Table of Contents
Journal of Thermodynamics
Volume 2010 (2010), Article ID 238365, 10 pages
http://dx.doi.org/10.1155/2010/238365
Research Article

A MultiScale Gibbs-Helmholtz Constrained Cubic Equation of State

Department of Chemical Engineering, University of Rhode Island, Kingston, RI 02881, USA

Received 21 July 2009; Accepted 18 August 2009

Academic Editor: Jae Lee

Copyright © 2010 Angelo Lucia. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

This paper presents a radically new approach to cubic equations of state (EOS) in which the Gibbs-Helmholtz equation is used to constrain the attraction or energy parameter, a. The resulting expressions for 𝑎 ( 𝑇 , 𝑝 ) for pure components and 𝑎 ( 𝑇 , 𝑝 , 𝑥 ) for mixtures contain internal energy departure functions and completely avoid the need to use empirical expressions like the Soave alpha function. Our approach also provides a novel and thermodynamically rigorous mixing rule for 𝑎 ( 𝑇 , 𝑝 , 𝑥 ) . When the internal energy departure function is computed using Monte Carlo or molecular dynamics simulations as a function of current bulk phase conditions, the resulting EOS is a multiscale equation of state. The proposed new Gibbs-Helmholtz constrained (GHC) cubic equation of state is used to predict liquid densities at high pressure and validated using experimental data from literature. Numerical results clearly show that the GHC EOS provides fast and accurate computation of liquid densities at high pressure, which are needed in the determination of gas hydrate equilibria.