Statistical Thermodynamic Approach to the Chemical Activities in Two-Component Solutions

Jörg Rösgen, Bernard Pettitt, John Perkyns, David Wayne Bolen

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

It is shown how the leading terms of a semi grand canonical partition function (GCPF) can be used to develop analytic expressions relating activity to concentrations in two-component systems. The simple analytic expressions for activity coefficients can be fitted to activity coefficient versus concentration data for a wide range of aqueous solute systems. Only one or two parameters are required to accurately describe the activity coefficients of nonelectrolyte and electrolyte aqueous solute systems over their entire range of solubility. These forms derive from low-order number expressions of the GCPF that take into account the effective solvent interactions with the solute and between solute molecules for a variable amount of solvent. The GCPF leading terms and fitting parameters define apparent solute-solute oligomerization and solute packing phenomena that increase with solute concentration. Advantages using this grand canonical approach versus previous approaches are discussed.

Original languageEnglish (US)
Pages (from-to)2048-2055
Number of pages8
JournalJournal of Physical Chemistry B
Volume108
Issue number6
StatePublished - Feb 12 2004
Externally publishedYes

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Statistical mechanics
Activity coefficients
solutes
thermodynamics
Oligomerization
partitions
Electrolytes
Solubility
Molecules
coefficients
nonelectrolytes
solubility
electrolytes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Statistical Thermodynamic Approach to the Chemical Activities in Two-Component Solutions. / Rösgen, Jörg; Pettitt, Bernard; Perkyns, John; Bolen, David Wayne.

In: Journal of Physical Chemistry B, Vol. 108, No. 6, 12.02.2004, p. 2048-2055.

Research output: Contribution to journalArticle

Rösgen, Jörg ; Pettitt, Bernard ; Perkyns, John ; Bolen, David Wayne. / Statistical Thermodynamic Approach to the Chemical Activities in Two-Component Solutions. In: Journal of Physical Chemistry B. 2004 ; Vol. 108, No. 6. pp. 2048-2055.
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