P-V-T behaviour of hard body fluids. Theory and experiment

Boublı́k, Tomáš; Nezbeda, Ivó

doi:10.1135/cccc19862301

Cited by 386 publications

(226 citation statements)

References 0 publications

Supporting

Mentioning

216

Contrasting

Unclassified

Order By: Relevance

“…18 We have checked our code by comparing with bibliographic results for the Lennard-Jones fluid, 7,9 and for hard-dumbbells. 4 Good agreement was found in all cases. In 6 .…”

Section: Resultssupporting

confidence: 51%

“…The reason is that the statistical error bars very much increase with increasing r c , so that whichever gain in accuracy due to better convergence is disguised by the increased error bars. As expected, similar difficulties were found for B 4 , so that we keep this value here for consistency. A single B 4 calculation involved averaging 200 independent blocks, while each block was obtained as a Monte Carlo average over 90ϫ10 6 configurations.…”

Section: Model and Calculation Detailsmentioning

confidence: 69%

“…23,22 In a second approximation ͑VSB4͒, we attempt to improve on the previous equation by considering a virial series truncated to fourth order, using the results of this work for B 4 ,…”

Section: Resultsmentioning

confidence: 99%

“…1 Despite of its formal simplicity, the use of this equation of state has been limited, since both experimental and theoretical calculations beyond the second virial coefficient have proven to be rather difficult. 2 Nevertheless, the study of virial coefficients has been extremely fruitful in the development of widely employed equations of state for hard fluids, such as hard spheres, 3 hard convex bodies, 4 or even hard sphere chain fluids. 5 The information on virial coefficients of more realistic fluids incorporating attractive interactions is much more limited, however.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Critical properties of molecular fluids from the virial series

MacDowell

Menduiña

Vega

et al. 2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

We present results for the fourth virial coefficient of quadrupolar Lennard-Jones diatomics for several quadrupole moments and elongations. The coefficients are employed to predict the critical properties from two different truncated virial series. The first one employs the exact second and third virial coefficients, calculated in our previous work. The second includes also the exact fourth virial coefficient as obtained in this work. It is found that the first method yields already fairly good predictions. The second method significantly improves on the first one, however, yielding good results for both the critical temperature and pressure. Particularly, when compared with predictions from perturbation theories available in the literature, the virial series to fourth order compares favorably for the critical temperature. The results suggest that the failure of perturbation theories to predict the critical temperature and pressure is not only related to the neglect of density fluctuations, but also to poor prediction of the virial coefficients.

show abstract

“…18 We have checked our code by comparing with bibliographic results for the Lennard-Jones fluid, 7,9 and for hard-dumbbells. 4 Good agreement was found in all cases. In 6 .…”

Section: Resultssupporting

confidence: 51%

Section: Model and Calculation Detailsmentioning

confidence: 69%

“…23,22 In a second approximation ͑VSB4͒, we attempt to improve on the previous equation by considering a virial series truncated to fourth order, using the results of this work for B 4 ,…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Critical properties of molecular fluids from the virial series

MacDowell

Menduiña

Vega

et al. 2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…(5) to coincide with the fourth-order virial expansion reported in Eq.(1). The quantities B αβ and C αβγ are the second and third virial coefficients, respectively, which are available analytically [1]. In the limit ∆ → 0, the first three terms of Eq.…”

Section: The Virial Coefficients and The Barboy-gelbart Equation Of Smentioning

confidence: 99%

Virial Coefficients and Demixing of Athermal Nonadditive Mixtures

et al. 2007

View full text Add to dashboard Cite

We compute the fourth virial coefficient of a binary nonadditive hard-sphere mixture over a wide range of deviations from diameter additivity and size ratios. Hinging on this knowledge, we build up a y expansion [B. Barboy and W. N. Gelbart, J. Chem. Phys. 71, 3053 (1979)] in order to trace the fluid-fluid coexistence lines which we then compare with the available Gibbs-ensemble Monte Carlo data and with the estimates obtained through two refined integral-equation theories of the fluid state. We find that in a regime of moderately negative nonadditivity and largely asymmetric diameters, relevant to the modelling of sterically and electrostatically stabilized colloidal mixtures, the fluid-fluid critical point is unstable with respect to crystallization.

show abstract

Solute excluded-volume effects on the stability of globular proteins: A statistical thermodynamic theory

Zhou

Hall

1998

Biopolymers

View full text Add to dashboard Cite

A statistical thermodynamic theory is developed to investigate the effects of solute excluded volume on the stability of globular proteins. Proteins are modeled as two states in chemical equilibrium: the denatured state is modeled as a flexible chain of tangent hard spheres (pearl‐necklace chain) while the native state is modeled as a single hard sphere. Study of model proteins bovine pancreatic trypsin inhibitor and lysozyme in a McMillan‐Mayer model solution of hard spheres indicates that the excluded volume of solutes has three distinct types of effects on protein stability: (1) small‐size solutes strongly denature proteins, (2) medium‐size solutes stabilize proteins at low solute concentrations and destabilize them at high concentrations, and (3) large‐size solutes stabilize native‐state proteins across the whole liquid region. The study also finds that increasing the chain length of hard‐chain polymer solutes has an effect on protein stability that is similar to increasing the diameter of spherical solutes. This work qualitatively explains why stabilizers tend to be large size molecules such as sugars, polymers, polynols, nonionic, and anionic surfactants while denaturants tend to be small size molecules such as alcohols, glycols, amides, formamides, ureas, and guanidium salts. Quantitative comparison between theoretical predictions and experimental results for folding free energy changes shows that the excluded‐volume effect is at least as important as the binding and/or electrostatic effects on solute‐assisted protein‐denaturation processes. Our theory may also be able to explain the effect of excluded volume on the Φ condensation of DNA. © 1996 John Wiley & Sons, Inc.

show abstract

P-V-T behaviour of hard body fluids. Theory and experiment

Cited by 386 publications

References 0 publications

Critical properties of molecular fluids from the virial series

Critical properties of molecular fluids from the virial series

Virial Coefficients and Demixing of Athermal Nonadditive Mixtures

Solute excluded-volume effects on the stability of globular proteins: A statistical thermodynamic theory

Contact Info

Product

Resources

About