Validity of Tolman's equation: How large should a droplet be?

Kenichiro Koga, X. C. Zeng, A. K. Shchekin

Research output: Contribution to journalArticle

120 Citations (Scopus)

Abstract

Surface tension and the length δ (distance between the Gibbs surface of tension Rs and the equimolar surface Re) of simple liquid droplet (Lennard-Jones and Yukawa) are computed over a wide range of droplet sizes up to about 4×106 molecules. The study is based on the Gibbs theory of capillarity combined with the density-functional approach to gas-liquid nucleation. Since this method provides behavior of the surface tension fully consistent with the tension of the planner surface, the constant in Tolman's equation δ can be determined unequivocally from the asymptotic behavior of σs. Comparison of the tension given by Tolman's equation against the result of exact thermodynamic relations reveals that Tolman's equation is valid only when the droplet holds more than 106 molecules for the simple fluid systems near their triple points, in contrast to the conventional wisdom that Tolman's equation may be applicable down to droplets holding a few hundreds of molecules.

Original languageEnglish
Pages (from-to)4063-4070
Number of pages8
JournalJournal of Chemical Physics
Volume109
Issue number10
DOIs
Publication statusPublished - 1998

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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