Kinetics and Mechanism of Electron Transfer Reactions in Fluoride-coordinated Bismuth(v) Complex Oxidation of Phosphorous Acid in Aqueous HClO4-HF Nlixture
| Main Authors: | CHETNA GUPTA, K. M. INANI, P. D. SHARMA |
|---|---|
| Format: | Article Journal |
| Bahasa: | eng |
| Terbitan: |
, 1991
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| Subjects: | |
| Online Access: |
https://zenodo.org/record/5969880 |
Daftar Isi:
- Department of Chemistry, University of Rajasthan, Jaipur-502 004 Manuscript received 17 January 1991, revised 6 August 1991, accepted 3 September 1991 Kinetics of oxidation of phosphorous acid with bismuth(V) fluoride complex have been studied in HCIO4 - HF mixture. The reaction is first order with respect to each reactant and the second order rate constant at 45o was evaluated. The hydrogen ion dependence is complex. Free radicals are indicated in the reaction. The mode of electron transfer from the substrate to the oxidant has been indicated via a bridge outer-sphere mechanism. The enthalpy of activation for the hydrogen ion independent step and the entropy of activation were calculated. The rate of the reaction was found to be independent of sodium fluoride and HF concentrations.