Mechanisms of peroxide reactions: kinetics of reduction of peroxo-monosulphuric and peroxomonophosphoric acids by iodide ion
- 1 January 1976
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 14,p. 1410-1414
- https://doi.org/10.1039/dt9760001410
Abstract
The kinetics of iodide-ion oxidation by H2SO5 and H2PO5 have been investigated. The rate of the first reaction is given by equation (i) where k= 1.73 × 103 dm3 mol–1 s–1 in aqueous solution at 25 °C and I= 0.2 mol dm–3. Rate =k[HSO5 –][I–](i) The rate equation for rhe second reaction is given by the three-term expression (ii) with k1= 1.57 × 103. k2= 57.5, and k3= 0.418 dm3 mol–1 s–1 under the same conditions. Rate =(k1[H3PO5]+k2[H2PO5 –]+k3[HPO5 2–])[I–](ii) The effect of electrolyte addition has been investigated. An inverse linear dependence of the logarithms of the rate constants on the basiclty of the leaving group has been found. The mechanism is consistent with nucleophilic attack by I– on the external peroxidic oxygen leading to breaking of the oxygen–oxygen bond.Keywords
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