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Acta Physico-Chimica Sinica  2010, Vol. 26 Issue (09): 2473-2480    DOI: 10.3866/PKU.WHXB20100922
PHOTOCHEMISTRY AND SPECTROSCOPY     
Effects of Salts on theMicrostructure ofMethanol
YU Xiao-Chun, LIN Ke, HU Nai-Yin, ZHOU Xiao-Guo, LIU Shi-Lin
Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics,University of Science and Technology of China, Hefei 230026, P. R. China
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Abstract  

We studied the effects of salts on the microstructure of liquid methanol using the Raman spectra. We compared the excess Raman spectra of different methanolic salt solutions in the O—H and C—O stretching regions. These regions reflect the interactions between anions (cations) and methanol molecules. In the O—H stretching region, the excess spectra show that the anions interact with methanol molecules by weak hydrogen bonding and the strength of the hydrogen bonds decrease according to the order: CH3OH-CH3OH>Cl--CH3OH>NO- 3 -CH3OH>ClO- 3 -CH3OH. Additionally, no interactions between cations and methanol molecules are apparent, as determined after analysis of this region. In the C—O stretching region, the excess Raman spectra show the interactions between anions (cations) and methanol molecules. The C—O stretching vibration frequencies of methanol that interact with the anions and cations increase according to the order: CH3—OH (anions)3—OH (bulk)3—OH (cations). According to the excess Raman spectra in the C—O stretching region, we fitted the Raman spectra and used the fitting results to determine the solvation numbers in the first solvation shell of the ions. The Raman spectra show that the ions do not affect the microstructure of liquid methanol beyond the first solvation shell at this concentration (~0.005).



Key wordsRaman spectrum      Anion      Cation      Methanol      First solvation shell     
Received: 25 May 2010      Published: 15 July 2010
MSC2000:  O645  
Fund:  

The project was supported by the National Natural Science Foundation of China (20873131, 20928002) and National Key Basic Research Programof China (973) (2007CB815204).

Corresponding Authors: LIU Shi-Lin     E-mail: slliu@ustc.edu.cn
Cite this article:

YU Xiao-Chun, LIN Ke, HU Nai-Yin, ZHOU Xiao-Guo, LIU Shi-Lin. Effects of Salts on theMicrostructure ofMethanol. Acta Physico-Chimica Sinica, 2010, 26(09): 2473-2480.

URL:

http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB20100922     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2010/V26/I09/2473

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