Solvation of hydrophobes in water and simple liquids

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The solvation of nonpolar molecules in water and that in simple liquids are compared and contrasted. First, solvation thermodynamics is reviewed in a way that focuses on how the enthalpy and entropy of solvation depend on the choice of microscopic volume change v in the solvation process - including special choices v being zero (fixed-volume condition) and v being the partial molecular volume of a solute molecule (fixed-pressure condition) - and how the solvation quantities are related with temperature derivatives of the solvation free energy. Second, the solvation free energy and the solvation enthalpy of a Lennard-Jones (LJ) atom in model water are calculated in the parameter space representing the solute size and the strength of the solute-solvent interaction, and the results are compared with those for an LJ atom in the LJ solvent. The solvation diagrams showing domains of different types of solvation in the parameter space are obtained both for the constant-volume condition and for the constant-pressure condition. Similarities between water and the simple liquid are found when the constant-volume solvation is considered while a significant difference manifests itself in the fixed-pressure solvation. The domain of solvation of hydrophobic character in the parameter space is large in the constant-volume solvation both for water and for the simple liquid. When switched to the constant-pressure condition accompanying a microscopic volume change, the hydrophobic domain remains large in water but it becomes significantly small in the simple liquid. The contrasting results are due to the smallness of the thermal pressure coefficient of water at low temperatures.

Original languageEnglish
Pages (from-to)19749-19758
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number44
DOIs
Publication statusPublished - Nov 28 2011

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Solvation
solvation
Water
Liquids
liquids
water
solutes
Free energy
Enthalpy
enthalpy
free energy
Atoms
Molecules
atoms
molecules
Entropy

ASJC Scopus subject areas

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

Cite this

Solvation of hydrophobes in water and simple liquids. / Koga, Kenichiro.

In: Physical Chemistry Chemical Physics, Vol. 13, No. 44, 28.11.2011, p. 19749-19758.

Research output: Contribution to journalArticle

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