Thephase behavior and mesoscopic inhomogeneities in the ternarysystem of tertiary butyl alcohol (TBA), water, and propylene oxide(PO) have been studied by static and dynamic light scattering, gaschromatography, mass spectrometry, and molecular dynamics simulations.Mesoscale inhomogeneities are observed in this system in a broad rangeof PO concentrations, from 0.02 to about 65 mass %, and at certainTBA/water mass ratios varying from about 3/97 to about 30/70. ThisTBA/water composition domain corresponds to a region where short-livedmicelle-like molecular clustering and thermodynamic anomalies areobserved in the TBA–water binary system. At dilute PO concentrations(0.02 to about 1 mass %) the mesoscale inhomogeneities are Browniandiffusive droplets, with a size of the order of a hundred nanometers.We hypothesize that these droplets have a hydrophobic core enrichedby oily impurities and oligomerized PO molecules. A hydrogen-bondedlayer of TBA, water, and PO molecules surrounds this hydrophobic core.At high PO concentrations (beyond 50 mass %), the interfacial curvatureof the mesoscopic inhomogeneities changes its sign and the exteriorsof these inhomogeneities become hydrophobic. The inversion of theinternal curvature may result in the formation of a spongelike bicontinuousmesoscale structure at intermediate PO concentrations. This mesostructureappears to be at a nonequilibrium state, although extremely long-lived. [ABSTRACT FROM AUTHOR]