TY - JOUR
T1 - The pulse radiolysis of aqueous solutions of potassium ferrocyanide
AU - Rabani, J.
AU - Matheson, M. S.
PY - 1966
Y1 - 1966
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=33947333303&partnerID=8YFLogxK
U2 - 10.1021/j100875a025
DO - 10.1021/j100875a025
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AN - SCOPUS:33947333303
SN - 0022-3654
VL - 70
SP - 761
EP - 769
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 3
ER -