Rate constants of reactions of carboxymethylcellulose with hydrated electron, hydroxyl radical and the decay of CMC macroradicals. A pulse radiolysis study

Abstract

The method of pulse radiolysis was used to study radiation-induced transformations of carboxymethylcellulose (CMC) of various degree of substitution (DS) in aqueous solution. The kinetics of the reactions of intermediate products of water radiolysis with this polymer indicated that hydroxyl radicals react very rapidly with the CMC, i.e. the rate constant is about 1×10 9 dm 3 mol −1 s −1 and independent of the DS of the CMC. On the other hand, the hydrated electron can be practically neglected as a precursor for macroradicals formation since its reaction rate constant with CMC is low, i.e. 4.0–5.0×10 6 dm 3 mol −1 s −1. As the result of OH radicals attack on the CMC, radicals on the main-chain, as well as on side groups (carboxymethyl) are formed. Environmental conditions determine the life-time of macroradicals, typically tens of minutes were detected. Most importantly, the pH level of the solution was observed to determine the preferential reaction pathway. Lowering the pH led to increased macroradicals recombination and gel formation.