PVA unveiled the actual role of starch in the Briggs-Rauscher reaction
The Briggs Rauscher reaction (BR reaction) is one of the famous oscillating reactions; the aqueous mixture of KIO3, H2SO4, H2O2, C3H4O4, MnSO4, and starch exhibit color change between yellow and blue-purple repeatedly. The blue-purple color formation is due to the iodine test reaction caused by inclusions of polyiodides such as I3- and I5- in the helical structure of starch.
Therefore, starch has been regarded as only an indicator in the BR reaction. But our seniors have found that the oscillation did not last without starch. They hypothesized that starch’s linear helical framework is necessary to elongate the lifetime of the oscillating reaction. If this hypothesis is correct, similar BR-type oscillations must be observed when other polymers with helical structures are used instead of starch.
We found the literature which reports that polyvinyl alcohol (PVA) forms a helical structure and indicates the iodine test reaction. In our research, we studied the BR reactions using PVA, with different saponification degrees and viscosities. First, we studied the correlation between the structural features of PVA and the iodine color reaction by spectroscopic approach, exhibiting that PVA with low saponification form helical structures and show the iodine color reactions, which gives red color solutions. Second, we found that additions of the helical-structured PVA to the reaction solution instead of starch induces the BR-type oscillating reactions, while PVA without helical structure induces only a few numbers of oscillations. This is the world-first example of the oscillating reaction using PVA. The oscillation that lasted for 6 minutes with 23 oscillations was almost the same as that of the general BR reaction using starch. We concluded that the polymers with helical structures are intrinsic to elongate the lifetime of the BR reaction.
Furthermore, we found that the addition of K3[Fe(CN)6], which has a high redox activity, in the reaction solution with PVA drastically elongated the lifetime (50 min) and increased the numbers of the oscillations (nearly 100 times). This result suggests that the oxidation-reduction reactions by the ferricyanide ion promotes the redox process of iodine and iodide ions.