Molecular dynamics study of n-alcohols adsorbed on an aqueous electrolyte solution

Abstract

The distribution of normal alcohol (n-alcohol) on water and the effect of salt on the structural and dynamical properties of n-alcohol on aqueous electrolyte solutions were investigated using molecular dynamics simulation. The stability of the alcohol distribution was studied for three types of n-alcohol (n-propanol, C3H7OH; n-heptanol, C7H15OH; and n-undecanol, C11H23OH), four or five concentrations of alcohol, and three concentrations of salt. The simulation results reveal the following. The distribution of n-propanol on water is homogeneous at all n-alcohol concentrations studied here and the distribution of n-heptanol and n-undecanol on water is heterogeneous. The n-alcohol concentration at which fluctuations in the alcohol distribution begin to increase depends on the length of the hydrocarbon chain of the n-alcohol. Salt concentration affects the surface excess concentration of n-alcohol and the stability of the adsorbed layer of n-alcohol. The degree of each effect depends on the length of the hydrocarbon chain of the n-alcohol. For n-undecanol, the surface structure of n-alcohol is independent of salt concentration because interaction between the hydrocarbon chains is sufficiently strong. In absorption refrigeration technology, to enhance the absorption rate of water vapor into a highly concentrated aqueous electrolyte solution, a small amount of alcohols is added to the aqueous electrolyte solution, which induces cellular convection referred to as Marangoni instability. Among the three types of n-alcohol studied here, only n-heptanol induces strong cellular convection. The simulations reveal two required conditions for Marangoni instability: generation of fluctuations in the alcohol distribution on water, and strong correlation between the structural and dynamical properties and salt concentration. Among the three types of n-alcohol studied here, based on the simulations, only n-heptanol satisfies both conditions.