TL;DR: The complete potential diagram enables complex systems to be rationalized, such as production of OH by H2O2 plus Fe3+.
Abstract: Successive one-electron reductions of molecular oxygen yield the superoxide radical (O2-) H2O2, the hydroxyl radical (OH) and water. Redox potentials at pH 7 for one-, two- and four-electron couples involving these states are presented as a potential diagram. The significance of each of these potentials is explained. The complete potential diagram enables complex systems to be rationalized, such as production of OH by H2O2 plus Fe3+.
TL;DR: In this paper, a simple formalism for a two phase redox equilibrium system in the presence of a partitioning ion is presented, where the role of the partitioning ions is to fix the interfacial Galvani potential difference, thereby determining the position of the equilibrium.
TL;DR: The ionic partition diagram methodology has been generalized to address both hydrophilic and lipophilic compounds and to consider biphasic systems with variable phase volume ratios and an interesting consequence is the definition of an extraction pK(a,ext) which is the apparent pk(a) of neutral acids and bases when dissolved in the organic phase.
Abstract: The ionic partition diagram methodology has been generalized to address both hydrophilic and lipophilic compounds and to consider biphasic systems with variable phase volume ratios. With this generalized approach electrochemical measurements of ion transfer potentials afford the determination of the standard partition coefficients of all forms of ionizable molecules, including the neutral form, as well as the evaluation of the dissociation constant of monoprotic substances. An interesting consequence of this approach is the definition of an extraction pKa,ext which is the apparent pKa of neutral acids and bases when dissolved in the organic phase.
TL;DR: In this article, Sildenafil (Viagra) was examined for its ionization and lipophilicity by two-phase titration and electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) in the 12-dichloroethane/H2O system.
Abstract: Sildenafil (Viagra(TM)) was examined for its ionization and lipophilicity by two-phase titration and electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) in the 12-dichloroethane/H2O system. The dissociation constants (basic pK(a) = 6.78, acidic pK(a) = 9.12) and partition coefficients of the various species, together with the effects of electrical potential, were used to construct an ionic partition diagram (pH-potential representation). This allowed to interpret the transfer mechanisms of sildenafil at liquid/liquid interfaces, suggesting in particular that an intramolecular H-bond influences the lipophilicity of the neutral and cationic species. Conformational calculations confirmed this hypothesis