Chemical Kinetics
Lecture 5
CML101
August 06, 2024
This is a plot of [B] versus time for a typical temperature-
jump experiment. From [B] = [B]0exp(-t/) (as per
expression derived), we see that a plot of ln([B]/[B]0)
versus t is linear and has a slope of -(k1 + k-1), which is the
negative of the sum of the forward and reverse rate
constants for the reaction at T2. If we know the equilibrium
constant at T2 and the rate laws for the forward and
reverse reactions, then the rate constants k1 and k-1 can be
independently determined.
We now to consider this chemical reaction and assume that both the forward
and reverse reactions are first order in their respective reactants
Derive expression for ,
the relaxation time!
Reaction Mechanisms
The study of reaction rates leads to an understanding of the mechanism
of a reaction, its analysis into a sequence of elementary steps.
Many reactions occur in a sequence of steps called elementary
reactions, each of which involves only a small number of molecules or
ions. A typical elementary reaction is
H + Br2 → HBr + Br
Note that the phase of the species is not specified in the chemical
equation for an elementary reaction and the equation represents the
specific process occurring to individual molecules. This equation, for
instance, signifies that an H atom attacks a Br 2 molecule to produce an
HBr molecule and a Br atom.
The molecularity of an elementary reaction is the number of molecules
coming together to react in an elementary reaction. In a unimolecular
reaction, a single molecule shakes itself apart or its atoms into a new
arrangement, as in the isomerization of cyclopropane to propene. In a
bimolecular reaction, a pair of molecules collide and exchange energy,
atoms, or groups of atoms, or undergo some other kind of change.
It is important to distinguish molecularity from order:
• reaction order is an empirical quantity, and obtained from the
experimentally determined rate law;
• molecularity refers to an elementary reaction proposed as an
individual step in a mechanism.
The molecularity of an elementary reaction is defined to be the
number of reactant molecules involved in the chemical reaction.
Elementary reactions that involve one, two, and three molecules
are termed unimolecular, bimolecular, and termolecular reactions,
respectively. These terms should be used to describe only
elementary reactions.
Consecutive Elementary Reactions
[P]
Examine the shapes of curves k2 is constant
[A] [P]
[I] 𝒌𝟏
𝒌𝟐
=𝟐
𝒌𝟏
𝒌𝟐
=𝟒
𝒌𝟏
𝒌𝟐
=𝟏𝟎 k1 > k2
[ 𝑨] k1 k2
[ 𝑨 ]𝟎 AIP
𝒌𝟏 𝟏
=
𝒌𝟐 𝟐
𝒌𝟏 𝟏
=
𝒌𝟐 𝟒
𝒌𝟏
=
𝒌𝟐 𝟏𝟎
𝟏 k1 < k2
k1 is constant
Problem:
This plot shows the concentrations of 210Bi,
210
Po, and 206Pb over time. Note the
“temporary” buildup of 210Po, which does
start at 0. Note that the x-axis is in units of
seconds, but in this example the right side of
the plot is equivalent to a time of 1.9 years.
[P]
Can you distinguish between single step and a two-step reaction
mechanism?
k2 >> k1
For a single-step reaction, the kinetics
of A and P depend upon the same rate
constant.
For the two-step mechanism in which
the second step is rate determining,
the kinetics of A depend upon k1 and
the kinetics of P depend upon k2 .
k1 >> k2 Therefore, if we measure both the
decay kinetics of A and the formation
kinetics of P, we can distinguish
between a single-step and two-step
mechanism when the second step of
the two-step reaction scheme is rate
determining
The Steady-State Approximation
Imagine the intermediate
being so reactive that it
does not accumulate at an
appreciable level compared
to concentration of
reactants or products!
The basis of the steady‑state approximation: It is
supposed that the concentrations of
intermediates remain small and hardly change
during most of the course of the reaction
There is a considerable increase in mathematical complexity
as soon as the reaction mechanism has more than a couple
of steps or reverse reactions are taken into account.
Need to make an approximation
Steady-state Approximation
Steady-state approximation assumes that the intermediate, I, is
in a low, constant concentration. More specifically, after an initial
induction period, an interval during which the concentrations of
intermediates rise from zero, the rates of change of the
concentrations of all reaction intermediates are negligibly small
during the major part of the reaction.
