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Abstract: The electron transfer reaction between bis(phthalocyaninato)lutetium(III) ([Lu(pc)2]0) in 1,2-dichloroethane (1,2-DCE) and hexacyanoferrate(II/III) redox couple ([Fe(CN)6]4−/3−) in water (W) at the interface was studied by the use of normal pulse voltammetry and ac-voltammetry. The ac-voltammetric results have reconfirmed that the electron transfer reaction between [Lu(pc)2] in 1,2-DCE and [Fe(CN)6]4−/3− in W takes place by way of the heterogeneous electron transfer at the interface, but not by the homogeneous electron transfer reaction associated with the ion transfer of redox species across the interface. The kinetic parameters of the heterogeneous electron transfer reaction at the interface were determined. [Copyright &y& Elsevier]

Abstract: The electron transfer (ET) reaction between bis(butylcyclopentadienyl)iron(II) ([FeII(C5H4Bu)2]) in 1,2-dichloroethane (1,2-DCE) and the hexacyanoferrate redox couple ([FeII/III(CN)6]4−/3−) in water (W) at the 1,2-DCE∣W interface has been studied by use of normal pulse voltammetry and cyclic voltammetry. In normal pulse voltammetry, S-shaped current vs. potential curves with well-defined limiting currents attributable to the interfacial ET reaction were observed. The voltammetric results can be explained well by the theoretical equations [M. Senda, Rev. Polarogr. (Jpn), 49 (2003) 219; 50 (2004) 60] according to a so-called IT-mechanism, that is, the [FeII(C5H4Bu)2] molecule is transferred from the 1,2-DCE to the W phase across the interface, then the ET reaction takes place homogeneously in the W phase between [FeIII(CN)6]3−(W) and [FeII(C5H4Bu)2](W) to produce [FeII(CN)6]4−(W) and [FeIII(C5H4Bu)2]+(W), which is followed by the transfer of the [FeIII(C5H4Bu)2]+ ion from the W to the 1,2-DCE phase across the interface to give the voltammetric current. Experimental results from cyclic voltammetry are also explained well by the IT-mechanism. [Copyright &y& Elsevier]

The usefulness of 1,6-dichlorohexane (1,6-DCH) and 1,4-dichlorobutane (1,4-DCB) as organic solvent (O) for ion-transfer voltammetry at O|water (W) interface has been examined, and the results are compared with those with 1,2-dichloroethane (1,2-DCE). The width of potential window of the 0.1 M tetraoctylammonium tetrakis(4-chlorophenyl)borate (O)|0.05 M Li2SO4 (W) interface increased in the sequence: O = 1,6-DCH > 1,4-DCB > 1,2-DCE. The voltammetric behavior of the transfer of various cations and anions at the 1,6-DCH|W and 1,4-DCB|W interfaces has been shown to be of reversible nature, and the midpoint potentials or the reversible half-wave potentials have been determined. The midpoint potentials of hydrophilic ions have also been determined by the analysis of anodic final rise or cathodic final decent of the voltammograms with the O|W interfaces, where the W contains a salt of the hydrophilic ion. Also, the effect of ion-pair formation in O on the midpoint potentials has also been discussed. [Copyright &y& Elsevier]