Download e-book for kindle: Advances in Electrochemical Science and Engineering, Volume by Richard C. Alkire, Charles W. Tobias

By Richard C. Alkire, Charles W. Tobias

ISBN-10: 352729385X

ISBN-13: 9783527293858

ISBN-10: 3527616799

ISBN-13: 9783527616794

ISBN-10: 3527616888

ISBN-13: 9783527616886

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 by means of scientists world-wide that is mirrored within the stories of the former volumes:

'This is a vital booklet for researchers in electrochemistry; it covers parts of either basic and useful significance, with reports of top quality. the fabric is especially good offered and the alternative of subject matters displays a balanced editorial coverage that's welcomed.' The Analyst

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

Example text

Analogously W ~ ( I - 1 2 is ) the energy required to bring the products into the precursor complex. Both quantities ~ ~ ( 1 - 1 and 2 ) ~ ~ ( 2 1 correspond 2) mainly to electrostatic interactions; thus their values may be calculated using the familiar Coulomb expression. , cation and anion radicals) it takes the form: In the case of neutral organic ECL systems the wp(r12) value may be neglected, but it should be taken into account in the case of charged transition-metal complexes. The driving forces AGl and AG3 for reactions (33) and (34) can be calculated in a similar way, using the corresponding energies El and E3 of both (singlet and triplet) excited states: Equations (40) and (41) are not exactly correct because of the mixing of Gibbs energy and energy terms.

ECL data for other intramolecular donor-acceptor systems (shown in Fig. 19) indicate that the rate k3 depends upon the reaction exothermicity AG3 in a manner consistent with the Marcus inverted region [138] (according to Eq. (67) k3/kcT = (1 - 44es)/34es). It was possible [138] to evaluate those rates (and also to predict the experimentally observed q ! ~ ~ ~from ) pertinent electrochemical and spectroscopic data. The necessary thermodynamic quantities may be evaluated using the literature data for relatively well-understood electron exchange between the neutral species (A or D) and its own radical anion or cation (A- or D+, respectively), but a somewhat different approach seems to be more accurate.

For the solvent name The reaction mechanism described above also allows an explanation for the influence of the magnetic field on ECL efficiencies. In the case of DPA, the absence of magnetic field effects [104,114] in ECL supports the dominance of the S-route. Moreover, results reported in [ 104,112,1331 for the rubrene ECL system are not in conflict with the reaction mechanism proposed; it can be explained by assuming that Marcus Theory in the Description of Electrochemiluminescence Phenomena 33 triplet-triplet annihilation (within a triplet encounter pair) is being altered in the magnetic field.

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Advances in Electrochemical Science and Engineering, Volume 5 by Richard C. Alkire, Charles W. Tobias

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