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CHAPTER FIFTEEN
CHEMICAL KINETICS
1 INTRODUCTION.
There are two practical considerations that are involved in the evaluation
of any chemical synthetic process.
We have already dealt with the question of reaction yield. The other
concern is with the rate at which reactants are converted into products.
The branch of chemistry that is focused upon the study of the rates of
chemical reactions is called chemical kinetics.
A + B Æ C + D
The figure shows quite clearly that the rate of the reaction, which is the
slope of the curve, is gradually decreasing.
Rate = - Δ [Α] / Δ t
Where Δ[A] is the change of concentration of a reactant species and Δt is the
elapsed time.
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For this reaction to take place the bonds of the two reactant molecules
need to be broken. We envision that this is the result of a collision between two
molecules. The fragments formed when the molecules break apart might come
back together to form A-A and B-B molecules or they might trade partners and
give rise to the product species.
In this scenario, it is clear that two factors affect the rate of formation of
products.
The number of collisions per unit time will depend primarily upon
the concentrations of the reactant species. There will be a slight
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It needs to be emphasized that one cannot anticipate the rate law by the
simple expedient of looking at the balanced equation for the reaction.
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Rate = k [A]m[B]n
Where the sum m + n is called the order of the reaction.
Rate = k1 [A]
Alternatively, the rate may depend upon the square of the concentration of
only one of the species:
Rate = k2 [A]2
Higher order reactions exist and some have non – integer orders.
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The reaction is carried out several times. For each “run”, the combination
of initial reactant concentrations is different. In each case, we are only interested
in determining the initial rate of the reaction. This approach is particularly useful if
the equilibrium constant is small enough for the reverse reaction to kick in after a
short time.
A + B Æ products
Rate = k [A]m[B]n
The data might be of the form:
Or 4 = 2m Thus m = 2
Or 1 = 2n Thus n = 0
Rate = k [A]2
Attention is drawn to the fact that when [A]2 / [A]1 = 0.5 the time t2 – t1 is
called the half life. The half - life of a first order reaction is the same no matter
what the initial concentration.
ln (0.5) = - k1 t1/2
k1 = t1/2 / 0.693
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We see the linear dependence of the log of concentration upon time. That
verifies that we are dealing with a first order reaction. The slope of that line is the
rate constant.
Rate = k2 [A]2
The integrated version of the second order rate equation is:
k = A exp(- ΔEact / RT )
The rate constants for most, but not all, reactions vary in this fashion.
which cis –butene is converted into trans butene. We look first at representations
We see that in order to go from one isomer to the other, we need to break
There is a modest drop in energy going from the one isomer to the other,
but there is a substantial barrier.
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The values that are given for the activation energy and the energy of the
reaction are both referring to single molecules. Multiplying these numbers by
Avogadro’s number to give the molar quantities, gives.
4 Reaction Mechanisms.
Many chemical reactions do not take place in one single step but are,
instead, achieved by the performance of a sequence of steps. We refer to the
sequence of steps as the mechanism of the chemical reaction.
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The rates of the individual steps of a reaction are likely to differ quite
significantly and far more often than not one step is so much slower than the
others that it alone controls the rate of formation of products. This is referred to
as the rate determining step.
What was found was that the reaction has to be initiated by the
decomposition of iodine molecules to atoms.
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The decomposition:
I2(g) Å Æ 2 I(g)
is actually a two-way process.
Both of the iodine atoms then collide with the hydrogen molecule. This is a
three – body collision:
We can write the rate equation for this slow step, knowing that it is also
the rate equation for the overall reaction. For the three – body collisions, it must
be:
Rate = k3 [I(g)]2 [H2(g)]
This does not qualify to be described as a rate law, however, since rate
laws are supposed to be expressed in terms of the concentrations of the original
reactant species.
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We get around this problem by rearranging the equation for the initial rapid
equilibrium.
[I(g)]2 = Kequ / [I2(g)]
Since the product of the two constants Kequ and k3 must also be a
constant, this rate equation is completely consistent with the rate law.
5 Catalysts.
It is possible to increase the rate of a chemical reaction by adding a
substance that helps the reaction along without itself being a reactant or product.
Such additives are called catalysts.
The function of a catalyst is to lower the activation energy for the reaction.
An additive, that has the opposite effect by slowing down a reaction, is called an
inhibitor.
catalysts.
Many reactions, that take place in solution, have rates that are sensitive to
the acidity. Adding hydrogen ions can have a profound catalytic effect on many
reactions in aqueous solution.