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通过介电弛豫光谱法研究水溶液中的硫酸钪络合作用。

Scandium sulfate complexation in aqueous solution by dielectric relaxation spectroscopy.

作者信息

Schrödle Simon, Wachter Wolfgang, Buchner Richard, Hefter Glenn

机构信息

Chemistry Department, Murdoch University, Murdoch, WA 6150, Australia.

出版信息

Inorg Chem. 2008 Oct 6;47(19):8619-28. doi: 10.1021/ic702396r. Epub 2008 Aug 29.

Abstract

Ion association in aqueous solutions of scandium sulfate has been investigated at 25 degrees C and at concentrations from 0.01 to 0.8 M by broadband dielectric spectroscopy over the frequency range 0.2 <or= nu/GHz <or= 89. Detailed analysis of the spectra reveals the presence of both inner- and outer-sphere 1:1 [ScSO 4] (+)(aq) complexes, similar to solutions of other high-valent metal sulfates. Outer-outer-sphere 1:1 complexes are probably also formed, but their contribution is swamped by the presence of higher-order inner-sphere complexes. The latter predominate in the more concentrated solutions, causing major changes to the low-frequency end of the spectrum. The data, while not definitive, are consistent with fac-[Sc(SO 4) 3(OH 2) 3] (3-) as the major species present. The speciation is strikingly different from that recently reported for aluminum sulfate solutions and indicates that the often-postulated similarity between the aqueous chemistry of Al(III) and Sc(III) has to be treated with caution.

摘要

通过宽带介电谱在0.2≤ν/GHz≤89的频率范围内,研究了25℃下硫酸钪水溶液中离子缔合情况,浓度范围为0.01至0.8M。对光谱的详细分析表明,存在内球和外球1:1 ScSO₄(aq)络合物,这与其他高价金属硫酸盐溶液类似。外-外球1:1络合物可能也会形成,但其贡献被高阶内球络合物的存在所掩盖。后者在浓度较高的溶液中占主导,导致光谱低频端发生重大变化。这些数据虽不确凿,但与fac-Sc(SO₄)₃(OH₂)₃作为主要存在物种相符。其物种形成与最近报道的硫酸铝溶液显著不同,表明通常假定的Al(III)和Sc(III)水化学之间的相似性必须谨慎对待。

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