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  • 标题:A van der Waals-type equation of state for fluids with associating molecules
  • 本地全文:下载
  • 作者:Robert A. Heidemann ; J. M. Prausnitz
  • 期刊名称:Proceedings of the National Academy of Sciences
  • 印刷版ISSN:0027-8424
  • 电子版ISSN:1091-6490
  • 出版年度:1976
  • 卷号:73
  • 期号:6
  • 页码:1773-1776
  • DOI:10.1073/pnas.73.6.1773
  • 语种:English
  • 出版社:The National Academy of Sciences of the United States of America
  • 摘要:The basic assumptions of van der Waals theory are contained in two well-known concepts: excluded volume (repulsive forces) and a homogeneous, isotropic field potential (attractive forces). We have superimposed on these, one more well-known concept: the existence of dimers, trimers, etc., at chemical equilibrium. With reasonable simplifying assumptions, we obtain a closed-form equation of state, applicable to all fluid densities, and potentially useful for fluids containing strongly polar or hydrogen-bonded molecules. At all temperatures and at high densities, the equation of state suggests a phase transition where, because of extensive association, a new (solid-like) phase is in equilibrium with a "normal" fluid phase. The boundary between these phases has no critical point.
  • 关键词:molecular clusters ; virial coefficients ; phase transition
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