Brooksby Paula A, Fawcett W Ronald
Department of Chemistry, University of California, Davis, CA 95616, USA.
Spectrochim Acta A Mol Biomol Spectrosc. 2006 May 15;64(2):372-82. doi: 10.1016/j.saa.2005.07.033. Epub 2005 Dec 27.
Attenuated total reflection infrared spectroscopy was used to examine the concentration dependent solvation of LiClO4 and NaClO4 electrolytes in propylene carbonate (PC). Factor analysis and curve fitting techniques were performed on the measured spectra and the results compared with ab initio computations to provide evidence for ion-solvent solution geometries. Factor analysis of the measured data allowed the identification of the spectrum of ion-associated PC that is uniquely different from the self-associated PC spectrum. The results indicate Li+ and ClO4- ions are contact ion-paired even at relatively low electrolyte concentrations whereas Na+ and ClO4- ions are not, up to approximately 2 mol dm-3.
采用衰减全反射红外光谱法研究了高氯酸锂和高氯酸钠电解质在碳酸丙烯酯(PC)中的浓度依赖性溶剂化作用。对测量光谱进行了因子分析和曲线拟合技术,并将结果与从头算计算进行了比较,以提供离子-溶剂溶液几何结构的证据。对测量数据的因子分析允许识别与自缔合PC光谱独特不同的离子缔合PC光谱。结果表明,即使在相对较低的电解质浓度下,Li⁺和ClO₄⁻离子也是接触离子对,而Na⁺和ClO₄⁻离子在高达约2 mol dm⁻³时不是。