ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the reversible reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H}_3 {\rm AsO}_3 + {\rm I}_{3^-} + {\rm H}_2 {\rm O}\rightleftharpoons{\rm H}_3 {\rm AsO}_4 + 2{\rm H}^+ + 3{\rm I}^- $$\end{document} have been studied spectrophotometrically in acid solution under conditions in which both the forward and reverse reactions go to virtual completionand in which the reaction comes to a practical equlibrium. The rates of theforward (Rf) and reverse (Rr) reactions are given by \documentclass{article}\pagestyle{empty}\begin{document}$$R_f = \{f + g/[\rm H^+] + h/[\rm H^+]^2\} [\rm H_3 {\rm AsO}_3][I_{3^-}]/[I^-]^2 $$ $$ R_r = \{u[\rm H^+] + \upsilon [\rm H^+]^2\} [{\rm H}_3 {AsO}_4][I^-] $$\end{document} where f, g, h, u, and v have the values (4 ± 1) × 10-5 mole/1.·s, (4.2 ± 0.2) × 10-5 mole2/1.2·s, (5.0 · 0.3) × 10-7 mole3/1.3·s, (1.1 ± 0.1) × 10-3 1.2/mole2·s, and (3.7 ± 0.2) × 10-3 1.3/mole3·s at 298.2°K and at an ionic strength of 2.00M maintained by adding sodium chloride. The stoichiometric equilibrium constant under similar conditions is 0.022 ± 0.003. Differentvalues of these parameters were obtained when sodium perchlorate and sodiumnitrate were used to control ionic strength.The results are compared with those from previous reports and a mechanism is proposed based upon an initial rapid equilibrium \documentclass{article}\pagestyle{empty}\begin{document}$${\rm H}_3 {\rm AsO}_3 + {\rm I}_2 \rightleftharpoons{\rm H}_3 {\rm AsO}_3 {\rm I}^ + + {\rm I}^ -$$\end{document} followed by a rate-determining attack of water upon H3AsO3I+, H2AsO3I, and HAsO3I-.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550060505
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