English

Analytic representation of critical equations of state

Statistical Mechanics 2014-02-07 v2

Abstract

We propose a new form for equations of state (EOS) of thermodynamic systems in the Ising universality class. The new EOS guarantees the correct universality and scaling behavior close to critical points and is formulated in terms of the scaling fields only -- unlike the traditional Schofield representation, which uses a parametric form. Close to a critical point, the new EOS expresses the square of the strong scaling field Σ\Sigma as an explicit function Σ2=D2e1Γ(De0Θ)\Sigma^2=D^{2e_{-1}}\Gamma(D^{-e_0}\Theta) of the thermal scaling field Θ\Theta and the dependent scaling field D>0D>0, with a smooth, universal function Γ\Gamma and the universal exponents e1=δ/(δ+1)e_{-1}=\delta/(\delta+1), e0=1/(2α)e_0=1/(2-\alpha). A numerical expression for Γ\Gamma is derived, valid close to critical points. As a consequence of the construction it is shown that the dependent scaling field can be written as an explicit function of the relevant scaling fields without causing strongly singular behavior of the thermodynamic potential in the one-phase region. Augmented by additional scaling correction fields, the new EOS also describes the state space further away from critical points. It is indicated how to use the new EOS to model multiphase fluid mixtures, in particular for vapor-liquid-liquid equilibrium (VLLE) where the traditional revised scaling approach fails.

Keywords

Cite

@article{arxiv.1401.0291,
  title  = {Analytic representation of critical equations of state},
  author = {Arnold Neumaier},
  journal= {arXiv preprint arXiv:1401.0291},
  year   = {2014}
}

Comments

27 pages with 4 figures; v2 corrects an error in v1. arXiv admin note: text overlap with arXiv:1307.8388. text overlap with arXiv:1307.8388