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Protonation and sodium ion-pairing of the sulfite ion in concentrated aqueous electrolyte solutions
Authors:S. G. Capewell  G. T. Hefter  P. Sipos  P. M. May
Affiliation:(1) A. J. Parker Cooperative Research Center for Hydrometallurgy, Murdoch University, W.A. 6150 Murdoch, Australia;(2) Department of Chemistry and Mineral Science, Division of Science, Murdoch University, W.A. 6150 Murdoch, Australia;(3) CSIRO Division of Minerals, W.A. 6152 Waterford, Australia
Abstract:A protocol has been developed for the reliable titration of aqueous sulfite solutions which minimizes photodecomposition effects. This procedure has been used to measure the protonation constants of the sulfite ion in aqueous solution by glass electrode potentiometry at 25.0‡C and ionic strengths (I) from 0.1 to 5.0M in NaCI media and atI = 1.0M in KC1 and Me4NCl media. These measurements provided evidence of weak but significant ionpairing between SO2/3 -and Na+ with a formation constant of logK Na = 0.431 in 1.0M Me4NCl. This was in very good agreement with the value logK Na = 0.410 measured directly by Na+ ion-selective electrode potentiometry. Evidence is also presented for an extremely weak association of K+ and SO 2 3 -with logK k = 0.22 in 1.0M Me4NCl.
Keywords:Potentiometry  sulfite  protonation constant  sodium ion  potassium ion  ion-pairing  concentrated electrolytes  ion-selective electrode
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