Lecture Notes Chapter 15 04/12/08

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.

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

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 = - [] / t
Where [A] is the change of concentration of a reactant species and t is the elapsed time.

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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:

AA

BB

2AB

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

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

For a reaction:

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.

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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 products

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

[A]0
Run 1 Run 2 Run 3

mol L-1

[B]0

mol L-1

Rate0

mol L-1 s-1 3.0 x 10-4 1.2 x 10-3 1.2 x 10-3

0.010 0.020 0.020

0.010 0.010 0.020

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From the general rate law expression, we can write that: Rate 2 / Rate 1 Or 4 = = ( [A]2 / [A]1 )m 2m Thus m = 2

Rate 3 / Rate 2 Or 1 =

= ([B3] / [B2])n 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.

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)}

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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 The relationship between the natural

9 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)

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That means that it is the reciprocal of the reactant concentration that varies in a linear manner with time.

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:

A exp(- Eact / RT )

A is a constant that is simply referred to as the pre-exponential factor. The energy Eact has become known as the activation energy for the reaction.

The equation may also be written in the form:

ln (k) =

ln (A) - Eact / RT

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

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

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

In the figure, our symbol Eact 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.

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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.

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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 Avogadros number to give the molar quantities, gives.

Eact = 266 kJ / mol and Erxn = -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 cisbutene 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)
The rate law has long been known to be:

2 HI(g)

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 The decomposition:

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I2(g)
is actually a two-way process.

2 I(g)

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)

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.

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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.

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.

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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.