REACTION MECHANISMS
INTRODUCTION
The form of the rate law determined from the
kinetics of a reaction does not tell us the actual
mechanism, but it gives important clues.
For instance, the complex rate law for the H2 +
Br2 reaction indicates that the process does not
proceed through a single-step collision between
the two molecules, but consists of several
elementary reactions.
That said, there are several methods of linking
rate laws to reaction mechanism.
DEFINITIONS
Elementary Reaction: A simple and single-step process,
whose stoichiometry agrees with the rate law. An
elementary reaction is described in terms of their
molecularity.
Complex Reaction: One that is made up of multiple
elementary reactions.
Molecularity is the number of reactant particles
involved in the elementary reaction.
Unimolecular Reactions are those that involve only a
single reactant particle, which, due to high energy,
shakes itself and converts into more stable products; e.g.
radioactive decay processes.
DEFINITIONS
Bimolecular Reactions occur between two particles,
which collide to form an activated complex. They exhibit
second-order kinetics, but the converse is not true. In
fact, many kinetically second-order reactions are
actually complex.
Termolecular Reactions involve collisions of three
particles and are more likely to occur at high pressures
or in liquid solution.
The concept of molecularity was developed largely for
gas-phase reactions. It is a difficult concept to carry
over to liquid solutions, where solvent participation
makes it hard to determine the reacting particle.
DETERMINATION OF MECHANISMS
Itis useful to hypothesize the mechanism in terms of a
set of elementary reactions and derive the rate law
that can be compared with experimental findings; an
agreement endorses the suggested mechanism.
One general method is to see if one elementary
reaction controls the overall kinetics; i.e. to look for
the rate-determining step.
For certain mechanisms one elementary reaction is
found to dominate the kinetics of the complex
reaction; its rate law closely approximates that of the
overall process.
PARALLEL REACTIONS
Parallel reactions are of the following type
k1 B
A
k2
C
The substance A can decompose by either of the
two paths, giving rise to different products , B and
C. The rate expressions are:
-d[A]/dt = k1 [A] + k2 [A] = (k1 + k2) [A]
d[B]/dt = k1 [A]
d[C]/dt = k2 [A]
PARALLEL REACTIONS
The solution to the first equation, which has the
form of the first-order rate law, is
ln [A] = ln [A]o - (k1 +k2)t
[A] = [A]o exp{-(k1+k2)t}
If k1 >> k2, then k2 ≈ 0, and
[A] = [A]o exp(-k1 t)
Now, the overall integrated rate law is expressed
in terms of k1, meaning that the faster reaction is
rate-determining for parallel reactions.
PARALLEL REACTIONS
EXAMPLE:
Radioactive decay frequently occurs simultaneously
by two separate paths. For example, 64Cu is unstable
against decay, giving either an electron or a positron.
k-
64
Zn30 + - (62%)
64
Cu29
k+ 64
Ni28 + + (38%)
Ifthe decay of 64Cu occurs exponentially with a single
half-life of 12.8 hours, determine the rate-
determining step by calculating all rate constants.
SERIES REACTIONS (FIRST-ORDER)
Series reactions are of the type
k1 k2
A B C
The rate expressions are
v1 = - d[A]/dt = k1 [A]
[A] = [A]o exp(-k1 t)
d[B]/dt = k1[A] - k2[B]
= k1[A]o exp(-k1t) – k2[B]
Integrating the above expression and using [B]o= 0,
gives k 1 [ A]0 -k t -k t
[ B] = e 1 e 2
k2 - k1
SERIES REACTIONS (FIRST-ORDER)
Similarly
v2 = d[C]/dt = k2 [B]
k 1k 2 [ A]0
= e - k1 t e - k2 t
k2 - k1
Variables [C] and t can be separated to give, for [C]o = 0
1 k2 e - k1 t -k t
[ C] = [ A]0 1 - k1 e 2
k2 - k1
If k1 >> k2, then the expression is described by k2; i.e.
[ C] = [ A] 1 - e - k 2 t
0
Therefore, the slower step is rate determining.
EQUILIBRIUM AND KINETICS
All reactions approach equilibrium.
In principle, for every forward reaction step,
there is a backward process.
The backward step is sometimes ignored
because either the equilibrium constant is very
large or the product concentration is kept very
small.
It is important, however, to know the general
relation between kinetic rate constants (k) and
thermodynamic equilibrium constants (K).
EQUILIBRIUM AND KINETICS
Consider an elementary first-order reversible
reaction k1
A k-1 B
The rate of disappearance of A is
- d[A]/dt = k1 [A] - k-1 [B]
At equilibrium, -d[A]/dt = 0, therefore,
[B]eq / [A]eq = k1 / k-1 = K
COMPLEX REACTIONS
For many reactions, particularly those involving enzymes
as catalysts, a series of reversible steps is encountered.
An example is a set of coupled elementary reactions:
k1 k3
A + B k2 C P
The following rate equations apply:
d[A]/dt = - k1 [A][B] + k2 [C]
d[C]/dt = k1 [A][B] - k2 [C] - k3 [C]
d[P]/dt = k3 [C]
The exact solution to these rate laws is complex; hence it
is useful to introduce simplifying approximations.
COMPLEX REACTIONS
INITIAL VELOCITY APPROXIMATION
“At the beginning of the reaction, the
product concentrations are usually very small
or zero”
Therefore, the terms that involve the products
are ignored, in this case leaving out the second
and third equations and dropping the last term
in the first equation. i.e.
d[A]/dt = - k1 [A][B]
Thus, the overall rate law is second-order.
COMPLEX REACTIONS
STEADY-STATE APPROXIMATION
“During the major part of the reaction (close
to equilibrium) the concentration of the
intermediate is constant or very small”
Hence,
d[C]/dt = 0
And
0 = k1 [A][B] - k2 [C] - k3 [C]
k1
[ C] = [ A][ B]
k2 + k3
COMPLEX REACTIONS
STEADY-STATE APPROXIMATION
The overall rate is described by the equation
involving the appearance of P.
d[P]/dt = k3 [C]
Substituting for [C] in the above equation;
d[ P] k1 k3
= [ A][ B]
dt k2 + k3
Or d[P]/dt = k’ [A][B]
Thus, the overall rate law is second-order.
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