Droplet-like heterogeneity of aqueous tetrahydrofuran solutions at the submicrometer scale

J Chem Phys. 2016 Nov 14;145(18):184501. doi: 10.1063/1.4966187.

Abstract

A droplet formation in aqueous solutions of tetrahydrofuran (THF) has been experimentally detected at the submicrometer scale using two independent laser diagnostic techniques (dynamic light scattering and laser phase microscopy) and described in terms of THF-water intermolecular hydrogen bonding. It is shown that the nanodroplets have a mean size of 300 nm, their refractive index is higher than that of the ambient liquid, and they are highly enriched with THF molecules. The maximum of light scattering intensity falls within the THF concentration range 2-8 mol. %, which corresponds to the volume number density of the nanodroplets ∼1010-1011 cm-3. A theoretical explanation of forming the nanodroplets with a high content of THF, which is based on a model of dichotomous noise being applied to the so-termed "twinkling" hydrogen bonds and involves spinodal decomposition in the unstable region enclosed within the dichotomous binodal, is proposed. The parameters of hydrogen bonds in the molecular system "water-THF" were found, and the phase diagram of the solution with allowance for cross-linking hydrogen bonds was constructed.