Chapter 14 Worksheet

Section 14.1 Rates of Reaction

For each of the following chemical equations, write an equation to express the reaction rate in
terms of the changes in concentration of both the reactants and products.

a. 2A + B  C + 3D

b. A + 3B  2C + 2D

c. 2NO(g) + O2(g)  2NO2(g)

d. 2H2O2(g) + Br2(g)  2H2O(l) + O2(g)

e. H2(g) + 2ICl(g)  2HCl(g) + I2(g)

For the reaction 3A + B  2C + 2D, the rate of change of reactant A is determined to be -3.56x10-3 M
s-1.

a. What is the rate of the reaction at this point in time?

b. What is the rate of change of reactant B?

c. What is the rate of change of product D?

Section 14.2 Reaction Rates and Concentration: Rate Laws

For the following reaction: Cl2(g) + CHCl3(g)  HCl(g) + CCl4(g), calculate the average rate of
reaction based on the following time and concentration data.

Time(s) [CCl4](M)
7.00 0.167
148.0 0.374

Concentration and time data for the reaction A  B are provided.

Time(s) [B](M)
0.00 0.00
20.0 0.0231
40.0 0.0398
60.0 0.0513
80.0 0.0589
100.0 0.0635

a. Calculate the average rate of change from 0.00 s to 100.0 s

b. Calculate the instantaneous rate of change at 40.0 s

For the generic unbalanced reaction A+B products, the rate law was determined to be k=[A]:

a. What is the order of the reaction with respect to A?

 b. What is the order of the reaction with respect to B?

c. What is the overall reaction order?

For the generic unbalanced reaction A+B products, the rate law was determined to be k=[A][B]2:

a. What is the order of the reaction with respect to A?

b. What is the order of the reaction with respect to B?

c. What is the overall reaction order?

The reaction

A+BC+D rate = k[A][B]2

has an initial rate of 0.0470 M/s.

a. What will the initial rate be if [A] is halved?

b. What will the initial value be if [A] is tripled and [B] is halved?

Consider the initial rate data at a certain temperature for the reaction

2 NO(g) + 2 H2(g)  N2(g) + 2H2O(g)

Experiment [H2] (M) [NO] (M) Initial Rate (M/s)

1 0.200 0.200 2.06 x 10-4
2 0.200 0.400 8.24 x 10-4
3 0.400 0.400 1.65 x 10-3

a. Determine the rate law for the reaction.

 b. Calculate the rate constant.

Consider the initial rate data at a certain temperature for the reaction

NO2(g) + CO(g)  NO(g) + CO2(g)

Experiment [NO2] (M) [CO] (M) Initial Rate (M/s)

1 0.0250 0.0250 2.12 x 10-3
2 0.0250 0.0500 2.12 x 10-3
3 0.0500 0.0500 8.48 x 10-3

a. Determine the rate law for the reaction.

b. Calculate the rate constant.

Using the given information for each reaction, provide the overall reaction order, the rate law, and
the units of k.

a. For the reaction 2 A(g)  4 B(g) + C(g), the rate doubles when [A] is doubled.

b. The reaction A(aq) + B(aq)  C(aq) + D(aq), is first order with respect to A and first order with
respect to B.
 c. For the reaction of 2 A(g)  2 B(g) + C(g), the reaction rate quadruples when the
concentration of A is doubled.

d. The reaction 2 A(g) + 2 B(g)  C(g) + 2 D(g) is first order with respect to B and second order
with respect to A.

Consider the initial rate data collected at 298 K for the reaction

CH3Br(aq) + OH-(aq)  CH3OH(aq) + Br-(aq)

Experiment [CH3Br] (M) [OH-] (M) Initial Rate (M/s)

1 0.40 0.40 4.48 x 10-5
2 0.80 0.40 8.96 x 10-5
3 0.40 0.20 2.24 x 10-5
4 0.40 0.80 8.96 x 10-5
5 0.20 0.20 1.12 x 10-5

a. Write the rate law.

b. Calculate the rate constant.

c. What is the rate when [CH3Br] = 0.350 M and [OH-] = 0.950 M?

Section 14.3 Integrated Rate Laws and Half-Lives

The decomposition of sulfuryl chloride, SO2Cl2, is a first-order process with a rate constant of 4.50 x
10-2 s-1 at 660 K.

SO2Cl2 (g)  SO2 (g) + Cl2 (g)

The initial concentration of SO2Cl2 is 0.693 M.

a. Calculate the concentration of SO2Cl2 after 24.5 s.

b. How many seconds does it take for the concentration of SO2Cl2 to drop to 3.59 x 10-3 M?

The first-order reaction A  B has a rate constant of 0.0793 s-1. How many seconds will it take for
65.7% of A to react?

The following data was collected for the first-order decomposition of acetone, CH3COCH3, at a
certain temperature:

Time (s) [CH3COCH3] (M)

0.00 0.583
40.0 0.429
80.0 0.302
120.0 0.209
160.0 0.148
200.0 0.101
 a. Calculate the value of the rate constant.

b. Calculate the concentration of acetone remaining after 93.0 s.

A first-order reaction has a rate constant of 4.38 x 10-4 s-1 at a certain temperature. Calculate the
half-life for this reaction in minutes.

For the first-order reaction A  B, 21.2% of A remains after 32.8 min. Calculate the half-life in
minutes.

The decomposition reaction A  B + C is a second-order process with a rate constant of 6.92 x 10-3
M-1 s-1. The initial concentration of A is 0.0248 M.

a. Calculate the concentration of A after 78.9 min.

 b. How many minutes does it take for the concentration of A to drop to 4.28 x 10 -3 M?

The half-life of a second-order decomposition reaction is 278 s when the initial concentration of
there reactant is 0.059 M. Calculate the rate constant for this reaction.

The rate constant for this zero-order reaction is 0.0271 M/s at a certain temperature.

2 NH3 (g)  3 H2 (g) + N2 (g)

How long does it take for the concentration of NH3 to decrease from 0.850 M to 0.320 M?

For the zero-order reaction A  B + C, the rate constant at 300 K is 0.0711 M/s. If the initial
concentration of A is 0.671 M, calculate the half-life.
The time and concentration data for the reaction A  products are shown here.

Time (s) [A] (M)

0.00 0.750
30.0 0.596
60.0 0.473
90.0 0.376

a. Determine the reaction order with respect to A.

b. Calculate the rate constant for the reaction

Time and concentration data were collected for the reaction A  B.

Time (s) [A] (M)

0.00 0.600
30.0 0.484
60.0 0.405
90.0 0.349

a. Determine the reaction order with respect to A.

 b. Calculate the rate constant for the reaction.

Section 14.4 Reaction Rates and Temperature: Activation Energy

For a certain reaction, the activation energy and enthalpy of reaction were determined to be 245
kJ/mol and 56 kJ/mol, respectively. Sketch an energy diagram for this reaction that shows the
potential energy diagram for this reaction that shows the potential energy of the reactants,
products, and transition state, and include labels for Ea and ΔH.

Calculate the rate constant for a reaction at 75 °C that has an activation energy of 80.2 kJ/mol and a
frequency factor of 3.58 x 10-11 s-1.

The rate constant of a certain reaction was experimentally determined at several temperatures. Use
the data in the table to determine the activation energy and frequency factor for this reaction.
 T (K) k (s-1)
500.0 0.00000105
520.0 0.0000658
540.0 0.000348
560.0 0.00159
580.0 0.00643
600.0 0.0232
620.0 0.0758
640.0 0.227
660.0 0.629
680.0 1.62

Rate constants for the reaction 2 NO2 (g)  2 NO (g) + O2 (g) are 0.77 M-1 s-1 at 603 K and 4.7 M-1 s-1 at
656 K.

a. Calculate the value of the activation energy in kJ/mol.

b. Calculate the rate constant at 626 K.

The rate constant for the reaction of 2 N2O5 (g)  4 NO2 (g) + O2 (g) is 5.2 x 10-3 s-1 at 65 °C. Calculate
the rate constant for the reaction at 85 °C. The activation energy is 103 kJ/mol.
A certain reaction proceeds three times faster at 465 K than it did at 435 K. Calculate the activation
energy in kJ/mol for this reaction.

Section 14.5 Reaction Mechanisms

Write the overall balanced reaction, and identify any intermediates for the following reaction
mechanism:

Step 1: O2 (g) ⇌ 2 O (g)

Step 2: O (g) + N2 (g)  NO (g) + N (g)

Step 3: N (g) + O (g)  NO (g)

Write the overall balanced reaction, and identify any intermediates for the following reaction
mechanism.

Step 1: N2O5 (g)  NO3 (g) + NO2 (g)

Step 2: NO3 (g)  NO2 (g) + O (g)

Step 3: 2 O (g)  O2 (g)

Write the rate law and identify the molecularity of the following elementary reactions:

a. 2 NO2 (g)  NO3 (g) + NO (g)

b. ClO (g) + O (g)  Cl (g) + O2 (g)

c. 2 NO (g) + Br2 (g)  2 NOBr (g)

d. I2 (g)  2 I (g)

e. 2 NO2 (g)  NO3 (g) + NO (g)

f. O3 (g) + Cl (g)  O2 (g) + ClO (g)

The formation of nitryl fluoride, NO2F, is thought to occur by the following two-step mechanism:

Step 1: NO2 (g) + F2 (g)  NO2F (g) + F (g) (slow)

Step 2: F (g) + NO2 (g)  NO2F (g) (fast)

Write the overall balanced reaction and rate law.

The decomposition of hydrogen peroxide is thought to occur by the following three-step
mechanism:

Step 1: H2O2 (g)  2 OH (g) (slow)

Step 2: H2O2 (g) + OH (g)  H2O (g) + HO2 (g) (fast)

Step 3: HO2 (g) + OH (g)  H2O (g) + O2 (g) (fast)

Write the overall balanced equation and rate law.

The following mechanism has been proposed for the formation of HI (g), which has a rate law of rate
= k[H2][I2]:

Step 1: I2 (g) ⇌ 2 I (g) (fast, equilibrium)

Step 2: H2 (g) + 2 I (g)  2 HI (g) (slow)

a. Write the overall balanced reaction.

b. Show that the proposed mechanism is consistent with the rate law.
 c. Express the overall rate constant k in terms of the rate constants for the elementary
reactions.

The following three-step mechanism has been proposed for the reaction of nitric oxide with
hydrogen, which has a rate law of rate = k[NO]2[H2]:

Step 1: 2 NO (g) ⇌ N2O2 (g) (fast, equilibrium)

Step 2: N2O2 (g) + H2 (g)  N2O (g) + H2O (g) (slow)

Step 3: N2O (g) + H2 (g)  N2 (g) + H2O (g) (fast)

a. Write the overall balanced reaction.

b. Show that the proposed mechanism is consistent with the rate law.

c. Express the overall rate constant k in terms of the rate constants for the elementary
reactions.