Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5413836 | Journal of Molecular Liquids | 2006 | 12 Pages |
Abstract
Infrared OH stretching spectra of n-butanol in n-hexane mixtures have been measured at three temperatures as a function of mixture composition up to a mole fraction 0.3 of n-butanol. The spectra were analyzed using DFT (B3LYP) and ab initio (MP2) calculations. Hydrogen-bonded n-butanol clusters up to four members have been calculated using DFT and high-level ab initio methods, including cyclic trimers and tetramers. A distinct cooperative effect of the hydrogen bonding energy has been observed. On the basis of these theoretical results, a new modified ERAS (extended real associated solution) model incorporating tetramer cyclic species in addition to the linearly associated species was applied for describing simultaneously the measured monomer concentration of n-butanol obtained from the IR spectra, the chemical shift of the hydroxyl proton of n-butanol (δOH) obtained from 1H NMR measurements, and experimental data of the molar excess enthalpy (HE). 1H NMR- and HE-data covering the whole range of concentration in the mixture have been used.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
D. Wandschneider, M. Michalik, A. Heintz,