Solvatochromism: a dielectric continuum model applied to supercritical fluids
The solvatochromic behavior of nonpolar supercritical fluids, in terms of the ..pi..* Kamlet and Taft polarity/polarizability parameter, is compared to the McRae-Bayliss model. A break in the plot of ..pi..* against the Onsager reaction field (F/sub 0/) is seen for the fluids studied at low reaction field values (low densities). The relationship between ..pi..* and the Onsager reaction field (F/sub 0/) shows two regions of nearly linear behavior. The transition from the low-density region to higher density region, where a smaller dependence of ..pi..* upon (F/sub 0/) is observed, is tentatively attributed to extensive solvent clustering about the solute. This hypothesis is supported by the behavior previously observed for the partial molar volume of the solute in the fluid anti v/sub 2/ infinity as a function of pressure. The rapid change in anti v/sub 2/ infinity is also shown to occur in the same region where the solvatochromic behavior of the fluid changes and the solute's solubility increases dramatically.
- Research Organization:
- Pacific Northwest Lab., Richland, WA
- DOE Contract Number:
- AC06-76RL01830
- OSTI ID:
- 5477672
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:1; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKANES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
DATA
ELECTRICAL PROPERTIES
ETHANE
FLUIDS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
MATHEMATICAL MODELS
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
POLARIZABILITY
SOLVATION
SULFUR COMPOUNDS
SULFUR FLUORIDES
SUPERCRITICAL STATE
THEORETICAL DATA