Observation of Liquid-Liquid Phase Transitions in Ethane at 300 K

We have conducted Raman spectroscopy experiments on liquid ethane (C₂H₆) at 300 K, obtaining a large amount of data at very high resolution. This has enabled the observation of Raman peaks expected but not previously observed in liquid ethane and a detailed experimental study of the liquid that was not previously possible. We have observed a transition between rigid and nonrigid liquid states in liquid ethane at ca. 250 MPa corresponding to the recently proposed Frenkel line, a dynamic transition between rigid liquid (liquidlike) and nonrigid liquid (gaslike) states beginning in the subcritical region and extending to arbitrarily high pressure and temperature. The observation of this transition in liquid (subcritical) ethane allows a clear differentiation to be made between the Frenkel line (beginning in the subcritical region at higher density than the boiling line) and the Widom lines (emanating from the critical point and not existing in the subcritical region). Furthermore, we observe a narrow transition at ca. 1000 MPa to a second rigid liquid state. We propose that this corresponds to a state in which orientational order must exist to achieve the expected density and can view the transition in analogy to the transition in the solid state away from the orientationally disordered phase I to the orientationally ordered phases II and III.