Mechanisms

1. For the overall reaction

O3 + M = O + O2 + M fast steady state

O + O3 => 2O2 slow

a) Derive the equation: rate = k[O3]2[M]/(k'[O2][M]+[O3])

b) What are k and k' in terms of the rate constants for reactions 1 and 2?

2. For a reversible reaction near equilibrium,

a) derive the equation

dln(A-Aeq) = -(kf+kr)dt

where A-Aeq is the difference in the concentration of A from it equilibrium value.

b) A reversible reaction at equilibrium contains .05 M of A and .26 M of B. When additional A is quickly added to bring the concentration to .06 M, it takes 320 s to reach 0.055 M of A and the system eventual reaches the same equilibrium mixture. What are the values of Keq, kf, and kr?

3. For the formation of phosgene by the reaction

CO + Cl₂ = COCl₂

appears to follow the mechanism:

Cl₂ -> 2 Cl k₁

Cl + CO -> ClCO k₂

ClCO -> Cl + CO k_-2

ClCO + Cl₂ -> Cl₂CO + Cl k3

Cl +Cl -> Cl₂ k_-1

Derive the rate equation assuming a steady state in both Cl and COCl.

4. In #3 , which step or steps represent a) initiation b) propagation c) termination