English

Thermodynamic curvature from the critical point to the triple point

Statistical Mechanics 2015-06-11 v1

Abstract

I evaluate the thermodynamic curvature RR 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, RR is evaluated in both the coexisting liquid and vapor phases. RR is an invariant whose magnitude R|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<0R<0) or repulsive (R>0R>0). I discuss five principles for RR in pure fluids: 1) near the critical point, the attractive part of the interactions forms loose structures of size R|R| proportional to the correlation volume ξ3\xi^3, and sign of RR negative, 2) in the vapor phase, there are instances of compact clusters of size R|R| formed by the attractive part of the interactions and prevented from collapse by the repulsive part of the interactions, and sign of RR positive, 3) in the asymptotic critical point regime, the RR's in the coexisting liquid and vapor phases are equal to each other, i.e., commensurate, 4) outside the asymptotic critical point regime incommensurate RR's may be associated with metastability, and 5) the compact liquid phase has R|R| on the order of the volume of a molecule, with sign of RR negative for a liquidlike state held together by attractive interactions and sign of RR positive for a solidlike state held up by repulsive interactions. These considerations amplify and extend the application of thermodynamic curvature in pure fluids.

Keywords

Cite

@article{arxiv.1208.3265,
  title  = {Thermodynamic curvature from the critical point to the triple point},
  author = {George Ruppeiner},
  journal= {arXiv preprint arXiv:1208.3265},
  year   = {2015}
}

Comments

29 page, 7 figures