Harcourt-Essen Reaction:

The Harcourt-Essen reaction is a variation of the iodine clock reaction which

displays chemical kinetics in action. Chemical kinetics is the study of rates of
chemical processes through the investigation of different experimental
conditions and their effect on the speed of a reaction. These investigations can
then produce information from which the reaction mechanisms and transition
states can be deduced.
The reaction is carried out by producing a solution in a conical flask using known
volumes of potassium iodide, sodium thiosulphate, starch and sulphuric acid.
Hydrogen peroxide of a known volume is added to this solution.
As the potassium iodide is an ionic solid but as it is dissolved in solution, it
dissociates in water. The reason it is able to do this is because water is a polar
solvent and is able to stabilise the ions. As the potassium is positively charged
and Iodine negatively charged, it is attracted to the polar end of water and is in
turn dissociated to form K+ and I- ions. It is a better source of iodine as it is less
hygroscopic (absorbs water less readily) than sodium iodide which makes it
easier to work with.
Hydrogen peroxide is a strong oxidiser and can decompose to form water and
oxygen in the presence of light.

2H2O2 2H2O + O2 + energy

The rate of decomposition can be increased with increased temperatures,
concentration and PH. Decomposition can also be catalysed by transition metal
compounds such manganese dioxide and platinum. As the rate of decomposition
is more likely at a higher PH, the addition of sulphuric acid will act as a stabiliser
which will decrease the likelihood of H 2O2 decomposing.
Due to its properties of being a strong oxidising agent it is used in this reaction
for the purpose of oxidising iodide ions to iodine.
When the hydrogen peroxide is added to the reaction, it reacts with the iodide
ions as iodine ions are a mild reducing agent so are easily oxidised. The reaction
that takes place is the following:
H2O2 + 2I- + 2H+ I2 + 2H2O
The iodine which has been produced from the previous reaction then reacts with
the thiosulphate ions which has resulted from the dissociation of sodium
thiosulphate in solution following similar principles as before.
2S2O32- + I2 S4O62- + I2
As all of the thiosulphate ions have reacted, the remaining iodine in the solution
accumulates. This leads to a complexation reaction between the Starch/Iodine in
the solution. However in reality, it is not starch but amylose that is participating
in the reaction. In the solution triiodide (I3-) forms from the reaction of I2 with I-.
The complexation reaction occurs as amylose is rolled up into a helix that is
caused by the carbon back bone of its ring structure and this creates a tube with
a high hydrophobicity which the triiodide ion has affinity for. Following the
movement of the triiodide ion into the amylose helix, water molecules flow
through the helix and interact with the triiodide to form a charge transfer

complex. Water molecules can still flow through the helix even though it is a
hydrophobic environment.
A charge transfer complex is where electrons from the donor molecule excite the
electrons in the acceptor molecule. When the accepter molecules electrons
return to their ground state, electromagnetic radiation is given off which is why
the reaction turns to blue/black colour towards the end of its reaction; it is due to
the starch/iodine complex.
(Starch +I2 blue-black complex)2

Translation of title: Amylase Molecule The owner

Translation of side text: Amylase Starch
Translate of text below: Iodine part.

Hydrogen Peroxide

Potassium Iodide