Poly(vinyl alcohol)–iodine complexes

Abstract The poly(vinyl alcohol)–iodine blue color reaction in dilute aqueous solution has been investigated, and extinctions at the absorption maximum have been measured as a function of the concentrations of polymer, iodine, iodide ions, and boric acid. Depending upon the reaction conditions, the main absorption maximum can be made to appear at any wavelength between 580 and 700 mμ, with the longest wavelengths and highest extinctions per vinyl alcohol group showing up at high boric acid concentrations. Poly(vinyl alcohol) samples from various sources displayed, under identical reaction conditions, great differences in staining intensities. This can be ascribed to differences in the regularity of the polymer chain structures. To account for the behavior of poly(vinyl alcohol) towards iodine under a wide variety of reaction conditions, as well as for a number of irreversible or only slowly reversible phenomena, a model for the mechanism of the PVA–iodine complex formation is proposed involving a dual process of helix formation and intramolecular helix association. There is evidence to indicate that at full iodine saturation of the polymer, 12 vinyl alcohol residues supported by one boric acid molecule form a single turn of a helix which enwraps one iodine atom, out of a long polyiodide chain nested in the interior of a poly(vinyl alcohol) helix.