A study of solvatochromic linear energy relationships in a homologous series of n-alkanes and n-alkanenitriles

Brady, James E.; Carr, Peter W.

doi:10.1021/j100255a055

Cited by 38 publications

(24 citation statements)

References 10 publications

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“…While the experimental enhancement for solubilities of solutes in supercritical carbon dioxide by fluorination of the solutes has been reported by several papers [3][4][5][6][7], the interaction between carbon dioxide and fluorinated compounds and the reason of the solubility enhancement remains controversial [8,9]. An IR spectroscopic study [10] and a NMR study [11] revealed specific interactions were not the source of enhanced interaction.…”

Section: Introductionmentioning

confidence: 97%

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Higashi

Iwai

Miyazaki

et al. 2005

Molecular Simulation

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A molecular dynamics simulation was applied to carbon dioxide + trifluoromethylbenzoic acid isomer and carbon dioxide + methylbenzoic acid isomer systems to investigate the interactions between carbon dioxide and the solutes. The pair correlation functions between the carbon dioxide and trifluoromethyl group or methyl group in the solutes were calculated to study the fluorination effect of solvation. As a result, it was found that the interactions between carbon dioxide and trifluoromethyl group in trifluoromethylbenzoic acid isomers were stronger than those between carbon dioxide and the methyl group in methylbenzoic acid isomers. The simulation results had the same tendency as the experimental solubility enhancements and coincided with the trend of the interaction parameters of the Peng-Robinson equation of state that were determined from the solubility data.

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Section: Introductionmentioning

confidence: 97%

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Higashi

Iwai

Miyazaki

et al. 2005

Molecular Simulation

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“…Whether this is due to specific interactions remains controversial. 6,7 For instance, IR spectrocopic studies on butanol vs. perfluorobutanol did not reveal specific interactions. 8 A similar conclusion was obtained from an NMR study of perfluorobenzene vs. benzene 9 while another NMR study of n-hexane vs. perfluorohexane concluded that specific interactions between CO 2 and fluorine existed.…”

Section: Introductionmentioning

confidence: 99%

Solvation of benzene derivatives in SC-CO2: a molecular dynamics study of fluorination effectsElectronic supplementary information (ESI) available: structures and interaction energies of X-Benz(CO2)n aggregates in the gas phase and table of force field parameters. See http://www.rsc.org/suppdata/nj/b3/b304300b/

Galand

Wipff

2003

New J. Chem.

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According to a molecular dynamics study of benzene (C 6 H 6 ) and its derivatives C 6 F 6 , CH 3 -C 6 H 5 and CF 3 -C 6 H 5 in SC-CO 2 solution, the fluoro compounds are better solvated than the H analogs. This is supported by the analysis of average solute-solvent interaction energies and by free energy perturbation simulations at 305 and 350 K. Stepwise model building of C 6 X 6 (CO 2 ) n aggregates (X ¼ H and F) in the gas phase, however, indicates that up to n ¼ 6, interactions with CO 2 are stronger with benzene, while perfluorobenzene becomes better solvated at higher coordination numbers. Thus, the enhancement of the CO 2 -philicity upon fluorination does not stem from enhanced individual interactions with the CO 2 molecule, but from the higher coordination number, due to the increase of solvent accessible surface. Finally, simulations of C 6 H 6 and C 6 F 6 at the CO 2water interface reveal that the former is somewhat surface active due to specific O-HÁ Á Áp facial interactions between interfacial water molecules, while C 6 F 6 mostly sits in the CO 2 phase, in keeping with its larger CO 2 -philicity.

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“…Values are available for more than 200 solvents (2) including supercritical fluids, perfluorinated alkanes, several homologous series of liquids, and highly dipolar solvents such as dimethyl sulfoxide and acetonitrile. The relationship of it* to such fundamental electrostatic properties as dielectric strength (e) and refractive index (n) has been explored in detail (3)(4)(5)(6)(7)(8).…”

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confidence: 99%

Kamlet-Taft .pi.* polarizability/dipolarity of mixtures of water with various organic solvents

Cheong

Carr²

1988

Anal. Chem.

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139

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The Kamlet-Taft * values of mixtures of water with four organic solvents over the entire range of composition have been estimated by solvatochromlc measurements with a series of carefully selected Indicators. The measured tr* value of each Indicator is colHnear with the average * value. We Interpret these results as indicating that the Indicators sense the polarlzabHIty/dlpolarlty and not the hydrogen bond acidity of the solvent. Examination of relationships between * and < and between £T and ir* and excess properties of *, ET, and e with respect to volume fraction of the organic cosolvent leads to the conclusion that the principal effect of changing the solvent composition on the observed * values operates through the dielectric properties of the local medium about the solute. This also supports the previous observation that solvatochromlc shifts of the Indicators used In this study are not very sensitive to solvent hydrogen bond acidity. The measured ir* values together with literature ET values were used to estimate a values, the hydrogen bond acidity parameter, of aqueous organic solvents.

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A study of solvatochromic linear energy relationships in a homologous series of n-alkanes and n-alkanenitriles

Cited by 38 publications

References 10 publications

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Kamlet-Taft .pi.* polarizability/dipolarity of mixtures of water with various organic solvents

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