title: Analysis of electron transfer processes across liquid/liquid interfaces: estimation of free energy of activation using diffuse boundary model.
abstract: The evaluation of the free energy of activation pertaining to the electron-transfer reactions occurring at liquid/liquid interfaces is carried out employing a diffuse boundary model. The interfacial solvation numbers are estimated using a lattice gas model under the quasichemical approximation. The standard reduction potentials of the redox couples, appropriate inner potential differences, dielectric permittivities, as well as the width of the interface are included in the analysis. The methodology is applied to the reaction between [Fe(CN)6](3-/4-) and [Lu(biphthalocyanine)](3+/4+) at water/1,2-dichloroethane interface. The rate-determining step is inferred from the estimated free energy of activation for the constituent processes. The results indicate that the solvent shielding effect and the desolvation of the reactants at the interface play a central role in dictating the free energy of activation. The heterogeneous electron-transfer rate constant is evaluated from the molar reaction volume and the frequency factor.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Madras 600036, India.
authors.forename: S
authors.initials: S
authors.lastname: Harinipriya
authors.forename: M V
authors.initials: MV
authors.lastname: Sangaranarayanan