Kinetics of Formation of Peroxyacetic Acid

The kinetics of the reaction of acetic acid with hydrogen peroxide, leading to peroxyacetic acid, were studied at various molar reactant ratios (AcOH-H₂O₂ from 6 : 1 to 1 : 6) at 20, 40, and 60°C and sulfuric acid (catalyst) concentrations of 0 to 9 wt %. The reaction is reversible, and the equilibrium constant decreases as the temperature rises: K = 2.10 (20°C), 1.46 (40°C), 1.07 (60°C); Δ_r H ⁰ = − 13.7±0.1 kJ mol⁻¹, Δ_r S = −40.5±0.4 J mol⁻¹ K⁻¹. The maximal equilibrium concentration of peroxyacetic acid (2.3 M) is attained at 20°C and a molar AcOH-to-H₂O₂ ratio of 2.5 : 1. The rate constants of both forward and reverse reactions increase with increase in sulfuric acid concentration from 0 to 5 wt %. Further raising the catalyst concentration does not affect the reaction rate. The reaction mechanism is discussed.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1187–1193.Original Russian Text Copyright © 2005 by Dul’neva, Moskvin.