Kinetics of Formic Acid-autocatalyzed Preparation of Performic Acid in Aqueous Phase

Performic acid (PFA) is an oxidant used in chemical processing, synthesis and bleaching. The macro kinetic models of synthesis, hydrolysis and decomposition of PFA were investigated via formic acid-autocatalyzed reaction. It was found that the intrinsic activation energies of PFA synthesis and hydrolysis were 75.2 kJ·mol−1 and 40.4 kJ·mol−1 respectively. The observed activation energy of PFA decomposition was 95.4 kJ·mol−1. The experimental results indicated that the decomposition of PFA was liable to occur even at the ambient temperature. Both the spontaneous decomposition and the radical-introduced decomposition contributed to the decomposition of PFA.