By Noyes W

ISBN-10: 1061301311

ISBN-13: 9781061301312

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This method is simple to apply as long as the selected enthalpies of formation of CHCl3, CH3•, and CH4 are known either from experiment or high quality firstprinciple estimates. The success of the isodesmic strategy is controlled by several factors including the accuracy of ΔfH° for the reference species, level of the ab initio theory, size of the basis set used to calculate the electronic energy difference, and accuracy of the molecular vibration corrections. One should also bear in mind that it is often possible to use several different isodesmic reactions to estimate the enthalpy of formation of the same species.

III. On the disproportionation of molecular iodine added to seawater. Mar. Chem. 1995, 51, 55–60. Truesdale, V. ; Luther, G. , III; Greenwood, J. E. The kinetics of iodine disproportionation: a system of parallel second-order reactions sustained by a multi-species pre-equilibrium. Phys. Chem. Chem. Phys. 2003, 5, 3428–3435. Brookins, D. G. Eh-pH diagrams for Geochemistry. Springer-Verlag: Berlin, 1988; p176. Luther, G. , III; Cole, H. Iodine speciation in Chesapeake Bay waters. Mar. Chem. 1988, 24, 315–325.

The quantitative property that is most often used to describe the rate-limiting SET steps in these contaminant redox reactions is the one-electron reduction potential (E1) for the corresponding half-reaction (24, 25). Experimental values of E1 for these half-reactions are relatively scarce, but there are a number of methods by which they can be obtained (26, 27). E1 data can be obtained from voltammetry, but aprotic solvents are usually necessary to stabilize the radical intermediates (3, 26, 28, 29), or from pulse radiolysis, but this method usually requires the use of an intervening mediator compound (19, 26, 30).

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Advances in Photochemistry by Noyes W


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