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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (18): 1693-1698. 上一篇    下一篇

研究论文

高浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用

轩小朋，王键吉*，赵扬，卓克垒   

  1. (河南师范大学化学与环境科学学院 新乡 453007)
  • 投稿日期:2004-12-09 修回日期:2005-05-09 发布日期:2010-12-10
  • 通讯作者: 王键吉

Ion-solvent and Ion-ion Interactions at High Concentration LiClO4 Solutions in Acetone

XUAN Xiao-Peng, WANG Jian-Ji*, ZHAO Yang, ZHUO Ke-Lei   

  1. (School of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007)
  • Received:2004-12-09 Revised:2005-05-09 Published:2010-12-10
  • Contact: WANG Jian-Ji

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2010

利用红外和拉曼光谱技术研究了不同浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用. 红外和拉曼光谱的分析表明, Li＋与丙酮分子发生了强烈的相互作用, 导致丙酮C—C伸缩振动谱带、C＝O伸缩振动谱带等发生了分裂. Li＋的溶剂化数随溶液浓度的增加逐渐降低, 在所研究的LiClO4浓度范围(0.31～3.98 mol•kg－1)内由3.4减小到1.9. 此外, 根据的谱带变化确定了溶液中存在的多种离子对的形式, 计算了缔合平衡常数, 并与电导实验结果进行了比较, 解释了这两种方法测定的离子缔合常数存在差异的主要原因.

关键词: 高氯酸锂, 丙酮, 离子溶剂化, 离子缔合, 红外光谱, 拉曼光谱

The Infrared and Raman spectra of LiClO4/acetone solutions have been investigated from diluted to high concentrations. It was found that the C＝O and C—C stretches of acetone were very sensitive to the interaction between Li＋ and acetone molecules. Apparent solvation numbers of 1. 9～3. 4 for Li＋ have been inferred at different molalities of LiClO4 and the carbonyl group was suggested to be the main bonding site. The bands reveal the evidence for the presence of contact ion pair and its dimer. The association constants of LiClO4 in acetone has been calculated and compared with the data obtained from conductivity measurements.

Key words: lithium perchlorate, acetone, ion solvation, ion association, raman spectroscopy, infrared spectroscopy