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Oxidation of thiocyanate by iron(V) in alkaline medium |
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| Authors: | Virender K. Sharma,Donald B. O&rsquo Connor |
| Affiliation: | a Department of Chemistry, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901, USA b Department of Chemistry, University of Texas at Austin, Austin, TX 78712, USA c Chemistry Department, Brookhaven National Laboratory, Upton, Long Island, NY 11973, USA |
| 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)]/dt = k10{[H+]2/([H+]2 + K2[H+] + K2K3)}[Fe(V)][SCN−], where k10 = 5.72 ± 0.19 × 106 M−1 s−1, pK2 = 7.2, and pK3 = 10.1. The reaction precedes via a two-electron oxidation, which converts Fe(V) to Fe(III). Thiocyanate reacts approximately 103× faster with iron(V) than does with iron(VI). |
| Keywords: | Iron(V) Oxidation Thiocyanate Pulse radiolysis |
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