Unit 6 – Kinetics - Problem Set #2

1. The compound SO2Cl2 decomposes according to the equation:

SO2Cl2 (g) 🡪 SO2 (g) + Cl2 (g)

The reaction is first order with a rate constant k = 2.2 x 10-5 s-1 at 320 0C. If the
initial SO2Cl2 concentration in a container is 0.0040 mol∙dm-3 , what will its
concentration be (a) after 1 h (b) after 1 day

2. The decomposition of HI follows the equation

2HI (g) 🡪 H2 (g) + I2 (g)

The reaction is second order and has a rate constant equal to 1.6 x 10-3 L∙mol-1∙s-1
At 700 0C. At 2.0 x 10 3 minutes after a particular experiment had begun, the HI
concentration was equal to 3.0 x 10-4 mol∙dm-3. What was the initial molar
concentration of HI in the experiment?

3. The concentration of a drug in the body is often expressed in units of milligrams per
kilogram of body weight. The initial dose of a drug in an animal was 30.0 mg/kg
body weight. After 2.00 hours this concentration had dropped to 10.0 mg/kg body
weight. If the drug is eliminated metabolically by a first order process, what is the
rate constant for the process in units of min-1?

4. If it takes 45.0 min for the concentration of a reactant to drop to 10% of its original
value in a first order reaction, what is the rate constant for the reaction in the units
min-1 ?

5. What is meant by the term half life? How is the half life of a first order reaction
affected by initial concentration?

6. A first order reaction has a rate constant of k = 1.6 x 10-3 s-1. What is the half life for
this reaction?

7. Strontium-90 has a half life of 28 a. How long will it take for all of the strontium-90
presently on earth to be reduced to 1/32 of its present amount?

8. Draw a potential energy diagram of an endothermic reaction. Indicate the following

on the diagram: reactants, products, ∆Hrxn of the forward and reverse reactions, Ea of
the forward and reverse reactions, activated complex or transition state, and label
the axes.

9. In terms of kinetic theory, explain why an increase in temperature will increase the
reaction rate.

10. The following data were collected for a reaction:

Rate Constant (s-1) Temperature (0C)

2.88 x 10-4 320
4.87 x 10-4 340
7.96 x 10-4 360
 1.26 x 10-3 380
1.94 x 10-3 400
Determine the activation energy for this reaction in kJ/mol both graphically and using the
appropriate equation. For the calculation method use the first and last sets of data
from the table.

11. The decomposition of NOCl according to the reaction:

2 NOCl (g) 🡪 2 NO (g) + Cl2 (g)

has k = 9.3 x 10-5 L∙mol-1∙s-1 at 100 0C and k = 1.0 x 10-3 L∙mol-1∙s-1 at 130 0C. What is
the Ea for this reaction in kJ/mol. Use the data at 100 0C to calculate the frequency
factor (A).

12. It has been mentioned that the rates of many reactions approximately double for
each 10 0C increase in temperature. Assuming a starting temperature of 25 0C ,
what would the activation energy be, in kJ, if the rate of a reaction were to be twice
as large at 35 0C?

13. At 35 0C , the rate constant for the reaction

C12H22O11 + H2O 🡪 C6H12O6 + C6H12O6

sucrose glucose fructose

is k = 6.2 x 10-5 s-1. The activation energy for the reaction is 108 kJ/mol. What is the
rate constant for the reaction at 45 0C?

14. What is an elementary process and what is its relationship to a reaction mechanism?

15. What is a rate determining step? In what way is the rate law for a reaction related to
the rate determining step?

16. If the reaction NO2 + CO 🡪 CO2 + NO occurs by a one-step collision

process, what would be the expected rate law for the reaction? The actual rate law
was experimentally determined to be rate = k[NO2]2. Could the reaction actually
occur by a one step collision between NO2 and CO? Explain.

17. A reaction has the following mechanism:

CO + ∙OH 🡪 CO2 + H∙
O2 + H∙ 🡪 HOO∙
HOO∙ + NO 🡪 ∙OH + NO2

What is the net overall change that occurs in this reaction? What molecule(s), if any,
are reaction intermediates?

18. The experimental rate law for the reaction NO2 + CO 🡪 CO2 + NO is rate = k[NO2]]2.
If the mechanism is :

2 NO2 🡪 NO3 + NO (slow)

NO3 + CO 🡪 NO2 + CO2 (fast)
 show that the predicted rate law is the same as the experimental rate law.

19. The reaction of hydrogen with bromine appears to follow the mechanism:
hf
Br2 🡪 2 Br∙
Br∙ + H2 🡪 HBr + H∙
H∙ + Br2 🡪 HBr + Br∙
2Br∙ 🡪 Br2

a) Identify the initiation step in the mechanism.

b) Identify any propagation steps.
c) Identify the termination step.

The mechanism also contains the reaction: H∙ + HBr 🡪 H2 + Br∙

How does this reaction affect the rate of production of HBr?

20. What is a homogeneous catalyst and how does it work?

What is a heterogeneous catalyst and how does it work?

Answers:

1. a) 3.7 x 10-3 mol∙dm-3 b) 6.0 x 10-4 mol∙dm-3

2. 3.2 x 10-4 mol∙dm-3
3. k = 9.17 x 10-3 min-1
4. k = 5.1 x 10-2 min-1
5. time it takes for ½ the original sample to decompose/react; half life of a first order reaction is independent
of initial concentration
6. 4.3 x 102 s
7. 140 years
8.

9. Increasing T, increases KE, which increases velocity of molecules (KE = 1/2mv 2), which increases the
frequency of collisions, which increases rate BUT increase KE also increases the % effective collisions
(more molecular collisions have sufficient energy to meet Ea requirements) therefore rate increases more
than expected.
10. Ea = 79.1 kJ/mol
11. Ea = 99 kJ/mol, A = 6.8 x 10 9 L∙mol-1∙s-1
12. 52.9 kJ/mol
13. 2.3 x 10-4 s-1
14. An elementary step is an equation which represents a single molecular event (collision or decomposition)
or step in the series of steps that makes up the whole mechanism
15. rate determining step is the slowest step/step with highest Ea in a reaction mechanism,
Coefficients of each of the reactants in a rate determining step indicates the molecularity and therefore
determines the order of the reaction with respect to that molecule.
16. rate = k [NO][CO]. It cannot be a one step mechanism, otherwise the predicted rate law and the actual
rate law would be the same.
17. CO + O2 + NO 🡪 CO2 + NO2 ; intermediates are H∙ and HOO∙
18. For the first step (the r.d.s.) rate = k[NO2]2
19. a) first equation b) second and third equations c) fourth equation
This other reaction removes HBr (the product) and thereby slows down the rate of formation of HBr –
therefore decreases the rate of the reaction.
20. homogeneous catalyst is a catalyst that is in the same phase as the reactant molecules, they work by
providing an alternate pathway or mechanism with a rate determining step that has a lower activation
energy than the r.d.s. in the original mechanism
Heterogeneous catalyst is in a different phase (usually solid) than the reactant molecules (l, aq or g). The
reactant molecules adhere to the surface of the catalyst, the bonds within the reactant molecule are
weakened as bonding electrons are now delocalized/polarized therefore reducing the energy required to
break them and therefore reducing the Ea of the reaction, thereby increasing the rate of the reaction. The
molecules adsorption to the catalyst surface in a specific orientation may also improve the steric factor
and this could also increase the reaction rate