Gas or Liquid? The Supercritical Behavior of Pure Fluids.

By definition, the distinction between a gas and a liquid ceases to exist beyond the critical point for pure fluids. Nevertheless, there remains a strong desire to attribute gas-like or liquid-like behavior to fluids corresponding to different parts of the supercritical region, especially as this becomes important for understanding and designing the properties of supercritical fluids. Here, we use a combination of fluctuation solution theory and accurate equation of state data to elucidate an easily accessible dividing line and corresponding transition regime between liquid-like and gas-like behavior in the supercritical region of all pure fluids. Liquid-like behavior in the supercritical region is characterized by a negative skewness in the particle number distribution for an equivalent open system, indicating that particle deletion is favored for liquids, whereas gas-like behavior is characterized by a positive skewness, indicating that particle insertion is favored for gases. Identical behavior is observed either side of the liquid-vapor line. The possible consequences for the behavior of fluids at the critical point are also discussed.