Thermodynamics of hydrogen bonding of weak bases in alcohol solutions: Calorimetry of solution, IR-spectroscopy and vapor pressure analysis
- 作者：Ksenia V. Zaitseva zaitseva.ksenia@gmail.com ; Mikhail A. Varfolomeev ; vma.ksu@gmail.com ; Boris N. Solomonov boris.solomonov@ksu.ru
- 关键词：Hydrogen bonding ; Enthalpy ; Gibbs energy ; Entropy ; Weak base ; Aliphatic alcohol
- 刊名：Journal of Molecular Structure
- 出版年：2012
- 期刊代码：62_00222860
- 类别：ch
- 出版时间：27 June, 2012
- 卷：1018
- 期：Complete
- 页码：14-20
- 文件大小：380 K
摘要
The properties of solutes and their reactivity in aliphatic alcohols significantly depend on the formation of hydrogen bonds. In this work, calorimetric, FTIR-spectroscopic and gas chromatographic vapor pressure studies of hydrogen bonds of weak bases in solution of aliphatic alcohols were carried out. Enthalpies of solutions at infinite dilution of ketones, nitriles and acetates in methanol and octan-1-ol were measured. Obtained from the calorimetric data, the enthalpies of specific interaction of weak bases in aliphatic alcohols unexpectedly found to be positive. IR spectra of solutions of ketones in aliphatic alcohols at infinite dilution were measured at different temperatures. Enthalpies of specific interaction in studied systems obtained from the spectroscopic data confirmed the endothermic process and are in good agreement with calorimetric results. Gibbs energies and entropies of specific interaction of weak bases in aliphatic alcohols were determined.
Obtained results show, that the hydrogen bonding process of weak bases in aliphatic alcohols differs substantially from the formation of complexes 1:1 ROH鈰疊 (B - weak proton acceptor) in aprotic media. The complicated process of hydrogen bonding of weak bases in aliphatic alcohols apparently is controlled by the entropy factor, because these values are above zero.