KINETICS

By

Dr. rer. nat. H. Muharram, M.Si

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Chemical kinetics
Kinetics is the study of the rates of chemical
processes in an effort to understand what it is that
influences these rates and to develop theories which can be
used to predict them.

Rate of reaction
change
The rate in concentration, c, inTime t
is defined:
t

the rate of formation or loss of any species –

reactant, intermediate or product
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The rate is the instantaneous slope, and this varies

with time.
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Simple rate laws
A first order rate law is one in which the rate is
proportional to the concentration raised to the power 1
(hence "first")
r = k1st [A]1
As the units of r are concentration time–1 and the
units of [A] are concentration, the units of k1st are
found as r conc.time 1 1
r = k1st so k1st = [ A]   time
conc.

Hence first order rate constants have units of

time–1.
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Importance of rate laws
• If we know the rate law and the constants in it we can
use this to predict the rate for any set of conditions
(concentrations). The rate law is thus a very succinct
and practical way of expressing the rate. You might use
this, for example, in a model of the atmosphere or in
predicting the rate of an enzyme catalysed reaction.
• The form of the rate law can tell us something about the
mechanism of the reaction. This is a point which we will
consider in more detail below.
• Knowing the rate law enables us to separate the
concentration dependence from the underlying,
fundamental effect which is the size of the rate
constant.
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First order rate law
For a reaction of the form A → products, a first
order rate law takes the form
r = k1st [A]1
writing the rate in the differential form this
d [ A]
becomes   k [ A]
dt 1st
We need the minus sign as A is a reactant and so its
concentration decreases with time i.e. the slope of a
graph of [A] against time will be negative. The variables
[A] and t can be separated
1 to give:
d [ A]   k1st dt
[ A]
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which can then be integrated
1
 [ A] d [ A]    k dt
1st asln[ A]  k1st t  const.
The constant of integration can be
removed by supposing that at t = 0 [A] =
[A]0, the initial concentration of A; so:
Ln[A]o = const Substituting this gives the
final form ln[ A]  k1st t  const. This can also be
expressed as . [ A]  [ A]0 exp(k1st )
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The plot of [A] with t as bellow,