Why Does Iodine Turn Starch Blue?

Author: Catharina Goedecke

Published Date: 06 December 2016
Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image: Why Does Iodine Turn Starch Blue?
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Iodine Test
Using iodine to test for the presence of starch is a common experiment. A solution
of iodine (I2) and potassium iodide (KI) in water has a light orange-brown color. If it
is added to a sample that contains starch, such as the bread pictured above, the
color changes to a deep blue. But how does this color change work?

Starch is a carbohydrate found in plants. It consists of two different types of

polysaccharides that are made up of glucose units which are connected in two
different ways. One is the linear amylose and the other is the branched amylopectin
(pictured below).

Components of starch

Amylose is the compound that is responsible for the blue color. Its chain forms a
helix shape, and iodine can be bound inside this helix (pictured below).
Amylose helix

Charge-Transfer Complexes
The colors are caused by so-called charge transfer (CT) complexes. Molecular iodine
(I2) is not easily soluble in water, which is why potassium iodide is added. Together,
they form polyiodide ions of the type In, for example, I3, I5, or I7. The
negatively charged iodide in these compounds acts as charge donor, the neutral
iodine as a charge acceptor. Electrons in such charge-transfer complexes are easy
to excite to a higher energy level by light. The light is absorbed in the process and
its complementary color is observed by the human eye.

In the case of the aqueous solution of polyiodides, the absorptions of the different
species lead to an overall brownish color. Once amylose is added, it forms another
CT complex, Here, the amylose acts as a charge donor and the polyiodide as an
acceptor. This complex absorbs light of a different wavelength than polyiodide, and
the color turns dark blue.

Polyiodide Chains
The exact structure of the polyiodides inside the amyloid helix is not clear. The
amylose-iodine complex is amorphous (i.e., it does not form ordered crystals), which
has made it difficult to determine its structure. It has been proposed that the
species inside the helix are repeated I3 or I5 units.

However, Ram Seshadri, Fred Wudl, and colleagues, University of California, Santa
Barbara, USA, have found evidence that infinite polyiodide chains Inx are contained
in the amylose-iodine complex [1]. The team investigated a related system, a
pyrroloperyleneiodine complex, to study its properties as an organic electronic
conductor. The material is crystalline, and therefore, the team was able to
determine its structure using X-ray crystallography. They found nearly linear
polyiodide chains in-between stacks of pyrroloperylene. It turned out that the
material containing these chains absorbs light at very similar wavelengths to the
amylose-iodine complex, which supports the hypothesis that similar polymeric
chains form in the iodine test for starch.