Timothy W. Stephens

Thermochemical investigations of solute transfer into ionic liquid solvents: updated Abraham model equation coefficients for solute activity coefficient and partition coefficient predictions

Experimental data have been compiled from the published chemical and engineering literature pertaining to the infinite dilution activity coefficients, gas solubilities and chromatographic retention factors for solutes dissolved in ionic liquid (IL) solvents. Chromatographic retention factors for 45 solutes on a 1-butyl-1-methylpyrrolidinium tricyanomethanide IL gas–liquid chromatographic stationary phase are included in the compilation. The published experimental data were converted to gas-to-IL and water-to-IL partition coefficients and correlated with the ion-specific equation coefficient version of the Abraham general solvation model. Ion-specific equation coefficients were calculated for 40 different cations and 16 different anions. The calculated ion-specific equation coefficients describe the experimental gas-to-IL and water-to-IL partition coefficient data to within 0.123 and 0.149 log units, respectively.

Abraham model correlations for describing solute transfer into ionic liquid solvents: calculation of ion-specific equation coefficients for the 4,5-dicyano-2-(trifluoromethyl)imidazolide anion

Gas-to-ionic liquid (IL) partition coefficients have been compiled from the published literature for solutes dissolved in anhydrous 1-butyl-3-methylimidazolium 4,5-dicyano-2-(trifluoromethyl)imidazolide, ([BMIm]+[TDI]–), and 3-methyl-N-butylpyridinium 4,5-dicyano-2-(trifluoromethyl)imidazolide, ([3-MBPy]+[TDI]–). The compiled partition coefficients were converted to water-to-IL partition coefficients using the corresponding gas-to-water partition coefficients. Both sets of partition coefficients were analysed using the ion-specific equation coefficient version of the Abraham solvation parameter model. Equation coefficients are determined for the first time for 4,5-dicyano-2-(trifluoromethyl)imidazolide. Mathematical correlations derived from the Abraham model describe the observed gas-to-IL and water-to-IL partition coefficient data to within a standard deviation of 0.07 and 0.11 log units, respectively.

Determination of Abraham model solute descriptors for benzoin based on measured solubility ratios

Experimental solubilities are reported for benzoin dissolved in 1 chloroalkane, 15 alcohols, 5 aromatic hydrocarbons, 5 alkyl acetates, 5 alkoxyalcohols and 3 ethers at 298.15 K. The measured solubility data were mathematically correlated with the Abraham solvation parameter model. The solute descriptors that were calculated for benzoin describe the experimental molar solubility data to within an overall average standard deviation of 0.097 log units.

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 (log10K) and water-to-IL (log10P) partition coefficient data to within average standard deviations of about 0.10 and 0.15 log10 units, respectively.

Correlation of Solute Transfer Into Toluene and Ethylbenzene from Water and from the Gas Phase Based on the Abraham Model

Experimental data have been compiled from the published literature on the partition coefficients of solutes and vapors into ethylbenzene and toluene at 298 K. The logarithms of the water-to-ethylbenzene and water-to-toluene partition coefficients, log P, and gas-to-ethylbenzene and gas-to-toluene partition coefficients, log K, were correlated with the Abraham solvation parameter model. The derived mathematical expressions described the observed log P and log K data for the two aromatic hydrocarbon solvents to within average deviations of 0.13 log units or less.

Determination of Abraham model solute descriptors for three dichloronitrobenzenes from measured solubilities in organic solvents

Mole fraction solubilities are reported for 1,4-dichloro-2-nitrobenzene dissolved in 24 organic solvents of varying polarity and hydrogen-bonding character. The experimental data are used to calculate Abraham solute descriptors. The calculated solute descriptors describe the experimental data to within an overall average standard deviation of 0.081 log units. Also reported in the manuscript are Abraham model solute descriptors for both 3,4-dichloro-1-nitrobenzene and 2,3-dichloro-1-nitrobenzene based on published literature data.

Correlation of the Solubilizing Abilities of 1-Butyl-1-methyl-pyrrolidinium Tris(pentafluoroethyl)trifluorophosphate, 1-Butyl-1-methylpyrrolidinium Triflate and 1-Methoxyethyl-1-methylmorpholinium Tris(pentafluoroethyl)trifluorophosphate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrolidinium tris(pentafluoroethyl)trifluorophosphate ([BMPyrr]+[FAP]−), 1-butyl-1-methylpyrrolidinium triflate, ([BMPyrr]+[Trif]−), and 1-methoxyethyl-1-methylmorpholinium tris(pentafluoroethyl)trifluorophosphate, ([MeoeMMorp]+[FAP]−), stationary phases at (323, 353 and 383) 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. The three sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log10K) and water-to-IL (log10P) partition coefficient data to within average standard deviations of about 0.11 and 0.15 log10 units, respectively.

Comments Regarding "Density, Speed of Sound, Refractive Index and Derivatives Properties of the Binary Mixture N-Hexane + N-Heptane (or N-Octane or N-Nonane), T = 288.15 - 313.15 K"

Communication shows that not all of the measured excess molar data reported in the paper is consistent with the cited literature reference as the authors had claimed.

Comments concerning ‘study of molecular interaction in binary liquid mixtures of ethyl acetoacetate with chloroform and dimethylsulphoxide using excess acoustic parameters and spectroscopic methods’

The measured excess molar volume data in the recently published paper for the binary chloroform + ethyl acetoacetate system are shown to differ significantly from previously published data. Excess adiabatic compressibilities reported in the paper are shown to be calculated from an incorrect thermodynamic expression.