Calculation of the viscosity of binary liquids at various temperatures using Jouyban-Acree model

Applicability of the Jouyban-Acree model for calculating absolute viscosity of binary liquid mixtures with respect to temperature and mixture composition is proposed. The correlation ability of the model is evaluated by employing viscosity data of 143 various aqueous and non-aqueous liquid mixtures at various temperatures collected from the literature. The results show that the model is able to correlate the data with an overall percentage deviation (PD) of 1.9+/-2.5%. In order to test the prediction capability of the model, three experimental viscosities from the highest and lowest temperatures along with the viscosities of neat liquids at all temperatures have been employed to train the model, then the viscosity values at other mixture compositions and temperatures were predicted and the overall PD obtained is 2.6+/-4.0%.     

Commentary on “Study of assorted interactions of an ionic liquid in significant solvent systems using compensated equation of fuoss conductance and vibrational mode”

Several computational errors in the paper are pointed out pertaining to the calculation of Gibbs energy from the measured overall pairing association constant. The calculation of ionic limiting molar conductances is discussed based on the tetrabutylammonium tetraphenylboride reference electrolyte method.     

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 (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.11 and 0.15 log₁₀ units, respectively.     

Comparison of solubility of gases and vapours in wet and dry alcohols,especially octan‐1‐ol

Equations for the solubility of gases and vapours into dry alcohols from methanol to decan‐1‐ol and into water‐saturated alcohols from butan‐1‐ol to decan‐1‐ol have been compared through the use of the Abraham solvation equation. It is shown that there are noticeable differences in solvation into the dry and wet alcohols, and that these differences become larger as the alcohols become smaller and take up more water. The two main factors that lead to the differences in solvation are the solute hydrogen‐bond basicity, B, and solute size, L. Increase in solute hydrogen‐bond basicity favours the wet alcohols and increase in solute size favours the dry alcohols. Solute hydrogen‐bond acidity plays no part, because the hydrogen‐bond basicity of water, wet alcohols and dry alcohols is almost the same. Copyright © 2008 John Wiley & Sons, Ltd.     

Energetic and structural characterization of 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl): experimental and computational studies

The gaseous standard molar enthalpies of formation of two 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl), at T = 298.15 K, were derived using the values for the enthalpies of formation of the compounds in the condensed phase, measured by static bomb combustion calorimetry, and for the enthalpies of sublimation, measured by Knudsen effusion, using a quartz crystal oscillator. The three dimensional structure of 2‐tert‐butoxycarbonyl‐3‐methylquinoxaline‐1,4‐dioxide has been obtained by X‐ray crystallography showing that the two N? O bond lengths in this compound are identical. The experimentally determined geometry in the crystal is similar to that obtained in the gas‐phase after computations performed at the B3LYP/6‐311 + G(2d,2p) level of theory. The experimental and computational results reported allow to extend the discussion about the influence of the molecular structure on the dissociation enthalpy of the N? O bonds for quinoxaline 1,4‐dioxide derivatives. As found previously, similar N? O bond lengths in quinoxaline‐1,4‐dioxide compounds are not linked with N? O bonds having the same strength. Copyright © 2007 John Wiley & Sons, Ltd.     

PH-Bestimmungsmethoden

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Solubility of phenobarbital in aqueous cosolvent mixtures revisited: IKBI preferential solvation analysis

The preferential solvation parameters of phenobarbital in aqueous binary mixtures of 1,4-dioxane, t-butanol, n-propanol, ethanol, propylene glycol and glycerol were derived from solution thermodynamic properties by using the IKBI method. This drug is sensitive to preferential solvation effects in all these mixtures. The preferential solvation parameter by the cosolvent (δx_1,3) is negative in almost all the water-rich mixtures but positive in mixtures with similar proportions of solvents and cosolvent-rich mixtures, except in 1-propanol + water mixtures, where negative values are also found in mixtures with x₁ ≥ 0.70. Hydrophobic hydration around the non-polar ethyl and phenyl groups of this drug in water-rich mixtures could play a relevant role in drug solvation. Otherwise, in mixtures of similar solvent compositions and in cosolvent-rich mixtures the preferential solvation by cosolvent could be due to the acidic behaviour of the drug.