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Study Microstructure of Salt/methanol Solution

Author: YuXiaoChun
Tutor: LiuShiLin
School: University of Science and Technology of China
Course: Physical and chemical
Keywords: Raman Spectra ion association anions cations methanol the first solvation shell
CLC: O621.2
Type: Master's thesis
Year: 2010
Downloads: 28
Quote: 0
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Abstract


Ion association in solution of lithium perchlorate/methanol of different concentrations has been studied by using Raman spectra as a function of concentration of lithium perchlorate. Excess spectra revealed the contributions of free ions, solvent separated ion pairs (SIP), contact ion pairs (CIP), and Clusters ({M+N-}n) in the concentrated solutions. With excess spectra, we make assignment of these ion pairings. Simultaneity, we make quantitative analysis about changes of solution conductivities by Raman spectroscopic techniques and conclude that the concentration of free ions is the only positive factor that affects the solution conductivities, while SIP and other ion pairs all reduce the solution conductivities.On the other hand, the effects of salts on the micro-structure of liquid methanol have been studied from Raman spectra. We compared excess Raman spectra of different methanolic salts at the molarity of saltĪ‡salt~0.5% in the O-H stretching and C-O stretching region, which reflect the interactions between anions, cations and methanol molecules. In the O-H stretching region, excess spectra show obviously that anions interact with methanol with weak hydrogen bonds, and the strength of hydrogen bonds has this relationship: CH3OH-CH3OH>Cl--CH3OH>NO3--CH3OH>ClO4--CH3OH, and in the same region we do not observe the interactions between cations and methanol molecules. And in C-O stretching region, excess Raman spectra reflect obviously the interactions between anions, cations and methanol molecules, and the frequencies of C-O stretching vibration of methanol that interact with anions and cations have this relationship: CH3-OH(anions)<CH3-OH(bulk)<CH3-OH(cations). According to the excess Raman spectra in the C-O stretching region, we fit Raman spectra in this region, and employing the fitting results, we deduce the solvation numbers in the first solvation shell of the ions. The Raman spectra demonstrate the ions do not affect the micro-structure of liquid methanol beyond the first solvation shell at the low concentration.

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CLC: > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Organic Chemistry general issues > Properties of organic compounds
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