Organic compounds half-wave potentials

TABLE 8.31 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C The solvent systems in this table are listed below ... 

Section 8 now combines all the material on electrolytes, electromotive force, and chemical equilibrium, some of which had formerly been included in the old Analytical Chemistry section of earlier editions. Material on the half-wave potentials of inorganic and organic materials has been thoroughly revised. The tabulation of the potentials of the elements and their compounds reflects recent lUPAC (1985) recommendations. 

The half-wave potentials observed with some selected organic compounds... 

The role of the pH of the medium in the electrode reactions of organic compounds in aqueous solutions is well understood and has been recently reviewed in detail (Zuman, 1969). In particular, our understanding of this parameter is due to the large number of polarographic investigations where it has been found that the half-wave potential, the limiting current and the shape of the wave for an oxidation or reduction process may all be dependent on the acidity of the medium. 

Relation between the LUMO and the half-wave potential of the first reduction wave When an organic compound, Q, is reduced, it accepts an electron from the electrode to its lowest unoccupied molecular orbital (LUMO). Here, the energy of the LUMO of Q corresponds to its electron affinity (EA). If the energies of LUMO ( lu) for a series of analogous compounds are obtained by the molecular orbital method, there should be a relationship ... 

It is certain that, in the first reduction step in aprotic solvents, an electron is accepted by the LUMO of the organic compound. However, it was fortunate that this conclusion was deduced from studies that either ignored the influence of solvation energies or used the results in different solvents. Recently, Shalev and Evans [55] estimated the values of AG V(Q/Q ) for 22 substituted nitrobenzenes and nine quinones from the half-wave potentials measured by cyclic voltammetry. For quinones and some substituted nitrobenzenes, the values of AG V(Q/Q ) in a given solvent were almost independent of the EA values. Similar results had been observed for other aromatic hydrocarbons in AN (Section 8.3.2) [56]. If AG V(Q/ Q ) does not vary with EA, there should be a linear relation of unit slope between El/2 and EA. Shalev and Evans [55], moreover, obtained a near-linear relation between AG V(Q/Q ) and EA for some other substituted nitrobenzenes. Here again, the Ey2-EA relation should be linear, although the slope deviates from unity.8)... 

For an organic compound (Q) in dipolar aprotic solvents, the half-wave potential ( 1/2) of the first reduction step tends to shift to the positive direction with an increase in solvent Lewis acidity (i.e. acceptor number). This is because, for the redox couple Q/Q, the reduced fonn (Q ) is energetically more stabilized than the oxidized fonn (Q) with increasing solvent acidity. The positive shift in E1/2 with solvent acceptor number has been observed with quinones [57 b], benzophenone [57 a, c] and anthracene [57 c], With fullerene (C60), the positive shift in E1/2 with solvent acidity parameter, ET, has been observed for the reductions of C60 to Qo, Qo to Clo, and Cf)0 to Cli, [54c], However, the positive shift in E1/2 is not apparent if the charge in Q is highly delocalized, as in the cases of perylene and fluoren-9-one [57 c]. 

Fig. 8.17 Relationship between the half-wave potential and the standard rate constant for the first reduction wave of various organic compounds in AN. The influence of R4N+ of the supporting electrolyte [61 a). Compounds 1, hexafluorobiacetyl 2, p-benzoquinone 3, 1,4-naphthoquinone 5, oxygen 6, 9,10-anthra-quinone 8, p-nitrotoluene 9, 4,4 -methoxyben-zyl 10, 2,3-butanedione 11, nitromesitylene ...

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