Kinetics of Thiocyanate Formation by Reaction of Cyanide with Tetrathionate

Irina Kurashova, Alexey Kamyshny

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

In aquatic systems a reaction between tetrathionate and cyanide results in the formation of thiocyanate. We have studied kinetics of the reactions of tetrathionate with free cyanide and two cyanide complexes, hexacyanoferrate(II) and hexacyanoferrate(III), at the environmentally relevant conditions. For the reaction between tetrathionate and free cyanide, the rate constant and the activation energy, but not the reaction order, strongly depend on pH. Our observations allow to propose the following pathways of thiocyanate formation by the reactions of free cyanide with tetrathionate: (1) tetrathionate reacts relatively slow with hydrogen cyanide at acidic and neutral conditions; and (2) tetrathionate reacts relatively fast with cyanide anion under highly alkaline conditions. Depending on environmental conditions, the half-lives of the reaction between free cyanide and tetrathionate will be in the ranges of hours to several years. Reactions of tetrathionate with hexacyanoferrate(II) and hexacyanoferrate(III) have no environmental significance as they are slower than the decomposition of tetrathionate. Strategy for improvement of analytical protocols for analysis of tetrathionate and cyanide is proposed based on the detected kinetics parameters.

Original languageEnglish
Pages (from-to)63-77
Number of pages15
JournalAquatic Geochemistry
Volume27
Issue number1
DOIs
StatePublished - 1 Mar 2021

Keywords

  • Cyanide
  • Sulfide oxidation intermediates
  • Tetrathionate
  • Thiocyanate

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