Advances in Catalysis and Related Subjects, Volume 4 by W G Frankenberg

By W G Frankenberg

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As will be seen, there is now much evidence for the existence of radicals in some of the reactions of hydrogen peroxide, and their presence in others, although not yet proved, must be considered as a possibility. However, although the Haber-Willstatter chain reactions have been assumed to occur in certain catalytic systems, notably tbe ferrous-ferric ion system (4), more recent evidence to be described subsequently, does not support this assumption. On the other hand, such reactions appear to offer the most plausible explanation for the photochemical decomposition of hydrogen peroxide, although even here a satisfactory analysis of the kinetics has yet to be made.

Bray and Caulkins (30) observed that during the 44 J. H . BAXENDALE reaction the solution is faintly colored with iodine. Subsequent work by Liebhafsky (31) showed that provided the iodine was removed as it forms, the iodate can be almost quantitatively reduced to iodine according t o the equation: 2103’ + 5HZO2+ 2H++ Iz + 6Hz0 + 5 0 2 (1) On the other hand, in acid solution iodine is slowly oxidized to iodate by hydrogen peroxide. The oxidation can be speeded up considerably by high acidities and also by the addition of iodate.

11. Halides and Halogens.. . . . . . . . . . . . . . . . . . . . . . . Paw 31 35 1. , . . . . . . . . . . . 2. Reduction of Halogens by Hydrogen Peroxide.. . . . . . . . . . . 3. The Steady State . . . . . . . . . . . . . . . . . . . . . . . . 36 37 37 ..................... 43 2. Active Intermediates. . . . . . . . . . . . . . . . . . . . . .

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