Preparation of peracetic acid from hydrogen peroxide: Part I: Kinetics for peracetic acid synthesis and hydrolysis

A homogeneous kinetic model for preparation of peracetic acid (PAA) from acetic acid (AA) and hydrogen peroxide (HP) under the catalysis of sulfuric acid (SA) in the liquid phase was investigated. The kinetic equations of PAA synthesis and hydrolysis were given and the kinetic constants were estimated according to the experimental data by a simplex optimization method. It was found that the synthesis and hydrolysis of PAA were both first-order reactions with respect to reactant concentrations and H+ concentration. Linear relationships were discovered between the observed rate constants and H+ concentrations at a certain temperature, with the slopes being corresponding intrinsic rate constants. The intrinsic activation energies of PAA synthesis and hydrolysis were 57.8 and 60.4 kJ mol−1, respectively. The mechanisms of PAA synthesis and hydrolysis were discussed. It has been proved that the rate-determining step in the synthesis of PAA is the reaction between H2O2 with active carbonyl intermediary, and in the hydrolysis of PAA the reaction between water and corresponding active carbonyl intermediary.

Graphical abstractA homogeneous kinetic model for sulfuric acid-catalyzed preparation of peracetic acid by the reaction of hydrogen peroxide and acetic acid in the liquid phase was developed. The kinetic constants were determined by fitting the experimental data. Sufficient accuracy was obtained by using the model to describe the concentrations of peracetic acid in the reaction system, as shown in the following figure. Figure optionsDownload full-size imageDownload as PowerPoint slide