Kinetics and mechanism of the reduction of thallium(III) by arsenic(III) in perchloric acid solution
- 1 January 1972
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 52-55
- https://doi.org/10.1039/dt9720000052
Abstract
Thallium(III) and Arsenic(III) react in aqueous perchloric acid solution to give TlI and AsV. The kinetics were followed by determining TlIIIiodometrically under critical conditions. The empirical rate law is: –d[TlIII]//dd =k3′[TlIII][AsIII]//[H+] (a)k3′ was found to be 88·5 ± 5·7 min–1 at 35 ± 0·1 °C. The energy and entropy of activation were found to be 21·5 ± 1 kcal and –15·5 ± 3 cal mol–1deg–1 respectively. The reactive species are TlOH2+ and HAsO2. The rate decreases with increasing ionic strength and with decreasing dielectric constant. Chloride ions strongly inhibit the reaction.Keywords
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