An eutectic Mixture in the Tetrabutylammonium Bromide-Octanol System: Macroscopic and Microscopic Points of View.

Abstract

An eutectic mixture of tetrabutylammonium bromide and octanol in the molar ratio 1-10 exhibited a melting point of -17°C. This system was investigated by means of infrared spectroscopy, in the liquid and in the solid state. Classical molecular dynamics was performed to study the fine details of the hydrogen bond interactions established in the mixture. Both octanol and the mixtures displayed an almost featureless far-infrared spectrum in the liquid state but it becomes highly structured in the solid phase. DFT calculations suggest that new vibrational modes appearing in the mixture at low temperatures may be related to the population of the higher energy conformers of the alcohol. Mid-infrared spectroscopy measurements evidenced no shift of the CH stretching bands in the mixture compared to the starting materials, while the OH stretching are blue shifted by a few cm-1. Consistently, molecular dynamics provides a picture of the mixture in which the hydrogen bonds (HB) of pure octanol are replaced by weaker HB formed with the TBA ion and the Br cation. Due to these interactions the ionic couple becomes more separated. In agreement with this model, the lengths of all HB are much larger than those observed in acids in previous studies.