Homogeneous and heterogeneous electron transfer to benzyl phenyl sulfide

Journal Article · Thu Jan 15 00:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100286a041· OSTI ID:6810637

Severin, M G; Arevalo, M C; Farnia, G; Vianello, E

The thermodynamic and kinetic parameters of the electron transfer (ET) to benzyl phenyl sulfide in DMF have been determined by cyclic voltammetry. The heterogeneous ET has been studied at three different electrodes: Hg, Pt, and glassy carbon. The activation parameters, namely the standard rate constant and the transfer coefficient, corrected for the double-layer contribution, show no significant difference for the three materials. The rate constants for the homogeneous ET to benzyl phenyl sulfide from eight electrogenerated anion radicals have been determined and compared with the corresponding reaction free energies, according to the current theories of the ET process. The results indicate that the ET is an endergonic process driven by a fast bond breaking of the ET product. Both the homogeneous and the heterogeneous reactions are consistent with an outer-sphere adiabatic electron-exchange process, characterized by a relatively high activation free energy. To account for the latter, inner reorganization energies must be considered, together with solvent reorganization. This is in agreement with the easy breaking of the C-S bond in the primary ET product.

• Research Organization: Universita di Padova, Italy
• OSTI ID: 6810637
• Journal Information: J. Phys. Chem.; (United States), Vol. 91:2
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ELECTRON TRANSFER
CHEMICAL REACTION KINETICS
THERMODYNAMICS
ORGANIC SULFUR COMPOUNDS
SULFIDES
CARBON
ELECTRODES
EXPERIMENTAL DATA
MERCURY
PLATINUM
VOLTAMETRY
CHALCOGENIDES
DATA
ELEMENTS
INFORMATION
KINETICS
METALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PLATINUM METALS
REACTION KINETICS
SULFUR COMPOUNDS
TRANSITION ELEMENTS
400400* - Electrochemistry
400500 - Photochemistry