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Generalized Flory theory for hard alkane fluids

 

作者: SameerD. Mehta,   KevinG. Honnell,  

 

期刊: Molecular Physics  (Taylor Available online 1996)
卷期: Volume 87, issue 6  

页码: 1285-1297

 

ISSN:0026-8976

 

年代: 1996

 

DOI:10.1080/00268979600100871

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Generalized Flory-dimer (GF-D) theory is extended to hard n-alkane fluids modelled as fused hard spheres constrained according to the rotational isomeric state approximation. Theoretical predictions for the second to the fifth virial coefficients for each conformer from n-butane to n-octane are compared with numerical results. Predictions for the second viral coefficient are in excellent agreement with recent simulation results; however, GF-D theory systematically overpredicts the third virial coefficient and underpredicts the fourth and the fifth virial coefficients. GF-D predictions for the compressibility factor for n-alkanes from n-butane to n-octane are compared with molecular dynamic simulation results for a closely related model. Despite the over- and underprediction of the individual virial coefficients, excellent agreement is observed between theory and simulation for the compressibility factors of n-butane and n-pentane using no adjustable parameters. However, in the cases of n-hexane, n-heptane and n-octane, GF-D theory slightly underpredicts the pressure at high volume fractions. Theoretical considerations suggest that probably the predictions of GF-D theory will deteriorate with increasing chain length.

 

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