Determination of excess Gibbs free energy from computer simulation by the single charging-integral approach. I. Theory

Journal Article · Mon Jan 01 04:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.458420· OSTI ID:7108212

Chialvo, A A ^[1]

---

1. Department of Chemical Engineering, Princeton University, Princeton, New Jersey 08544-5263 (US)

A recently proposed procedure for the determination of excess Gibbs free energy by computer simulation, due to Chialvo and Haile, and based on Kirkwood's coupling parameter interpretation of the chemical potential, is revised and improved. New theoretical expressions for excess Gibbs free energy, excess enthalpy and excess volume, are derived in this paper. The new equations allow the simultaneous determination of these quantities via isobaric--isothermal (NPT) simulations involving coupling-parameter charging from only one ideal solution (i.e., pure component), irrespective of either the number of components in the mixture or the number of potential parameters involved. Theoretical expressions are derived which allow the determination of infinite dilution activity coefficients, pure component fugacity ratios, and Henry's constant ratios without resorting to infinite dilution simulations.

• OSTI ID: 7108212
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 92:1; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
COMPUTERIZED SIMULATION
DISPERSIONS
ENERGY
FLUIDS
FREE ENERGY
INTERMOLECULAR FORCES
MIXTURES
PHYSICAL PROPERTIES
SIMULATION
STRUCTURE FACTORS
THERMODYNAMIC PROPERTIES