The kinetics of the reaction of acetic acid with hydrogen peroxide, leading to peroxyacetic acid, were studied at various molar reactant ratios (AcOH3H 2 O 2 from 6 : 1 to 1 : 6) at 20, 40, and 60oC 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 (20oC), 1.46 (40oC), 1.07 (60oC); D r H 0 = 313.7 + 0.1 kJ mol !1 , D r S = 340.5 + 0.4 J mol !1 K !1 . The maximal equilibrium concentration of peroxyacetic acid (2.3 M) is attained at 20oC and a molar AcOH-to-H 2 O 2 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.
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