Geometric view of the thermodynamics of adsorption at a line of three-phase contact

The Journal of Chemical Physics
Yuri Djikaev, B Widom

Abstract

We consider three fluid phases meeting at a line of common contact and study the linear excesses per unit length of the contact line (the linear adsorptions Lambda(i)) of the fluid's components. In any plane perpendicular to the contact line, the locus of choices for the otherwise arbitrary location of that line that makes one of the linear adsorptions, say Lambda(2), vanish, is a rectangular hyperbola. Two of the adsorptions Lambda(2) and Lambda(3) then both vanish when the contact line is chosen to pass through any of the intersections of the two corresponding hyperbolas Lambda(2)=0 and Lambda(3)=0. There may be two or four such real intersections. It is found most surprisingly, and confirmed in a numerical example, that Lambda(1(2,3)), the adsorption of component 1 in a frame of reference in which the adsorptions Lambda(2) and Lambda(3) are both 0, depends on which intersection of the hyperbolas Lambda(2)=0 and Lambda(3)=0 is chosen for the location of the contact line. This implies that what had long been taken to be the line analog of the Gibbs adsorption equation is incomplete; there must be additional, previously unanticipated terms in the relation, consistent with the invariance of the line tension to choice of location...Continue Reading

References

Dec 1, 1995·Physical Review. E, Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics·J L LebowitzL Samaj
Jan 4, 2001·Physical Review. E, Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics·G PacittoM Widom

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Citations

Nov 6, 2007·The Journal of Chemical Physics·L SchimmeleS Dietrich
Mar 3, 2010·The Journal of Chemical Physics·A R Herring, J R Henderson
Sep 3, 2010·Annual Review of Physical Chemistry·Benjamin Widom
Mar 10, 2012·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·Chang-You LinRobert F Sekerka
May 1, 2009·The Journal of Physical Chemistry. B·Daniel W Siderius, David S Corti
Aug 14, 2021·Proceedings of the National Academy of Sciences of the United States of America·Romain BeyCyril Picard
Nov 3, 2006·The Journal of Physical Chemistry. B·B Widom

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