Chapter 16

Kinetics : Rates and Mechanisms of Chemical Reactions

Until now weve taken a rather simple approach to chemical change: reactants mix and
products form. A balanced equation is essential for calculating product yields from
reactant amounts, but it tells us nothing about three dynamic aspects of a reaction: how
fast the reaction proceeds, how far it proceeds toward products, and whether it proceeds
by itself or needs some energy input to occur. We discuss the rst of these aspects here
and examine the others in upcoming chapters. Chemical kinetics is the study of
reaction rates, the changes in concentrations of reactants (or products) as a function of
time (Figure 16.1).
FIGURE 16.1 Reaction rate: the central focus of chemical kinetics. The rate at which
reactant becomes product is the underlying theme of chemical kinetics. As time elapses,
reactant (purple) decreases and product (green) increases.

Reactions occur at a wide range of rates. Some, like a neutralization, a

precipitation, or an explosive redox process, seem to be over as soon as the reactants
make contact in a fraction of a second. Others, such as the reactions involved in cooking
or rusting, take a moderate length of time, from minutes to months. Still others take
much longer: the reactions that make up the human aging process continue for decades,
and those involved in the formation of coal from dead plants take hundreds of millions
of years.
Knowing how fast a chemical change occurs can be essential. How quickly a
medicine acts or blood clots can make the difference between life and death. How long
it takes for cement to harden or polyethylene to form can make the difference between
 prot and loss. In general, the rates of these diverse processes depend on the same
variables, most of which chemists can manipulate to maximize yields within a given
time or to slow down an unwanted reaction.
In this chapter, we rst discuss reaction rate and then focus on the reaction
mechanism, the steps a reaction goes through as reactant bonds are breaking and product
bonds are forming.

16.1 Factors that influence reaction rate

Lets begin our study of kinetics with a qualitative look at the key factors that
affect how fast a reaction proceeds. Under any given set of conditions, each reaction
has its own characteristic rate, which is determined by the chemical nature of the
reactants. At room temperature, for example, hydrogen reacts explosively with uorine
but extremely slowly with nitrogen:

We can control four factors that affect the rate of a given reaction: the
concentrations of the reactants, the physical state of the reactants, the temperature at
which the reaction occurs, and the use of a catalyst. We consider the rst three factors
here and discuss the fourth in Section 16.8.
1. Concentration: molecules must collide to react. A major factor inuencing the rate of
a given reaction is reactant concentration. A reaction can occur only when the
reactant molecules collide. The more molecules present in the container, the more
frequently they collide, and the more often a reaction between them occurs. Thus,
reaction rate is proportional to the concentration of reactants:
Rate collision frequency concentration
2. Physical state: molecules must mix to collide. The frequency of collisions between
molecules also depends on the physical states of the reactants. When the reactants are
in the same phase, as in an aqueous solution, random thermal motion brings them
into contact. When they are in different phases, contact occurs only at the interface,
so vigorous stirring and grinding may be needed. In these cases, the more nely
divided a solid or liquid reactant, the greater its surface area per unit volume, the
more contact it makes with the other reactant, and the faster the reaction occurs.
 Thus, a thick steel nail heated in oxygen glows feebly, but the same mass of ne steel
wool bursts into ame. For the same reason, you start a campre with wood chips
and thin branches, not logs.
3. Temperature: molecules must collide with enough energy to react. Temperature
usually has a major effect on the speed of a reaction. Recall that molecules in a
sample of gas have a range of speeds, with the most probable speed dependent on the
temperature (see Figure 5.12, p. 168). Thus, at a higher temperature, more collisions
occur in a given time. Even more important, however, is the fact that temperature
affects the kinetic energy of the molecules, and thus the energy of the collisions.
Most collisions result in the molecules simply recoiling, with no reaction taking
place. However, some collisions occur with sufcient energy for the molecules to
react. Figure 16.2 shows the outcomes of a few collisions in the reaction between
nitric oxide (NO) and ozone (O3). At higher temperatures, more of the sufciently
energetic collisions occur. Thus, raising the temperature increases the reaction rate
by increasing the number and, especially, the energy of the collisions:
Rate collision energy temperature
The qualitative idea that reaction rate is inuenced by the frequency and energy of
reactant collisions leads to several quantitative questions: How can we describe the
dependence of rate on reactant concentration mathematically? Do all changes in
concentration affect the rate to the same extent? Do all rates increase to the same extent
with a given rise in temperature? How do reactant molecules use the collision energy to
form product molecules, and is there a way to determine this energy? What do the
reactants look like as they are turning into products? We address these questions in the
following sections.

SECTION 16.1 SUMMARY

Chemical kinetics deals with reaction rates and the stepwise molecular events by which
a reaction occurs. Under a given set of conditions, each reaction has its own rate.
Concentration affects rate by inuencing the frequency of collisions between reactant
molecules. Physical state affects rate by determining the surface area per unit volume
of reactant(s). Temperature affects rate by inuencing the frequency and, even more
importantly, the energy of the reactant collisions.
16.2 EXPRESSING THE REACTION RATE
A rate is a change in some variable per unit of time. The most common examples relate
to the rate of motion (speed) of an object, which is the change in its position (that is, the
distance it travels) divided by the change in time. Suppose, for instance, we measure a
runners starting position, x1, at time t1 and nal position, x2, at time t2. The runners
average speed is

In the case of a chemical change, we are concerned with the reaction rate, the changes in
concentrations of reactants or products per unit time: reactant concentrations decrease
while product concentrations increase. Consider a general reaction, A B. We quickly
measure the starting reactant concentration (conc A1) at t1, allow the reaction to
proceed, and then quickly measure the reactant concentration again (conc A2) at t2. The
change in concentration divided by the change in time gives the average rate:

Note the minus sign. By convention, reaction rate is a positive number, but conc A2 will
always be lower than conc A1, so the change in (nal initial) concentration of reactant
A is always negative. We use the minus sign simply to convert the negative change in
reactant concentration to a positive value for the rate. Suppose the concentration of A
changes from 1.2 mol/L (conc A1) to 0.75 mol/L (conc A2) over a 125-s period. The
average rate is

We use square brackets, [ ], to express concentration in moles per liter. That is, [A] is
the concentration of A in mol/L, so the rate expressed in terms of A is

The rate has units of moles per liter per second (mol L-1s-1, or mol/L-s), or any time unit
convenient for the particular reaction (minutes, years, and so on). If instead we measure
the product to determine the reaction rate, we nd its concentration increasing over
time. That is, conc B2 is always higher than conc B1. Thus, the change in product
concentration, [B], is positive, and the reaction rate for AB expressed in terms of B
is

Average, Instantaneous, and Initial Reaction Rates

Examining the rate of a real reaction reveals an important point: not only the
concentration, but the rate itself varies with time as the reaction proceeds. Consider the
reversible gas-phase reaction between ethylene and ozone, one of many reactions that
can be involved in the formation of photochemical smog:

For now, we consider only reactant concentrations. You can see from the equation
coefcients that for every molecule of C2H4 that reacts, a molecule of O3 reacts with it.
In other words, the concentrations of both reactants decrease at the same rate in this
particular reaction:

By measuring the concentration of either reactant, we can follow the reaction rate.
Suppose we have a known concentration of O3 in a closed reaction vessel kept at 30C
(303 K). Table 16.1 shows the concentration of O3 at various times during the first
minute after we introduce C2H4 gas. The rate over the entire 60.0 s is the total change in
concentration divided by the change in time:
This calculation gives us the average rate over that period; that is, during the rst 60.0 s
of the reaction, ozone concentration decreases an average of 3.50 10-7 mol/L each
second. However, the average rate does not show that the rate is changing, and it tells us
nothing about how fast the ozone concentration is decreasing at any given instant.
We can see the rate change during the reaction by calculating the average rate
over two shorter periods-one earlier and one later. Between the starting time 0.0 s and
10.0 s, the average rate is

The earlier rate is six times as fast as the later rate. Thus, the rate decreases during the
course of the reaction. This makes sense from a molecular point of view: as O3
molecules are used up, fewer of them are present to collide with C2H4 molecules, so the
rate, the change in their concentration over time, decreases.
The change in rate can also be seen by plotting the concentrations vs. The times at
which they were measured (Figure 16.3). A curve is obtained, which means that the rate
changes. The slope of the straight line (, that is, [3 ]) joining any two
points gives the average rate over that period.
 The shorter the time period we choose, the closer we come to the instantaneous
rate, the rate at a particular instant during the reaction. The slope of a line tangent to the
curve at a particular point gives the instantaneous rate at that time. For example, the rate
of the reaction of C2H4 and O3 at 35.0 s after it began is 2.50 10-7 mol/Ls, the slope of
the line drawn tangent to the curve through the point at which t = 35.0 s (line d in Figure
16.3). In general, we use the term reaction rate to mean the instantaneous reaction rate.

FIGURE 16.3 The concentration of O3 vs. time during its reaction with C2H4.
Plotting the data in Table 16.1 gives a curve because the rate changes during the
reaction. The average rate over a given period is the slope of a line joining two points
along the curve. The slope of line b is the average rate over the rst 60.0 s of the
reaction. The slopes of lines c and e give the average rate over the rst and last 10.0-s
intervals, respectively. Line c is steeper than line e because the average rate over the
earlier period is higher. The instantaneous rate at 35.0 s is the slope of line d, the
tangent to the curve at t = 35.0 s. The initial rate is the slope of line a, the tangent to the
curve at t = 0 s.
As a reaction continues, the product concentrations increase, and so the reverse
reaction (reactants products) speeds up. To nd the overall (net) rate, we would have
to take both forward and reverse reactions into account and calculate the difference
between their rates. A common way to avoid this complication fo many reactions is to
measure the initial rate, the instantaneous rate at the moment the reactants are mixed.
Under these conditions, the product concentrations are negligible, so the reverse rate is
negligible. The initial rate is measured by determining the slope of the line tangent to
the curve at t = 0 s. In Figure 16.3, the initial rate is 10.0 10-7 mol/L.s (line a). Unless
stated otherwise, we will use initial rate data to determine other kinetic parameters.

Expressing Rate in Terms of Reactant and Product Concentrations

So far, in our discussion of the reaction of C2H4 and O3, weve expressed the rate in
terms of the decreasing concentration of O3. The rate is the same in terms of C2H4, but
it is exactly the opposite in terms of the products because their concentrations are
increasing. From the balanced equation, we see that one molecule of C2H4O and one of
O2 appear for every molecule of C2H4 and of O3 that disappear. We can express the rate
in terms of any of the four substances involved:

Again, note the negative values for the reactants and the positive values for the products
(usually written without the plus sign). Figure 16.4 shows a plot of the simultaneous
monitoring of one reactant and one product. Because, in this case, product concentration
increases at the same rate that reactant concentration decreases, the curves have the
same shapes but are inverted.
In many other cases, though, the reactants disappear and the products appear at
different rates. Consider the reaction between hydrogen and iodine to form hydrogen
iodide:

For every molecule of H2 that disappears, one molecule of I2 disappears and two
molecules of HI appear. In other words, the rate of [H2] decrease is the same as the rate
of [I2] decrease, but both are only half the rate of [HI] increase. By referring the change
in [I2] and [HI] to the change in [H2], we have

If we refer the change in [H2] and [I2] to the change in [HI] instead, we obtain
 FIGURE 16.4 Plots of [C2H4] and [O2] vs. time. Measuring
reactant concentration, [C2H4], and product concentration,
[O2], gives curves of identical shapes but changing in
opposite directions. The steep upward (positive) slope of
[O2] early in the reaction mirrors the steep downward
(negative) slope of [C2H4] because the faster C2H4 is used
up, the faster O2 is formed. The curve shapes are identical
in this case because the equation coefcients are identical.

Notice that this expression is just a rearrangement of the previous one; also note that it
gives a numerical value for the rate that is double the previous value. Thus, the
mathematical expression for the rate of a particular reaction and the numerical value of
the rate depend on which substance serves as the reference.
We can summarize these results for any reaction,

where a, b, c, and d are coefcients of the balanced equation. In general, the rate is
related to reactant or product concentrations as follows:

SAMPLE PROBLEM 16.1

Expressing Rate in Terms of Changes in Concentration with Time
Problem Because it has a nonpolluting combustion product (water vapor), hydrogen gas
is used for fuel aboard the space shuttle and in prototype cars with Earth-bound engines:

(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with time.
(b) When [O2] is decreasing at 0.23 mol/Ls, at what rate is [H2O] increasing?
Plan
(a) Of the three substances in the equation, lets choose O2 as the reference because its
coefcient is 1. For every molecule of O2 that disappears, two molecules of H2
disappear, so the rate of [O2] decrease is one-half the rate of [H2] decrease. By
similar reasoning, we see that the rate of [O2] decrease is one-half the rate of [H2O]
increase.
(b) Because [O2] is decreasing, the change in its concentration must be negative. We
substitute the negative value into the expression and solve for [2 ].
Solution
(a) Expressing the rate in terms of each component:

(b) Calculating the rate of change of [H2O]:

Check
(a) A good check is to use the rate expression to obtain the balanced equation: [H2]
changes twice as fast as [O2], so two H2 molecules react for each O2. [H2O] changes
twice as fast as [O2], so two H2O molecules form from each O2. From this reasoning,
we get 2H2 + O2 2H2O. The [H2] and [O2] decrease, so they take minus signs;
[H2O] increases, so it takes a plus sign. Another check is to use Equation 16.2, with
A = H2, a = 2; B = O2, b = 1; C = H2O, c = 2. Thus,

(b) Given the rate expression, it makes sense that the numerical value of the rate of
[H2O] increase is twice that of [O2] decrease. Comment Thinking through this type
of problem at the molecular level is the best approach, but use Equation 16.2 to
conrm your answer.
FOLLOW-UP PROBLEM 16.1
(a) Balance the following equation and express the rate interms of the change in
concentration with time for each substance:

(b) How fast is [O2] decreasing when [NO] is decreasing at a rate of 1.6010-4 mol/L.s?

SECTION 16.2 SUMMARY

The average reaction rate is the change in reactant (or product) concentration over a
change in time, t. The rate slows as reactants are used up. The instantaneous rate at
time t is obtained from the slope of the tangent to a concentration vs. Time curve at time
t. The initial rate, the instantaneous rate at t = 0, occurs when reactants are just mixed
and before any product accumulates. The expression for a reaction rate, as well as its
numerical value, depend on which reaction component is being monitored.