Kinetics Homework 3

1. For each of the following expressions, give the reaction order in terms of each
reagent and for the overall reaction.
a. Rate = k[A][B]2
b. Rate = k[A][B]
c. Rate = k[A]
d. Rate = k[A]3[B]
2.

A reaction between molecules A and B (A + B products) is found to be second

order overall. Which rate law below cannot be correct?
a. Rate = k[A][B]
b. Rate = k[A]2
c. Rate = k[A][B]2
d. Rate = k[B]2

3.

For a reaction of the type A + B C, it is experimentally observed that doubling

the concentration of B causes the reaction rate to be increases fourfold, but
doubling the concentration of A has no effect on the rate. The rate equation is
therefore
a. Rate = k[A]2
b. Rate = k[A][B]
c. Rate = k[B]2
d. Rate = k[A]

4.

A study of the reaction 2A + B C + D gave the following results

Expt
[A]
[B]
Rate(M/sec)
1
.10
.05
6.0 x 10-3
2
.20
.05
1.2 x 10-2
3
.30
.05
1.8 x 10-2
4
.20
.15
1.1 x 10-1
a. What are the rate expression and overall order for this reaction?

b. Calculate the rate constant for the reaction, making certain to give the
correct units of k.

5.

Iodide ion, I-1, is oxidized to hypoiodite ion, IO-1, by hypochlorite, ClO-1in basic
solution according to the equation, I-1 + ClO-1 IO-1 + Cl-1. Three initial rate
experiments were conducted; the results are shown on the following table.
Expt
I-1
ClO-1
Rate (M/sec)
1
0.017
0.015
0.156
2
0.052
0.015
0.476
3
0.016
0.061
0.596
a. Determine the order of the reaction with respect to each reactant listed
below
i. I-1

ii.

ClO-1

b. For the reaction,

i. Write the rate law that is consistent with the calculations in part(a)
ii.

6.

Calculate the value of the specific rate constant, and specify units.

The catalyzed decomposition of hydrogen peroxide, H2O2, is represented by the following

equation. 2H2O2 2H2O + O2. The kinetics of the decomposition reaction were studied and the
analysis of the results show that it is a first order reaction. Some of the experimental data are
shown in the table below.
[H2O2]
Time (minutes)
1.0
0.0
0.78
5.0
0.61
10.0
a. During the analysis of the data, the graph below was produced.

Time (min)
i. Label the vertical axis of the graph
ii. What are the units of the rate constant, k, for the decomposition of H2O2?
iii. On the graph, draw the line that represents the plot of the uncatalyzed first order
decomposition of 1.00 M H2O2

Kinetics Day 3B
7. Draw a graph to illustrate how the presence of a catalyst can affect the rate of a
reaction.

8.

For a gas phase reaction, Ea = 103 kJ/mol, and the rate constant is 0.0850 min-1 at
273 K. Find the rate constant at 323K.

9.

The rate constant for the decomposition of N2O:2N2O 2N2 + O2 is 2.6 x 10-11s-1
at 300C and 2.1 x 10-10s-1 at 330C. Calculate the activation energy for this
reaction.

10.

The following gas phase reaction follows first order kinetics: ClO2F ClOF + O.
The activation energy of this reaction is 186 kJ/mol. The value of k at 322C is
6.76 x 10-4s-1.
a. What would be the value of k for this reaction at 25C?

b. At what temperature would this reaction have a k value of 3.00 x 10-2 s-1?

11.

The following gas phase reaction is first order: N2O5 NO2 + NO3. The
activation energy of this reaction is 88kJ/mol. The value of k at 0C is 9.16 x 10-3
sec-1.
a. What would be the value of k for this reaction at room temperature, 25C?

b. At what temperature would this reaction have a k value of 3.00 x 10-2 s-1?

12.

The rate equation for the following reaction Cl2 + H2S S + 2HCl is found to be
rate = k[Cl2][H2S]. Which of the following mechanisms are most consistent

with the rate law?

a. Cl2 Cl+ + Cl- (slow)
Cl-1 + H2S HCl + HS- (fast)
Cl+ + HS- HCl + S (fast)
b. Cl2 + H2S HCl + Cl+1 + HS- (slow)

Cl+ + HS-1 HCl + S (fast)

c. Cl2 Cl + Cl (fast)

Cl + H2S HCl + HS (fast)

HS + Cl HCl + S (slow)
13.

Write the overall reaction and rate expressions that c orrespond to the following
reaction mechanisms. Be sure to eliminate intermediates from the answers.
a. A + B C + D (fast)
C + E F (slow)
b. A B + C (fast)
C + D E (fast)
E F (slow)
c. 2A + B D (fast)
D + B E + F (slow)
F G (fast)
d. A + B C (fast)
C + D F (fast)
F G (slow)