The effect of apolar solutes on water structure: Alcohols and tetraalkylammonium ions

Abstract

Neutron diffraction with hydrogen/deuterium isotope substitution on the solvent water hydrogens is used to investigate changes in water structure around the apolar groups on alcohols and tetraalkylammonium ions at room temperature. The HH and HX correlations (where X is a nonsubstituted atom) are calculated for the following solutes in water: ethanol (5 mol%), tertiary butanol (3 mol%), tetrapropylammonium bromide (2.4 mol%), and tetrabutylammonium bromide (1.7 mol%). The correlation functions suggest that the water structure in all four systems is very similar to bulk water. There is no evidence of structural enhancement in going from pure water to water in the alcohol–water mixtures. There is a small but probably significant increase in structure in the tetraalkylammonium bromide solutions compared to both pure water and the alcohol–water mixtures. There is very little measurable difference between the two alcohol–water mixtures or the two tetraalkylammonium bromide solutions in terms of water structure. The results are consistent with the view that apolar solutes are located in cavities in the hydrogen-bonded water network, but they suggest that the increase in order associated with apolar hydration is a small effect in terms of structure.