Supercritical Ethanol–CO2 Mixtures Exhibit Microscopic Immiscibility: A Combined Study Using X‑ray Scattering and Molecular Dynamics Simulations

Supercritical mixtures of ethanol (EtOH) and carbon dioxide (CO2) are classified as type-I mixtures, with complete macroscopic miscibility. However, differences in molecular polarity and interactions suggest a distinct phase behavior at the microscopic level. Here, we combine small angle X-ray scattering experiments and molecular dynamics (MD) simulations to investigate the microscopic structure of EtOH–CO2 mixtures under supercritical conditions. The structure factor exhibits nonlinear composition-dependent behavior, revealing pronounced local density fluctuations. The complementary MD simulations, using optimized force field parameters, provide atomistic insight, showing that EtOH forms self-associated, hydrogen-bonded aggregates, while CO2 remains more uniformly distributed. Cluster analysis identifies a preferential EtOH-rich composition exceeding the bulk average, governed by a balance between energetic and entropic competition. These results demonstrate that, contrary to macroscopic expectations, the mixture exhibits significant microscopic heterogeneity and immiscibility, which may influence solubility, reactivity, transport properties, and thermodynamic response functions. These findings challenge the conventional views of type-I fluids and emphasize the necessity of revising mixture states and considering molecular polarity.