Ion Solvation and Ion Association in High-Concentration of NaBF4 /DMF Solutions
XUAN Xiao-peng1, 2, TANG Jun-ming1, WANG Jian-ji1*, WANG Han-qing2
1. Department of Chemistry, Henan Normal University, Xinxiang 453007, China 2. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
Abstract：Ion solvation and ion association in solutions of NaBF4/DMF were studied by infrared and Raman spectroscopy and ab initio quantum chemistry. It was found that the sodium cation interacts on oxygen atom of CO group in DMF molecules. The solvation number of Na+, four, was obtained according to the change analysis of CH3 rocking band. The splitting of the ν1 mode of BF-4 anion indicates the presence of contact ion pairs. Ionic association degree increases with increasing molality of the salt. The solvated structure of Na+ and the geometry of Li+BF-4 ion pair were also suggested based on the ab initio calculations.
轩小朋1，2，汤俊明1，王键吉1*，汪汉卿2 . 高浓度NaBF4/DMF溶液中的离子溶剂化和离子缔合[J]. 光谱学与光谱分析, 2005, 25(04): 548-552.
XUAN Xiao-peng1, 2, TANG Jun-ming1, WANG Jian-ji1*, WANG Han-qing2 . Ion Solvation and Ion Association in High-Concentration of NaBF4 /DMF Solutions . SPECTROSCOPY AND SPECTRAL ANALYSIS, 2005, 25(04): 548-552.
[1] Venkatasetty H V. Lithium battery Technology(Ed. by H. V. Venkatasetty). New York: John Wiley and Sons, 1984. 137. [2] Alia J M, Edwards H G M. Vib. Spectrosc., 2000, 24: 185. [3] Alia J M, Mera D, Edwards H G M, Garcia F J, Lawson E E. Z. Phys. Chem., 1996, 196: 209. [4] Xuan X P, Wang J J, Tang J M et al. Spectrochim. Acta A, 2001, 56: 2131. [5] Xuan X P, Wang J J, Lu J S et al. Spectrochim. Acta A, 2001, 57: 1555. [6] Wang J J, Xuan X P, Lu J S et al. Z. Phys. Chem., 2001, 215: 437. [7] Frisch M J, Trucks G W, Schlegel H B et al. Gaussian 98 (Revision A.11), Gaussian, Inc., Pittsburgh PA, 2003. [8] Becke A O. J. Chem. Phys., 1993, 98: 5648. [9] Marcus Y. Ion Solvation. Chichester: John Wiley and Sons, 1985. 130. [10] Umebayashi Y, Matsumoto K, Watanabe M, Ishiguro S. Phys. Chem. Chem. Phys., 2001，3: 5475. [11] Xuan X P, Zhang H, Wang J J, Wang H. J. Raman Spectrosc., 2003, 34: 465. [12] Deng Z, Irish D E. Can. J. Chem., 1991; 69: 1766. [13] Krestov G A, Novosyolov N P, Perelygin I S, Safonova L P, Ovachinnikova V D, Trostin V N. Ioinic Solvation. Chichester: Ellis Horwood Ltd., 1994. 148. [14] Schultz G, Hargittai I. J. Phys. Chem., 1993, 97: 4966. [15] Lewis L R, Edwards H. Handbook of Raman Spectroscopy. New York: Marcel Dekker, Inc., 2001. [16] Cances M T, Mennucci V, Tomasi J. J. Chem. Phys., 1997, 107: 3032.
