The Periodate-Glycol Reaction. 5. Complex Formation and Kinetic Analyses of 1,2-Propanediol and 1,2-Butanediol

Abstract

The reactions of periodate with 1,2-propanediol and 1,2-butanediol were investigated in detail. These reactions are similar to that of ethanediol in that there are extensive formations of a periodate−glycol complex, and the IO4- form of periodate appears to be the primary reactant. However, they differ at pH 5.4 in that a small induction period was noted and rate equations previously used with ethanediol were inapplicable. At pH 1.08, the reactions proceeded similarly to ethanediol without a noticeable induction period. All data were fitted using a finite difference simulation (FDS) technique, and rates of the complex's formation, dissociation, and conversion to products have been evaluated at three temperatures. When feasible, the FDS rate constants were found to compare favorably to those obtained from an analytical integration procedure. The activation energies for product formation and the enthalpies of complex formation are similar to those of ethanediol.