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E4-4

Many reactions, however, proceed in a number of small steps. Let us consider the
hypothetical composite reaction 2A + B D. Of the many possible ways this reaction
might occur, two are given below:

mechanism (1) A + A C, followed rapidly by C + B D, or
mechanism (2) A + B C, followed rapidly by C + A D

To determine which of these two possible mechanisms is operating, one could carry out
kinetic experiments on the dependence of the rate of formation of D on the concentrations
of the reactants A and B. Because in each mechanism the first step is much slower than
the second step, it will be a bottleneck and totally determine the rate of formation of D.
Under these conditions the rate of formation of D, v, for the two mechanisms would be
given by:

rate of formation of D via mechanism (1): v = k[A]2, or
rate of formation of D via mechanism (2): v = k[A][B].

Therefore, measurements of the rate of the reaction at different concentrations of A and B
would allow one to distinguish easily between the two mechanisms. If the rate depended
on the square of the concentration of A and not at all on the concentration of B, this
would support mechanism (1). If the rate of the reaction were directly proportional to the
concentrations of both A and B, this would support mechanism (2). If the reaction rate
does not conform to either of these relationships, then some other mechanism must apply.
This is a simple example of how kinetics research can be used to determine how a
reaction occurs.
I odine Clock Reaction
The iodine clock reaction was discovered by the Swiss chemist Hans Heinrich Landolt in
1886. There are a number of variations of it, but all of them involve the mixing of two
colourless solutions. Initially there is no visible reaction, but after a certain period of time
the mixed solution suddenly turns dark blue. In this experiment you will study the iodate
variation of the iodine clock reaction, which involves the reaction between iodate ions,
IO3, hydrogensulfite ions, HSO3, and hydronium ions, H+. The stoichiometry of the
overall reaction is as follows:
2IO3(aq) + 5HSO3(aq) + 2H+(aq) I2(aq) + 5HSO4(aq) + H2O(l) (1)
If the solution contains starch, it will react with I2, the elemental iodine produced by the
reaction, and form a blue starch-iodine complex. But why doesnt the blue colour appear
immediately? The trick is that as soon as any I2 is formed, it immediately reacts with any
HSO3 still present and is converted into colourless I:
I2(aq) + HSO3(aq) + H2O(l) 2I(aq) + HSO4(aq) + 2H+(aq) (2)
Thus, reaction (2) efficiently removes any I2 produced by reaction (1). Only after all of
the HSO3 has been consumed by reactions (1) and (2) will the I2 concentration increase
and its reaction with the starch begin. This not only explains the sudden appearance of the
blue colour, but it also allows us to determine the rate of the reaction. A measure of the
rate of HSO3 consumption can be made by dividing the initial concentration of HSO3 by
t, the time it takes for the blue colour to appear, [HSO3]o/t.
A Sample Lab Report
The Iodine Clock Reaction

Introduction:
The factors that affect the rate of a chemical reaction are important to understand due to
the importance of many such reactions to our health, well-being and comfort. It would be
advantageous to slow down some of these reactions such as food spoilage and rust
formations, while in the cases of reactions such as the Tums-stomach acid reaction and
the conversion of organic matter to fossil fuels, it would be beneficial to them speed up.

The rate of a reaction is governed by the collision theory. In order for a reaction to occur,
there must be a collision between reactant molecules. This collision must have enough
energy to break and form the appropriate bonds as well as have the correct orientation
when colliding.(1) When all of these things happen, a chemical reaction has occurred. If
we can increase the amount of these favourable collisions, then we increase the rate of the
reaction.(1)

One of the factors that affects reaction rate is reactant concentration. The more reactant
molecules in a given area, the greater the number of collisions possible.(1) Whenever we
have a larger number of collisions possible, there is a probability of having a favourable
collision increases. The opposite is true if we have a lower concentration of reactant
molecules.

Another factor that affects the rate of reaction is temperature. In this case, there are not
more reactant molecules to collide. Temperature is proportional to the average kinetic
energy, which is the energy associated with motion.(2) All reactions have what is called
the Minimum Threshold Energy. This is the amount of kinetic energy it takes for reactant
bonds to break, re- arrange and form the bonds necessary to make products.(1) This
energy is equivalent to the activation energy of the reaction. When we increase the
temperature of a reaction, the average kinetic energy of the reactants increase.(1) This
change results in two things. First, the molecules show an increase in motion within the
confines of the same area causing an increase in the amount of collisions. Second, more
molecules now have an energy equal to the Minimum Threshold Energy and can now
form products. More collisions, more energy, and a greater probability of favourable
collisions leads to an increase in reaction rate. Again, the opposite is true if we decrease
the temperature.


Purpose/Objective: The purpose of this lab is to observe the effect of temperature and
concentration on the rate of a chemical reaction. (OR The objective of this lab is to
observe the effect of temperature and concentration on the rate of a chemical reaction.)


Procedure: Please refer to Heath Chemistry: Laboratory Experiments (Canadian Edition),
DiSpezio, Michael, A., et al, 1987, D.C. Heath Canada, Ltd. pg. 197-203