Bulletin of the Chemical Society of Japan p. 2068 - 2073 (1982)
Update date:2022-08-11
Topics:
Kimura, Masaru
Kobayashi, Akiko
Boku, Keiko
Kinetic studies of the oxidation reaction of L-ascorbic acid by the peroxodisulfate ion(S2O82-) are carried out in an aqueous solution over the pH range of 3.4-4.6 at various ionic-strengths from 0.071 to 1.07 M (1 M=1 mol dm-3) with NaClO4, and at four temperatures between 15 and 30 deg C, at an ionic-strength of 1.07 M.The variations in the rate of the oxidation with the hydrogen-ion concentrations are consistent with the reaction schemes involving two pH-related species; ascorbic acid H2A (k1=0.032 M-1 s-1 at 25 deg C, ΔH<*>1=17 kJ mol-1, ΔS<*>1=-220 J deg-1 mol-1) and the ascorbic anion HA- (k2=0.43 M-1 s-1 at 25 deg C, ΔH<*>2=45 kJ mol-1, ΔS<*>2=-102 J deg-1 mol-1).A relationship of log k2=-1.47+2.17 I1/2/(1+I1/2) is found with the ionic-strength (I) at 25 deg C.The reaction rate is greatly catalyzed by the presence of trace amounts of the copper(II) ion; the mechanisms of the copper(II)-catalyzed reaction are discussed.
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