Optimized cluster theory correction to the van der Waals model of mixtures

Journal Article · Thu Aug 01 04:00:00 EDT 1974 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.1682038· OSTI ID:6643795

Sung, S H; Chandler, D; Alder, B J

The correction to the van der Waals mean field model for mixtures is shown to be significant compared to the excess thermodynamic properties of mixing hard spheres and square-well molecules under typical experimental conditions. Calculation of this correction to higher powers in the perturbation series of the attractive potential relative to the kinetic energy but in the mean field approximation, which leads to the one fluid model, results in an order of magnitude error. On the other hand, the optimized cluster theory, which reorders the perturbation series by graph theoretical techniques, provides quantitative predictions of the correction except near the critical line. The cluster theory is sufficiently accurate that it predicts heat capacities of mixtures larger than those of the pure components at the same volume and temperature as the mixture, in nearly quantitative agreement with the results obtained from molecular dynamics.

• Research Organization: Illinois Univ., Urbana
• OSTI ID: 6643795
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 61:3; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

42 ENGINEERING
420400* -- Engineering-- Heat Transfer & Fluid Flow
CORRECTIONS
DISPERSIONS
ENERGY TRANSFER
ENGINEERING
HEAT TRANSFER
MIXTURES
PHYSICAL PROPERTIES
RESERVOIR ENGINEERING
SIMULATION
SPECIFIC HEAT
SPHERES
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
VAN DER WAALS FORCES