Comparison of static and gas chromatographic solubility data

Філоненко, Г. В.; Korol, A. N.

doi:10.1016/s0021-9673(00)86778-3

Cited by 9 publications

(6 citation statements)

References 11 publications

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“…For the n-paraffin data, the values were in good agreement, though those for aromatics were found to be slightly higher (Figure 2). Interestingly again, Korol's (44) data for benzene in ODPN determined by static as well as GLC methods are in good agreement with ours.…”

Section: Methodssupporting

confidence: 88%

Gas-liquid chromatographic study of the thermodynamics of solution in dipropionitriles

Kuchhal¹,

Mallik²

1979

Anal. Chem.

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Gas-liquid chromatography has been employed to study the thermodynamic solution properties of a number of hydrocarbons and oxygenated compounds in d,.i'-oxydipropionitrile, j,d'-lhiodipropionitrile, and /3,S'-iminodipropionitrile. Comparative data on these three solvents are reported for three temperatures 40, 50, and 60 °C. The data in TDPN for some solutes are compared with previously published data. The activity coefficient data are presented after correction for surface effects (solute adsorption at the gas-liquid interface).The 2,i" data are correlated with a linear relation between the partial molar excess free energy and the hydrocarbon chain length of the solute for a homologous series in a given solvent. The results are also discussed in terms of statistical approaches (thermal and athermal contribution) and partial excess molar thermodynamic quantities.

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Section: Methodssupporting

confidence: 88%

Gas-liquid chromatographic study of the thermodynamics of solution in dipropionitriles

Kuchhal¹,

Mallik²

1979

Anal. Chem.

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“…Furthermore, Serpinet has discussed the experimental problems that arise from the fact that the distribution of the liquid phase between a thin film and a capillary condensate in packed columns is not well-understood and that the estimates of surface areas used in eq 1 might be wrong by as much as 2 orders of magnitude, thereby invalidating the conclusions of many chromatographic experiments. Nevertheless, irrespective of the importance of adsorption phenomena, there is general agreement that meaningful thermodynamic solution properties can be determined from chromatographic measurements using packed and capillary column gas chromatography when these measurements are carried out for a range of phase loadings and analyte concentrations. ,,,, Finally, an improved understanding of interfacial adsorption effects and their competition with bulk partitioning not only will prove valuable for chromatographic studies, but is also of major importance for understanding many environmental processes. − …”

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confidence: 99%

Molecular Simulation of Concurrent Gas−Liquid Interfacial Adsorption and Partitioning in Gas−Liquid Chromatography

2002

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The importance of adsorption at the gas-liquid interface on retention in gas-liquid chromatography has been controversial since the pioneering work of Martin in the 1960s. In particular, experimental studies using chromatographic and static techniques to quantify partitioning and adsorption of polar analytes on nonpolar liquid phases yielded conflicting results. In this work, Monte Carlo simulations were carried out for a free-standing liquid slab of squalane surrounded by a helium vapor to investigate interfacial adsorption effects for n-pentane, n-hexane, n-heptane, 1-butanol, and benzene solutes at infinite dilution. The simulations indicate preferential adsorption for the flexible alkane and alcohol solutes in a narrow region just inside the Gibbs dividing surface, but no such effect was observed for the rigid benzene solute. Nevertheless, the extent of the interfacial enrichment is small, as measured by the partition coefficient between the bulk liquid and the interfacial region (K(bulk-interface) approximately 1.5). In addition, a region that is slightly depleted for all solute molecules is found to separate the interfacial and bulk regions of the squalane slab. Thus, adsorption at the gas-liquid interface should not contribute significantly to the retentive behavior observed in gas-liquid chromatography on nonpolar capillary columns but might play a role in packed-bed columns with low bonded-phase loadings. The origin for the small enrichments and more favorable free energies for solutes at the interface is that the enthalpies of solvation decrease to a smaller relative extent than the entropies of solvation compared to the bulk liquid.

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“…The infinite-dilution activity coefficients are obtained by extrapolating to concentrations of solutes in a stationary phase approaching zero. The other method uses a GC as the measuring device. − The stationary phase to be characterized is coated inside a capillary column. Solutes are partitioned inside this GC column between the stationary phase and the carrier gas.…”

Section: Introductionmentioning

confidence: 99%

“…The solubility of compounds in a particular stationary phase dictates how these compounds are partitioned between a mobile phase (gaseous) and the stationary polymer phase, and how the separation is accomplished. The advances in gas chromatography also give researchers a new tool for studying physicochemical properties of various solutions, [1][2][3][4] which aids the further understanding of solute-solvent interaction. On the application side, the studies provided important knowledge about how a polymer interacts with various types of solutes and enabled researchers to characterize properties of different polymeric stationary phases.…”

Section: Introductionmentioning

confidence: 99%

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Studying Activity Coefficients of Probe Solutes in Selected Liquid Polymer Coatings Using Solid Phase Microextraction

Zhang

Pawliszyn

1996

J. Phys. Chem.

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The study of solute-polymeric liquid solvent interaction contributes to the understanding of the fundamental principles of chromatography since liquid polymers are often used as stationary phases in gas chromatography (GC) and high-performance liquid chromatography (HPLC). The knowledge of how a polymeric stationary phase interacts with different types of compounds helps researchers to select and synthesize the right phase for successful separation of mixtures in a time-efficient manner. The development of a simple, cost effective, and time-efficient method for studying solute-solvent interaction can aid significantly the ever-expanding applications of chromatography. In this work, a new approach, solid phase microextraction (SPME), is used for investigations of activity coefficients of the McReynolds probe solutes in selected liquid polymers. The probe solutes are absorbed by an immobilized liquid polymer phase coated on the outside surface of a fused silica fiber, and quantitated by a GC technique using a commercially available GC column. The research in this study shows that activity coefficients measured by SPME are equivalent to those by the commonly used GC method. This new method eliminates the need to prepare a GC column using the polymer of interest as in the GC method and, thus, significantly simplifies the whole measuring process. It also allows convenient investigation of the prepared coating by other surface and spectroscopic techniques.

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Comparison of static and gas chromatographic solubility data

Cited by 9 publications

References 11 publications

Gas-liquid chromatographic study of the thermodynamics of solution in dipropionitriles

Gas-liquid chromatographic study of the thermodynamics of solution in dipropionitriles

Molecular Simulation of Concurrent Gas−Liquid Interfacial Adsorption and Partitioning in Gas−Liquid Chromatography

Studying Activity Coefficients of Probe Solutes in Selected Liquid Polymer Coatings Using Solid Phase Microextraction

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