Kinetics of one-electron oxidation by the cyanate radical

Zeev B. Alfassi, Robert E. Huie, S. Mosseri, P. Neta

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

The reaction of cyanate ions with hydroxyl radicals was studied by pulse radiolysis and found to lead to formation of a transient absorbing at 330 nm (∈ = 970 M-1 cm-1). The rate of formation of this transient is slower than the rate of reaction of NCO- with OH, in agreement with previous results. This indicates that the initial OH adduct, NC(OH)O-, which is known from ESR experiments to rearrange to NHCO2-, reacts with another NCO- to form the observed transient. Rate constants for oxidation by this cyanate radical were determined for several compounds, including ascorbate, urate, and several phenols and anilines. They were found to vary from <106 to 3 × 108 M-1 s-1. Comparing these rate constants with those for other oxidizing radicals, and taking into consideration the redox potentials of the radicals and the substrates, we conclude that the cyanate radical has a one-electron oxidation potential of about 0.6-0.7 V vs. NHE. Such a weak oxidant cannot be assigned the structure (NCO)2•- and we suggest, therefore, the alternate structure (-O2CNHNCO-).

Original languageEnglish
Pages (from-to)3888-3891
Number of pages4
JournalJournal of Physical Chemistry
Volume91
Issue number14
DOIs
StatePublished - 1 Jan 1987

ASJC Scopus subject areas

  • General Engineering
  • Physical and Theoretical Chemistry

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