When starch is mixed with iodine in water, an intensely colored starch/iodine complex is formed. Many of the details of the reaction are still unknown. But
it seems that the iodine (in the form of I5- ions) gets stuck in the coils of beta amylose molecules (beta amylose is a soluble starch). The starch forces the iodine atoms into a linear arrangement in the central groove of the amylose coil. There is some transfer of charge between the starch and the iodine. That changes the way electrons are confined, and so, changes spacing of
the energy levels. The iodine/starch complex has energy level spacings that are just so for absorbing visible light- giving the complex its intense blue color.
The complex is very useful for indicating redox titrations that involve iodine because the color change is very sharp. It can also be used as a general redox indicator: when there is excess oxidizing agent, the complex is blue; when there is excess reducing agent, the I5- breaks up into iodine and iodide and the color disappears.
Author: Fred Senese senese@antoine.frostburg.edu