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By Richard C. Alkire, Charles W. Tobias

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

'This is a vital e-book for researchers in electrochemistry; it covers components of either primary and functional significance, with studies of top of the range. the cloth is especially good awarded and the alternative of issues displays a balanced editorial coverage that's welcomed.' The Analyst

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Extra resources for Advances in Electrochemical Science and Engineering, Volume 5

Example text

According to Eq. (54) the “effective” PF value may be approximately described as follows: Figure 14 shows the relationship between PF values and the rate of separation calculated from the standard Debye equation (ksep = kdiff = 8RT/3). The slope of the solid line corresponds to the value of 1 x 101°~-1s-’, which agrees well with the triplet-triplet up conversion rates found for aromatic hydrocarbons [ 1311. The kupc estimated on this way seems to be constant in all solvents as well as over the whole range of temperatures studied; possible differences were less than the experimental errors.

6. Logarithm of the electron transfer rate as a function of the reaction exothermicity, without (H = 0) and with (H > 0) limitation caused by the solvent molecular dynamics. The case S = 0 corresponds to neglect of the vibrational excitation. If S = 1 the vibrational excitation is taken into account. Vibrational excitation of the high-frequency intramolecular modes accompanying the electron transfer lowers the energy gaps in the inverted Marcus region. It results in the lowering of the effective activation energy and in the relative enhancement of the reaction rate.

According to Eqs. (47) and (48), both 4sand are given by the ratio of the rate constants for electron transfer processes producing the excited-state and 28 A. Kapturkiewicz the ground-state products: and In Eqs. (47) and (48)the factor 9 connected to the k n rate may be not exactly correct. For two interacting triplets nine encounter pair spin states (which constitute the sublevels of encounter pairs with quintet, triplet, and singlet multiplicities) are formally possible. However, two from the quintet sublevels (with the spin quantum numbers 2) may not be directly accessible because of the spin conservation rule.

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