Abraham model correlations for describing the thermodynamic properties of solute transfer into pentyl acetate based on headspace chromatographic and solubility measurements

doi:10.1016/j.jct.2018.05.003

The Journal of Chemical Thermodynamics

Volume 124, September 2018, Pages 133-140

https://doi.org/10.1016/j.jct.2018.05.003 Get rights and content

Highlights

•
Limiting activity coefficients measured for organic solutes dissolved in pentyl acetate.
•
Solubilities determined for crystalline organic compounds in pentyl acetate.
•
Abraham model correlations developed for describing solute transfer into pentyl acetate.

Abstract

Infinite dilution activity coefficients were measured for 32 liquid organic solutes dissolved in pentyl acetate at 298.15 K. The organic solutes included both saturated (hexane through decane, cyclohexane) and unsaturated hydrocarbons (1-hexene, 1-heptene, cyclohexene, 1-octyne, 1,7-octadiene), several substituted benzene derivatives (benzene, methylbenzene, ethylbenzene, propylbenzene, 1,3-dimethylbenzene, 1-dimethylbenzene, fluorobenzene, bromobenzene), four haloalkanes (trichloromethane, 1-chlorobutane, 1,2-dichloropropane, isopropyl bromide) and three alcohols (ethanol, 1-propanol, 2-propanol), as well six miscellaneous organic compounds (acetonitrile, ethyl acetate, tetrahydrofuran, 1,4-dioxane, propanone, nitromethane). Mole fraction solubilities were also determined for 10 crystalline nonelectrolyte organic solutes dissolved in pentyl acetate. Results of the experimental measurements were used to derive Abraham model correlations for describing thermodynamic properties of solute transfer into pentyl acetate. The derived Abraham model correlations mathematically described the observed data to within 0.12 log units (or less).

Introduction

This study continues our systematic examination of the solubilizing properties and hydrogen-bonding character of organic solvents that are utilized in commercial manufacturing processes. Organic solvents serve as reaction media in the synthesis of important medicinal and cosmetic products, as dispersing agents in drug formulations and skincare products, as extraction and pre-concentration solvents for unknown sample and quality control assurance analyses, and as recrystallization solvents for removing unwanted impurities from crystalline chemical products. Currently more than 300 solvents are used in industrial processes [1]. Governmental regulations regarding environmental disposal and worker safety has encouraged the chemical manufacturing sector to replace the more toxic and more hazardous industrial solvents with less toxic and more environmentally friendly solvent alternatives. Each year considerable time and monetary resources are devoted to finding suitable solvent replacements.

Our contribution towards the solvent selection processes has been to measure the thermodynamic quantities that can be used to characterize the solubilizing and hydrogen-bonding properties of different industrial solvents and potential solvent candidates. We have determined the limiting activity coefficients, saturation solubilities and partition coefficients of various organic solutes dissolved in many industrial solvents [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13]. Activity coefficient and solubility data can be used in the design of chemical separation processes based on liquid–liquid extraction, fractional distillation and recrystallization. As part of our studies [5], [6], [7], [8], [9], [10], [11] we have developed mathematical correlations that can permit the prediction of activity coefficients and solubilities of additional organic solutes in the solvent being studied. Mathematical correlations have been published for more than 100 common organic solvents [5], [6], [7], [8], [9], [10], [11], [14], [15], [16], [17], [18] and for than 70 ionic liquid solvents [19], [20]. In the case of the ionic liquid solvents we have calculated selectivities and capacity values for several practical separation problems based on measured infinite dilution activity coefficients. We have also considered the change in solvation properties in homological series of solvents differing by one or several methylene groups [21], [22], [23], [24]. Small modifications of solvent structure can be useful to fine-tune their interactions with dissolved species. In particular, correlations of gas-solvent and gas–water partition coefficients with solute descriptors for methyl, ethyl, propyl, and butyl acetate solvents were developed [21], [22].

In the present study we employ headspace chromatographic methods to measure the infinite dilution activity coefficients of 32 liquid organic solutes dissolved in pentyl acetate at 298 K. The organic solutes include both saturated (hexane through decane, cyclohexane) and unsaturated hydrocarbons (1-hexene, 1-heptene, cyclohexene, 1-octyne, 1,7-octadiene), several substituted benzene derivatives (benzene, methylbenzene, ethylbenzene, propylbenzene, 1,3-dimethylbenzene, 1-dimethylbenzene, fluorobenzene, bromobenzene), four haloalkanes (trichloromethane, 1-chlorobutane, 1,2-dichloropropane, isopropyl bromide) and three alcohols (ethanol, 1-propanol, 2-propanol), as well six miscellaneous organic compounds (acetonitrile, ethyl acetate, tetrahydrofuran, 1,4-dioxane, propanone, nitromethane). As part of the current study we also measured the solubility of 10 crystalline nonelectrolyte organic compounds in pentyl acetate in order to increase the chemical diversity of the compounds that will be used in determining the Abraham model correlations. Once determined, the Abraham model correlations will allow one to predict gas-to-liquid partition coefficients, water-to-organic solvent partition coefficients, infinite dilution activity coefficients and solubilities of additional organic compounds in pentyl acetate. All that is needed to perform these predictions is the numerical values of the solute descriptors of the additional organic compounds. Abraham model solute descriptors are currently available for more than 8000 chemical compounds [25]. In the case that the solute descriptor is not available in the published database it can be estimated by entering the SMILES code [25].

Section snippets

Measurements of limiting activity coefficients of liquid organic solutes

Chemicals used in the headspace chromatographic studies were purchased from commercial sources and purified as summarized in Table 1. Purities are given in terms of mass fractions as provided by the manufacturers. The purities given by the manufacturers were verified by gas chromatographic measurements. For all chemical substances, we observed no chromatographic peaks with the area exceeding 0.5% of the main compound peak area. The absence of significant amounts of water was confirmed by Karl

Results and discussion

Abraham model correlations have been reported for describing solute transfer process into both traditional organic solvents [5], [6], [7], [8], [9], [10], [11], [14], [15], [16], [17], [18] and into ionic liquid solvents [19], [20]. As noted in the introduction once the Abraham model correlations have been developed for a given solvent, one can predict gas-to-liquid partition coefficients, water-to-organic solvent partition coefficients, infinite dilution activity coefficients and solubilities

Conclusion

Expressions based on the Abraham solvation parameter model have been shown to provide reasonably accurate mathematical description of the transfer properties of a chemically diverse set of inorganic and organic solutes into pentyl acetate. Solute transfer properties included molar solubility ratios, the gas-to-pentyl acetate partition coefficient and the water-to-pentyl acetate partition coefficient. The water-to-pentyl acetate partition coefficient refers to solute transfer into dry pentyl

Acknowledgements

Igor Sedov acknowledges financial support from the Russian Federation President Grant MK-6547.2018.3. Part of the work was performed according to the Russian Government Program of Competitive Growth of Kazan Federal University. Anisha Wadawadigi, Olivia Zha, and Ellen Qian thank the University of North Texas Texas Academy of Mathematics and Science (TAMS) program for providing a summer research scholarship to each student.

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Citation Excerpt :
Our experiments have also included calorimetric determinations of ∆solnH of liquid and crystalline organic compounds dissolved in several common organic solvents used in industrial manufacturing processes. Second, we have reported mathematical correlations based on the Abraham solvation parameter model that describe solute transfer into 2-methyl-2-butanol [1], propylene glycol [16], diethylene glycol [3], triethylene glycol [4], 2-methoxyethanol [5], 2-ethoxyethanol [6], 2-propoxyethanol [7], 2-butoxyethanol [8], 2-isopropoxyethanol [7], propyl acetate [9], pentyl acetate [10], pyridine [11], and formamide [16]. To date Abraham model correlations have been reported for more than 130 different organic mono-solvents [1,3–11,15–24], and for both binary aqueous-methanol [25] and aqueous-ethanol [26,27] solvent mixtures.
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ReviewAbraham model correlations for describing the thermodynamic properties of solute transfer into pentyl acetate based on headspace chromatographic and solubility measurements

Highlights

Abstract

Introduction

Section snippets

Measurements of limiting activity coefficients of liquid organic solutes

Results and discussion

Conclusion

Acknowledgements

Int. J. Pharm.

Thermochim. Acta

Fluid Phase Equilib.

J. Mol. Liq.

J. Mol. Liq.

J. Mol. Liq.

J. Mol. Liq.

J. Pharm. Sci.

J. Mol. Liq.

Chemosphere

J. Mol. Liq.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Mol. Liq.

Fluid Phase Equilib.

Phys. Chem. Liq.

Phys. Chem. Liq.

J. Solution Chem.

J. Solution Chem.

Phys. Chem. Liq.

J. Chem. Eng. Data

Phys. Chem. Liq.

Phys. Chem. Liq.

Phys. Chem. Liq.

J. Solution Chem.

Phys. Chem. Liq.

Purification of Laboratory Chemicals

Review
Abraham model correlations for describing the thermodynamic properties of solute transfer into pentyl acetate based on headspace chromatographic and solubility measurements