Kinetics and mechanism of the oxidation of iodide by trans-dioxoruthenium (VI)
Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal
Author(s)
Detail(s)
Original language | English |
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Pages (from-to) | 3091-3093 |
Journal / Publication | Journal of the Chemical Society, Dalton Transactions |
Issue number | 21 |
Publication status | Published - 1994 |
Link(s)
Abstract
The kinetics of reduction of trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) by iodide has been studied in aqueous acidic solution. The reaction has the following stoichiometry; trans-[RuVI(tmc)O2]2+ + 3I- + 2H+ → trans-[RuIV(tmc)O(OH2)]2+ + I3
-. The rate law is -d[RuVI]/dt = (ka + kb[H+])[RuVI][I-] with ka = 0.041 ± 0.013 dm3 mol -1 s-1 and kb = 18.5 ± 0.2 dm6 mol -2 s-2 at 25.0°C and 0.1 mol dm-3 ionic strength. For ka ΔH‡ = 42.9 ± 9.4 kJ mol-1 and ΔS‡ = -131 ± 40 J K-1 mol-1, while for kb, ΔH‡ = 36.9 ± 2.9 kJ mol-1 and ΔS‡ = -97 ± 10 J K-1 mol-1. A mechanism involving oxygen-atom transfer from RuVI to iodide is consistent with the data.
Citation Format(s)
Kinetics and mechanism of the oxidation of iodide by trans-dioxoruthenium (VI). / Lau, Tai-Chu; Lau, Kent W. C.; Lau, Keung.
In: Journal of the Chemical Society, Dalton Transactions, No. 21, 1994, p. 3091-3093.
In: Journal of the Chemical Society, Dalton Transactions, No. 21, 1994, p. 3091-3093.
Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal