The sequence of elementary steps that leads to the formation of products is
called the reaction mechanism. There are three types of elementary steps:
unimolecular A product rate = k[A]
bimolecular A+A or A+B product rate = k[A]2 or k[A][B]
termolecular A+A+A or A+A+B product rate = k[A]3 or k[A]2[B] etc.
These describe literally what is happening at the atomic scale.
The sum of the elementary steps must give the overall balanced equation.
They must also explain the experimentally determined rate law. The slowest
step in the reaction mechanism will determine the overall rate of the reaction and
is called the rate determining step.
1. The kinetics of the reaction: 2 X + Y Z was studied and the results are:
Expt [X]0 (M) [Y]0(M) Initial rate (M/s) a. Deduce the rate law including the
1 0.20 0.10 7.0 x 10-4 value of k with units
2 0.20 0.20 1.4 x 10-3
3 0.40 0.20 1.4 x 10-3
4 0.60 0.60 4.2 x 10-3
b. The following 3 mechanism have been proposed. The species M and N
are called intermediates, they are formed in early steps and consumed in
later steps. What is the overall reaction for each mechanism?
What is the molecularity of each step? What is the rate law derived from
each? Which mechanism is consistent with the rate law from part a?
Mechanism I X+YM (slow)
X+MZ (fast)
Mechanism II Y M (slow)
X+MZ (fast)
Mechanism III YM (slow)
M+XN (fast)
N+XZ (fast)
There are often equilibrium steps in mechanisms. We will usually assume that
they are not rate limiting. The concentration of the species involved can be
determined by setting up the equilibrium expression:
K = [product]p / [reactant]r so that, for example, [reactant]r = K [product]p
2. Given the following mechanism:
step 1 2 NO N2O2
step 2 N2O2 + H2 N2O + H2O (slow)
step 3 N2O + H2 N2 + H2O
a. Determine the overall reaction.
b. Are there any intermediates in this reaction mechanism?
c. Determine the rate law. Intermediates may not appear in rate
laws. Use the equilibrium expression to write the rate law only in
terms of [reactants].
d. What is the overall order of the reactions?
e. What is the molecularity of the rate determining step?
Another common component of reaction mechanisms is a catalyst. These are
compounds that change the reaction mechanism and provide a pathway with a
lower activation energy, and correspondingly faster reaction rate. They are a
reactant in an early step in the mechanism and a product in a later step. They
do not appear in the overall reaction, but do appear in the rate law.
3. A reaction occurs by the following mechanism.
step 1 Ce4+ + Mn2+ Ce3+ + Mn3+
step 2 Ce4+ + Mn3+ Ce3+ + Mn4+
step 3 Tl+ + Mn4+ Tl3+ + Mn2+
a. Write the overall reaction
b. Identify each of the components as a reactant, product, intermediate or
catalyst:
Mn2+ = Mn4+ =
Mn3+ = Tl+ =
4+
Ce = Tl3+ =
Ce3+ =
c. Assuming that the catalyst is involved in the rate determining step,
what is the rate law for this reaction?
d. Why is the uncatalyzed reaction so slow? (Hint: look at the
molecularity)
4. Under certain conditions, the reaction:
2 NO + Cl2 2 NOCl
is found to be second order in NO and first order in Cl2.
Given the following mechanism,
step 1 NO + Cl2 NOCl2
step 2 NOCl2 + NO 2 NOCl
what are the relative rates of the two elementary steps under these
conditions?
5. The rate of the reaction shown below was studied:
2 NO + H2 N2O + H2O
It was found that the rate doubled when the [H2] was doubled. It
was also found that the rate increased by a factor of four when the
NO concentration was doubled. Which of the following
mechanisms is/are consistent with these data?
step 1 NO + H2 N + H2O (slow)
step 2 N + NO N2O
step 1 NO + NO N2O2
step 2 N2O2 + H2 N2O + H2O (slow)
step 1 H2 2 H
step 2 H + 2 NO N2O + OH (slow)
step 3 OH + H H2O
step 1 NO + NO NO2 + N (slow)
step 2 NO2 + H2 NO + H2O
step 3 N + NO N2O
