Chapter 14

CHEMICAL KINETICS
 Chemical Kinetics
• The speed at which reactions take place is
called reaction rate.
• The study of reaction rate is called chemical
kinetics.
• A step-by-step view of the change of
reactants to products is called a
mechanism.
Factors That Affect Reaction Rates
1) Physical state of the reactants
2) Reactant concentrations
3) Reaction temperature
4) Presence of a catalyst
Physical State of the Reactants
• The more readily the reactants collide, the
more rapidly they react.
• Homogeneous reactions (all gases or
liquids) are often faster.
• Heterogeneous reactions that involve solids
are slower; the faster of these reactions
occurs if the surface area is increased; that
is, a fine powder reacts faster than a pellet
or tablet.
 Reactant Concentrations
• Increasing reactant
concentration
generally increases
reaction rate.
• Since there are more
molecules, more
collisions occur.
 Temperature
• Reaction rate generally increases with
increased temperature.
• Kinetic energy of molecules is related to
temperature.
• At higher temperatures, molecules move
more quickly, increasing numbers of
collisions and the energy the molecules
possess during the collisions.
 Presence of a Catalyst
• Catalysts affect rate without being in the
overall balanced equation.
• Catalysts affect the kinds of collisions,
changing the mechanism (individual
reactions that are part of the pathway from
reactants to products).
• Catalysts are critical in many biological
reactions.
 Reaction Rate
• Rate is a change in concentration over
a time period: Δ[ ]/Δt.
• Δ means “change in.”
• [ ] means molar concentration.
• t represents time.
• Types of rate measured:
– average rate
– instantaneous rate
– initial rate
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.

Solve
 Following Reaction Rates

• Rate of a reaction is
measured using the
concentration change
for a reactant or a
product over time.
• In this example,
[C4H9Cl] is followed to
find average rate.
Rate = –Δ[C4H9Cl]/Δt
 Plotting Rate Data
• A plot of the data gives more
information
about rate.
• The slope of the curve at
one point in time gives the
instantaneous rate.
• The instantaneous rate at
time zero is called the initial
rate; this is often the rate of
interest to chemists.
• This figure shows
instantaneous and initial rate Note: Reactions typically
of the earlier example. slow down over time!
 Relative Rates
• As was said, rates are followed using a reactant
or a product. Does this give the same rate for
each reactant and product?
• Rate is dependent on stoichiometry.
• If we followed use of C4H9Cl and compared it to
production of C4H9OH, the values would be the
same. Note that the change would have
opposite signs — one goes down in value, the
other goes up.
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).
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 C4H9Cl at t = 300 s.
Relative Rates and Stoichiometry
• What if the equation is not 1:1?
• What will the relative rates be for:
2 O3 (g) 3 O2 (g)
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:
Determining Concentration Effect
on Rate
• How do we determine what effect the
concentration of each reactant has on the
rate of the reaction?
• We keep every concentration constant
except for one reactant and see what
happens to the rate. Then, we change a
different reactant. We do this until we
have seen how each reactant has affected
the rate.
 An Example of How
Concentration Affects Rate
• Experiments 1–3 show how [NH4+] affects rate.
• Experiments 4–6 show how [NO2−] affects rate.
 An Example of How
Concentration Affects Rate
• In experiments 1–3, the concentration of NO2– is
constant, so any change in rate is due to the NH4+.
• As [NH4+] doubles, the rate doubles.
• rate2/rate1 = [NH4+]2/[NH4+]1
• The math becomes 2 = 2x, so the order is 1.
 An Example of How
Concentration Affects Rate
• In experiments 4–6, the concentration of NH4+ is
constant, so any change in rate is due to the NO2–.
• As [NO2–] doubles, the rate doubles.
• rate2/rate1 = [NO2–]5/[NO2–]4
• The math becomes 2 = 2y, so the order is 1.
 An Example of How
Concentration Affects Rate
• Experiments 1–3 show how [NH4+] affects rate.
• Experiments 4–6 show how [NO2–] affects rate.
• Result: The rate law, which shows the relationship
between rate and concentration for all reactants:
Rate = k [NH4+] [NO2–]
 More about Rate Law
• The exponents tell the reaction order with respect
to each reactant.
• In our example from the last slide:
Rate = k [NH4+] [NO2–]
• The order with respect to each reactant is 1. (It is
first order in NH4+ and NO2–.)
• The reaction is second order (1 + 1 = 2; we just add
up all of the reactants’ orders to get the overall
reaction order).
• What is k? It is the rate constant. It is a
temperature-dependent quantity.
 Order ≠ Stoichiometry
• The order of the reaction must be
determined experimentally. It is not
necessarily related to the balanced
equation!
 Relative Value of k
• The rate constant is often used to
determine the relative rate of a reaction.
• For reactions with k ~ 109 or higher, the
reaction is considered fast.
• For reactions with k ~ 10 or lower, the
reaction is considered slow.
Sample Exercise 14.4 Relating a Rate Law to the Effect of
Concentration on Rate
Consider a reaction A + B C for which
2
rate = k[A][B] . Each of the following boxes
represents a reaction mixture in which A is
shown as red spheres and B as purple ones.
Rank these mixtures in order of increasing rate
of reaction.

Solution
Analyze We are given three boxes containing different numbers of spheres representing mixtures containing
different reactant concentrations. We are asked to use the given rate law and the compositions of the boxes to rank
the mixtures in order of increasing reaction rates.

Plan Because all three boxes have the same volume, we can put the number of spheres of each kind into the rate
law and calculate the rate for each box.

Solve Box 1 contains 5 red spheres and 5 purple spheres, giving the following rate:
Box 1: Rate = k(5)(5)2 = 125k
Box 2 contains 7 red spheres and 3 purple spheres:
Box 2: Rate = k(7)(3)2 = 63k
Sample Exercise 14.4 Relating a Rate Law to the Effect of
Concentration on Rate
Continued

Box 3 contains 3 red spheres and 7 purple spheres:

Box 3: Rate = k(3)(7)2 = 147k

The slowest rate is 63k (Box 2), and the highest is 147k (Box 3). Thus, the rates vary in the order 2 < 1 < 3.

Check Each box contains 10 spheres. The rate law indicates that in this case [B] has a greater influence on rate than
[A] because B has a larger reaction order. Hence, the mixture with the highest concentration of B (most purple
spheres) should react fastest. This analysis confirms the order 2 < 1 < 3.

Practice Exercise 1
Suppose the rate law for the reaction in this Sample Exercise were rate = k[A]2[B]. What would be the ordering of
the rates for the three mixtures shown above, from slowest to fastest?
(a) 1 < 2 < 3 (b) 1 < 3 < 2 (c) 3 < 2 < 1 (d) 2 < 1 < 3 (e) 3 < 1 < 2

Practice Exercise 2
Assuming that rate = k[A][B], rank the mixtures represented in this Sample Exercise in order of increasing rate.
Sample Exercise 14.5 Determining Reaction Orders and Units for
Rate Constants
(a) What are the overall reaction orders for the reactions described in Equations 14.9 and 14.11?
(b) What are the units of the rate constant for the rate law in Equation 14.9?

Solution
Analyze We are given two rate laws and asked to express (a) the overall reaction order for each and (b) the units for the
rate constant for the first reaction.

Plan The overall reaction order is the sum of the exponents in the rate law. The units for the rate constant, k, are found
by using the normal units for rate (M/s) and concentration (M) in the rate law and applying algebra to solve for k.

Solve
(a) The rate of the reaction in Equation 14.9 is first order in N2O5 and first order overall. The reaction in Equation 14.11
is first order in CHCl3 and one-half order in Cl2. The overall reaction order is three halves.
(b) For the rate law for Equation 14.9, we have
Units of rate = (units of rate constant)(units of concentration)

so

Note that if the reaction order changes, the units of the rate constant change.
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.
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].
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.
 First-Order Reactions
• Some rates depend only
on one reactant to the first
power.
• These are first-order
reactions.
• The rate law becomes:
Rate = k [A]
• The conversion of methyl
isonitrile to acetonitrile is a
first-order reaction.
 Relating k to [A] in a First-Order
Reaction
• rate = k [A]
• rate = −Δ [A] / Δt
• So: k [A] = −Δ [A] / Δt
• Rearrange to: Δ [A] / [A] = − k Δt
• Integrate: ln ([A] / [A]o) = − k t
• Rearrange: ln [A] = − k t + ln [A]o
• Note: This follows the equation of a line:
y = mx + b
• So, a plot of ln [A] vs. t is linear.
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

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.
Evidence That Conversion of Methyl
Isonitrile to Acetonitrile
• The equation for the reaction:
CH3NC CH3CN
• It is first order. The plot of ln[CH3CN] vs. time is
linear.
Rate = k [CH3NC]
 Finding the Rate Constant, k
• Besides using the rate law, we can find the
rate constant from the plot of ln [A] vs. t.
• Remember the integrated rate law:
ln [A] = − k t + ln [A]o
• The plot will give a line. Its slope will
equal −k.
 Half-Life
• Definition: The amount of time it takes for one-
half of a reactant to be used up in a chemical
reaction.
• First-Order Reaction:
– ln [A] = − k t + ln [A]o
– ln ([A]o/2) = − k t½ + ln [A]o
– − ln ([A]o/2) + ln [A]o = k t½
– ln ([A]o / [A]o/2) = k t½
– ln 2 = k t½ or t½ = 0.693/k
 Second-Order Reactions
• Some rates depend only on a reactant
to the second power.
• These are second-order reactions.
• The rate law becomes:
Rate = k [A]2
 Solving the Second-Order
Reaction for A Products
• rate = k [A]2
• rate = − Δ [A] / Δ t
• So, k [A]2 = − Δ [A] / Δ t
• Rearranging: Δ [A] / [A]2 = − k Δ t
• Using calculus: 1/[A] = 1/[A]o + k t
• Notice: The linear relationships for first-
order and second-order reactions differ!
 An Example of a Second-Order
Reaction: Decomposition of NO2
• A plot following NO2
decomposition shows
that it must be second
order because it is linear
for 1/[NO2], not linear for
ln [NO2].
• Equation:
NO2 NO + ½ O2
 Half-Life and Second-Order
Reactions
• Using the integrated rate law, we can
see how half-life is derived:
– 1/[A] = 1/[A]o + k t
– 1/([A]o/2) = 1/[A]o + k t½
– 2/[A]o −1/[A]o = k t½
– t½ = 1 / (k [A]o)
• So, half-life is a concentration dependent
quantity for second-order reactions!
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:
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.
 Zero-Order Reactions
• Occasionally, rate is
independent of the
concentration of the
reactant:
Rate = k
• These are zero-order
reactions.
• These reactions are linear
in concentration.
• [A]t = – k t + [A]0
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.
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.
 Factors That Affect Reaction
Rate
1) Temperature
2) Frequency of collisions
3) Orientation of molecules
4) Energy needed for the reaction to take
place (activation energy)
 Temperature and Rate
• Generally, as temperature
increases, rate increases.
• The rate constant is
temperature dependent: It
increases as temperature
increases.
• Rate constant doubles
(approximately) with
every 10 °C rise.
 Frequency of Collisions
• The collision model is based on the kinetic
molecular theory.
• Molecules must collide to react.
• If there are more collisions, more reactions can
occur.
• So, if there are more molecules, the reaction rate
is faster.
• In a chemical reaction, bonds are broken and
new bonds are formed. Molecules can only react
if they collide with each other.
 Orientation of Molecules
• Molecules can often collide without forming products.
• Aligning molecules properly can lead to chemical
reactions.
• Bonds must be broken and made, and atoms need to
be in proper positions.
 Energy Needed for a Reaction to
Take Place (Activation Energy)
• The minimum energy needed for a reaction to
take place is called activation energy.
• An energy barrier must be overcome for a
reaction to take place, much like the ball must be
hit to overcome the barrier in the figure below.
Transition State (Activated Complex)
• Reactants gain energy as the reaction
proceeds until the particles reach the
maximum energy state.
• The organization of the atoms at this highest
energy state is called the transition state
(or activated complex).
• The energy needed to form this state is
called the activation energy.
 Reaction Progress
• Plots are made to show
the energy possessed by
the particles as the
reaction proceeds.
• At the highest energy
state, the transition state
is formed.
• Reactions can be
endothermic or
exothermic after this.
• Rate constant depends on
the magnitude of Ea.
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.
 Distribution of the Energy of
Molecules
• Gases have an average temperature, but each
individual molecule has its own energy.
• At higher energies, more molecules possess the
energy needed for the reaction to occur.
The Relationship between Activation
Energy and Temperature
• Arrhenius noted the relationship between activation
energy and temperature: k = Ae−Ea/RT
• Activation energy can be determined graphically by
reorganizing the equation: ln k = −Ea/RT + ln A
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.
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).

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
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.
 Law vs. Theory
• Kinetics gives what happens. We call the
description the rate law.
• Why do we observe that rate law? We
explain with a theory called a
mechanism.
• A mechanism is a series of stepwise
reactions that show how reactants
become products.
 Reaction Mechanisms
• Reactions may occur all at once or
through several discrete steps.
• Each of these processes is known as an
elementary reaction or elementary
process.
 Molecularity

The molecularity of an elementary reaction

tells how many molecules are involved in that
step of the mechanism.
 Termolecular?
• Termolecular steps require three molecules
to simultaneously collide with the proper
orientation and the proper energy.
• These are rare, if they indeed do occur.
• These must be slower than unimolecular or
bimolecular steps.
• Nearly all mechanisms use only
unimolecular or bimolecular reactions.
 What Limits the Rate?
• The overall reaction cannot occur faster than
the slowest reaction in the mechanism.
• We call that the rate-determining step.
 What Is Required of a
Plausible Mechanism?
• The rate law must be able to be devised
from the rate-determining step.
• The stoichiometry must be obtained when
all steps are added up.
• Each step must balance, like any equation.
• All intermediates are made and used up.
• Any catalyst is used and regenerated.
A Mechanism with a Slow Initial Step
• Overall equation: NO2 + CO NO + CO2
• Rate law: Rate = k [NO2]2
• If the first step is the rate-determining step, the
coefficients on the reactants side are the same
as the order in the rate law!
• So, the first step of the mechanism begins:
NO2 + NO2
A Mechanism with a Slow Initial Step
(continued)
• The easiest way to complete the first step is
to make a product:
NO2 + NO2 NO + NO3
• We do not see NO3 in the stoichiometry, so it
is an intermediate, which needs to be used in
a faster next step.
NO3 + CO NO2 + CO2
A Mechanism with a Slow Initial
Step (completed)
• Since the first step is the slowest step, it
gives the rate law.
• If you add up all of the individual steps
(two of them), you get the stoichiometry.
• Each step balances.
• This is a plausible mechanism.
 Intermediates
• An intermediate is NOT
a reactant or a product.
• It is also NOT the
transition state.
• Intermediates
are stable.
• In some instances, it is
possible to isolate or
identify an intermediate.
Sample Exercise 14.12 Determining Molecularity and Identifying
Intermediates
It has been proposed that the conversion of ozone into O 2 proceeds by a two-step mechanism:
O3(g) O2(g) + O(g)
O3(g) + O(g) 2 O2(g)
(a) Describe the molecularity of each elementary reaction in this mechanism.
(b) Write the equation for the overall reaction.
(c) Identify the intermediate(s).

Solution
Analyze We are given a two-step mechanism and asked for (a) the molecularities of each of the two elementary
reactions, (b) the equation for the overall process, and (c) the intermediate.

Plan The molecularity of each elementary reaction depends on the number of reactant molecules in the equation for
that reaction. The overall equation is the sum of the equations for the elementary reactions. The intermediate is a
substance formed in one step of the mechanism and used in another and therefore not part of the equation for the
overall reaction.

Solve
(a) The first elementary reaction involves a single reactant and is consequently unimolecular. The second reaction,
which involves two reactant molecules, is bimolecular.
(b) Adding the two elementary reactions gives
2 O3(g) + O(g) 3 O2(g) + O(g)
Sample Exercise 14.12 Determining Molecularity and Identifying
Intermediates
Continued

Because O(g) appears in equal amounts on both sides of the equation, it can be eliminated to give the net equation
for the chemical process:
2 O3(g) 3 O2(g)

(c) The intermediate is O(g). It is neither an original reactant nor a final product but is formed in the first step of the
mechanism and consumed in the second.

Practice Exercise 1
Consider the following two-step reaction mechanism:
A(g) + B(g) X(g) + Y(g)
X(g) + C(g) Y(g) + Z(g)
Which of the following statements about this mechanism is or are true?
(i) Both of the steps in this mechanism are bimolecular.
(ii) The overall reaction is A(g) + B(g) + C(g) Y(g) + Z(g).
(iii)The substance X(g) is an intermediate in this mechanism.
(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.
Sample Exercise 14.14 Determining the Rate Law for a Multistep
Mechanism
The decomposition of nitrous oxide, N2O, is believed to occur by a two-step mechanism:
N2O(g) N2(g) + O(g) (slow)
N2O(g) + O(g) N2(g) + O2(g) (fast)
(a) Write the equation for the overall reaction. (b) Write the rate law for the overall reaction.

Solution
Analyze Given a multistep mechanism with the relative speeds of the steps, we are asked to write the overall
reaction and the rate law for that overall reaction.

Plan (a) Find the overall reaction by adding the elementary steps and eliminating the intermediates. (b) The rate
law for the overall reaction will be that of the slow, rate-determining step.

Solve
(a) Adding the two elementary reactions gives
2 N2O(g) + O(g) 2 N2(g) + O2(g) + O(g)
Omitting the intermediate, O(g), which occurs on both sides of the equation, gives the overall reaction:
2 N2O(g) 2 N2(g) + O2(g)

(b) The rate law for the overall reaction is just the rate law for the slow, rate-determining elementary reaction. Because
that slow step is a unimolecular elementary reaction, the rate law is first order:
Rate = k[N2O]
A Mechanism with a Fast Initial Step
• Equation for the reaction:
2 NO + Br2 2 NOBr
• The rate law for this reaction is found to be
Rate = k [NO]2 [Br2]
• Because termolecular processes are rare,
this rate law suggests a multistep
mechanism.
A Mechanism with a Fast Initial
Step (continued)
• The rate law indicates that a quickly
established equilibrium is followed by a
slow step.
• Step 1: NO + Br2 NOBr2
• Step 2: NOBr2 + NO 2 NOBr
 What Is the Rate Law?
• The rate of the overall reaction depends
upon the rate of the slow step.
• The rate law for that step would be

Rate = k2[NOBr2] [NO]

• But how can we find [NOBr2]?

 [NOBr2] (An Intermediate)?
• NOBr2 can react two ways:
– With NO to form NOBr
– By decomposition to reform NO and Br2
• The reactants and products of the first
step are in equilibrium with each other.
• For an equilibrium (as we will see in the
next chapter):
Ratef = Rater
 The Rate Law (Finally!)
• Substituting for the forward and reverse rates:
k1 [NO] [Br2] = k−1 [NOBr2]
• Solve for [NOBr2], then substitute into the
rate law:
Rate = k2 (k1/k−1) [NO] [Br2] [NO]
• This gives the observed rate law!
Rate = k [NO]2 [Br2]
• So, whenever the first step is NOT the
slowest step, equilibrium must be used.
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]
Sample Exercise 14.15 Deriving the Rate Law for a Mechanism with a
Fast Initial Step
Continued

We solve for the concentration of the intermediate N2O2 by assuming that an equilibrium is established in step 1;
thus, the rates of the forward and reverse reactions in step 1 are equal:

k1[NO]2 = k–1[N2O2]

Solving for the concentration of the intermediate, N2O2, gives

Substituting this expression into the rate expression gives

Thus, this mechanism also yields a rate law consistent with the experimental one. Remember: There may be more
than one mechanism that leads to an observed experimental rate law!
 Catalysts
• Catalysts increase the rate of a reaction by
decreasing the activation energy of the reaction.
• Catalysts change the mechanism by which the
process occurs.
 Types of Catalysts
1) Homogeneous catalysts
2) Heterogeneous catalysts
3) Enzymes
 Homogeneous Catalysts
• The reactants and catalyst are in the same phase.
• Many times, reactants and catalyst are dissolved
in the same solvent, as seen below.
 Heterogeneous Catalysts
• The catalyst is in a
different phase than
the reactants.
• Often, gases are
passed over a solid
catalyst.
• The adsorption of the
reactants is often the
rate-determining step.
 Enzymes
• Enzymes are
biological catalysts.
• They have a region
where the reactants
attach. That region
is called the active
site. The reactants
are referred to as
substrates.
 Lock-and-Key Model

• In the enzyme–substrate model, the

substrate fits into the active site of an
enzyme, much like a key fits into a lock.
• They are specific.
Selected Problems: 19, 23, 25, 28, 29, 33, 35, 37, 41, 42, 43, 46, 49, 55,
57, 62, 67, 69, 71, 79.