Note on the calculation of the second osmotic virial coefficient in stable and metastable liquid states

B. Widom, Kenichiro Koga

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The second osmotic virial coefficient is calculated from analytical equations of state as illustrated with the van der Waals two-component equation. It is shown that when the fixed solvent chemical potential or pressure at which the virial coefficient is calculated is taken to be that of the pure solvent in coexistence with its vapor, as in a recent report, the liquid solution is in a metastable state. When, by contrast, that fixed chemical potential or pressure is that of the pure solvent in its one-phase liquid state, the solution, with increasing solute concentration, is initially in a stable state; then, on crossing the liquid-vapor equilibrium line, it becomes metastable and ultimately approaches a spinodal and incipient instability. Nevertheless, in practice, as seen in a numerical illustration for a hydrocarbon dissolved in water, there is scarcely any difference in the virial coefficient calculated with the fixed solvent chemical potential or pressure of the pure solvent at its vapor pressure (metastable states of the solution) or at 1 bar (initially stable states). It is also seen in that example that the virial coefficient may be reliably calculated only for solute concentrations that are neither too small nor too large; typically only for mole fractions roughly from 10-7 to 10 -3.5.

Original languageEnglish
Pages (from-to)1151-1154
Number of pages4
JournalJournal of Physical Chemistry B
Volume117
Issue number4
DOIs
Publication statusPublished - Jan 31 2013

Fingerprint

virial coefficients
Chemical potential
Liquids
liquids
metastable state
solutes
liquid-vapor equilibrium
Hydrocarbons
Vapor pressure
Equations of state
Phase equilibria
vapor pressure
liquid phases
equations of state
hydrocarbons
Vapors
vapors
Water
water

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Note on the calculation of the second osmotic virial coefficient in stable and metastable liquid states. / Widom, B.; Koga, Kenichiro.

In: Journal of Physical Chemistry B, Vol. 117, No. 4, 31.01.2013, p. 1151-1154.

Research output: Contribution to journalArticle

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