ISSN:
0538-8066
Schlagwort(e):
Chemistry
;
Physical Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Analysis is made of reported results on the kinetics and mechanism of ascorbic acid oxidation with oxygen in the presence of cupric ions. The diversities due to methodological reasons are cleared up. A kinetic study of the mechanism of Cu2+ anaerobic reaction with ascorbic acid (DH2) is carried out. The true kinetic regularities of catalytic ascorbic acid oxidation with oxygen are established at 2.7 ≤ pH 〈 4, 5 × 10-4 ≤ [DH2] ≤ 10-2M, 10-4 ≤ [Cu2+] ≤ 10-3M, and 10-4 ≤ [O2] ≤ 10-3M: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_0 = {}_{K1}[{\rm Cu}^{{\rm 2} +}][{\rm DH}_2][{\rm O}_2]{}^{0.5}/[{\rm H}^ +] $$\end{document} wherek1 (25°C) = 0.13 ± 0.01 M-0.5·sec-1. The activation energy for this reaction is E1 = 22 ± 1 kcal/mol. It is found by means of adding Cu+ acceptors (acetonitrile and allyl alcohol) that the catalytic process is of a chain nature. The Cu+ ion generation at the interaction of the Cu2+ ion with ascorbic acid is the initiation step. The rate of the chain initiation at [Cu2+] ± 10-4M, [DH2] ± 10-2M, 2.5 〈 pH 〈 4, is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_{\rm i} = {}_{K{\rm i,1}}[{\rm Cu}^{{\rm 2} +}]^2 [{\rm DH}_2]/[{\rm H}^ +] $$\end{document} whereki,1 (25°C) = (1.8 ± 0.3)M-1·sec-1, Ei,1 = 31 ± 2 kcal/mol. The reaction of the Cu+ ion with O2 is involved in a chain propagation, so that the rate of catalytic ascorbic acid oxidation for the system Cu2+—DH2—O2 is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_{\rm 0} = {}_{k{\rm 1}}[{\rm Cu}^ +][{\rm O}_2] $$\end{document} wherek1 (25°C) = (5 ± 0.5) × 104 M-1·sec-1. The Cu+ ion and a species interacting with ascorbate are involved to quadratic chain termination. By means of photochemical and flow electron spin resonance methods we obtained data characteristic of the reactivities of ascorbic acid radicals and ruled out their importance for the catalytic chain process. A new type of chain mechanism of catalytic ascorbic acid oxidation with oxygen is proposed: .
Zusätzliches Material:
16 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/kin.550110503
