Au (slow)
Step 3: (CH3)Au + PH3 ¡k3 1(CH3)AuPH3 (fast)
(c) What is the molecularity of each of the elementary steps?
In a hydrocarbon solution, the gold compound (CH3)3AuPH3 decomposes into ethane (C2H6) and a different gold compound, (CH3)AuPH3. The following mechanism has been proposed for the decomposition of (CH3)3AuPH3:
Step 1: (CH3)3AuPH3 k1 k -1 (CH3)3Au + PH3 (fast)
Step 2: (CH3)3Au k2 C2H6 + (CH3)Au (slow)
Step 3: (CH3)Au + PH3 ¡k3 1(CH3)AuPH3 (fast)
(e) What is the rate law predicted by this mechanism?
In a hydrocarbon solution, the gold compound (CH3)3AuPH3 decomposes into ethane (C2H6) and a different gold compound, (CH3)AuPH3. The following mechanism has been proposed for the decomposition of (CH3)3AuPH3:
Step 1: (CH3)3AuPH3 k1 k -1 (CH3)3Au + PH3 (fast)
Step 2: (CH3)3Au k2 C2H6 + (CH3)Au (slow)
Step 3: (CH3)Au + PH3 ¡k3 1(CH3)AuPH3 (fast)
(f) What would be the effect on the reaction rate of adding PH3 to the solution of (CH3)3AuPH3?