By W G Frankenberg
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Extra info for Advances in Catalysis and Related Subjects, Volume 4
Further although the above free radical reactions for the reduction of the halogens will explain the experimental results in certain concentration ranges, no radical mechanism has yet been suggested to include the more extended observations of Connick. On the other hand the experiments of Griffiths and McKeown (23,29) would indicate that in the photochemical bromide-bromine catalysis radicals and atoms do participate. The position at present in this field is that it is well established that the catalytic decomposition of hydrogen peroxide in halide-halogen systems is the result of compensating reactions which can be written stoichiometrically as Eqs.
Paw 31 35 1. , . . . . . . . . . . . 2. Reduction of Halogens by Hydrogen Peroxide.. . . . . . . . . . . 3. The Steady State . . . . . . . . . . . . . . . . . . . . . . . . 36 37 37 ..................... 43 2. Active Intermediates. . . . . . . . . . . . . . . . . . . . . . . . . 62 VI. Copper Compounds.. . . . . . . . . . . . . . 71 VII. ,. . . . . . .
A) above, and have determined klo, k,, and the constants in the Arrhenius equation k = A exp ( - E / R T ) in each case. These are given in Table I. The numerical values for chloride and bromide do not agree exactly with those obtained by other workers, the reason being that the rate constants vary with ionic strength. Livingston and Bray (8,15) have considered this salt effect in some detail and have shown that it is of the order expected on the Bronsted theory. The iodide reaction was thought to be anomalous in that no salt effect could be observed (16).
Advances in Catalysis and Related Subjects, Volume 4 by W G Frankenberg