Chemistry of Solutions SN2

Problem Set II – Chemical Kinetics

Teacher: Alieh Kazemeini

1. A reaction obeys the rate law: Rate = k [A][B]2.

a) If [A] changes, will the rate change? Will the rate constant change? Explain. b) What are the reaction
orders for A and B? What is the overall reaction order? c) What are the units of the rate constant?

2. The following scheme represents the progress of the reaction: A B in which A molecules are converted
to B molecules.

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a) What is the order of the reaction? Suppose that each sphere represents 6.30 x 1021 molecules and that the
volume of the container is 1.00 L. b) What are the rate constant for the reaction and its units? Hint: use graphical
method and excel to answer this question.

3. a) What is the difference between a rate law and a rate constant? b) What is the difference between the
reaction order for a specific reactant and the overall reaction order? c) What are the units of the rate constant
for a reaction in solution that has an overall reaction order of two?

4. The following reaction was experimentally determined to be first order with respect to O2 and second order
with respect to NO. O2 (g) + 2NO (g) 2NO2 (g)
These diagrams represent reaction mixtures in which the number of each type of molecule represents
its relative initial concentration. Which mixture has the fastest initial rate?

5. Consider the reaction: CHCl3 (g) + Cl2 (g) CCl4 (g) + HCl (g)
The reaction is first order in CHCl3 and one-half order in Cl2. Which reaction mixture would you expect to
have the fastest initial rate?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

6. Below graphs are the concentrations measured as a function of time when gaseous N2O5 at an initial
concentration of 0.020 M decomposes to gaseous NO2 and O2 at 55 °C.

2N2O5 (g) 4NO2 (g) + O2 (g)

a) Use the graph of [N2O5] as a function of time to calculate the rate of disappearance of N2O5 for the time
interval between 300 s and 400 s.
b) Using the graph of [NO2] as a function of time, calculate the rate of formation of NO2 for the time interval
between 300 s and 400 s.
c) Using the graph of [O2] as a function of time, calculate the rate of formation of O2 for the time interval between
300 s and 400 s.
d) Using the graphs and balanced equation, calculate the average rate of reaction for the time interval between
300 s and 400 s.
e) Using the graph of [NO2] as a function of time, calculate the instantaneous rate of reaction at t = 350 s.
f) Using the graph of [NO2] as a function of time, calculate the instantaneous rate of reaction NO2 at t = 0 s (also
known as the initial rate).

7. For the reaction: A + B + C products, the following observations are made: Doubling the concentration
of A doubles the rate, tripling the concentration of B has no effect on the rate, and tripling the concentration of
C increases the rate by a factor of 9.
a) What is the rate law for the reaction?
b) By what factor will the rate change if the concentrations of A, B and C are halved.

8. The rearrangement of methyl isonitrile (CH3NC) to acetonitrile (CH3CN) is a first-order reaction and has a
rate constant of 5.11 x 10–5 s–1 at 472 K:
CH3N≡C CH3C≡N

If the initial concentration of CH3NC is 0.0340 M: a) What is the molarity of CH3NC after 2.00 h? b) How
many minutes does it take for the CH3NC concentration to drop to 0.0300 M? c) How many minutes does it
take for 20% of the CH3NC to react?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

9. The images shown below depict the first order reaction A B at various times during the reaction process.
What is the half life of the reaction?

10. The reaction: 2NOBr 2NO + Br2 exhibits the rate law: Rate = k[NOBr]2, where k = 1.0 x 10–5 M–1• s–1 at
25 ⁰C. This reaction is run where the initial concentration of NOBr ([NOBr]0) is 1.00 x10–1 M. What is the
half-life of this reaction?

11. This plot shows the rate of the decomposition of 12. This graph shows a plot of the rate of a reaction
SO2Cl2 into SO2 and Cl2 as a function of the versus the concentration of the reactant.
concentration of SO2Cl2. What is the order of the a) What is the order of the reaction with respect to
reaction? A? b) Make a rough sketch of a plot of [A] versus
time. c) Write a rate law for the reaction including
the value of k.

Copyright © 2015 Pearson Prentice Hall Inc.

Copyright © 2015 Pearson Prentice Hall Inc

13. These images represent the first-order reaction A B initially and at some later time. The rate law for the
–1
reaction is Rate = 0.0100 s [A]. How much time has passed between the two images?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

14. The decomposition of N2O5 in carbon tetrachloride proceeds as follows: 2 N2O5 4 NO2 + O2. The
rate law is first order in N2O5. At 64 ⁰C, the rate constant is 4.82 x 10–3 s–1.
a) Write the rate law for the reaction.
b) What is the rate of the reaction when [N2O5] = 0.0240 M?
c) What happens to the rate when the concentration of N2O5 is doubled?
d) What is the half-life of this reaction?

15. For the gas decomposition of acetic anhydride:

(CH3CO)2O CH2CO + CH3COOH
−1
the rate constant in s has been determined at several temperatures. When ln k is plotted against reciprocal
of Kelvin temperature, the resulting linear plot has a slope of – 1.730 x 104 K and a y-intercept of 27.60.
a) Calculate the frequency factor and activation energy for the gas phase decomposition of acetic anhydride.
b) Calculate the rate constant for this reaction at 485.0 K.

16. The isomerization of methyl isonitrile (CH3NC) to acetonitrile (CH3CN) in the gas phase at 215 ⁰C was
studied, and the following data were obtained:
a) Calculate the average rate of reaction, in M /s, for the time interval Time (s) [CH3NC] (M)
between each measurement. 0 0.0165
b) Calculate the average rate of reaction over the entire time of the 2000 0.0110
data from t = 0 to t = 15000 s. 5000 0.00591
c) Graph [CH3CN] versus time and determine the instantaneous rates 8000 0.00314
in M /s, at t = 5000 s and t = 8000 s. Use excel. 12000 0.00137
15000 0.00074
17. The activation energy for the equilibrium below is 85.0 kJ.
I2 (g) + Cl2 (g) ⇌ 2ICl (g) ΔH = + 35.0 kJ
a) Sketch a clearly labelled potential energy diagram for this reaction, showing all energy terms for the
forward and reverse reactions. b) Illustrate the effect of adding a catalyst on the same diagram.

18. Antacids impair the absorption of many drugs. Cyclosporine is a medication used to prevent organ rejection.
Cyclosporine rate constant for absorption is 1.35 h–1. Assuming the blood concentration as low as 0.010 %
of initial concentration of this medication is required before antacid can be taken, how long after the
administration of Cyclosporine should a patient wait before taking an antacid?

19. Hydrogen peroxide, H2O2 (aq) reacts with MnO4– (aq) according to the following balanced equation:
2MnO4– (aq) + 5H2O2 (aq) + 6H+ (aq) 2Mn2+ (aq) + 8H2O (l) + 5O2 (g)
If the rate of appearance of O2 is 1.2 x 10–3 mol• L–1• s–1, what is the rate of disappearance of MnO4–?

20. Consider the following reaction:

2N2O5 (g) 4NO2 (g) + O2 (g)
At a certain moment, N2O5 is decomposing at a rate of ─ 2.50 x 10–6 mol• L–1• s–1, what is the rate of formation
of NO2?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini
21. Iodide ion reacts with hypochlorite ion as follows:
OCl– (aq) + I– (aq) OI– (aq) + Cl– (aq)
The reaction is rapid and gives the following data:

Experiment Initial Concentrations (M) Rate of formation of Cl–

[OCl–] [I–] (M / s)
1 1.7 x 10–3 1.7 x 10–3 1.75 x 10–4
2 3.4 x 10–3 1.7 x 10–3 3.50 x 10–4
3 1.7 x 10–3 3.4 x 10–3 3.50 x 10–4

a) Determine the order for each reactant. b) What is the order of overall reaction? c) Write the rate law for the
reaction. d) Determine the rate constant for the first experiment. e) Determine the rate for an experiment with
[OCl–] = 5.0 x 10–2 M and [I–] = 3.5 x 10–2 M.

22. Consider the decay curve for bismuth-210.

a) What is the half-life for the radioisotope?
b) What percent of the isotope remains after 20 days?
c) How many half-lives have passed after 25 days?
d) How many days would pass if 32 g decayed to 8
g?

23. The first order rate constant for the decomposition of N2O5 at 70 ⁰C is 6.82 x 10–3 s–1.
2N2O5 4NO2 + O2
a) Suppose the reaction starts with 0.0300 mol of N2O5, how many moles of N2O5 will remain after 2.50 min.
b) How many minutes will it take for the quantity of N2O5 to drop to 0.0100 mol? c) What is the half-life of
N2O5 at 70 ⁰C?

24. Radioactive decay exhibits a first-order rate law, rate = –ΔN / Δt = k N where N denotes the number of
radioactive nuclei present at time t. The half-life of strontium-90, a dangerous nuclear fission product, is 29
years. a) What fraction of the strontium-90 remains after three half-lives? b) What is the value of the rate
constant for the decay of strontium-90? c) How many years are required for 99% of the strontium- 90 to
disappear?

25. The age of any remains from a once-living organism can be determined by radiocarbon dating, a procedure
that works by determining the concentration of radioactive 14C in the remains. All living organisms contain
an equilibrium concentration of radioactive 14C that gives rise to an average of 15.3 nuclear decay events per
minute per gram of carbon. At death, however, no additional 14C is taken in, so the concentration slowly
drops as radioactive decay occurs. What is the age of a bone fragment from an archaeological dig if the bone
shows an average of 2.3 radioactive events per minute per gram of carbon? Radioactive decay is kinetically
a first-order process, and half life for 14C is 5730 years.

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini
26. Carbon-14, which is present in all living tissue, radioactively decays via a first-order process. A one-gram
sample of wood taken from a living tree gives a rate for carbon-14 decay of 13.6 counts per minute per g of
carbon. If the half-life for carbon-14 is 5720 years, how old is a wood sample that gives a rate for carbon-14
decay of 11.9 counts per minute per g of carbon?

27. The gas phase decomposition of NO2: 2NO2 (g) 2NO (g) + O2 (g), is studied at 383 ⁰C, giving the
following data:
Time (s) 0.00 5.00 10.0 15.0 20.0
[NO2] (M) 0.10000 0.01700 0.00900 0.00620 0.00480

a) Is the reaction, zero, first or second order with respect to [NO2]? b) What is the value of the rate constant?
c) What is the half-life of the reaction? d) Write the rate law and integrated rate law for this reaction? e) How
long does it take for the [NO2] to drop to 0.00330 M? f) How long does it take for the [O2] to be 0.03500 M?
Hint: use graphical method and excel to answer this question.

28. The following data were measured for the reaction:

– +
BF3(g) + NH3(g) F3B–NH3(g)

Experiment [BF3] (M) [NH3] (M) Initial Rate (M / s)

1 0.250 0.250 0.2130
2 0.250 0.125 0.1065
3 0.200 0.100 0.0682
4 0.350 0.100 0.1193
5 0.175 0.100 0.0596

a) What is the rate law for the reaction? b) What is the overall order for the reaction? c) What is the value
of the rate constant for the reaction?

29. The decomposition of H2O2 in aqueous solution proceeds by the first order reaction shown below:
2H2O2 (aq) 2H2O (l) + O2 (g)
The rate constant for the reaction was found to be 7.30 x 10–4 s–1 at 25 ⁰C.
a) At what time during the reaction of 2.00 mol/L of H2O2, would the concentration of H2O2 remaining be
0.950 mol/L.
b) What is the half-life of this reaction at this temperature?
c) If the temperature is raised to 50 ⁰C, will the half-life increase, decrease or stay the same?

30. At high temperatures, carbon dioxide can react with itself to form carbon monoxide and oxygen. The method
of initial rates was used to collect the kinetics data provided in the table.
2CO2 (g) 2CO (g) + O2 (g)

Run [CO2]0 Initial Rate ([Link]–1)

1 0.025 4.7 x 10–3
2 0.037 7.0 x 10–3

a) What is the reaction rate law? b) What is the rate of appearance of O2 if the rate of disappearance of CO2
is ─2.0×10–3 M• min–1?
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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

31. Mercury (II) chloride oxidizes oxalate anion via the reaction shown. The method of initial rates was used at
298 K to collect the kinetics data for this reaction.

2HgCl2 + C2O42– 2 Cl– + 2CO2 + Hg2Cl2

Experiment [HgCl2]0 [C2O42–]0 Initial Rate

(M) (M) ([Link]–1)
1 0.105 0.15 1.8 x 10–5
2 0.105 0.30 7.2 x 10–5
3 0.053 0.30 3.6 x 10–5

a) What is the reaction rate law? b) What are the value of the rate constant and its units at 298 K? c) What is
the rate of appearance of Hg2Cl2 when the rate of disappearance of HgCl2 is ─ 4.0×10–5 M• min–1?

32. Determine the activation energy for a reaction that has, at 25.0 °C, a rate constant of 0.0100 s–1 and at 50.0 °C
a rate constant of 0.0200 s–1.

33. A certain first-order reaction has a half-life of 20.0 minutes. a) Calculate the rate constant for this reaction.
b) How much time is required for this reaction to be 75.0 % complete?

34. While studying the shelf life of a particular antibiotic a chemist found that when the initial concentration was
0.0036 M the rate of decay was 1.5 x 10–4 M• s–1. In another experiment under the same conditions a
concentration of 0.0013 M decayed at a rate of 1.9 x 10–5 M• s–1. What is the order of this decay reaction?

35. A specific ingredient in a nutritional supplement can slowly decompose while still in the package. The specific
rate constant for the first order kinetics of this decay, at 25.0°C, is 4.2 x 10–2 hr–1. If the initial concentration
were considered to be 100.0 % how long would it take to be reduced to 75.0 % of its potency?

36. Chemists commonly use a rule of thumb that an increase of 10 K in temperature doubles the rate of a reaction.
What must the activation energy be for this statement to be true for a temperature increase from 25 °C to 35
°C?

37. The first-order reaction, SO2Cl2 SO2 + Cl2, has a half-life of 8.75 hours at 593 K. How long will it take
for the concentration of SO2Cl2 to fall to 16.5% of its initial value?

38. A first-order reaction is 41% complete at the end of 43 minutes. What is the length of the half-life of this
reaction?

39. The below plot shows the fraction of molecules with a particular kinetic energy for two different temperatures:
a) Which is greater, T2 or T1? Explain your answer. b) What does this plot show about the correlation
between temperature and rate of a chemical reaction with the activation energy of Ea? Explain your answer.

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

40. The decomposition of ethanol (C2H5OH) on an alumina (Al2O3) surface

C2H5OH (g) C2H4 (g) + H2O (g)
was studied at 600 K. C2H5OH pressure versus time data were collected for this reaction, and a plot of C2H5OH
pressure versus time resulted in a straight line with a slope of – 4.00 x10–5 atm / s. a) Determine the rate law,
the integrated rate law, and the value of the rate constant for this reaction, all in terms of pressure units in atm
and time in seconds. b) If the initial pressure of C2H5OH was 1.25 x 10–2 atm, calculate the half-life for this
reaction? c) How much time is required for all the C2H5OH to decompose? d) Calculate the pressure of C2H4
in atm after 259 s from the start of the reaction.

41. The reaction

H2SeO3 (aq) + 6I– (aq) + 4H+ (aq) Se (s) + 2I3– (aq) + 3H2O (l)
was studied at 0 ⁰C, and the following data were obtained:

Experiment [H2SO3]0 (M) [H+]0 (M) [I– ]0 (M) Initial Rate (M / s)

1 1.0 x 10–4 2.0 x 10–2 2.0 x 10–2 1.66 x 10–7
2 2.0 x 10–4 2.0 x 10–2 2.0 x 10–2 3.33 x 10–7
3 3.0 x 10–4 2.0 x 10–2 2.0 x 10–2 4.99 x 10–7
4 1.0 x 10–4 4.0 x 10–2 2.0 x 10–2 6.66 x 10–7
5 1.0 x 10–4 1.0 x 10–2 2.0 x 10–2 0.42 x 10–7
6 1.0 x 10–4 2.0 x 10–2 4.0 x 10–2 13.2 x 10–7
7 1.0 x 10–4 1.0 x 10–2 4.0 x 10–2 3.36 x 10–7

These relationships hold only if there is a very small amount of I3– present. What are the rate law and
Δ[H2SeO3]
the value of the rate constant and its unit? Assume that: Rate = − Δ𝑡

42. The second-order reaction: 2Mn(CO)5 Mn2(CO)10

5 –1 –1
has a rate constant equal to 3.6 × 10 M • s at 25 °C.
a) If the initial concentration of Mn(CO)5 is 2.0 × 10–5 M, how long will it take for 90.0 % of the reactant to
disappear? b) What is the concentration of Mn2(CO)10 after 1.1 s?

43. At high temperature 1,3-butadiene, C4H6 reacts with itself to form a dimer with the formula C8H12:
2C4H6 (g) C8H12 (g)
The rate of the reaction was monitored at 750 K for a trial with the C4H6 starting concentration of 0.021 mol/L.
The data were plotted in three different ways as shown below:

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

a) What is the order of reaction with respect to C4H6? Explain. b) What are the rate constant k and its units,
if the initial rate is 0.0010 mol/L•s? c) Indicate the rate law and integrated rate law for this reaction.

44. Nitrosyl bromide decomposes at 10°C:

2NOBr (g) 2NO (g) + Br2 (g)
Use the following kinetic data to determine the order of the reaction and the value of the rate constant.

time (s) 0 10 20 30 40
[NOBr] (M) 0.0400 0.0303 0.0244 0.0204 0.0175
Hint: use graphical method and excel to answer this question.

[Link] reaction that occurs in a Breathalyzer, a device used to determine the alcohol level in a person's
bloodstream, is given below:
2K2Cr2O7 + 8H2SO4 + 3C2H6O 2Cr2(SO4)3 + 2K2SO4 + 11H2O + 3CH3COOH

If the rate of appearance of Cr2(SO4)3 is 1.64 mol/min at a particular moment, what is the rate of disappearance
of C2H6O at that moment?

46. The rate of the reaction NO2 (g) + CO (g) NO (g) + CO2 (g)
depends only on the concentration of nitrogen dioxide below 225 ⁰C. At a temperature below 225 ⁰C, the
following data were collected:

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

time (s) [NO2] (mol/L)

0 0.500
1.20 0.444
3.00 0.381
4.50 0.340
9.00 0.245
10.8 0.220
a) Determine the rate law, the integrated rate law, and the value of the rate constant and units b) Calculate
[NO2] at 8.00 s after the start of the reaction. c) Calculate the [CO2] at 5.00 s.
Hint: use graphical method and excel to answer this question.

47. The following data were collected for the decay of HO2 radicals:

time (s) [HO2] molecules/cm3

0 1.0 x 1011
2 5.0 x 1010
6 2.5 x 1010
14 1.25 x 1010
30 6.225 x 109

Determine the rate law and the value of the rate constant for this reaction in the unit of # molecules/cm3 and
second. Hint: use graphical method and excel to answer this question.

48. Hydrogen iodide decomposes at 800 K via a second-order process to produce hydrogen and iodine according
to the following chemical equation.
2HI(g) H2(g) + I2(g)
–2 –2
It takes 142 seconds for the initial concentration of HI to decrease from 6.75 × 10 M to 3.50 x 10 M. What
is the rate constant for the reaction?

49. The hydration of tris(1,10-phenanthroline) iron(II) in acid solution takes place according to the following
2+ + 2+ +
chemical equation: Fe(phen)3 + 3H3O + 3H2O Fe(H2O)6 + 3phenH
–3 –1
If the activation energy, Ea, is 126.0 kJ/mol and the rate constant at 30.0 °C is 9.8 × 10 min , what is the
rate constant at 35.0 °C?

50. Cyclopropane is the smallest cyclic hydrocarbon. Because its 60° bond angles allow poor orbital overlap, its
bonds are weak. As a result, it is thermally unstable and rearranges to propene at 1000°C via the following
first-order reaction:

the reaction rate constant is 9.2 s–1, a) What is the half-life of the reaction? b) How long does it take for the
concentration of cyclopropane to reach one-quarter of the initial value?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

51. Experimental values for the temperature dependence of the rate constant for the gas-phase reaction:
NO + O3 NO2 + O2
are as follow:
Temperature k (L/mol • s)
(K)
195.0 1.08 x 109
230.0 2.95 x 109
260.0 5.42 x 109
298.0 12.0 x 109
369.0 35.5 x 109

Make the appropriate graph using these data and determine the activation energy for this reaction. Use excel.

52. The reaction: (CH3)3CBr + OH– (CH3)3COH + Br–

in a certain solvent is first order with respect to (CH3)3CBr and zero order with respect to OH–. In several
experiments, the rate constant k (in s–1) was determined at different temperatures. A plot of ln(k) versus 1/T
was constructed resulting in a straight line with a slope value of –1.100 x 104 K and y-intercept of 33.50.
a) Determine the activation energy for this reaction. b) Determine the value of the frequency factor A. c)
Calculate the value of k at 25.0 ⁰C.

53. Theophylline is a pharmaceutical drug that is sometimes used to help with lung function. It was observed a
case where the initial lab results indicate that the concentration of theophylline in a patient’s body decreased
from 2.0 x 10–3 M to 1.0 x 10–3 M in 24 hours. In another 12 hours the drug concentration was found to be 5.0
x 10–4 M. What is the value of the rate constant for the metabolism of this drug in the body?

54. The OH• radical disproportionates according to the elementary chemical reaction:
HO• + •OH H2 O + O

The rate constant for the reaction is 2.0 x 10–12 cm3 •molecules–1 •s–1 at room temperature. If the initial •OH
concentration is 1.3 x 1013 molecules/cm3, what is the first half-life for the reaction?

55. The radioactive nuclide Ta-178 undergoes first-order decay with a half-life of 9.31 min. If a quantity of Ta-
178 is produced, what fraction remains after 82.5 seconds?
63
56. Ni decays by a first-order process via the emission of a beta particle. The 63Ni isotope has a half-life of 100
years. How long will it take for 67% of the nickel to undergo decay?

57. Two isomers (A and B) of a given compound dimerize as follows:

2A (g) A2 (g)
2B (g) B2 (g)
Both processes are known to be second order in reactant, and k1 is known to be 0.25 L• mol–1• s–1 at 25°C,
where, . In a particular experiment, A and B were placed in separate containers at
25°C, where [A]0 = 1.0 x 10–2 M and [B]0 = 2.5 x 10–2 M. It was found that [A] = 3[B] after the reactions
progressed for 3.0 minutes. a) Calculate the concentration of A2 after 3.0 minutes. b) Calculate the value of
k2 where,

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

58. The reaction 2NO2 2NO + O2 obeys the below rate law at 500 K:

If the initial concentration of NO2 is 1.00 M, how long will it take for the [NO2] to decrease to 35.8% of its
initial value?

59. The reaction 3NO N2O + NO2 is found to obey the rate law, Rate = k[NO]2. If the first half-life of
the reaction is found to be 2.00 s, what is the length of the fourth half-life?

60. The elementary chemical reaction O + ClO Cl + O2 is made pseudo-first order in oxygen atoms by using
a large excess of ClO radicals. The rate constant for the reaction is 2.7 x 10–12 cm3/(molecules • s). If the initial
concentration of ClO is 1.0 x 1011 molecules/cm3, how long will it take for the oxygen atoms to decrease to
10.0 % of their initial concentration?

61. Suppose that a catalyst lowers the activation barrier of a reaction from 125.00 kJ/mol to 55.00 kJ/mol. By
what factor would you expect the reaction rate to increase at 25.0 °C? (Assume that the frequency factors for
the catalyzed and uncatalyzed reactions are identical.)

62. The activation barrier for the hydrolysis of sucrose into glucose and fructose is 108 kJ/mol. If an enzyme
increases the rate of the hydrolysis reaction by a factor of 1 million, how much lower must the activation
barrier be when sucrose is in the active site of the enzyme? (Assume that the frequency factors for the
catalyzed and uncatalyzed reactions are identical and a temperature of 25.0 °C.)

63. The enzyme carbonic anhydrase catalyzes the reaction CO2 (g) + H2O (l) HCO3– (aq) + H+ (aq)
In water, without the enzyme, the reaction proceeds with a rate constant of 0.039 s–1 at 25.0 ⁰C. In the presence
of the enzyme in water, the reaction proceeds with a rate constant of 1.0 x 106 s–1 at 25.0 ⁰C. Assuming the
collision factor is the same for both situations, calculate the difference in activation energies for the
uncatalyzed versus enzyme-catalyzed reaction.

64. Consider these two gas-phase reactions

a) AA(g) + BB(g) 2AB(g)
b) AB(g) + CD(g) AC(g) + BD(g)

If the reactions have identical activation barriers and are carried out under the same conditions, which one
would you expect to have the faster rate?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

65. Consider a reaction that occurs by the following

mechanism:
A + BC AC + B
AC + D A + CD
The potential energy profile for the reaction is shown
a) What is the equation for the overall reaction?
b) Write structural formulas for all species present at
reaction stages 1–5. Identify each species as a reactant,
product, catalyst, intermediate, or transition state.
c) Which of the two steps in the mechanism is the rate-
determining step?
d) Is the reaction endothermic or exothermic?
Add labels to the diagram that show the values of the
energy of reaction and the activation energy for the
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overall reaction.

66. Consider the reaction energy profile for A D:

a) How many intermediates are formed during
the reaction?
b) How many elementary steps are in the reaction
mechanism?
c) How many transition states are formed?
d) Which step is the fastest?
e) Which step is Rate Determining Step?
f) Is the overall reaction A D exothermic or
endothermic?

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67. The thermal decomposition of nitryl chloride, NO2Cl is believed to occur by the following mechanism:
k1
NO2Cl (g) NO2 (g) + Cl (g)
k2
Cl (g) + NO2Cl (g) NO2 (g) + Cl2 (g)

a) What is the overall reaction? b) What is the molecularity of each of the elementary steps? c) What rate law
is predicted by this mechanism if the first step is rate-determining?

68. NO (g) catalyzes the decomposition of N2O (g), possibly by the following mechanism:
NO (g) + N2O (g) N2 (g) + NO2 (g)
2NO2 (g) 2NO (g) + O2 (g)
a) What is the chemical equation for the overall reaction? b) Why is NO considered a catalyst and not an
intermediate? c) If experiments show that during the decomposition of N2O, NO2 does not accumulate in
measurable quantities, does this rule out the proposed mechanism? Why or why not? If not, suggest what might
be going on.

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

69. Consider the following mechanism for the reaction of nitric oxide and hydrogen:

k1
2 NO (g) ⇄ N2O2 (g) fast
k–1
k2
N2O2 (g) + H2 (g) N2O (g) + H2O (g) slow
k3
N2O (g) + H2 (g) N2 (g) + H2O (g) fast

a) Write an equation for the overall reaction. b) Identify all reaction intermediates. c) Write the rate law for
the rate-determining step.

70. Draw a plausible transition state for the bimolecular reaction of nitric oxide with ozone. Use dashed lines to
indicate the atoms that are weakly linked together in the transition state.
NO (g) + O3 (g) NO2 (g) + O2 (g)

71. The decomposition of hydrogen peroxide, H2O2 was studied, and the following data were obtained at a
particular temperature:
time (s) [H2O2] mol/L
0 1.000
120 0.910
300 0.780
600 0.590
1200 0.370
1800 0.220
2400 0.130
3000 0.082
3600 0.050
Assuming that: Rate = – Δ[H2O2] / Δt

a) Determine the rate law, the integrated rate law, and the value of the rate constant. b) A possible mechanism
for the decomposition of hydrogen peroxide is:
H2O2 (g) 2•OH (g)
H2O2 (g) + •OH (g) H2O (g) + HO2 (g)
HO2 (g) + •OH (g) H2O (g) + O2 (g)
What is the overall balanced equation for the reaction?
Hint: use graphical method and excel to answer this question.

72. Activation energy and frequency factor have been determined as 6.30 kJ/mol and 6.0 x 108 M–1•s–1 for the
bimolecular reaction: NO (g) + F2 (g) ONF(g) + F(g)
a) Calculate the rate constant for this reaction at 25.0 °C. b) Based on the geometry of reactants and products,
draw a plausible transition state for the reaction. Use dashed lines to indicate the atoms that are weakly linked
together in the transition state. c) Why does the reaction have such a low activation energy?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

73. Values of Ea = 248 kJ/mol and ΔH = 41 kJ/mol have been determined for the reaction:
H2 (g) + CO2 (g) H2O (g) + CO (g)
a) Sketch a potential energy profile for this reaction that shows the potential energy of reactants, products,
and the transition state. Include labels that define Ea and ΔH. b) Considering the geometry of the reactants
and products, suggest a plausible structure for the transition state.

74. A friend studies a first-order reaction and obtains

the following three graphs for experiments done
at two different temperatures.
a) Which two graphs represent experiments done
at the same temperature? What accounts for the
difference in these two graphs?
b) Which two graphs represent experiments
done with the same starting concentration but at
different temperatures? Which graph probably
represents the lower temperature? How do you
know? Copyright © 2012 Pearson Prentice Hall

75. Consider this three-step mechanism for radical chlorination reaction:

k1
Cl2 (g) ⇄ 2•Cl (g) fast
k2
k3
•Cl(g) + CHCl3 (g) HCl (g) + •CCl3 (g) slow

k4
•Cl(g) + •CCl3 (g) CCl4 (g) fast

a) What is the overall reaction? b) Identify the intermediates in the mechanism. c) What is the rate law of the
rate determining step?

76. Consider the overall reaction: 4HBr + O2 2H2O + 2Br2

A proposed three-step mechanism is:
step 1: HBr + O2 HOOBr
step 2: ?
step 3: HBr + HOBr H2O + Br2

a) Write the equation for step 2. b) Identify the intermediate(s).

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

77. The accompanying graph shows the concentration of a reactant as a function of time for two different
reactions. One of the reactions is first order and the other is second order. Which of the two reactions is first
order? Second order? How would you change each plot to make it linear?

Copyright © 2012 Pearson Prentice Hall Inc.

78. Plutonium-236 is an alpha emitter with a half-life of 2.86 years. If a sample initially contains 1.35 mg of Pu-
236, what mass of Pu-236 is present after 5.00 years?

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini
Answers:

1. a) Rate changes upon changing A but rate constant stays the same. b) first order with respect to A and
second order with respect to B. overall order is third order. c) L2 • mol–2 • s–1
2. a) second order b) k= 7.61 M–1•min–1

3. a) rate law is an equation which shows the relationship between the rate of reaction and the concentration
of reactant (s), rate constant is a constant of proportionality between rate of reaction and concentrations
b) The exponent for each reactant in the rate law is called order of reaction with respect to that reactant
and determines how the rate depends on the concentration of that reactant, adding all the orders of all
reactants in the rate law gives the overall reaction order. c) L • mol–1 • s–1

4. Initial rate for c is the highest: initial rate for a = 27 k, initial rate for b = 16 k, initial rate for c = 32 k
5. Initial rate for b is the highest

6. a) – 2.2 x 10–5 M / s; b) + 4.0 x 10–5 M / s; c) + 1.0 x 10–5 M / s; d) +1.1 x 10–5 M /s;

e) + 9.17 x 10–6 M / s; f) + 2.6 x 10–5 M / s
7. a) Rate = k [A][C]2 b) New rate will be 1/8th of the original rate
8. a) 0.0235 M; b) 41.1 min; c) 72.8 min
9. 90 s
10. 1.0 x 106 s
11. First order
12. a) zero order; b) c) [A] = –k t + [A]0
Concentration, [A]

time, s

13. 139 s
14. a) Rate = 4.82 x 10–3 s–1 [N2O5]; b) 1.16 x 10–4 M / s ; c) Rate also is doubled; d) 1.44 x102 s
15. a) Ea = 1.438 x 102 kJ/mol; A= 9.7 x 1011 s–1; b) 3.1 x 10–4 s–1
16. a) 2.8 x 10–6 M / s, 1.7 x 10–6 M / s, 9.23 x 10–7 M / s, 4.43 x 10–7 M / s, 2.1 x 10–7 M / s; b) 1.05 x 10–6
M / s; c) Instantaneous rate at 5000 s = 1.1 x 10–6 M / s, Instantaneous rate at 8000 s = 5.6 x 10–8 M / s

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini
17. Ea1 = 85.0 kJ; Ea2 = activation energy with catalyst

18. 6.82 hours

19. ─ 4.8 x 10–4 mol• L–1• s–1
20. 5.00 x 10–6 mol• L–1• s–1
21. a) First order for each reactant; b) second order; c) Rate = k [OCl–][I–]; d) 6.1 x 10+1 M–1•s–1 d) 0.11 M•s–1
22. a) 5 days; b) 6.25 % ; c) 5 half lives; d) 10 days
23. a) 0.011 mol; b) 2.68 min; c) 102 s
24. a) 0.125 of the initial amount; b) 0.024 y–1; c) 192 years
25. 16000 years
26. 1.10 x 103 years
27. a) second order; b) 10.2 L• mol–1• s–1; c) 0.980 s; d) Rate = 9.98 L• mol–1• s–1 [NO2]2,
1
[NO2]
= 9.98 t + 10.1 e) 29.4 s; f) 2.33 s

28. a) Rate = k [BF3][NH3]; b) second order; c) 3.41 L • mol–1 • s–1

29. a) 1.0 x 103 s; b) 949 s; c) half life will decrease
30. a) Rate = k [CO2]; b) 1.0×10–3 M• min–1
31. a) and b) Rate = 7.6 x 10–3 M–2• min–1 [HgCl2][C2O42– ]2 ; c) 2.0×10–5 M• min–1
32. 2.22 x 104 J
33. a) 3.47 x 10–2 min–1; b) 40.0 min
34. Second order
35. 6.85 hr
36. 52.9 kJ
37. 22.8 hr
38. 56 min

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini
39. a) T2>T1, as the temperature increases, the distribution of kinetic energies shifts to the right meaning there
are fewer molecules with small kinetic energies and more molecules with larger kinetic energies compared
to the distribution at a lower temperature. b) as the temperature increases the number of molecules having
enough thermal energy to surmount reaction activation barrier increases as a result rate of reaction
increases. At any given temperature, a sample of molecules has a distribution of energy as shown in the
plot. Under common circumstances, only a small fraction of the molecules has enough energy to make it
over the activation barrier. Because of the shape of distribution curve, a small change in the temperature
results in a large difference in the number of molecules having enough energy to surmount the activation
barrier. This explains the sensitivity of reaction rates to temperature.

40. a) Based on the information provided, reaction is zero order so rate law:
Rate = 4.00 x10–5 atm• s–1 (PC2H5OH)^0 = 4.00 x10–5 atm• s–1
(no concentration or pressure appears in the rate law)
k = 4.00 x10–5 atm• s–1
Integrated rate law: PC2H5OH = –4.00 x10–5 atm• s–1 • t + 1.25 x 10–2 atm
b) 156 s; c) 313 s; d) 1.0 x 10–2 atm
41. Rate = k[H2SeO3][H+]2[I−]3; k = 5.2 × 105 L5• mol–5• s–1
42. a) 1.3 s; b) 8.9 x 10–6 M
43. a) second order, because the graph of 1/[C4H6] versus time is the only graph which is linear
1 1
b) 2.3 M–1• s–1 c) Rate = 2.3 M–1• s–1[C4H6]2; [C H ] = 2.3 t + [C H ]
4 6 4 60
44. Second order, k = 0.803 M–1• s–1
45. ─2.46 mol/min
1 1
46. a) Rate = k [NO2]2 = 0.237 M–1• s–1[NO2]2 ; [NO2] = 0.237 t + [NO2]0
b) 0.257 M; c) 0.186 M
2 8
47. Rate = k [HO2] ; k = 5.0 x 10 molecules• cm–3• s–1
48. 9.70 × 10–2 M–1•s–1
49. 2.2 × 10–2 min–1
50. a) 0.075 s ; b) 0.15 s
51. 11.9 kJ
52. a) 91.45 kJ; b) 3.5 x 1014 s–1; c) 0.034 s–1
53. 4.2 x 10–5 M• hr–1
54. 0.038 s
55. 0.903
56. 160 years
57. a) 1.6 x 10–3M; b) 2.2 L• mol–1• s–1
58. 128 s
59. 16.0 s
60. 8.5 s
61. Reaction rate is 1.8 x 1012 times higher
62. 74 kJ/mol
63. Carbonic anhydrase lowers the activation energy of the reaction by 42.00 kJ.
64. Reaction a would have a faster rate because it has larger orientation factor.

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini
65. a) overall reaction: BC + D B + CD;
b)1: Catalyst A reacts with BC reactant, 2:Transition state (1), 3:Intermediate AC reacts with second
reactant D, 4: Transition state (2), 5:Catalyst A releases and product CD formed

c) first step, d) endothermic

66. a) two intermediates: B and C, b) three elementary steps, c) three transition states, d) C to D, e) B to C,
f) endothermic

67. a) 2NO2Cl (g) 2NO2 (g) + Cl2 (g), b) first step: unimolecular, second step: bimolecular,
c) Rate = k1 [NO2Cl]

68. a) 2N2O (g) 2N2 (g) + O2 (g) , b) because NO reacts as a reactant in the first step of the mechanism
and does not produce in the first step(s) like an intermediate, NO is a reactant added to the mixture in
order to catalyze the reaction and is regenerated in the second step, a catalyst react in one step during the
mechanism and regenerate in another step, catalyst does not appear in the overall reaction c) The fact that
NO2 does not accumulate in measurable quantities, does not rule out the proposed mechanism as long as
this mechanism is consistent with the kinetics data for this reaction, the reason that NO2 does not
accumulate in measurable quantities is because the rate of the second step is much faster than the rate of
the first step. First step is the rate determining step for this mechanism.

69. a) 2NO (g) + 2H2 (g) N2 (g) + 2 H2O (g), b) N2O and N2O2, c) Rate = k2 [N2O2][H2]

70.

71. a) Rate= 8.0 x 10–4 s–1 [H2O2], Ln[H2O2] = – kt + Ln[H2O2]0, k = 8.0 x 10–4 s–1
b) 2H2O2 (g) 2H2O (g) + O2 (g)

72. a) 5 x 107 M–1 •s–1 , b)

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 Problem Set II – Chemical Kinetics Teacher: Alieh Kazemeini

c) The electron-deficient NO molecule is attracted to electron-rich F2, so the driving force for formation
of the transition state is greater than simple random collisions.

73. a) and b)

74. a) graphs 1 and 2 are for experiments done at the same temperature, they both have the same slope k value
but they have different initial concentration, [A]0 and y-intercept, b) graphs 2 and 3 have the same y-
intercept and are for experiments with the same initial concentration [A]0 but they are done at different
temperature, because they have different slope and k values, the graph 3 with the smaller slope or k value
are for experiments done at the lower temperature.

75. a) Cl2 (g) + CHCl3 (g) CCl4 (g) + HCl (g), b) •Cl and •CCl3, c) Rate (RDS) = k3 [•Cl][CHCl3]

76. a) step 2: HOOBr + 2HBr HOBr + H2O + Br2 b) HOOBr and HOBr

77. B is first order and A is second order, B will be linear if you plot ln[B] vs. time; A will be linear if you
plot 1/[A] vs. time.

78. 0.40 mg Pu-236

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