Solvation properties and limiting activity coefficients of halogenated hydrocarbons in C78H158 branched saturated alkane solvent

Dallos, András; Kresz, Richárd; Kováts, Ervin sz.

doi:10.1016/s0378-3812(03)00161-4

Cited by 7 publications

(4 citation statements)

References 14 publications

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“…Gas–liquid chromatography (GLC) is a valuable analytical technique of proven power for physicochemical measurements and generating thermodynamic data of analytes, with the advantage of its simplicity as compared with direct techniques such as the calorimetric and equilibrium methods. , Basic physicochemical quantities, namely the vapor pressure, − heat of vaporization, − equilibrium distribution constant K , − enthalpy of solvation, and entropy of solvation, , and even the octanol–air partition coefficient − can be determined from the retention data, such as specific or net retention volumes, , Kovats retention indices ( I ), , or retention factors ( k ) − and their temperature dependence. In this study, we use the isothermal retention factor k as the most relevant and reproducible chromatographic measure of the retention.…”

Section: Introductionmentioning

confidence: 99%

Regression against Temperature of Gas–Liquid Chromatography Retention Factors. Van’t Hoff Analysis

et al. 2020

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The present work deals with the precise experimental determination of the gas–liquid chromatography (GLC) retention factors (k) in a sufficiently large temperature range to allow the calculation of the thermodynamic quantities associated with the sorption process. Once isothermal retention factors of three homologous series members of the type H-(CH2) n -Y (Y = CH3, OH, CN) were measured over a temperature range of about 110 K on a low-polar PDMS (HP-1) capillary column and checked for accuracy and precision by “arc plot” representation, the data were analyzed by applying different forms of the van’t Hoff relationship. We compared the linear versus nonlinear van’t Hoff plots representing situations characterized by Δsolv C p ° = 0, Δsolv C p °≠ 0 = constant, and Δsolv C p ° = f(T), respectively (Δsolv C p ° represents the difference in isobaric heat capacity associated with movement of the analyte between the mobile and the stationary phase). The “logarithmic” and “quadratic” nonlinear van ‘t Hoff equations were shown to be more appropriate than the linear van‘t Hoff equation for determining enthalpy and entropy of solvation. Special attention was devoted to the fitting performance and extrapolation capability of models with nonzero Δsolv C p °. By several metrics, the quadratic model exhibits better behavior in extrapolations yielding reasonable accuracy for retention time and/or enthalpy of solvation predictions at temperatures located below the experimental range.

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Section: Introductionmentioning

confidence: 99%

Regression against Temperature of Gas–Liquid Chromatography Retention Factors. Van’t Hoff Analysis

et al. 2020

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“…5−10 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. 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.…”

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confidence: 99%

“…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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confidence: 99%

“…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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confidence: 99%

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

Dallos

Kresz

2006

Fluid Phase Equilibria

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Solvation properties and limiting activity coefficients of halogenated hydrocarbons in C78H158 branched saturated alkane solvent

Cited by 7 publications

References 14 publications

Regression against Temperature of Gas–Liquid Chromatography Retention Factors. Van’t Hoff Analysis

Regression against Temperature of Gas–Liquid Chromatography Retention Factors. Van’t Hoff Analysis

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

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

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