Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Electrochemical Studies of Viologens in Homogeneous Aqueous and Sodium Dodecyl Sulfate Micellar Solutions

  • Park Joon Woo (Department of Chemistry and Ewha Womans University) ;
  • Ko Seung Hyeon (Department of Chemistry and Ewha Womans University) ;
  • Park Jong-Yoon (Department of Chemistry and Ewha Womans University)
  • Published : 1992.06.20
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Abstract

Cyclic voltammetric behavior of symmetric (dimethyl, diheptyl, dioctyl, dibenzyl) and asymmetric (methyloctyl, methyldodecyl, methylbenzyl) viologens was investigated in homogeneous aqueous solution and sodium dodecyl sulfate (SDS) micellar media. In SDS-free 0.1 M NaCl solutions, the reduction potential is less negative as the chain length of alkyl substituent is longer. This is due to the stabilization of the reduced cationic radical and neutral form of viologen by adsorption on electrode surface. The adsorbed species show the "aging-effect". With the exceptions of methyldodecyl viologen and methylbenzyl viologen, the viologens show strong tendency of conproportionation reaction between viologen dications and neutral forms. In cases of methyldodecyl viologen and methylbenzyl viologen, the conproportionation reaction is kinetically disfavored, though it is thermodynamically favorable. SDS micelles dissolve the adsorbed species and the viologens exhibit two reversible redox processes in SDS micellar solutions. The reduction potentials of viologens in SDS micellar solutions depend little on the length of alkyl chain. Benzyl-substituted viologens are more easily reduced than the alkyl substituted viologens, presumably due to electron-withdrawing character of benzyl group.

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