Infinite dilution activity coefficients, specific retention volumes and solvation thermodynamics of hydrocarbons in C78H158 branched alkane solvent

Dallos, András; Kresz, Richárd

doi:10.1016/j.fluid.2006.07.015

Fluid Phase Equilibria

2006

DOI: 10.1016/j.fluid.2006.07.015

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Infinite dilution activity coefficients, specific retention volumes and solvation thermodynamics of hydrocarbons in C78H158 branched alkane solvent

András Dallos

Richárd Kresz

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Cited by 4 publications

(2 citation statements)

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“…11 −15 In order to determine the SP amount in WCOT columns, some researchers suggested an indirect calculating method. 11,12 They assumed the specific retention volume (V g ) of any component (e.g., n-alkanes) on a certain SP was independent with the applied column type; then the amount of SP in a WCOT column could be calculated by backward induction from the SP amount in a packed column. However, the V g values result from the combination of adsorption and partition processes.…”

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“…Despite the advantages of WGC, PGC is still the dominant method in the γ ∞ determination, due to the difficulty in quantifying the very small values of SP amount and carrier gas flow rate in WGC. − Only a few published papers used WGC in γ ∞ determination, in which the carrier gas flow rates were generally measured by gas flow meter and might suffer from large errors. − In order to determine the SP amount in WCOT columns, some researchers suggested an indirect calculating method. , They assumed the specific retention volume ( V g ) of any component (e.g., n -alkanes) on a certain SP was independent with the applied column type; then the amount of SP in a WCOT column could be calculated by backward induction from the SP amount in a packed column. However, the V g values result from the combination of adsorption and partition processes.…”

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Accurate Measurements of Infinite Dilution Activity Coefficients Using Gas Chromatography with Static-Wall-Coated Open-Tubular Columns

Luo

et al. 2012

Anal. Chem.

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Wall-coated open-tubular (WCOT) columns provide higher column efficiency and lower solute interfacial adsorption effect than packed columns. However, previous efforts used to measure the infinite dilution activity coefficient (γ(∞)) via a chromatographic technique have used packed columns, because the low carrier gas flow rate (U) and the small stationary phase amount (n(2)) in WCOT columns raise large errors. By rationally revising the γ(∞)-calculation equation for static-wall-coated open-tubular column, we observed that U and n(2) are not necessarily needed and the resulting error could be reduced, and WCOT column gas chromatography subsequently became a superior method for the accurate γ(∞) determination. In this study, we validate our revised γ(∞)-calculation equation by measuring γ(∞) in an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate system, in which 55 organic compounds covering a wide range of functional groups were used as probe solutes and their γ(∞) values in the ionic liquid were determined at 40.0, 50.0, and 60.0 °C. Experimental error analysis shows that our revised equation remarkably reduces the error compared to the common γ(∞)-calculation equation. Our data is consistent with previously reported values obtained via other techniques, which further proves the credibility of our revised equation. The accurately determined γ(∞) values can be directly used to calculate the partial molar excess enthalpy, selectivity, and capacity, which will benefit for the rapid screening of solvents (especially ionic liquids) in separation approaches.

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confidence: 99%

mentioning

confidence: 99%

Accurate Measurements of Infinite Dilution Activity Coefficients Using Gas Chromatography with Static-Wall-Coated Open-Tubular Columns

Luo

et al. 2012

Anal. Chem.

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Equilibrium parameters of a liquid—vapor system and thermodynamic characteristics of adsorption of cyclic and cage hydrocarbons in squalane

Yashkin

2010

Russ Chem Bull

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The thermodynamic characteristics of adsorption of adamantane molecules and its alkyl derivatives, as well as some mono and bicyclic hydrocarbons С 10 H n , were studied by equilibri um gas liquid chromatography on a column packed with the stationary liquid phase squalane under the conditions of infinitely low concentrations of the sorbate in the gas phase. The influence of specific features of the molecular structure of sorbates on the regularities of their retention on the column with squalane was shown. For the first time we obtained the limiting activity coefficients and excess thermodynamic functions of mixing, which made it possible to study in detail the thermodynamics of dissolution of cage molecules in the nonpolar liquid bulk. The changes in the molar isobaric heat capacity of sorbates during adsorption were determined by the chromatographic method. For reference compounds, these values agree well with the results of direct calorimetric measurements of the change in the molar standard isobaric heat capacity during vaporization.Modern gas chromatography (GC) is a universal method for physicochemical investigation of various adsorption processes. Potentialities of the GC method make it possi ble to obtain reliable thermodynamic information on the parameters of the vapor-condensed phase equilibrium during both adsorption on various interfaces (gas adsorp tion (GAC) 1 and gas liquid solid phase chromatography (GLSC) 2 ) and formation of dilute solutions involving mol ecules of nonelectrolytes, mesogens, and ionic liquids (gas liquid chromatography (GLC)). 3-5 The theoretical inter pretation of thermodynamic values obtained by the GC method has been actively pursued 6 ; GC is used for studies of the thermodynamics of phase equilibria and intermo lecular interactions in adsorption systems and in solu tions, as well as in analysis of nano and supramolecular systems. 7 The main data on the limiting activity coeffi cients and liquid-vapor partition constant in dilute so lutions of nonelectrolytes were obtained by the GLC method 8 ; GLC is widely used for the determination of the saturation vapor pressure, boiling point, enthalpy of va porization, diffusion coefficients, and other physicochem ical characteristics. 3 Most of published works on the application of GL for studying the physicochemical properties of adamantane and its derivatives deal with the determination of normal boiling points 9-14 ; the GC method was used to determine the equilibrium values of the saturation vapor pressure 15,16 for molecules of unsubstituted adamantane and other that sublimate easily compounds (cubane, naphthalene, cam phor, etc.). The thermodynamic parameters of the solid state-vapor equilibrium for molecules of adamantane and some its oxygen containing derivatives were studied by GC. 15,17 Available data on chromatographic retention of adamantane and its derivatives mainly concern logarith mic retention indices of stationary liquid phases (SLP). 18-25 Data on the thermodynamic characteristics of adsorption (TCA) (adsorption eq...

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Solvation molar enthalpies and heat capacities of n-alkanes and n-alkylbenzenes on stationary phases of wide-ranging polarity

Lebrón-Aguilar

Quintanilla-López

Santiuste

2010

Journal of Chromatography A

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Infinite dilution activity coefficients, specific retention volumes and solvation thermodynamics of hydrocarbons in C78H158 branched alkane solvent

Cited by 4 publications

References 39 publications

Accurate Measurements of Infinite Dilution Activity Coefficients Using Gas Chromatography with Static-Wall-Coated Open-Tubular Columns

Accurate Measurements of Infinite Dilution Activity Coefficients Using Gas Chromatography with Static-Wall-Coated Open-Tubular Columns

Equilibrium parameters of a liquid—vapor system and thermodynamic characteristics of adsorption of cyclic and cage hydrocarbons in squalane

Solvation molar enthalpies and heat capacities of n-alkanes and n-alkylbenzenes on stationary phases of wide-ranging polarity

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