21.

16 A COLLISION THEORY MODEL OF CHEMICAL REACTIONS

The reaction between ClN2 and NO is an example of a single-step reaction.

CIN2(g) + NO(g) NO2(g) + CINO(g)

The rate of this reaction is first-order in both CINO2 and NO and second-order
overall. The rate of formation of NO2, for example, is given by the following rate law.
(NO2)

= k (CINO2) (NO)

This rate law is easy to explain if we assume that molecules must collid in order to
react. Before a chlorine atom can be transferred from CINO2 to NO, for example, he
two molecules must collide.
Figure 2.11 shows a small portion af a system in which the reaction bertween
CINO2 and NO takes place. What factors influence the rate at which the molecules in
this container collide? In section 4.15, we conclude that the number of collisions per
second in a gas depends on the number of molecules per liter. Doubling the number
of CINO2 or NO molecules per liter of gas should double the rate at which these
molecules collide. The rate of this reaction is therefore directly proportional to the FIG.21.11 This figure
concentration of both CINO2 and NO. represents a snapshot of a
small portion of a container
(NO2) in which CINO2 reacts with
= k (CINO2) (NO)
NO to form NO2 and CINO.
Collisions between reactant molecules are nessesary in order for reaction to What factors aontrol the rate
take place. But they arent sufficient. One reason why collisions do not always at which this reaction
convert the reactant into products is the orientation of the molecules when they occurs? The collision theory
collide. Consider the lewis structure of the reactant and products for the reaction model of chemical reactions
between CINO2 and NO. assumes that molecules
must collide in order to
CIN2(g) + NO(g) NO2(g) + CINO(g) react. Anything that
increase the frequency of
O O collision increase the rate of
Cl N N O N Cl N O reaction, so the rate of
O O reaction must be
proportional to the
In the course of this reaction, a chlorine atom in transferred from one nitrogen atom
concentration of either
to another. In order for the reaction to occur, the nitrogen atom in NO must collide
reactant.
with the chlorine atom in CINO2.
O
O N Cl N
O
Reaction wont occur if the oxygen end of the NO molecule collides with the
chlorine atom on CINO2.
O
N O Cl N
O

FIG.21.12 The kinetic
molecular theory states that
the average kinetic energy of
a gas is proportional to the
temperature of the gas, and
nothing else. At any given
temperature, however, some
of the gas particles are
moving faster than others.
FIG 21.10 A useful model for
thinking about the rate of
chemical reactions is a plot of
the free energy of the system
versus the reaction
coordinate. Yhe overall free
energy of the reaction, GO,
is equal to the difference
between the free energiesof
the reactants and products.
The activation energy for the
reaction, Ea, is the difference
between the free energy of
the reactants and the top of an
energy barrier that must be
overcome before the reaction
can occure.
Nor will it occur if one of the oxygen atom on CINO2 collides with the nitrogen atom
on NO.
N O
O
Cl N
O
Another factor that influences whether reaction will occur is the energy the
molecules carry when they collide. Not all of the molecules have the same kinetic
energy, as shown in figure 21.12. the kinetic energy molecules carry when they collide
is important because it is principal source of the energy that must be invest in a reaction
to get it started.
The overall standart-state free energy for the reaction between CINO2 and NO is
favirable.
CINO2(g) + NO(g) NO2(g) + CINO(g) GO = -23,6 Kj/mol
But before the reactants can be converted into product, the free energy of the system
must climb a barrier. This barrier is the activation energy for the reaction, as shown in
Figure 21.13. The vertikal axis in this diagram represents the free energy of the system
at any moment in time. The horizontal axis represents the reaction coordinate, which
summarizes the infinitesimally small steps that must be taken in order for the reactants
to be converted into the products of this reaction.
Why does a reaction have an activation energy ? Think about what has to happen in
order for CINO2 to react with NO. first, and foremost, these two molecules have to
collide, thereby organizing the system. Not only do they have to be brought together
but they have to be held in exactly the righ orientation relative to each other to ensure
that reaction can occure. Both of these factors raise the free energy of the system by
lowering the entropy. Some energy also must be invested in the system to begin
breaking the CI NO2 bond before the CI NO bond can begin to form.
NO and CINO2 molecules that collide in the correct orientation, with enough
kinetic energy to climb the activation energy barrier, can react to form NO2 and CINO.
As the temperature of the system increase, the number of molecules that carry enough
energy to react when they collide also increase. The rate of reaction therefor increase
with temperature. As a general rule, the rate of a chemical reaction doubles for energy
10oC in the temperature of the system.
21.17 THE MECHANISMS OF CHEMICAL REACTIONS
The rate laws for chemical reactions can be explained by the following general
rules.
Reaction coordinate
 1. the rate of any sstep in a reaction is directly proportional to the
concentrations of the reagen consumed in that step
2. the overall rate law for a reaction is determined by the sequence of step, of the machanism, by
which the reactants are converted into the products of the reaction.
3. The overall rate law for a reaction is dominated by the rate law for the slowest step in the
reaction.
some reaction, such as the transfer of a chlorine atom from CINO2 to NO, occur in a single step.
CIN2(g) + NO(g) NO2(g) + CINO(g)
The rate of this reaction depends on the frequency of collisions between CINO2 and NO molecules.
Anything that changes the concentrations of either reactant will change the frequency with which
collicions occure and the rate of reaction. The overall rate of a one-step reaction is therfore proportional
to the product of the concentrations of the reactants consumed in the reaction.
(NO2)

= k (NO) (CINO2)

Many reaction, such as the decomposition of N2O5, occur in two or more steps. The first step in this case
is a relatively fast reaction in which N2O5 decomposed to form NO2 and NO3. The products of this step
then undergo a much slower reaction to form NO, NO2, and O2. The NO produced in the second step
then reacts with NO3 in a fast step to form more NO2.

Step 1: N2O5 NO2 + NO3 (fast step)

Step 2: NO2 + NO3 NO + NO2 + O2 (slow step)
Step 3: NO + NO3 2NO2 (fast step)
Combining these reaction in the proper ratio yields the overall equation for the decomposition of N2O5.

2N2O5 2NO2 + 2NO3

NO2 + NO3 NO + NO2 + O2
NO + NO3 2NO2
2N2O5 4NO2 + O2

The overll rate of the reaction can be no faster than the rate of the slowest step in the mechanism. The
slowet step is called the rate-limiting step, because it places a limit on the rate at which the overall
reaction can occur. In the decomposition of N2O5, the second step is the rate-limiting step. No matter
how fast the first and third steps take place, the decomposition of N2O5 cannot proceed any faster than
the rate-limiting secong step.
The rate of any step in a reaction is directly proportional to the concentrations of the reactants consumed
in that step. The following in the rate law for the second step in the decomposition of N2O5.
Step 2 : rate = k(NO2)(NO3)