The pulse radiolysis of aqueous solutions of potassium ferrocyanide

J. Rabani*, M. S. Matheson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

123 Scopus citations

Abstract

The pulse radiolysis of deaerated aqueous ferrocyanide has been studied in acid, neutral, and alkaline solutions. k(OH + ferrocyanide) was determined as (1.07 & 0.1) × 1010 M-1 sec-1. In experiments in which OH + ferrocyanide competed with OH recombination, 2k(OH + OH) = (1.26 ± 0.16) × 1010 M-1 sec-1 was obtained. It was shown that O- reacts much more slowly with ferrocyanide than does OH, and, from the pH dependence of the apparent rate constant for OH + ferrocyanide, it was established that [O-] = [OH] at pH 11.9 × 0.2 in the equilibrium OH + OH- ⇄ O- + H2O. Because of experimental difficulties, precise rate constants for O- + OH and O- + O- recombination were not measurable, but limits for these k values have been estimated. While the full mechanism of radiolysis of aqueous ferrocyanide solutions still has not been unraveled, the rate constants and pKOH of this paper will be essential to the unraveling.

Original languageEnglish
Pages (from-to)761-769
Number of pages9
JournalJournal of Physical Chemistry
Volume70
Issue number3
DOIs
StatePublished - 1966
Externally publishedYes

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