Reaction of water soluble polymers with oxidising agents: reaction of dextran with tetravalent cerium

Abstract

Dextran, an extracellular bacterial polysaccharide, was subjected to reaction with ceric ammonium nitrate in aqueous nitric acid at varying temperatures. The polymer has been found to be degraded due to the selective oxidative cleavage of vicinal glycol units present in the monosaccharide unit of each chain. The aldehyde groups produced upon cleavage at low temperature were found to undergo further oxidation to acids and formic acid with rise in temperature of the reaction. The course of the reaction has been followed by cerimetry and by spectrophotometrical measurements. The effect of the concentration of reacting components on the reaction has been studied and various kinetic aspects have been evaluated. Depending on the kinetic results, a plausible reaction mechanism for the oxidative degradation and the subsequent reactions have been suggested by the study of the changes of solution viscosity and initiation of graft copolymerization of vinyl monomers by Ce(IV)/dextran mixture. Various thermodynamic parameters have been evaluated.