Lecture Notes Chapter 15 04/12/08 1

CHAPTER FIFTEEN

CHEMICAL KINETICS

1 INTRODUCTION.

There are two practical considerations that are involved in the evaluation
of any chemical synthetic process.

We have already dealt with the question of reaction yield. The other
concern is with the rate at which reactants are converted into products.

The branch of chemistry that is focused upon the study of the rates of
chemical reactions is called chemical kinetics.

1.1 The Rate of a Chemical Reaction.

There are several ways in which we might quantify the rate of a chemical
reaction. If productivity were our sole preoccupation, we might measure the rate
in tank cars per week. That reflects the size of the manufacturing facility as much
as, or more than, it does any inherent characteristic of the reaction itself.

What we seek is an intensive, as opposed to extensive, measure of the

rate.

Let us look at a homogeneous reaction that is taking place in solution.

A + B Æ C + D

As the reaction proceeds, the concentrations of the reactants fall and

those of the products rise. It is the rate of change of concentrations that we refer
to when we talk about the rates of reaction.
Lecture Notes Chapter 15 04/12/08 2

Because of the stoichiometric relationship between the changes in

reactant and product concentrations, we only need to monitor the rate of change
of one species. We may either record the rate of disappearance of one of the
reactants or of the appearance of a product.

The following figure shows a typical plot of the concentration of a reactant

species as a function of time.

The figure shows quite clearly that the rate of the reaction, which is the
slope of the curve, is gradually decreasing.

We can determine the average rate, over a finite period of time by

calculating:

Rate = - Δ [Α] / Δ t
Where Δ[A] is the change of concentration of a reactant species and Δt is the
elapsed time.
Lecture Notes Chapter 15 04/12/08 3

More subtle means are needed to determine an instantaneous rate, which

is represented, in the symbolism of calculus, by:

Rate = - d[A] /dt

This is the tangent to (slope of) the concentration versus time curve.

1.2 Factors affecting the Rate of a Reaction.

In order to understand what factors influence the rate at which a reaction

proceeds, it is helpful to consider a couple of simple reaction scenarios.

We first consider a simple reaction of the type:

A–A + B–B Æ 2A–B

For this reaction to take place the bonds of the two reactant molecules
need to be broken. We envision that this is the result of a collision between two
molecules. The fragments formed when the molecules break apart might come
back together to form A-A and B-B molecules or they might trade partners and
give rise to the product species.

In this scenario, it is clear that two factors affect the rate of formation of
products.

1) The rate of the reaction must be directly proportional to the number of

collisions between reactant molecules that are taking place per unit time.

2) The rate is also going to be dependent upon the efficiency of the

collisions.

The number of collisions per unit time will depend primarily upon
the concentrations of the reactant species. There will be a slight
Lecture Notes Chapter 15 04/12/08 4

dependence upon the temperature because the molecules will move a

little faster as the temperature rises.

The collision efficiency depends upon a number of factors. There

needs to be enough impact in the collision to cause both of the reactant
molecules to split apart. Just how much impact energy is required will be
determined by the nature of the reacting species.

While temperature has relatively little effect on the collision

frequency, it has a substantial effect upon the efficiency. Raising the
temperature by only ten degrees can typically double the number of
collisions with the threshold energy.

For reactions involving molecules with elaborate structures, the

point of impact where one molecule strikes the other may be quite critical.

An alternative scenario would be one in which the reaction is initiated by

only one of the molecules breaking apart, without the necessity of a collision. In
that case the rate of reaction will depend only upon the concentration of that one
species.

2.1 Rate Laws.

The first stage of the investigation of the kinetics of a chemical reaction is

the determination of the nature of the dependence of the rate of the reaction
upon the concentrations of the various reactant species. There are various ways
in which that can be accomplished and we will discuss some of them later.

We refer to the equation that describes the concentration dependence of

the rate as a rate law, since it is obtained by observation.

It needs to be emphasized that one cannot anticipate the rate law by the
simple expedient of looking at the balanced equation for the reaction.
Lecture Notes Chapter 15 04/12/08 5

For a reaction: A + B Æ products

We might find any one of several different rate laws.

The general symbolism for a rate law is:

Rate = k [A]m[B]n
Where the sum m + n is called the order of the reaction.

2.2 First Order Reactions.

It may be found that the rate of the reaction is proportional to the

concentration of just one of the two reactants. For example:

Rate = k1 [A]

We would call this a first order reaction. The proportionality constant k1 is

called the rate constant for the reaction.

2.3 Second Order Reactions.

There are two types of second order reaction. The most obvious is that
where:

Rate = k2 [A] [B]

Alternatively, the rate may depend upon the square of the concentration of
only one of the species:

Rate = k2 [A]2
Higher order reactions exist and some have non – integer orders.
Lecture Notes Chapter 15 04/12/08 6

2.4 Zero Order Reactions.

Under special circumstances, reactions can proceed at a constant rate
which is unaffected by reactant concentrations. These are called zero – order
reactions. Reactions of this kind are likely to be taking place at the surface of the
containing vessel or a catalytic additive.

2.5 The Method of Initial Rates.

One of the most frequently used methods for determining a rate law is the
method of initial rates.

The reaction is carried out several times. For each “run”, the combination
of initial reactant concentrations is different. In each case, we are only interested
in determining the initial rate of the reaction. This approach is particularly useful if
the equilibrium constant is small enough for the reverse reaction to kick in after a
short time.

It is easiest to explain how the method works by inventing some typical

data.

For the reaction:

A + B Æ products

Rate = k [A]m[B]n
The data might be of the form:

[A]0 [B]0 Rate0

mol L-1 mol L-1 mol L-1 s-1

Run 1 0.010 0.010 3.0 x 10-4

Run 2 0.020 0.010 1.2 x 10-3

Run 3 0.020 0.020 1.2 x 10-3

Lecture Notes Chapter 15 04/12/08 7

From the general rate law expression, we can write that:

Rate 2 / Rate 1 = ( [A]2 / [A]1 )m

Or 4 = 2m Thus m = 2

Rate 3 / Rate 2 = ([B3] / [B2])n

Or 1 = 2n Thus n = 0

That gives the rate law to be:

Rate = k [A]2

We can now go ahead and calculate the rate constant.

k = Rate1 / [A1]2 = 3.0 L mol s-1

There is one special advantage to using the method of initial rates. Many
reactions are reversible so that there is a two-way traffic between the reactants
and products. At the instant that the reactants are brought together, there are no
products present and therefore no reverse reaction.

2.6 Integrated Rate Equations.

We may use the methods of calculus to derive equations for the

time dependence of the concentrations of different order reactions. These are
called integrated rate equations.

2.6.1 First Order.

If the rate of reaction is given by:

Rate = -d[A] / dt = k1[A]

ln[A]2 = ln[A]1 - k1(t2 - t1) : [A]2 / [A]1 = exp{ - k1(t2-t1)}

Lecture Notes Chapter 15 04/12/08 8

The figure shows the exponential decrease in the concentration of a

reactant of a first order reaction: the decomposition of hydrogen peroxide.

Attention is drawn to the fact that when [A]2 / [A]1 = 0.5 the time t2 – t1 is
called the half life. The half - life of a first order reaction is the same no matter
what the initial concentration.

From the equation:

ln (0.5) = - k1 t1/2

we can write that:

k1 = t1/2 / 0.693
Lecture Notes Chapter 15 04/12/08 9

The relationship between the natural logarithm of the reactant

concentration and the elapsed time is shown in the following figure:

We see the linear dependence of the log of concentration upon time. That
verifies that we are dealing with a first order reaction. The slope of that line is the
rate constant.

2.61 Second Order.

The simplest type of second order rate equation is:

Rate = k2 [A]2
The integrated version of the second order rate equation is:

1 / [A]2 - 1 / [A]1 = k2 ( t2 - t1)

Lecture Notes Chapter 15 04/12/08 10

That means that it is the reciprocal of the reactant concentration that

varies in a linear manner with time.

3 The Temperature Dependence of Rate Constants.

It is observed that raising the temperature of a reaction brings about a

substantial increase in the rate constant. A useful rule of thumb is that the rate
constant doubles for every 10 degree increase in temperature.

The exponential increase in the rate constant was originally expressed in

an algebraic form by the Swedish chemist Arrhenius. His equation is:

k = A exp(- ΔEact / RT )

A is a constant that is simply referred to as the pre-exponential factor. The

energy ΔEact has become known as the activation energy for the reaction.

The equation may also be written in the form:

ln (k) = ln (A) - ΔEact / RT

Lecture Notes Chapter 15 04/12/08 11

If we wish to compare the values of k at two different temperatures, we

can write:

ln (k2) – ln (k1) = ln (k2 / k1) = ΔEact/ R [ 1/T1 - 1/T2]

The rate constants for most, but not all, reactions vary in this fashion.

In the figure, our symbol ΔEact has been replaced by Ea.

The activation energy represents a barrier that needs to be overcome in

order for the reaction take place. This will generally involve breaking one or more
bonds in the reactant molecules.

The following figures are concerned with a simple isomerization reaction in

which cis –butene is converted into trans butene. We look first at representations

of the molecular structures of the two molecules.

Lecture Notes Chapter 15 04/12/08 12

We see that in order to go from one isomer to the other, we need to break

the second bond of the double bond.

There is a modest drop in energy going from the one isomer to the other,
but there is a substantial barrier.
Lecture Notes Chapter 15 04/12/08 13

The values that are given for the activation energy and the energy of the
reaction are both referring to single molecules. Multiplying these numbers by
Avogadro’s number to give the molar quantities, gives.

ΔEact = 266 kJ / mol and ΔErxn = -4.2 kJ / mol

Obviously the activation energy needs to come from somewhere. That

somewhere is the kinetic energy that is possessed by the reactant molecules. In
the next figure we see a plot of the distribution of molar kinetic energies for cis-
butene at two different temperatures.

We see that the number of molecules with kinetic energies in excess of

the required 266 kJ / mol increases rapidly from the lower to the higher
temperature.

4 Reaction Mechanisms.
Many chemical reactions do not take place in one single step but are,
instead, achieved by the performance of a sequence of steps. We refer to the
sequence of steps as the mechanism of the chemical reaction.
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The rates of the individual steps of a reaction are likely to differ quite
significantly and far more often than not one step is so much slower than the
others that it alone controls the rate of formation of products. This is referred to
as the rate determining step.

We can frequently dream up several alternative mechanisms for a specific

chemical reaction. What we need is to restrict the possibilities to those
mechanisms that are consistent with the observed rate law.

In that context, it is instructive to look at the kinetics of the gas phase

reaction in which molecular hydrogen and molecular iodine react to form
hydrogen iodide.

The equation for the reaction is:

H2(g) + I2(g) Æ 2 HI(g)

The rate law has long been known to be:

Rate = k2 [H2] [I2]

It was originally thought that this must be a one-step reaction involving the
collisions between hydrogen and iodine molecules. In fact, this reaction was used
as a model for explaining the nature of rate laws.

At some point in time, someone made the comment that prevailing

quantum mechanical theory predicted that the reaction could not possibly take
place by this simple mechanism. That, naturally, prompted a search for
alternative explanations for the second order rate law.

What was found was that the reaction has to be initiated by the
decomposition of iodine molecules to atoms.
Lecture Notes Chapter 15 04/12/08 15

The decomposition:
I2(g) Å Æ 2 I(g)
is actually a two-way process.

The forward reaction has a rate that is given by:

Ratefor = kfor [I2(g)]

The reverse reaction has a rate given by:

Raterev = krev [I(g)]2

Equilibrium is rapidly obtained in which the forward and reverse reaction
rates are identical. We can describe that equilibrium in terms of:

Kequ = kfor / krev = [I(g)]2 / [I2(g)]

Both of the iodine atoms then collide with the hydrogen molecule. This is a
three – body collision:

2 I(g) + H2(g) Æ 2 HI(g)

We refer to this as a termolecular step, since it involves three species

colliding at one and the same time. This is a very slow step and determines the
overall rate of the reaction.

We can write the rate equation for this slow step, knowing that it is also
the rate equation for the overall reaction. For the three – body collisions, it must
be:
Rate = k3 [I(g)]2 [H2(g)]

This does not qualify to be described as a rate law, however, since rate
laws are supposed to be expressed in terms of the concentrations of the original
reactant species.
Lecture Notes Chapter 15 04/12/08 16

We get around this problem by rearranging the equation for the initial rapid
equilibrium.
[I(g)]2 = Kequ / [I2(g)]

That gives us:

Rate = k3 Kequ / [I2(g)] [H2(g)]

Since the product of the two constants Kequ and k3 must also be a
constant, this rate equation is completely consistent with the rate law.

5 Catalysts.
It is possible to increase the rate of a chemical reaction by adding a
substance that helps the reaction along without itself being a reactant or product.
Such additives are called catalysts.

The function of a catalyst is to lower the activation energy for the reaction.

An additive, that has the opposite effect by slowing down a reaction, is called an

inhibitor.

We draw a distinction between homogeneous and heterogeneous

catalysts.

Many reactions, that take place in solution, have rates that are sensitive to
the acidity. Adding hydrogen ions can have a profound catalytic effect on many
reactions in aqueous solution.

The gas phase isomerization reaction that we mentioned earlier can be

significantly accelerated by the addition of gaseous iodine. The following figure
shows the reaction profile.
Lecture Notes Chapter 15 04/12/08 17

In the catalyzed reaction, there is an intermediate formed with the

formula C4H8I. The activation energy, by way of this intermediate, is less than
one-half of that of the uncatalyzed reaction.

The Platinum – Rhodium catalysts in automobile catalytic converters are

heterogeneous catalysts. They provide a surface on which carbon monoxide is
converted to carbon dioxide.

Enzymes are protein substances that catalyze important biological

reactions.