JOHN MANDONA NORTEC

REACTION MECHANISM

Chemical reactions very often occur in a step-wise fashion, involving two or

more distinct reactions taking place in sequence. A balanced equation
indicates what is reacting and what is produced, but it reveals no details about
how the reaction actually takes place. The reaction mechanism (or reaction
path) provides details regarding the precise, step-by-step process by which a
reaction occurs.

The decomposition of ozone, for example, appears to follow a mechanism

with two steps:

O3(g) ⟶ O2(g) + O

O + O3(g) ⟶ 2O2(g)

Each of the steps in a reaction mechanism is an elementary reaction.

These elementary reactions occur precisely as represented in the step
equations, and they must sum to yield the balanced chemical equation
representing the overall reaction:

2O3(g) ⟶ 3O2(g)

Notice that the oxygen atom produced in the first step of this mechanism is
consumed in the second step and therefore does not appear as a product in
the overall reaction. Species that are produced in one step and consumed in
a subsequent step are called intermediates.

While the overall reaction equation for the decomposition of ozone indicates
that two molecules of ozone react to give three molecules of oxygen, the
JOHN MANDONA NORTEC

mechanism of the reaction does not involve the direct collision and
reaction of two ozone molecules. Instead, one O3 decomposes to yield
O2 and an oxygen atom, and a second O3 molecule subsequently reacts
with the oxygen atom to yield two additional O2 molecules.

Unlike balanced equations representing an overall reaction, the equations

for elementary reactions are explicit representations of the chemical change
taking place. The reactant(s) in an elementary reaction’s equation undergo
only the bond-breaking and/or making events depicted to yield the
product(s).

For this reason, the rate law for an elementary reaction may be derived
directly from the balanced chemical equation describing the reaction.

This is not the case for typical chemical reactions, for which rate laws may
be reliably determined only via experimentation.

𝑼𝒏𝒊𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝑬𝒍𝒆𝒎𝒆𝒏𝒕𝒂𝒓𝒚 𝑹𝒆𝒂𝒄𝒕𝒊𝒐𝒏𝒔

The molecularity of an elementary reaction is the number of reactant

species (atoms, molecules, or ions). For example,
a unimolecular reaction involves the reaction of a single reactant species to
produce one or more molecules of product:

A ⟶ products

The rate law for a unimolecular reaction is first order:

rate = k[A]
JOHN MANDONA NORTEC

A unimolecular reaction may be one of several elementary reactions in a

complex mechanism. For example, the reaction:

O3 ⟶ O2 + O

illustrates a unimolecular elementary reaction that occurs as one part of a

two-step reaction mechanism as described above. However, some
unimolecular reactions may be the only step of a single-step reaction
mechanism. (In other words, an “overall” reaction may also be an elementary
reaction in some cases.) For example, the gas-phase decomposition of
cyclobutane, C4H8, to ethylene, C2H4, is represented by the following chemical
equation:

This equation represents the overall reaction observed, and it might also
represent a legitimate unimolecular elementary reaction. The rate law
predicted from this equation, assuming it is an elementary reaction, turns out
to be the same as the rate law derived experimentally for the overall reaction,
namely, one showing first-order behavior:
𝚫𝑪𝟒 𝑯𝟖
rate= − = k[C4H8]
𝚫𝒕

This agreement between observed and predicted rate laws is interpreted to

mean that the proposed unimolecular, single-step process is a reasonable
mechanism for the butadiene reaction.
JOHN MANDONA NORTEC

Bimolecular Elementary Reactions

A bimolecular reaction involves two reactant species, for example:

A + B ⟶ products

and

2A ⟶ products

For the first type, in which the two reactant molecules are different, the rate
law is first-order in A and first order in B

(second-order overall):

rate = k[A][B]

For the second type, in which two identical molecules collide and react, the
rate law is second order in A:

rate = k[A][A] = k[A]2

Some chemical reactions occur by mechanisms that consist of a single

bimolecular elementary reaction. One example is the reaction of nitrogen
dioxide with carbon monoxide:

NO2(g) + CO(g) ⟶ NO(g) + CO2(g)

(see Figure 12.17)

JOHN MANDONA NORTEC

Figure 12.17 The probable mechanism for the reaction between NO2 and CO
to yield NO and CO2.

Bimolecular elementary reactions may also be involved as steps in a

multistep reaction mechanism. The reaction of atomic oxygen with ozone is
the second step of the two-step ozone decomposition mechanism discussed
earlier in this section:

O(g) + O3(g) ⟶ 2O2(g)

Termolecular Elementary Reactions

An elementary termolecular reaction involves the simultaneous collision of

three atoms, molecules, or ions. Termolecular elementary reactions are
uncommon because the probability of three particles colliding simultaneously
is less than one one-thousandth of the probability of two particles colliding.
There are, however, a few established termolecular elementary reactions.
The reaction of nitric oxide with oxygen appears to involve termolecular steps:

2NO + O2 ⟶ 2NO2

rate = k[NO]2[O2]

Likewise, the reaction of nitric oxide with chlorine appears to involve

termolecular steps:

2NO + Cl2 ⟶ 2NOCl

rate = k[NO]2[Cl2]
JOHN MANDONA NORTEC

Relating Reaction Mechanisms to Rate Laws

It’s often the case that one step in a multistep reaction mechanism is
significantly slower than the others. Because a reaction cannot proceed faster
than its slowest step, this step will limit the rate at which the overall reaction
occurs. The slowest step is therefore called the rate-limiting step (or rate-
determining step) of the reaction Figure 12.18.

As described earlier, rate laws may be derived directly from the chemical
equations for elementary reactions. This is not the case, however, for ordinary
chemical reactions. The balanced equations most often encountered
represent the overall change for some chemical system, and very often this
is the result of some multistep reaction mechanisms. In every case, the rate
law must be determined from experimental data and the reaction mechanism
subsequently deduced from the rate law (and sometimes from other data).
The reaction of NO2 and CO provides an illustrative example:

NO2(g) + CO(g) ⟶ CO2(g) + NO(g)

For temperatures above 225 °C, the rate law has been found to be:

rate = k[NO2][CO]
JOHN MANDONA NORTEC

The reaction is first order with respect to NO2 and first-order with respect to
CO. This is consistent with a single-step bimolecular mechanism and it
is possible that this is the mechanism for this reaction at high temperatures.

At temperatures below 225 °C, the reaction is described by a rate law that is
second order with respect to NO2:

rate = k[NO2]2

This rate law is not consistent with the single-step mechanism, but is
consistent with the following two-step mechanism:

NO2(g) + NO2(g) ⟶ NO3(g) + NO(g) (slow)

NO3(g) + CO(g) ⟶ NO2(g) + CO2(g) (fast)

The rate-determining (slower) step gives a rate law showing second-order

dependence on the NO2 concentration, and the sum of the two equations
gives the net overall reaction.

In general, when the rate-determining (slower) step is the first step in a

mechanism, the rate law for the overall reaction is the same as the rate law
for this step. However, when the rate-determining step is preceded by a step
involving a rapidly reversible reaction the rate law for the overall reaction may
be more difficult to derive.

As discussed in several chapters of this text, a reversible reaction is

at equilibrium when the rates of the forward and reverse processes are equal.
Consider the reversible elementary reaction in which NO dimerizes to yield
an intermediate species N2O2. When this reaction is at equilibrium:
NO+NO⇋N2O2
 JOHN MANDONA NORTEC

rateforward=ratereverse

k1[NO]2=k−1[N2O2]

This expression may be rearranged to express the concentration of the

intermediate in terms of the reactant NO:

𝐾1 [𝑁𝑂]2
( ) = [N2O2]
𝐾−1

Since intermediate species concentrations are not used in formulating rate

laws for overall reactions, this approach is sometimes necessary, as
illustrated in the following example exercise.

Example 12.14

Deriving a Rate Law from a Reaction Mechanism

The two-step mechanism below has been proposed for a reaction between
nitrogen monoxide and molecular chlorine:

Step 1 : NO(g) + CL2(g) = NOCl2(g) Fast

Step 2 :NOCl2(g) + NO(g) ⟶ 2NOCl(g) Slow

Use this mechanism to derive the equation and predict rate law for overall
reaction.
JOHN MANDONA NORTEC

Solution

The equation for the overall reaction is obtained by adding the two
elementary reactions:

2NO(g) + Cl2(g) 2NOCl(g)

To derive a rate law from this mechanism, first write rates laws for each of
the two steps.

rate1 = k1[NO][Cl2] for the forward reaction of step 1

rate−1 = k−1[NOCl2] for the reverse reaction of step 1

rate2 = k2[NOCl2][NO] for step 2

Step 2 is the rate-determining step, and so the rate law for the overall
reaction should be the same as for this step. However, the step 2 rate law, as
written, contains an intermediate species concentration, [NOCl2]. To remedy
this, use the first step’s rate laws to derive an expression for the intermediate
concentration in terms of the reactant concentrations.

Assuming step 1 is at equilibrium:

rate1 = rate−1

k1 [NO][Cl2] = k−1 [NOCl2]

𝐾1
[NOCl2] = ( )
𝐾−1

Substituting this expression into the rate law for step 2 yields:
𝐾1
rate2 = rateoverall = ( )NO]2[Cl2]
𝐾−1
JOHN MANDONA NORTEC

Worked example:

The rate equation for a reaction is:

r = k [NO]2[H2]

The overall reaction is:

2NO(g) + 2H2(g) →N2(g) + 2H2O(g)

The following three step mechanism is suggested for the reaction.

Determine the rate-determining step.

Step 1: 2NO → X

Step 2: X + H2 → Y

Step 3: Y + H2 → N2 + 2H2O

Answer:

As the rate equation contains NO and is second order, this suggests that two moles of
NO are used. This means that rate determining step could be step 1.

However, H2 is also included. This means the rate determining step is step 2.

It can’t be step three, as the reaction is first order with respect to hydrogen, but not
second order. If step 3 were involved, then there would be 2 moles of hydrogen.