Diffusion of the carbon dioxide-ethanol mixture in the extended critical region

The effect of traces of ethanol in supercritical carbon dioxide on the mixture's thermodynamic properties is studied by molecular simulations and Taylor dispersion measurements. This mixture is investigated along the isobar p = 10 MPa in the temperature range between T = 304 and 343 K. Along this path, the mixture undergoes two transitions: First, the Widom line is crossed, marking the transition from liquid-like to gas-like conditions. A second transition occurs from the supercritical gas-like domain to a subcritical gas. The Widom line crossover entails inflection points for most of the studied properties, i.e. density, enthalpy, shear viscosity, Maxwell-Stefan and intradiffusion coefficients. On the other hand, the transition between the super- and subcritical regions is found to be generally smooth, an observation that is qualitatively confirmed by experimental Taylor dispersion measurements. Dedicated atomistic simulations show the presence of microheterogeneities due to ethanol self-association along the investigated path, which lead to the mixture's anomalous behavior in its extended critical region.

Automated summary

The study investigates the effect of traces of ethanol in supercritical carbon dioxide on the mixture's thermodynamic properties through molecular simulations and Taylor dispersion measurements. The study reveals two transitions along the isobar path, from liquid-like to gas-like conditions at the Widom line, and from supercritical gas-like domain to subcritical gas. The presence of microheterogeneities due to ethanol self-association leads to anomalous behavior in the mixture's extended critical region, as shown by dedicated atomistic simulations.