Solubility of xenon in 45 organic solvents including cycloalkanes, acids, and alkanals: Experiment and theory

Abstract

New measurements are reported of the Ostwald solubility L(T), as a function of temperature in the approximate range 10.0–50.0 °C, for 133Xe gas in 13 liquid organic solvents, viz., three cycloalkanes, six carboxylic acids, and four normal alkanals. From our data for each solute–solvent system we determine the mole-fraction solubility x2(T), and the following thermodynamic functions of solution: chemical potential Δμ0ρ2(T)=−RT ln L, enthalpy ΔH̄0ρ2, and entropy ΔS̄0ρ2, where Δμ0ρ2=ΔH̄0ρ2 −TΔS̄0ρ2S̄0ρ2, all based on the number density scale. New results are considered together with previous measurements of xenon solubility in liquid normal alkanes, alkanols, and perfluoroalkanes; in all, data and theory are treated for xenon solubility in 45 organic solvents from six homologous series. The average observed entropy of solvation of Xe is ΔS̄0ρ2=−4.1± 0.5 cal/mol K, remarkably independent of solvent. The results are analyzed with scaled-particle theory from which are obtained hard-core diameters a1, and cavity energies gcav and enthalpies hcav for all the solvents at 25 °C. Values of a1 range from 4.08 Å (for CH3OH) to 9.18 Å (n-C20H42), and gcav ranges from 2520 cal/mol (n-C6F14) to 9430 cal/mol (HCOOH). We discuss the application to solubility in these solvents of interaction site calculations; interaction potentials for the functional groups are available but difficult to apply to these solute–solvent systems. We also discuss the role of configurational entropy, as well as molecular dynamics approaches to calculation of free energies of solubility. Finally the results are examined empirically and values are given for the contribution to chemical potential, enthalpy, and entropy of solvation, of the six functional groups: CH2 (linear molecules), CH3, OH, COOH, CHO, and CH2 (cyclomolecules).

On the behaviour of solutions of xenon in liquid cycloalkanes: Solubility of xenon in cyclopentane

“…The solubility of xenon in liquid cyclopentane has been measured as a function of temperature from 254 K to 314 K and Henry's law coefficients calculated. This system had been previously studied by Pollack et al [27] in the range 278.15-303.15 K. The present work not only doubles the temperature range of the available results, but also provides experimental data with a precision that allows the calculation of the thermodynamic properties of solvation as a function of temperature and therefore the calculation of second derivative properties, such as the heat capacity of solvation.…”

“…1. The solubility of xenon in cyclopentane has been previously measured by Pollack et al [27] at six temperatures. Their values show positive deviations from ours up to 3.5% and a dispersion of 3%, which were included in Fig.…”

“…The temperature at which the solvation enthalpy reaches a maximum changes with the molecular weight of the n-alkanes (254.5 K for xenon + n-pentane and 275 K for xenon + n-hexane). Pollack et al [27] noticed that the average value of the entropy (squares) for (xenon + cyclopentane) (filled symbols, • and ) and (xenon + pentane) [59] (open symbols, and ) as a function of temperature.…”

Abraham model correlations for estimating solute transfer of neutral molecules into anhydrous acetic acid from water and from the gas phase

“…Pollack et al [48] measured the solubility of xenon in acetic acid from 293 K to 313 K, Kunerth [49] determined the solubility of carbon dioxide and nitrous oxide in acetic acid in 2 K increments from 291 K to 309 K, and Barton and Hsu [50] reported the solubility of cyclopropane in acetic acid in the temperature range of 273 K to 313 K.…”

Freeze-Trapping Isomorphous Xenon Derivatives of Protein Crystals

“…Owing to the high solubility of xenon in water (241 and 108 cm 3 1-l of xenon at 0.1 MPa gas pressure at 273 and 293 K, respectively; Weast & Astle, 1980) and the even higher solubility in organic solvents (Pollack et al, 1989), appreciable concentrations of dissolved xenon can be achieved at elevated xenon pressures. Thus, from the solubility of xenon in pure water one can estimate that the concentration of dissolved xenon exceeds 0.1 M at 298 K and 5.0 MPa (Kennan & Pollack, 1990).…”