Kinetics and mechanisms of the reduction of cobalt(II) 4,4′,4″,4‴-tetrasulfophthalocyanine by 2-mercaptoethanol under anoxic conditions

Ping Sang K. Leung, Eric A. Betterton, Michael R. Hoffmann

Research output: Contribution to journalArticle

20 Scopus citations

Abstract

The kinetics and mechanism of reduction of cobalt(II) 4,4′,4″,4‴-tetrasulfophthalocyanine by 2-mercaptoethanol to yield cobalt(I) tetrasulfophthalocyanine and 2-hydroxyethyl disulfide under anoxic conditions were investigated and the following rate law was found: v = -d[CoIITSP]T/dt = {k2k1[RSH]T[CoIITSP] T}/{2(1 + aH+/Ka1 + Ka2/aH+)(1 + α[RSH]T)}, where k2 is a rate constant for the rate-limiting electron-transfer step, and K1 is the equilibrium constant for the complexation of a CoTSP dimer with thioethanol; Ka1 and Ka2 are the apparent acid dissociation constants of HOC2H4SH and HOC2H4S-, respectively; α is K1/(1 + aH+/Ka1 + Ka2/aH+); aH+ is the hydrogen ion activity. A nonlinear least-squares fit of the experimental data to the above rate law gave k2 = 228 ± 3.8 s-1 and K1 = 117 ± 2.5 M-1 at 27°C at μ = 0.4 M.

Original languageEnglish (US)
Pages (from-to)430-433
Number of pages4
JournalJournal of physical chemistry
Volume93
Issue number1
DOIs
StatePublished - 1989
Externally publishedYes

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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