Sample Exercise 14.

1 Calculating an Average Rate of Reaction

From the data in Figure 14.2, calculate the average
rate at which A disappears over the time interval
from 20 s to 40 s.

Solution
Analyze We are given the concentration of A at 20 s (0.54 M) and at 40 s (0.30 M) and asked to calculate the average
rate of reaction over this time interval.

Plan The average rate is given by the change in concentration, [A], divided by the change in time, t. Because A is a
reactant, a minus sign is used in the calculation to make the rate a positive quantity.

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 Sample Exercise 14.1 Calculating an Average Rate of Reaction
Continued

Solve

Practice Exercise 1
If the experiment in Figure 14.2 is run for 60 s, 0.16 mol A remain. Which of the following statements is or are true?
(i) After 60 s there are 0.84 mol B in the flask.
(ii) The decrease in the number of moles of A from t1 = 0 s to t2 = 20 s is greater than that from t1 = 40 to t2 = 60 s.
(iii) The average rate for the reaction from t1 = 40 s to t2 = 60 s is 7.0 × 10–3 M/s.
(a) Only one of the statements is true.
(b) Statements (i) and (ii) are true.
(c) Statements (i) and (iii) are true.
(d) Statements (ii) and (iii) are true.
(e) All three statements are true.

Practice Exercise 2
Use the data in Figure 14.2 to calculate the average rate of appearance of B over the time interval from 0 s to 40 s.

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 Sample Exercise 14.2 Calculating an Instantaneous Rate of Reaction
Using Figure 14.3, calculate the instantaneous rate of
disappearance of C4H9Cl at t = 0 s (the initial rate).

Solution
Analyze We are asked to determine an instantaneous rate from a graph of reactant concentration versus time.

Plan To obtain the instantaneous rate at t = 0 s, we must determine the slope of the curve at t = 0. The tangent is drawn
on the graph as the hypotenuse of the tan triangle. The slope of this straight line equals the change in the vertical axis
divided by the corresponding change in the horizontal axis (which, in the case of this example, is the change in molarity
over change in time).

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 Sample Exercise 14.2 Calculating an Instantaneous Rate of Reaction
Continued

Solve The tangent line falls from [C4H9Cl] = 0.100 M to 0.060 M in the time change from 0 s to 210 s. Thus, the initial
rate is

Practice Exercise 1
Which of the following could be the instantaneous rate of the reaction in Figure 14.3 at t = 1000 s?
(a) 1.2 × 10–4 M/s
(b) 8.8 × 10–5 M/s
(c) 6.3 × 10–5 M/s
(d) 2.7 × 10–5 M/s
(e) More than one of these.

Practice Exercise 2
Using Figure 14.3, determine the instantaneous rate of disappearance of C 4H9Cl at t = 300 s.

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 Sample Exercise 14.3 Relating Rates at Which Products
Appear and Reactants Disappear
(a) How is the rate at which ozone disappears related to the rate at which oxygen appears in the
reaction 2 O3(g) 3 O2(g)?
(b) If the rate at which O2 appears, [O2]/t, is 6.0 × 10–5 M/s at a particular instant, at what rate is O3
disappearing at this same time, –[O3]/t?

Solution
Analyze We are given a balanced chemical equation and asked to relate the rate of appearance of the product to the
rate of disappearance of the reactant.

Plan We can use the coefficients in the chemical equation as shown in Equation 14.4 to express the relative rates of
reactions.

Solve
(a) Using the coefficients in the balanced equation and the relationship given by Equation 14.4, we have:

(b) Solving the equation from part (a) for the rate at which O3 disappears, –[O3]/t, we have:

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 Sample Exercise 14.3 Relating Rates at Which Products
Appear and Reactants Disappear
Continued

Check We can apply a stoichiometric factor to convert the O2 formation rate to the O3 disappearance rate:

Practice Exercise 1
At a certain time in a reaction, substance A is disappearing at a rate of 4.0 × 10–2 M/s, substance B is appearing at a
rate of 2.0 × 10–2 M/s, and substance C is appearing at a rate of 6.0 × 10–2 M/s. Which of the following could be
the stoichiometry for the reaction being studied?
(a) 2 A + B 3 C (b) A 2B+3C
(c) 2 A B + 3 C (d) 4 A 2B+3C
(e) A + 2 B 3C

Practice Exercise 2
If the rate of decomposition of N2O5 in the reaction 2 N2O5(g) 4 NO2(g) + O2(g) at a particular instant is
–7
4.2 × 10 M/s, what is the rate of appearance of (a) NO2 and (b) O2 at that instant?

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 Sample Exercise 14.6 Determining a Rate Law from Initial Rate Data
The initial rate of a reaction A + B C was measured for three different starting concentrations of A and B, and
the results are as follows:

Using these data, determine (a) the rate law for the reaction, (b) the rate constant, (c) the rate of the reaction when
[A] = 0.050 M and [B] = 0.100 M.

Solution
Analyze We are given a table of data that relates concentrations of reactants with initial rates of reaction and asked
to determine (a) the rate law, (b) the rate constant, and (c) the rate of reaction for a set of concentrations not listed
in the table.

Plan (a) We assume that the rate law has the following form: Rate = k[A]m[B]n. We will use the given data to
deduce the reaction orders m and n by determining how changes in the concentration change the rate. (b) Once we
know m and n, we can use the rate law and one of the sets of data to determine the rate constant k. (c) Upon
determining both the rate constant and the reaction orders, we can use the rate law with the given concentrations to
calculate rate.

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 Sample Exercise 14.6 Determining a Rate Law from Initial Rate Data
Continued

Solve
(a) If we compare experiments 1 and 2, we see that [A] is held constant and [B] is doubled. Thus, this pair of
experiments shows how [B] affects the rate, allowing us to deduce the order of the rate law with respect to B.

Inserting values of rate and concentration from the experiments gives:

The only way this equation can be true is if n = 0. Therefore, the rate law is zero order in B, which means that the
rate is independent of [B].

In experiments 1 and 3, [B] is held constant, so these data allow us to determine the order of the rate law with
respect to [A].

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 Sample Exercise 14.6 Determining a Rate Law from Initial Rate Data
Continued

Inserting values of rate and concentration from the experiments gives:

Because the rate increases by a factor of four when [A] is doubled, we can conclude that m = 2 and the rate law is
second order in B.

Combining these results, we arrive at the rate law: Rate = k[A]2[B]0 = k[A]2

(b) Using the rate law and the data from experiment 1, we have:

(c) Using the rate law from part (a) and the rate constant from part (b), we have:

Rate = k[A]2
= (4.0 × 10–3 M–1s–1)(0.050 M)2
= 1.0 × 10–5 M/s

Because [B] is not part of the rate law, it is irrelevant to the rate if there is at least some B present to react with A.

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 Sample Exercise 14.6 Determining a Rate Law from Initial Rate Data
Continued

Check A good way to check our rate law is to use the concentrations in experiment 2 or 3 and see if we can correctly
calculate the rate. Using data from experiment 3, we have

Rate = k[A]2 = (4.0 × 10–3 M–1 s–1)(0.200 M)2

= 1.6 × 10–4 M/s

Thus, the rate law correctly reproduces the data, giving both the correct number and the correct units for the rate.

Practice Exercise 1
Consider the reaction examined above in the Sample Exercise, A + B C. If the concentration of B is doubled, the
rate of disappearance of B ________, whereas if the concentration of A is doubled, the rate of disappearance of B
________.
(a) does not change; does not change
(b) increases by a factor of two; increases by a factor of two
(c) increases by a factor of four; increases by a factor of two
(d) does not change; increases by a factor of four
(e) increases by a factor of four; does not change

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 Sample Exercise 14.6 Determining a Rate Law from Initial Rate Data
Continued

Practice Exercise 2
The following data were measured for the reaction of nitric oxide with hydrogen:

2 NO(g) + 2 H2(g) N2(g) + 2 H2O(g)

(a) Determine the rate law for this reaction.

(b) Calculate the rate constant.
(c) Calculate the rate when [NO] = 0.050 M and [H2] = 0.150 M.

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 Sample Exercise 14.7 Using the Integrated First-Order Rate Law
The decomposition of a certain insecticide in water at 12 °C follows first-order kinetics with a rate constant of
1.45 yr–1. A quantity of this insecticide is washed into a lake on June 1, leading to a concentration of 5.0 × 10–7 g/cm3.
Assume that the temperature of the lake is constant (so that there are no effects of temperature variation on the rate).
(a) What is the concentration of the insecticide on June 1 of the following year? (b) How long will it take for the
insecticide concentration to decrease to 3.0 × 10–7 g/cm3?

Solution
Analyze We are given the rate constant for a reaction that obeys first-order kinetics, as well as information about
concentrations and times, and asked to calculate how much reactant (insecticide) remains after 1 yr. We must also
determine the time interval needed to reach a particular insecticide concentration.

Plan In part (a) we are given the rate constant, a period of time, and the initial concentration of the reactant, so we
can use Equation 14.13 to determine the concentration of the reactant after 1 year has passed. In part (b) we are
given the initial and final concentrations and the rate constant. In this case we can use Equation 14.13 to calculate
the time that must pass to reach the desired concentration.

Solve
(a) Substituting the known quantities into Equation 14.13, we have:

ln[insecticide]t = 1 yr = –(1.45 yr–1)(1.00 yr) + ln(5.0 × 10–7)

We use the ln function on a calculator to evaluate the second term on the right [that is, ln(5.0 × 10–7)], giving:

ln[insecticide]t = 1 yr = –1.45 + (–14.51) = –15.96

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 Sample Exercise 14.7 Using the Integrated First-Order Rate Law
Continued

To obtain [insecticide]t = 1 yr, we use the inverse natural logarithm, or ex, function on the calculator:

[insecticide]t = 1 yr = e–15.96 = 1.2 × 10–7g/cm3

Note that the concentration units for [A]t and [A]0 must be the same.

(b) Again substituting into Equation 14.13, with [insecticide]t = 3.0 × 10–7 g/cm3, gives:

ln(3.0 × 10–7) = –(1.45 yr–1)(t) + ln(5.0 × 10–7)

Solving for t gives:

t = –[ln(3.0 × 10–7) – ln(5.0 × 10–7)]/1.45 yr–1

= –(–15.02 + 14.51)/1.45 yr–1 = 0.35 yr

Check In part (a) the concentration remaining after 1.00 yr (that is, 1.2 × 10–7 g/cm3) is less than the original
concentration (5.0 × 10–7 g/cm3), as it should be. In (b) the given concentration (3.0 × 10–7 g/cm3) is greater than
that remaining after 1.00 yr, indicating that the time must be less than a year. Thus, t = 0.35 yr is a reasonable
answer.

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 Sample Exercise 14.7 Using the Integrated First-Order Rate Law
Continued

Practice Exercise 1
At 25 °C, the decomposition of dinitrogen pentoxide, N2O5(g), into NO2(g) and O2(g) follows first-order kinetics
with k = 3.4 × 10–5 s–1. A sample of N2O5with an initial pressure of 101.3 kPa decomposes at 25 °C until its partial
pressure is 86.7 kPa. How much time (in seconds) has elapsed?
(a) 5.3 × 10–6 (b) 2000 (c) 4600 (d) 34,000 (e) 190,000

Practice Exercise 2
The decomposition of dimethyl ether, (CH3)2O, at 510 °C is a first-order process with a rate constant of
6.8 × 10–4 s–1:

(CH3)2O(g) CH4(g) + H2(g) + CO(g)

If the initial pressure of (CH3)2O is 18 kPa, what is its pressure after 1420 s?

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 Sample Exercise 14.8 Determining Reaction Order from the Integrated
Rate Law
The following data were obtained for the gas-phase decomposition
of nitrogen dioxide at 300 °C, NO2(g) NO(g) + O2(g). Is the
reaction first or second order in NO2?

Solution
Analyze We are given the concentrations of a reactant at various times during a reaction and asked to determine
whether the reaction is first or second order.

Plan We can plot ln[NO2] and 1/[NO2] against time. If one plot or the other is linear, we will know the reaction is
either first or second order.

Solve
To graph ln[NO2] and 1/[NO2]
against time, we first make the
following calculations from the
data given:

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 Sample Exercise 14.8 Determining Reaction Order from the Integrated
Rate Law
Continued

As Figure 14.8 shows, only the plot of 1/[NO2] versus time is linear. Thus, the reaction obeys a second-order rate
law: Rate = k[NO2]2. From the slope of this straight-line graph, we determine that k = 0.543 M–1 s–1 for the
disappearance of NO2.

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 Sample Exercise 14.8 Determining Reaction Order from the Integrated
Rate Law
Continued

Practice Exercise 1
For a certain reaction A products, a plot of ln[A] versus time produces a straight line with a slope of
–2 –1
–3.0 × 10 s . Which of the following statements is or are true?
(i) The reaction follows first-order kinetics.
(ii) The rate constant for the reaction is 3.0 × 10–2 s–1.
(iii) The initial concentration of [A] was 1.0 M.
(a) Only one of the statements is true.
(b) Statements (i) and (ii) are true.
(c) Statements (i) and (iii) are true.
(d) Statements (ii) and (iii) are true.
(e) All three statements are true.

Practice Exercise 2
The decomposition of NO2 discussed in the Sample Exercise is second order in NO 2 with k = 0.543 M–1 s–1. If the
initial concentration of NO2 in a closed vessel is 0.0500 M, what is the concentration of this reactant after 0.500 h?

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 Sample Exercise 14.9 Determining the Half-Life of a First-Order
Reaction
The reaction of C4H9Cl with water is a first-order
reaction. (a) Use Figure 14.3 to estimate the half-life
for this reaction. (b) Use the half-life from (a) to
calculate the rate constant.

Solution
Analyze We are asked to estimate the half-life of a reaction from a graph of concentration versus time and then to
use the half-life to calculate the rate constant for the reaction.

Plan
(a) To estimate a half-life, we can select a concentration and then determine the time required for the concentration
to decrease to half of that value.
(b) Equation 14.17 is used to calculate the rate constant from the half-life.

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 Sample Exercise 14.9 Determining the Half-Life of a First-Order
Reaction
Continued

Solve
(a) From the graph, we see that the initial value of [C4H9Cl] is 0.100 M. The half-life for this first-order reaction is the
time required for [C4H9Cl] to decrease to 0.050 M, which we can read off the graph. This point occurs at
approximately 340 s.
(b) Solving Equation 14.17 for k, we have

Check At the end of the second half-life, which should occur at 680 s, the concentration should have decreased by yet
another factor of 2, to 0.025 M. Inspection of the graph shows that this is indeed the case.

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 Sample Exercise 14.9 Determining the Half-Life of a First-Order
Reaction
Continued

Practice Exercise 1
We noted in an earlier Practice Exercise that at 25 °C the decomposition of N2O5(g) into NO2(g) and O2(g) follows
first-order kinetics with k = 3.4 × 10–5 s–1. How long will it take for a sample originally containing 202.7 kPa of N2O5
to reach a partial pressure of 50.7 kPa?
(a) 5.7 h (b) 8.2 h (c) 11 h (d) 16 h (e) 32 h

Practice Exercise 2
(a) Using Equation 14.17, calculate t1/2 for the decomposition of the insecticide described in Sample Exercise 14.7.
(b) How long does it take for the concentration of the insecticide to reach one-quarter of the initial value?

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 Sample Exercise 14.10 Activation Energies and Speeds of Reaction
Consider a series of reactions having these energy profiles:

Rank the forward rate constants from smallest to largest assuming all three reactions have nearly the same value for
the frequency factor A.

Solution
The lower the activation energy, the larger the rate constant and the faster the reaction. The value of E does not
affect the value of the rate constant. Hence, the order of the rate constants is 2 < 3 < 1.

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 Sample Exercise 14.10 Activation Energies and Speeds of Reaction
Continued

Practice Exercise 1
Which of the following changes always leads to an increase in the rate constant for a reaction:
(i) Decreasing the temperature
(ii) Decreasing the activation energy
(iii) Making the value of E more negative
(a) Only one—(i), or (ii), or (iii)—increases the reaction rate.
(b) (i) and (ii)
(c) (i) and (iii)
(d) (ii) and (iii)
(e) All three—(i), (ii), and (iii)—increase the reaction rate.

Practice Exercise 2
Rank the rate constants of the reverse reactions from slowest to fastest.

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 Sample Exercise 14.11 Determining the Activation Energy
The table at right shows the rate constants for the
rearrangement of methyl isonitrile at various temperatures
(these are the data points in Figure 14.13):
(a) From these data, calculate the activation energy for
the reaction.
(b) What is the value of the rate constant at 430.0 K?

Solution
Analyze We are given rate constants, k, measured at several temperatures and asked to determine the activation
energy, Ea, and the rate constant, k, at a particular temperature.

Plan We can obtain Ea from the slope of a graph of ln k versus 1/T. Once we know Ea, we can use Equation 14.23
together with the given rate data to calculate the rate constant at 430.0 K.

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 Sample Exercise 14.11 Determining the Activation Energy
Continued

Solve
(a) We must first convert the temperatures from degrees Celsius to kelvins. We then take the inverse of each
temperature, 1/T, and the natural log of each rate constant, ln k. This gives us the table shown below:

A graph of ln k versus 1/T is a straight line (Figure 14.18).

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 Sample Exercise 14.11 Determining the Activation Energy
Continued

The slope of the line is obtained by choosing any two well-separated points and using the coordinates of each:

Because logarithms have no units, the numerator in this equation is dimensionless. The denominator has the units
of 1/T, namely, K–1. Thus, the overall units for the slope are K. The slope equals –Ea/R. We use the value for the gas
constant R in units of J/mol-K (Table 10.2).
We thus obtain

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 Sample Exercise 14.11 Determining the Activation Energy
Continued

We report the activation energy to only two significant figures because we are limited by the precision with which
we can read the graph in Figure 14.18.

(b) To determine the rate constant, k1, at T1 = 430.0 K, we can use Equation 14.23 with Ea = 160 kJ/mol and one of
the rate constants and temperatures from the given data, such as k2 = 2.52 × 10–5 s–1 and T2 = 462.9 K:

Note that the units of k1 are the same as those of k2 and the rate constant at 430.0 K is smaller than it is at 462.9 K,
as it should be.

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 Sample Exercise 14.11 Determining the Activation Energy
Continued

Practice Exercise 1
Using the data in Sample Exercise 14.11, which of the following is the rate constant for the rearrangement of methyl
isonitrile at 320 °C?
(a) 8.1 × 10–15 s–1
(b) 2.2 × 10–13 s–1
(c) 2.7 × 10–9 s–1
(d) 2.3 × 10–1 s–1
(e) 9.2 × 103 s–1

Practice Exercise 2
To one significant figure, what is the value for the frequency factor A for the data presented in Sample Exercise 14.11.

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 Sample Exercise 14.13 Predicting the Rate Law for an Elementary
Reaction
If the following reaction occurs in a single elementary reaction, predict its rate law:
H2(g) + Br2(g) 2 HBr(g)

Solution
Analyze We are given the equation and asked for its rate law, assuming that it is an elementary process.

Plan Because we are assuming that the reaction occurs as a single elementary reaction, we are able to write the rate
law using the coefficients for the reactants in the equation as the reaction orders.

Solve The reaction is bimolecular, involving one molecule of H2 and one molecule of Br2. Thus, the rate law is first
order in each reactant and second order overall:
Rate = k[H2][Br2]

Comment Experimental studies of this reaction show that the reaction

actually has a very different rate law:
Rate = k[H2][Br2]1/2

Because the experimental rate law differs from the one obtained by assuming a single elementary reaction, we can
conclude that the mechanism cannot occur by a single elementary step. It must, therefore, involve two or more
elementary steps.

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 Sample Exercise 14.13 Predicting the Rate Law for an Elementary
Reaction
Continued

Practice Exercise 2
Consider the following reaction: 2 NO(g) + Br2(g) 2 NOBr(g).
(a) Write the rate law for the reaction, assuming it involves a single elementary reaction. (b) Is a single-step
mechanism likely for this reaction?

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 Sample Exercise 14.14 Determining the Rate Law for a Multistep
Mechanism
Continued

Practice Exercise 2
Ozone reacts with nitrogen dioxide to produce dinitrogen pentoxide and oxygen:
O3(g) + 2 NO2(g) N2O5(g) + O2(g)
The reaction is believed to occur in two steps:
O3(g) + NO2(g) NO3(g) + O2(g)
NO3(g) + NO2(g) N2O5(g)
The experimental rate law is rate = k[O3][NO2]. What can you say about the relative rates of the two steps of the
mechanism?

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 Sample Exercise 14.15 Deriving the Rate Law for a Mechanism with a
Fast Initial Step
Show that the following mechanism for Equation 14.26 also produces a rate law consistent with the experimentally
observed one:
k1
Step 1: NO(g) + NO(g) N2O2(g) (fast, equilibrium)
k–1

k2
Step 2: N2O2(g) + Br2(g) 2 NOBr(g) (slow)

Solution
Analyze We are given a mechanism with a fast initial step and asked to write the rate law for the overall reaction.

Plan The rate law of the slow elementary step in a mechanism determines the rate law for the overall reaction.
Thus, we first write the rate law based on the molecularity of the slow step. In this case, the slow step involves the
intermediate N2O2 as a reactant. Experimental rate laws, however, do not contain the concentrations of
intermediates; instead they are expressed in terms of the concentrations of reactants, and in some cases products.
Thus, we must relate the concentration of N2O2 to the concentration of NO by assuming that an equilibrium is
established in the first step.

Solve The second step is rate determining, so the overall rate is

Rate = k2[N2O2][Br2]

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