Electrocatalytic Effects for the Reduction of Thionyl Chloride in $Li/SOCl_2$ Cell Containing Schiff Base Metal(II) Complexes

• Published in: Bulletin of the Korean Chemical Society 2000, Vol.21 (6), p.571-576
• Main Authors: 김우성, 정광일, 김신국, 전성원, 김연희, 성용은, 최용국, Kim, Woo-Seong, Chung, Kwang-Il, Kim, Shin-Kook, Jeon, Seung-Won, Kim, Yeon-Hee, Sung, Yung-Eun, Choi, Yong-Kook
• Format: Article
• Language: Korean
• ISSN: 0253-2964; 1229-5949

Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.