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Advances in Electrochemical Science and Engineering, Volume by Richard C. Alkire, Charles W. Tobias

By Richard C. Alkire, Charles W. Tobias

This sequence, previously edited through Heinz Gerischer and Charls V. Tobias, now edited by way of Richard C. Alkire and Dieter M. Kolb, has been warmly welcomed through scientists world-wide that is mirrored within the reports of the former volumes:

'This is an important booklet for researchers in electrochemistry; it covers components of either primary and functional significance, with experiences of top quality. the fabric is especially good provided and the alternative of themes displays a balanced editorial coverage that's welcomed.' The Analyst

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24 A. Kapturkiewicz according to Eq. 959 [107,108]. where tf is the duration of the first (forward) step of the triple-step sequence and tr is the time span of the second (reverse) step. In the case of the “pure” T-route (treated as a superposition of two bimolecular reactions) as well as for the “mixed” ST-route, ~ nonlinear [109]. This criterion may plots of the ECL intensities I ( & ) vs. ( ~ / t , ) ’ ’are be used to distinguish the S-route from the T- or ST-routes in ECL experiments. However, similar deviations from linearity are also caused by a reactant’s instability.

Solvent name abbreviations: ACN, acetonitrile; BL, y-butyrolactone; BN, butyronitrile; DME, 1,2-dimethoxyethane; DMF, N,Ndimethylformamide; NMP, N-methylpyrrolidone; THF, tetrahydrofuran; a, benzene; aCH3 toluene; QCN, benzonitrile. Adapted from [123]. As discussed above, the experimental values of the excited-state yields q5es are connected to competition between the parallel electron transfer processes. To a first approximation,in the case of DPA the q5ecl is given by the ratio of the rate constants of reactions (33), (34) and (35): 4ecl = 4es4o = kl/(kl + 3k3 + ko) (45) In Eq.

Integration of Eq. 4 nfi, M 2 -31n(10) c 4 % ~ (A0 - AG12 +jhvi - hCfia)2 4X, RT ~ 1 (17) The quantity ~ ( f i , ) is defined by log(Z/Zo) = -&(fia)CL, where C is the molar concentration of the solute, Z and ZO are the transmitted and incident light intensity, and L is the optical path length. From Eqs. (15) and (17) simple approximate expressions for the absorption fi," and emission fiymaxima may be obtained: h c f i y M -AG12 + A, + Xi and hcvfmaX M -AG12 - A, - Xi (18) Both maxima are also simply connected with AG12, allowing the independent determination of this quantity from the spectroscopic data: AG12 x -[hcfi?

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