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El objetivo general de este trabajo de tesis ha sido el desarrollo de columnas capilares basadas en distintos líquidos iónicos de fosfonio, el estudio de las propiedades cromatográficas de estas columnas, y la caracterización fisicoquímica de estos líquidos iónicos, demostrando que la medición de estas propiedades puede llevarse a cabo a partir de columnas de tubo abierto, con significativas ventajas respecto del método clásico que emplea columnas rellenas. Este objetivo implicó también la evaluación de distintos métodos de acondicionamiento de la superficie interna del capilar, a fin de mejorar la homogeneidad de la película de fase estacionaria depositada, así como el rendimiento general y la estabilidad de las columnas. Finalmente, se evaluó una posible aplicación analítica de estas columnas.

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In this paper, we report gas-liquid partition constants for thirty-five volatile organic solutes in the room temperature ionic liquid trihexyl(tetradecyl)phosphonium bromide measured by gas-liquid chromatography using capillary columns. The relative contribution of gas-liquid partition and interfacial adsorption to retention was evaluated through the use of columns with different the phase ratio. Four capillary columns with exactly known phase ratios were constructed and employed to measure the solute retention factors at four temperatures between 313.15 and 343.15K. The partition coefficients were calculated from the slopes of the linear regression between solute retention factors and the reciprocal of phase ratio at a given temperature according to the gas-liquid chromatographic theory. Gas-liquid interfacial adsorption was detected for a few solutes and it has been considered for the calculations of partition coefficient. Reliable solute's infinite dilution activity coefficients can be obtained when retention data are determined by a unique partitioning mechanism. The partial molar excess enthalpies at infinite dilution have been estimated from the dependence of experimental values of solute activity coefficients with the column temperature. A thorough discussion of the uncertainties of the experimental measurements and the main advantages of the use of capillary columns to acquire the aforementioned relevant thermodynamic information was performed.