Download Active Oxygen in Chemistry by Raymond Y. N. Ho, Joel F. Liebman, Joan Selverstone PDF

By Raymond Y. N. Ho, Joel F. Liebman, Joan Selverstone Valentine (auth.), Christopher S. Foote, Joan Selverstone Valentine, Arthur Greenberg, Joel F. Liebman (eds.)

Taking an interdisciplinary process, this publication and its counterpart, Active Oxygen in Biochemistry, discover the energetic learn sector of the chemistry and biochemistry of oxygen. Complementary yet autonomous, the 2 volumes combine topic parts together with drugs, biology, chemistry, engineering, and environmental studies.

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J. Chem. , 40, 146-149. PRIESTLEY, J. (1776) Experiments and Observations on Different Kinds of Airs, J. Johnson, London. SAWYER, D. T. (1991) Oxygen Chemistry, Oxford University Press, New York. SAWYER, D. , ANGELIS, C. , NANNI, E. , and TsuSHIYA, T. (1982) Effects of Media and Electrode Materials on the Electrochemical Reduction of Dioxygen. Anal. , 54, 1720-1724. SAWYER, D. , and VALENTINE, J. S. (1981) How Super Is Superoxide? Acc. Chem. , 14, 393-400. SCHEELE, C. W. (1777) Chemische Abhandlung von der Luft und Feuer.

At first glance, one might expect that comparison of k" values in Table 2-1 would provide an accurate measure of the relative reactivities of R-H bonds toward peroxy radical attack. However, it turns out that this is clearly not the case. Changing the substrate changes not only R-H but also ROO·, and the reactivities of peroxy radicals vary to a surprising degree with their structure. An ingenious way of measuring the rates of reaction of a number of substrates toward a single peroxy radical has been devised by Howard and Ingold [ef.

Curve A: "pure" hydrocarbon; curve B: with added initiator; curve C: with initiator and inhibitor. following set of equations, where Eq. (2-4) is the initiation step producing radicals from some source at rate Ri • Initiation: rate = Rj , Propagation: R· (2-4) + O2 - R-OO· (2-1) R-OO·, + R-H - R-OOH Termination: 2R-00'- X, R-OO· + R· - + R·, (2-2) (2-5) Y, 2R·-Z. (2-6) (2-7) As we shall see, kl » k21 so that at any appreciable O2 pressure [R-OO·] » [R·] and the only termination step that needs to be considered is reaction (2-5).

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