CHEMICAL KINETICS of COMPLEX REACTIONS

Question 1.

Series first order reaction:

Use Microsoft Excel to plot the concentrations of [A], [B], and [C] as a
function of reaction time for three cases:
1. [A]0 = 1.0 M, k1 = 0.2 min-1, k2 = 0.1 min-1
2. [A]0 = 1.0 M, k1 = 0.1 min-1, k2 = 0.2 min-1
3. [A]0 = 1.0 M, k1 = 0.1 min-1, k2 = 5.0 min-1

Which case can be assumed to be a steady-state-approximation?

Why?

Question 2.

Decomposition of di-2-methylpropan-2-yl peroxide produces

propanone and ethane:

and the generally accepted mechanism is:

1. Explain why this is not a chain reaction.

2. Using the steady-state-approximation to show that the reaction
follows the first order with respect to (CH3)3COOC(CH3)3, even
 though it occurs in three consecutive steps. Formulate the rate of
reaction in terms of production of C2H6.

Question 3.

The reaction between nitric oxide (nitrogen monoxide) and oxygen

gives nitrogen dioxide according to the stoichiometric equation:

This reaction is experimentally found to be the second order in NO

and first order in O2. The following mechanisms can be proposed:
Mechanism A

Mechanism B

1. Assuming the steady state approximation, deduce the rate

expressions for each mechanism.
2. Under what conditions these mechanisms will fit the experimental
data and be kinetically equivalent? Hint: consider the denominator
and the mathematical and chemical significance of each term.
 3. A further possibility is that the reaction occurs as an elementary
termolecular reaction: which mechanism(s) is the more likely?

Question 4.
This problem focuses on the difference between steady state
methods and the assumption of a pre-equilibrium for a reaction where
the first two steps are reversible.
The following mechanism is common to both inorganic and organic
reactions:

1. Carry out a steady state treatment, and find the conditions

under which this reaction would be:
(i) First order in both RX and Y¯ but inverse first order in X¯.
(ii) Simple first order in RX.
2. Now assume that the reversible reaction is at equilibrium, and
deduce the rate expression.
3. By comparing these two treatments in (1) and (2), find the
conditions under which the pre-equilibrium would be set up.