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Extension of scaled particle theory to inhomogeneous hard particle fluids. I. Cavity growth at a hard wall

Daniel W. Siderius and David S. Corti*

  • School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, Indiana 47907-2100, USA

  • *Electronic address: dscorti@ecn.purdue.edu
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Phys. Rev. E 71, 036141 – Published 25 March, 2005

DOI: https://doi.org/10.1103/PhysRevE.71.036141

Abstract

The methods of traditional scaled particle theory (SPT) are used to develop an extended scaled particle theory that is now applicable to hard particle fluids confined by hard walls. The new theory, labeled inhomogeneous SPT (I-SPT), introduces the function G¯ that describes the average value of the anisotropic density of hard particle centers contacting a cavity placed at or behind a hard wall. We present an exact relation describing G¯ for certain cavity sizes and, similar to the original SPT, an accurate interpolation scheme for larger cavity radii. Given G¯, the reversible work of inserting a cavity centered at or behind the hard wall can be estimated. The work predictions at low to moderate packing fractions are extremely accurate, though small deviations from simulation results become apparent at packing fractions close to the bulk hard sphere freezing transition. I-SPT also reveals the importance of the line tension in determining the free energy of cavity formation for cavities intersecting a hard wall, a term which has been previously neglected. Furthermore, this paper provides the initial groundwork needed to develop a more complete SPT-based theory that can accurately predict the depletion force between a hard particle and a hard structureless wall.

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See Also

Extension of scaled particle theory to inhomogeneous hard particle fluids. II. Theory and simulation of fluid structure surrounding a cavity that intersects a hard wall

Daniel W. Siderius and David S. Corti
Phys. Rev. E 71, 036142 (2005)

Article Text

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Phys. Rev. E 71, 036141– Published 25 March, 2005
  • Received 23 November 2004

© 2005 American Physical Society

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