Development of Abraham model correlations for describing the transfer of molecular solutes into propanenitrile and butanenitrile from water and from the gas phase

Experimental solubilities were measured for 20 crystalline organic solutes dissolved in propanenitrile and for 13 crystalline organic solutes dissolved in butanenitrile at 298.15 K. Infinite dilution activity coefficient data for solutes dissolved in propanenitrile and butanenitrile have been compiled from the published chemical and engineering literature and converted into gas-to-liquid partition coefficients and water-to-organic solvent partition coefficients through standard thermodynamic relationships. Abraham model correlations were developed for describing solute transfer into both propanenitrile and butanenitrile by combining our measured solubility data with the partition coefficients that we calculated from the published activity coefficient data. The derived Abraham model correlations were found to back-calculate the observed partition coefficients and molar solubility data to within 0.14 log units.     

Abraham Model Correlations for Triethylene Glycol Solvent Derived from Infinite Dilution Activity Coefficient,Partition Coefficient and Solubility Data Measured at 298.15 K

A gas chromatographic headspace analysis method was used to experimentally determine gas-to-liquid partition coefficients and infinite dilution activity coefficients for 29 liquid organic solutes dissolved in triethylene glycol at 298.15 K. Solubilities were also determined at 298.15 K for 23 crystalline nonelectrolyte organic compounds in triethylene glycol based on spectroscopic absorbance measurements. The experimental results of the headspace chromatographic and spectroscopic solubility measurements were converted to gas-to-triethylene glycol and water-to-triethylene glycol partition coefficients, and molar solubility ratios using standard thermodynamic relationships. Expressions were derived for solute transfer into triethylene glycol by combining our measured experimental values with published literature data. Mathematical correlations based on the Abraham model describe the observed partition coefficient and solubility data to within 0.16 log₁₀ units (or less).     

Abraham Model Expressions for Describing Water-to-Diethylene Glycol and Gas-to-Diethylene Glycol Solute Transfer Processes at 298.15 K

A gas chromatographic headspace analysis method was used to experimentally determine gas-to-liquid partition coefficients and infinite dilution activity dilution for 14 different aliphatic and cyclic hydrocarbons (alkanes, cycloalkanes, alkenes, alkynes), eight different aromatic compounds (benzene, alkylbenzenes, halobenzenes), five different chloroalkanes (dichloromethane, trichloromethane, 1-chlorobutane, 1,2-dichloropropane, isopropylbromide), tetrahydrofuran, butyl acetate, and acetonitrile dissolved in diethylene glycol at 298.15 K. Solubilities were also measured at 298.15 K for 31 crystalline nonelectrolyte organic solutes including several polycyclic aromatic hydrocarbons and substituted benzoic acid derivatives. The experimental results of the headspace chromatographic and spectroscopic solubility measurements were converted to gas-to-diethylene glycol and water-to-diethylene glycol partition coefficients, and molar solubility ratios using standard thermodynamic relationships. Expressions were derived for solute transfer into diethylene glycol from the calculated partition coefficients and solubility ratios. Mathematical correlations based on the Abraham model describe the observed partition coefficient and solubility data to within 0.14 log₁₀ units (or less).     

Ion-specific equation coefficient version of the Abraham model for ionic liquid solvents: determination of coefficients for tributylethylphosphonium, 1-butyl-1-methylmorpholinium, 1-allyl-3-methylimidazolium and octyltriethylammonium cations

Gas-to-ionic liquid partition coefficient data have been assembled from the published chemical literature for solutes dissolved in 1-allyl-3-methylimidazolium dicyanamide, 1-allyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide, octyltriethylammonium bis(trifluomethyl-sulphonyl)imide, tributylethylphosphonium diethylphosphate and 1-butyl-1-methylmorpholinium tricyanomethanide. The published experimental data were converted to water-to-ionic liquid partition coefficients using standard thermodynamic relationships. Both sets of partition coefficients were correlated with the Abraham solvation parameter model. The derived Abraham model correlations described the observed partition coefficient data to within 0.13 log units. Cation-specific equation coefficients were calculated for each of the cations present in the five ionic liquid solvents studied. The calculated cation-specific equation coefficients can be combined with previously reported ion-specific equation coefficients for 19 different anions to yield Abraham model correlations for predicting the partitioning the behaviour of solutes in 76 different anhydrous ionic liquid solvents.     

Updated Abraham model correlations for correlating solute transfer into dry butanone and dry cyclohexanone solvents

Updated Abraham solvation parameter model correlations are derived for describing the partitioning and solubility behaviour of organic nonelectrolyte solutes and inorganic gases in both anhydrous butanone and cyclohexanone solvents. The butanone and cyclohexanone correlations are based on data sets that contain 103 and 72 experimental data points, respectively. The derived correlations for butanone describe the experimental partitioning and solubility behaviour to within a standard deviation of 0.145 log units. A slightly smaller standard deviation of 0.135 was observed between the experimental and back-calculated values for the cyclohexanone solvent correlation equations.     

Abraham model ion-specific equation coefficients for the 1-butyl-2,3-dimethyimidazolium and 4-cyano-1-butylpyridinium cations calculated from measured gas-to-liquid partition coefficient data

Partition coefficient and gas solubility data have been assembled from the published chemical and engineering literature for solutes dissolved in anhydrous 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, and 4-cyano-1-butylpyrridinium bis(trifluoromethylsulfonyl)imide. More than 60 experimental data points were gathered for each IL solvent. The compiled experimental data were used to derive Abraham model correlations for describing the solute transfer properties into the three anhydrous IL solvents from both the gas phase and water. The derived mathematical correlations described the observed solute transfer properties, expressed as the logarithm of the water-to-IL partition coefficient and logarithm of the gas-to-IL solvent partition coefficient, to within standard deviations of 0.125 log units (or less). Abraham model ion-specific equation coefficients are also calculated for the 1-butyl-2,3-dimethylimidazolium and 4-cyano-1-butylpyridinium cations.     

Development of Abraham model IL-specific correlations for N-triethyl(octyl)ammonium bis(fluorosulfonyl)imide and 1-butyl-3-methylpyrrolidinium bis(fluorosulfonyl)imide

ABSTRACT

Abraham model correlations are derived for describing gas-to-ionic liquid and water-to-ionic liquid partition coefficients from published experimental data for solutes dissolved in both N-triethyl(octyl)ammonium bis(fluorosulfonyl)imide and 1-butyl-3-methyl-pyrrolidinium bis(fluorosulfonyl)imide. Derived Abraham model correlations describe the observed partition coefficient data to within 0.13 log units. As part of the current study the existing equation coefficients for the N-triethyl(octyl)ammonium cation were updated and reported for the first time were equation coefficients for the bis(trifluorosulfonyl)imide anion.     

Abraham model correlations for solute transfer into benzyl alcohol from both water and the gas phase

ABSTRACT

Experimental solubilities have been determined for anthracene, benzil, 2-chloroanthraquinone, 9-fluorenone, 2-hydroxybenzoic acid, 2-methoxybenzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, phenothiazine, pyrene, and thioxanthen-9-one dissolved in benzyl alcohol at 298.15 K. The measured solubility data, combined with previously published activity coefficient and solubility data, are used to determine Abraham model correlations for solute transfer to benzyl alcohol from both water and from the gas phase. The derived Abraham model correlations were found to back-calculate the experimental partition coefficients and solubility ratios to within 0.14 log units (or less).     

Development of Abraham model correlations for enthalpies of solvation of organic solutes dissolved in 1,3-dioxolane

Published excess enthalpy of mixing data has been assembled from the chemical literature for binary mixtures containing 1,3-dioxalane. The experimental data were converted into partial molar enthalpies of solution and enthalpies of solvation for solutes dissolved in 1,3-dioxolane using standard thermodynamic relationships. The compiled enthalpy of solvation data for 59 different organic solutes was used to derive mathematical correlations based on the Abraham solvation parameter model. The derived correlations describe the experimental enthalpy of solvation data in 1,3-dioxolane to within a standard deviation of 2.0 kJ mol^?1.     

Development of Abraham model correlations for predicting enthalpies of solvation of nonionic solutes dissolved in formamide

Experimental enthalpy of solution data for 81 solutes dissolved in formamide have been compiled from the published literature and converted to enthalpies of solvation data using standard thermodynamic relationships. Abraham model correlations were derived from the compiled enthalpy of solvation data. The derived mathematical equations describe the observed experimental to within overall standard deviations of 2.3 kJ mol^?1. A principal component analysis based on the calculated equation coefficients, and the coefficients for water and 23 organic solvents previously determined, shows that formamide is both a hydrogen-bond acid and a hydrogen-bond base. Of the solvents that we have studied thus far, formamide is the closest to water in terms of enthalpies of solvation of dissolved solutes.     

Experimental and predicted solubilities of 3,4-dichlorobenzoic acid in select organic solvents and in binary aqueous–ethanol mixtures

Experimental solubilities are reported for 3,4-dichlorobenzoic acid dissolved in methyl butyrate, and in 16 alcohol, 5 alkyl acetate, 5 alkoxyalcohol and 6 ether solvents. Solubilities were also measured in nine binary aqueous–ethanol solvent mixtures at 298.15?K. The measured solubility data were correlated with the Abraham solvation parameter model. Mathematical expressions based on the Abraham model predicted the observed molar solubilities to within 0.12 log units.     

Infinite Dilution Activity Coefficients and Gas-to-Liquid Partition Coefficients of Organic Solutes Dissolved in 1-Benzylpyridinium Bis(Trifluoromethylsulfonyl)Imide and 1-Cyclohexylmethyl-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide

Infinite dilution activity coefficients and gas-to-ionic liquid partition coefficients were measured for a chemically diverse set of 48 or more organic solute probes dissolved in the ionic liquids 1-benzylpyridinium bis(trifluoromethylsulfonyl)imide ([BzPy][Tf₂N]) and 1-cyclohexylmethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([ChxmPyrr][Tf₂N]) in the temperature range from 323.15 to 373.15 K using inverse gas chromatography. Selectivities and capacities for different separation problems were calculated from the measured chromatographic data. The measured partition coefficients were correlated using mathematical equations based on the Abraham general solvation parameter model. The derived Abraham model correlations back-calculated the observed partition coefficients to within 0.12 log₁₀ units.     

Correlation of the Solubilizing Abilities of Hexyl(trimethyl)ammonium <Emphasis Type="Italic">bis</Emphasis>((Trifluoromethyl)sulfonyl)imide, 1-Propyl-1-methylpiperidinium <Emphasis Type="Italic">bis</Emphasis>((Trifluoromethyl)sulfonyl)imide,and 1-Butyl-1-methyl-pyrrolidinium Thiocyanate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrrolidinium thiocyanate ([BMPyrr]⁺[SCN]⁻), hexyl(trimethyl)ammonium bis((trifluoromethyl)sulfonyl)imide ([HexM₃Am]⁺[(Tf)₂N]⁻), and 1-propyl-1-methylpiperidinium bis((trifluoromethyl)sulfonyl)imide ([PMPip]⁺[(Tf)₂N]⁻) stationary phases at 323 and 353 K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) partition coefficients and water-to-anhydrous IL partition coefficients. Both sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL and water-to-IL partition coefficient data to within average standard deviations of 0.116 and 0.156 log₁₀ units, respectively.     

Correlation of the Solubilizing Abilities of 1-Butyl-1-methylpiperidinium Bis(trifluoromethylsulfonyl)imide and 1-Butyl-1-methylpyrrolidinium Tetracyanoborate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrrolidinium tetracyanoborate ([BMPyrr]⁺[B(CN)₄]^?) and 1-butyl-1-methyl-piperidinium bis(trifluoromethylsulfonyl)imide ([BMPip]⁺[Tf₂N]^?) stationary phases at 323 K and 353 K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. Both sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.10 and 0.15 log₁₀ units, respectively.