Linear solvation energy relationships. Part 9. - Correlations of gas/liquid partition coefficients with the solvatochromic parameters, π*, α and β

Mortimer J. Kamlet, Robert W. Taft, Peter W Carr, Michael H. Abraham

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Abstract

When referenced to an alkane solute of similar molecular volume, i.e. log (Ksolute/Kalkane), gas/liquid partition coefficients for nitromethane, methylethylketone, dioxan, toluene and ethanol solutes are well correlated by the solvatochromic parameters, π*, δ, α and β. For nitromethane and dioxan solutes the partition coefficients depend only on the dipolarity/polarizability parameters (π*, δ). For methylethylketone, there is also a measurable dependence on hydrogen-bond donor acidity (α) of protic solvents. For ethanol in aliphatic non-hydrogen-bond donor solvents the dominant effects are solvent dipolarity/polarizability and solvent hydrogen-bond acceptor basicity (β). For toluene solute there appears to be a negative or desolvation effect in protic solvents which is attributed to a 'hydroxyphobic effect' of weakly basic solutes in alcohol solvents.

Original languageEnglish (US)
Pages (from-to)1689-1704
Number of pages16
JournalJournal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
Volume78
Issue number6
DOIs
StatePublished - Dec 1 1982

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Solvation
solvation
partitions
Gases
solutes
Liquids
coefficients
liquids
gases
nitromethane
Toluene
toluene
energy
Hydrogen bonds
ethyl alcohol
Ethanol
hydrogen bonds
Alkanes
Alkalinity
Acidity

Cite this

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abstract = "When referenced to an alkane solute of similar molecular volume, i.e. log (Ksolute/Kalkane), gas/liquid partition coefficients for nitromethane, methylethylketone, dioxan, toluene and ethanol solutes are well correlated by the solvatochromic parameters, π*, δ, α and β. For nitromethane and dioxan solutes the partition coefficients depend only on the dipolarity/polarizability parameters (π*, δ). For methylethylketone, there is also a measurable dependence on hydrogen-bond donor acidity (α) of protic solvents. For ethanol in aliphatic non-hydrogen-bond donor solvents the dominant effects are solvent dipolarity/polarizability and solvent hydrogen-bond acceptor basicity (β). For toluene solute there appears to be a negative or desolvation effect in protic solvents which is attributed to a 'hydroxyphobic effect' of weakly basic solutes in alcohol solvents.",
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AU - Kamlet, Mortimer J.

AU - Taft, Robert W.

AU - Carr, Peter W

AU - Abraham, Michael H.

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N2 - When referenced to an alkane solute of similar molecular volume, i.e. log (Ksolute/Kalkane), gas/liquid partition coefficients for nitromethane, methylethylketone, dioxan, toluene and ethanol solutes are well correlated by the solvatochromic parameters, π*, δ, α and β. For nitromethane and dioxan solutes the partition coefficients depend only on the dipolarity/polarizability parameters (π*, δ). For methylethylketone, there is also a measurable dependence on hydrogen-bond donor acidity (α) of protic solvents. For ethanol in aliphatic non-hydrogen-bond donor solvents the dominant effects are solvent dipolarity/polarizability and solvent hydrogen-bond acceptor basicity (β). For toluene solute there appears to be a negative or desolvation effect in protic solvents which is attributed to a 'hydroxyphobic effect' of weakly basic solutes in alcohol solvents.

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