title: Thermodynamic curvature from the critical point to the triple point.
abstract: I evaluate the thermodynamic curvature R for fourteen pure fluids along their liquid-vapor coexistence curves, from the critical point to the triple point, using thermodynamic input from the NIST Chemistry WebBook. In this broad overview, R is evaluated in both the coexisting liquid and vapor phases. R is an invariant whose magnitude |R| is a measure of the size of mesoscopic organized structures in a fluid, and whose sign specifies whether intermolecular interactions are effectively attractive (R<0) or repulsive (R>0). I discuss five principles for R in pure fluids: (1) Near the critical point, the attractive part of the interactions forms loose structures of size |R| proportional to the correlation volume ξ(3), and the sign of R is negative. (2) In the vapor phase, there are instances of compact clusters of size |R| formed by the attractive part of the interactions and prevented from collapse by the repulsive part of the interactions, and the sign of R is positive. (3) In the asymptotic critical point regime, the R's in the coexisting liquid and vapor phases are equal to each other, i.e., commensurate. (4) Outside the asymptotic critical-point regime incommensurate R's may be associated with metastability. (5) The compact liquid phase has |R| on the order of the volume of a molecule, with the sign of R being negative for a liquidlike state held together by attractive interactions and the sign of R being positive for a solidlike state held up by repulsive interactions. These considerations amplify and extend the application of thermodynamic curvature in pure fluids.
authors.affiliation: Division of Natural Sciences, New College of Florida, 5800 Bay Shore Road, Sarasota, Florida 34243-2109, USA.
authors.forename: George
authors.initials: G
authors.lastname: Ruppeiner