Cor J. Peters

First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water

First-principles molecular dynamics simulations in the canonical ensemble at temperatures of 333 and 363 K and at the corresponding experimental densities are carried out to investigate the behavior of the 1:2 choline chloride/urea (reline) deep eutectic solvent and its equimolar mixture with water. Analysis of atom-atom radial and spatial distribution functions and of the H-bond network reveals the microheterogeneous structure of these complex liquid mixtures. In neat reline, the structure is governed by strong H-bonds of the trans- and cis-H atoms of urea to the chloride ion. In hydrous reline, water competes for the anions, and the H atoms of urea have similar propensities to bond to the chloride ions and the O atoms of urea and water. The vibrational spectra exhibit relatively broad peaks reflecting the heterogeneity of the environment. Although the 100 ps trajectories allow only for a qualitative assessment of transport properties, the simulations indicate that water is more mobile than the other species and its addition also fosters faster motion of urea.

Chapter 11:Phase Behaviour of Ionic Liquid Systems

In the last two decades, ionic liquids have received much attention for use as novel environmentally benign solvents.1–3 Ionic liquids are molten salts that are liquid at temperatures below 373u200aK. They solely consist of ions. Commonly used cations (with different functional groups R, which are usual...

Monte Carlo simulations probing the liquid/vapour interface of water/hexane mixtures: adsorption thermodynamics, hydrophobic effect, and structural analysis

ABSTRACT Knowledge about the interfacial properties of water/oil mixtures is important for the petrochemical industry and for understanding detergency and hydrophobic effects. Here, we probe the liquid/vapour interface of water/n-hexane mixtures using configurational-bias Monte Carlo simulations in the osmotic Gibbs ensemble. We study the effect of n-hexane at several partial pressures ranging from 25% to 95% of its saturated vapour pressure and observe that the surface tension decreases with increasing n-hexane pressure. Additionally, we analyse the simulation trajectories to provide molecular-level insights on the spatial distribution of n-hexane and the structure of the interface. The n-hexane molecules strongly adsorb from the vapour phase onto the liquid interface with a preferentially parallel orientation with respect to the interface. The surface excess, from the Gibbs adsorption isotherm equation, is calculated and used to systematically define the domain of adsorbed n-hexane. Integrating over this gives the free energy of adsorption of n-hexane, which is highly favourable, varying from to u2009kJ/mol as the partial pressure of n-hexane is increased. The enrichment of n-hexane molecules on the interface yields a positive deviation from Henrys law at higher partial pressures, providing evidence for favourable adsorbate-adsorbate interactions. GRAPHICAL ABSTRACT