Rates of inorganic oxidation reactions

Eary, L. E., and Schramke, J. A., 1990, Rates of Inorganic Oxidation Reactions Involving Dissolved Oxygen in Melchior, D. C., and Bassett, R. L., eds., Chemical Modeling of Aqueous Systems II, American Chemical Society Symposium 416, p. 379-396. 

Rates of Inorganic Oxidation Reactions Involving Dissolved Oxygen... 

LE Eary, JA Schramke. Rates of inorganic oxidation reactions involving dissolved oxygen. In DC Melchior, RE Bassett, eds. Chemical Modeling of Aqueous Systems, II. Washington, DC American Chemical Society, 1990, pp 379-396. 

This reaction prevents the recombination of H and OH radicals to form water molecules and hence, increases the rate of other oxidation processes. In general, free radical reactions similar to those shown for water could occur with any organic or inorganic species capable of being present as a vapor during bubble collapse. 

Pulse radiolysis is the radiation chemical analogue of flash photolysis. It is a fast-kinetics technique that enables transitory processes, initiated by the absorption of ionizing radiation, to be observed in time frames as short as the submicrosecond region. It permits the detection and characterization of short-lived intermediates, the determination of the kinetics of their decay, and a probing of reaction mechanisms. The technique finds use in the study of radiation effects on materials, and as a tool for the examination of mechanistic details. For inorganic systems, pulse radiolysis is used to characterize metal complexes in unusual oxidation states, to examine the kinetics and rates of ligand-labilization reactions and to elucidate the mechanism of electron transfer. 

The nature and properties of metal complexes have been the subject of important research for many years and continue to intrigue some of the world s best chemists. One of the early Nobel prizes was awarded to Alfred Werner in 1913 for developing the basic concepts of coordination chemistry. The 1983 Nobel prize in chemistry was awarded to Henry Taube of Stanford University for his pioneering research on the mechanisms of inorganic oxidation-reduction reactions. He related rates of both substitution and redox reactions of metal complexes to the electronic structures of the metals, and made extensive experimental studies to test and support these relationships. His contributions are the basis for several sections in Chapter 6 and his concept of inner- and outer-sphere electron transfer is used by scientists worldwide. 

Oxidation. Hydrogen peroxide is a strong oxidant. Most of its uses and those of its derivatives depend on this property. Hydrogen peroxide oxidizes a wide variety of organic and inorganic compounds, ranging from iodide ions to the various color bodies of unknown stmcture in ceUulosic fibers. The rate of these reactions may be quite slow or so fast that the reaction occurs on a reactive shock wave. The mechanisms of these reactions are varied and dependent on the reductive substrate, the reaction environment, and catalysis. Specific reactions are discussed in a number of general and other references (4,5,32—35). 

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