Abstract
The oxidation of thiocyanate by iron(V) (Fe(V)) was studied as a function of pH in alkaline solutions by a premix pulse radiolysis technique. The rates decrease with an increase in pH. The rate law for the oxidation of SCN − by Fe(V) was obtained as −d[Fe(V)]/d t = k 10{[H +] 2/([H +] 2 + K 2[H +] + K 2 K 3)}[Fe(V)][SCN −], where k 10 = 5.72 ± 0.19 × 10 6 M −1 s −1, p K 2 = 7.2, and p K 3 = 10.1. The reaction precedes via a two-electron oxidation, which converts Fe(V) to Fe(III). Thiocyanate reacts approximately 10 3× faster with iron(V) than does with iron(VI).
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