Microinhomogeneity for aqueous mixtures of water-miscible organic solvents

Mixing states for aqueous solutions of water-miscible organic solvents, acetonitrile and 1,4-dioxane, have been investigated at the molecular level by means of small-angle neutron scattering (SANS) and NMR relaxation. It has been shown that the organic solvent and water molecules are inhomogeneously mixed each other at the molecular level, although their mixtures are homogeneous at the macroscopic scale. Thus, both organic solvent clusters and water clusters coexist in the mixtures. The present investigation has also revealed that the microinhomogeneity of acetonitrile-water and 1,4-dioxane-water mixtures is gradually enhanced by cooling or adding salts toward phase separation. Based on the results, the effect of microinhomogeneity for solvent mixtures on chemical reactions was considered.