Determining Brown's Characteristic Curves Using Molecular Simulation.

Abstract

Brown's characteristic curves define lines on the thermodynamic surface where special thermodynamic conditions hold. These curves are an important tool for the development of thermodynamic models of fluids. Yet, practically no experimental data for Brown's characteristic curves is available. In this work, a rigorous and generalized method for determining Brown's characteristic curves based on molecular simulation was developed. As multiple thermodynamic equivalent definitions apply for the characteristic curves, different simulation routes were compared. Based on this systematic approach, the most favorable route for determining each characteristic curve was identified. The computational procedure developed in this work combines molecular simulation, molecular-based equation of state, and the evaluation of the second virial coefficient. The new method was tested on a simple model system (the classical Lennard-Jones fluid) and different types of real substances (toluene, methane, ethane, propane, and ethanol). It is thereby shown that the method is robust and yields accurate results. Moreover, a computer code implementation of the method is presented.