Kinetics Practice Problems

1. Three major methods used to increase the rate of a reaction are adding a catalyst, increasing the
temperature, and increasing the concentration of a reactant. From the perspective of collision theory,
explain how each of these methods increases the reaction rate.
a. adding a catalyst
Adding a suitable catalyst lowers the energy demands of the reaction (the activation energy) by
providing a less demanding pathway. It does this by forming a different activated complex with a
lower activation energy.
b. increasing the temperature
Increasing the temperature increases the average kinetic energy of the molecules. However, what
is most important here is that the fraction of molecules that have the energy necessary to react (the
activation energy) is increased.
c. increasing the concentration of the reactants
Increasing the concentration of a reactant increases the probability of collisions, and therefore
increases the possibility of reaction, for the particles must collide to react. Note that not all
collisions result in successful reactions.

2. Why do large crystals of sugar burn more slowly than finely ground sugar?
The rate of combustion is proportional to the surface area of sugar exposed to oxygen. Smaller crystals
have more surface area and burn faster.

3. How do homogeneous catalysts and heterogeneous catalyst differ?

A homogeneous catalyst is a catalyst that exists in the same phase (liquid or gas) as the reactants. A
heterogeneous catalyst, on the other hand, is a catalyst that exists in a different phase form the reactants.

4. Express the rate of reaction in terms of the rate of change of each reactant and each product in the
following.
a. 3ClO-(aq) → ClO3-(aq) + 2Cl-(aq)
-
∆[ClO- ] ∆[ClO3 ] ∆[Cl- ]
rate of reaction = - = =
3∆t ∆t 2∆t
b. 3SO2(g) + O2(g) → 2SO3(g)
∆[SO2 ] ∆[O2 ] ∆[SO3 ]
rate of reaction = - =− =
3∆t ∆t 2∆t
c. C2H4(g) + Br2(g) → C2H4Br2(g)
∆[C2 H4 ] ∆[Br2 ] ∆[C2 H 4 Br2 ]
rate of reaction = - =− =
∆t ∆t ∆t
5. In the Haber process for the production of ammonia,
N2(g) + 3H2(g) → 2NH3(g)
What is the relationship between the rate of production of ammonia and the rate of consumption of
hydrogen?
∆[H 2 ] ∆[NH3 ]
rate of reaction = − =
3∆t 2∆t

6. The rate constant

A. always shows an exponential increase with the Kelvin or absolute temperature.
B. increases with increasing concentration.
C. usually increases with increased pressure for gases.
D. never changes (it is a constant).
E. is the same for a given reaction at the same Kelvin or absolute temperature.
Answer: (E) In this question be sure to note that it is the rate constant that is involved. Refer to
the Arrhenius equation for the specific relationship.

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7. What are the units for each of the following if the concentrations are expressed in moles per liter and the
time in seconds?

a. rate of a chemical reaction The units for rate are always mol/L•s.

b. rate constant for a zero-order rate law Rate=k; k must have units of mol/L•s

c. rate constant for a first-order rate law Rate=k[A], k must have units of s-1

d. rate constant for a second-order rate law Rate=k[A]2, k must have units of L/mol•s

8. The reaction

2I-(aq) + S2O82-(aq) → I2(aq) + 2SO42-(aq)

was studied at 25°C. The following results were obtained where

∆[S2O82− ]
Rate = -
∆t

[I-]0 (mol/L) [S2O82-]0 (mol/L) Initial Rate (mol/L • s)

0.080 0.040 12.5×10-6
0.040 0.040 6.25×10-6
0.080 0.020 6.25×10-6
0.032 0.040 5.00×10-6
0.060 0.030 7.00×10-6

a. Determine the rate law.

Rate = k[I-]x[S2O82-]y
Compare experiments 1 and 2.
rate k[I- ]x [S O 2− ]y
2 = 2 2 8 2
rate1 k[I- ]x [S O 2− ]y
1 2 8 1

6.25 × 10-6 k (0.040) x (0.040) y

= , 0.5 = 0.5x , x = 1
12.5 × 10-6 k (0.080) x (0.040) y
rate k[I- ]x [S O 2− ]y
3 = 3 2 8 3
rate1 k[I- ]x [S O 2− ]y
1 2 8 1

6.25 × 10-6 k (0.080) x (0.020) y

= , 0.5 = 0.5y , y = 1
12.5 × 10-6 k (0.080) x (0.040) y
Rate = k[I-][S2O82-]

b. Calculate a value for the rate constant for each experiment and an average value for the rate constant.

Kmean = 3.9×10-3 L/mol•s

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9. The following rate data were obtained at 25°C for the following reaction. What is the rate law expression?
What is the overall order of the reaction?

2A + B → 3C

Experiment [A]0 (mol/L) [B]0 (mol/L) Initial Rate (mol/L • s)

1 0.10 0.10 2.0 × 10-4
2 0.30 0.30 6.0 × 10-4
3 0.10 0.30 2.0 × 10-4
4 0.20 0.40 6.0 × 10-4

Rate = k[A]x[B]y
Experiments 1 and 3: [A] is constant = 0.10 M
[B] increases by a factor of 3 but the rate of reaction does NOT change
Therefore [B] does not affect the rate
Therefore the order of reaction with respect to B = y = 0
Experiments 2 and 3: [B] is constant = 0.30 M
[A] decreases by a factor of 3 and the rate of the reaction decreases by a
factor of 3
Therefore the reaction is first order with respect to A = x = 1
Rate law expression: Rate = k[A]1[B]0 = k[A]
The overall order of reaction is (1+0) = 1

10. What is the rate law expression for the following reaction, given the data below? What is the overall order
of the reaction?

2A + B + 2C → 3D + 2E

Experiment [A]0 (mol/L) [B]0 (mol/L) [C]0 (mol/L) Initial Rate (mol/L • min)
1 0.20 0.10 0.10 2.0 × 10-4
2 0.20 0.30 0.20 18.0 × 10-4
3 0.20 0.10 0.30 2.0 × 10-4
4 0.10 0.60 0.40 3.6 × 10-4

Rate = k[A]x[B]y[C]z
Experiments 1 and 3: [A], [B] are constant, [C] increases by a factor of 3 but the rate of the
reaction does NOT change.
Therefore the reaction [C] does not affect the rate
Therefore the order of reaction with respect to C = z = 0 and we can
ignore this data.
Experiments 1 and 2: [A] is constant = 0.20 M
[B] increases by a factor of 3
The rate increases by a factor of 9
Therefore the reaction is second order with respect to B = y = 2
There are no experiments where [A] varies and [B] remains constant, so we will have to evaluate the order
of the reaction with respect to A mathematically.
rate k[A]x [B]y
4 = 4 4
rate2 k[A]x2 [B]2y
3.6 × 10-3 k (0.1) x (0.6)2
=
1.8 × 10-3 k (0.2) x (0.3)2
2 = (0.5) x (2)2
x=1, therefore the reaction is first order with respect to A.
The rate law expression is Rate = k[A][B]2
The overall order is 1+2 = 3

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11. Use the rate law determined in question 9 to answer the following question. What would happen to the rate
of the reaction if the concentration of A was halved and the concentration of B was tripled during a
reaction?
Assume the initial concentrations of A and B were both 1 M.
Therefore Rate = k[A][B]2 = k(1)(1)2=k
After the change in the reaction, Rate = k(1/2)(3)2 = 9/2 k
Therefore the rate of the reaction would increase by a factor of 9/2.

12. Rate data were collected for the following reaction at a particular temperature.

2ClO2(aq) + 2OH-(aq) → ClO3-(aq) + ClO2-(aq) + H2O(l)

Experiment [ClO2]0 (mol/L) [OH-]0 (mol/L) Initial Rate (M/s)

1 0.012 0.012 2.07 × 10-4
2 0.024 0.012 8.28 × 10-4
3 0.012 0.024 4.14 × 10-4
4 0.024 0.024 1.66 × 10-3

a. What is the rate-law expression for this reaction?

Rate = k[ClO2]x[OH-]y
Experiments 1 and 3: [ClO2] is constant.
[OH-] doubles
The rate doubles.
Therefore the reaction is first order with respect to B = y = 1
Experiments 3 and 4: [ClO2] doubles
[OH-] is constant.
The rate quadruples.
Therefore the reaction is second order with respect to A= x = 2
Rate = k[ClO2]2[OH-]

b. Calculate a value for k.

Using the data from Experiment 1 to calculate k, we have
2.07 × 10-4 M/s = k(0.012 M)2(0.012 M)
k = 1.2 × 102 M-2• s-1

c. Describe the order of the reaction with respect to each reactant and to the overall order.
The reaction is second order with respect to ClO2, first order with respect to OH- and third order
overall.

13. Consider a chemical reaction between compounds A and B that is first order in A and first order in B.
From the information shown here, fill in the blanks.

Experiment [A] [B] Rate (M•s-1)

1 0.20 M 0.050 M 0.24

2 0.030 M 0.20

3 0.40 M 0.80

Rate=k[A][B]
Use experiment 1 to find the value of k:
Rate 0.24 M • s-1 -1 −1
k= = = 24 M • s
[A][B] (0.20 M )(0.050 M )
Then in experiment 2, we solve for [A] and in experiment 3, we solve for [B]
Rate 0.20 M • s−1 Rate 0.80 M • s−1
[A] = = = 0.28 M [B] = = = 0.083 M
k[B] (24 M -1 • s−1)(0.030 M ) k[ A] (24 M -1 • s−1 )(0.40 M )

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14. The rate of a chemical reaction
A. is always dependent of the concentration of all reactants.
B. is always increased with increasing temperatures.
C. is directly proportional to the value of ∆E.
D. is greater with higher activation energies.
E. is independent of surface area.
Answer: (B) The collision model indicates that molecular collision is necessary for reaction.
Because an increase in temperature raises molecular velocities and the percentage of effective
collisions, the reaction rate increases.

15. For the first-order reactions of different substances A and X

A → B t1/2 = 30.0 min
X → Y t1/2 = 60.0 min
This means that
A. doubling the concentration of A will have ½ the effect on half-life that doubling the
concentration of B will have on its half-life.
B. a certain number of grams of A will react twice as fast as the same number of grams of X.
C. a certain number of grams of X will react twice as fast as the same number of grams of A.
D. the rate constant for A → B is lower than the rate constant of X → Y.
E. 3 moles of A will react more rapidly than 3 moles of X.
Answer: (E) It takes half as much time for A to form B as for X to form Y, as seen by the smaller
half-life. Note that option “B” would be incorrect as the grams of A and the grams of X are not
the same number of moles.

16. A reaction is first order with respect to [X] and second order with respect to [Y]. When [X] is
0.20 M and [Y] = 0.20 M the rate is 8.00 × 10-3 M/min. The value of the rate constant, including
correct units, is
A. 1.00 M min-1
B. 1.00 M-2 min-1
C. 2.00 M-1 min-1
D. 2.00 M-2 min-1
E. 8.00 × 10-3 min-3
Answer: (B) From these data, it follows that the rate law is Rate = k[X]Y]2. Solving for the rate
constant and substituting data for this reaction:
K = Rate/[X][Y]2
= 8.00 × 10-3 M/min/(0.200 M)(0.200 M)2
= 0.008 M/min/0.008 M3
= 1.00 M-2min-1
17. What is meant by the half-life of a reactant?
The half-life of a reactant is the time required for half of that reactant to be converted into products. For a
first order reaction, the half-life is independent of concentration so that the same time is required to
consume half of any starting amount or concentration of the reactant. On the other hand, the half-life of a
second-order reaction does depend on the starting amount of the reactant.
18. It took 143 s for 50.0% of a particular substance to decompose. If the initial concentration was 0.060 M
and the decomposition reaction follows second-order kinetics, what is the value of the rate constant?
1 1
For a second order reaction: t = or k =
1/2 k[A] t [A]
0 1/2 0
1
k = = 0.12 L / mol • s
143 s(0.060 mol / L)

19. A certain first-order reaction is 45.0% complete in 65 s. What are the rate constant and the half-life for this
process?
If [A]0 = 100.0, then after 65 s, 45.0: of A has reacted or [A] = 55.0. For first order reactions:
ln[A]t - ln[A]0 = -kt
ln[55.0] - ln[100.0] = -k(65 s)
k = 9.2 × 10-3 s-1
0.693 0.693
t1/2 = = = 75 s
k 9.2 × 10−3s-1
t = 150. s

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20. A reaction mechanism
A. is the sum of all steps in a reaction except the rate determining step.
B. has a ∆H equal to the ∆H for the most demanding step.
C. always has a rate determining step.
D. may be absolutely proven from the rate law.
E. is determined from the balanced expression only.
Answer: (C) In all series of steps (the mechanism for the overall reaction), there must always be a
slowest step. The rate determining step is the slowest step.

21. Write the rate laws for the following elementary reactions.
a. CH3NC(g) → CH3CN(g)
Rate = k[CH3NC]

b. O3(g) + NO(g) → O2(g) + NO2(g)

Rate = k[O3][NO]

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 22. Most reactions occur by a series of steps. The energy profile for a certain reaction that proceeds by a
two-stop mechanism is

On the energy profile, indicate

a. The positions of reactants (R) and products (P).
b. The activation energy for the overall reaction (Ea).
c. ∆E for the reaction.
d. Which point on the plot represents the energy of the intermediate in the two-step reaction?
e. Which step in the mechanism for this reaction is rate determining, the first or the second
step? Explain. In a mechanism, the rate of the slowest step determines the rate of the
reaction. The activation energy for the slowest step will be the largest energy barrier that
the reaction must overcome. Since the second hump in the diagram is at the highest
energy, then the second stephas the largest activation energy and will be the rate
determining step (the slow step).

23. A proposed mechanism for a reaction is

C4H9Br → C4H9+ + Br- Slow

C4H9 + H2O → C4H9OH2+ Fast
C4H9OH2+ + H2O → C4H9OH + H3O+ Fast

a. What is the overall balanced equation for the

reaction?C4H9Br + 2H2O → C4H9OH + Br- +
H 3O +

b. What are the intermediates in the proposed

mechanism?C4H9+ and C4H9OH2+

c. Write the rate law expected for this mechanism.

Since step 1 is the rate determining step, the rate law for this mechanism is:
Rate = k[C4H9Br]

24. The mechanism for the reaction of nitrogen dioxide with carbon monoxide to form nitric oxide and
carbondioxide is though to be

NO2 + NO2 → NO3 + NO Slow

NO3 + CO → NO2 + CO2 Fast

a. What is the overall balanced equation for the reaction?

NO2 + CO → NO + CO2

b. What is the intermediate in the proposed mechanism?

NO3

c. Write the rate law expected for this mechanism.

Since step 1 is the rate determining step, the rate law for this mechanism is:
Rate = k[NO2]2
n