Volume 65, 1969

Gas-liquid chromatographic determination of cross-term second virial coefficients using glycerol. Benzene + nitrogen and benzene + carbon dioxide at 50°C

Abstract

This paper extends the theory of gas-chromatographic elution of a highly dilute solute to the second order in gas-phase imperfection terms, yielding a precise expression for the ideal retention volume in terms of the thermodynamic parameters of the system. The effect of carrier gas dissolution in the solvent is included explicitly; the cross-term second virial coefficient B12 for the system solute + carrier gas cannot be evaluated unambiguously for an appreciably soluble carrier gas. The use in such cases of polar solvents in which non-polar carrier gases are effectively insoluble is discussed with reference to surface adsorption and chromatographic non-ideality, which are important in polar solvents. Extrapolation of observed retention volume to zero flowrate for each of a series of columns covering a range of solvent loadings should give, corresponding to the limit of infinite loading, unambiguous values of bulk-phase solute-in-solvent activity coefficient and of B12. The theory has been applied to measurements on the systems benzene + nitrogen + glycerol, and benzene + carbon dioxide + glycerol, using four columns loaded at 15.7, 25.3, 33.6 and 23.3 % by weight glycerol on Celite, and the system benzene + hydrogen + glycerol using a column loaded at 44.0 %. The flowrate-dependence of the net retention volume is approximately linear on all columns, the gradient correlating well with empirical plate height and with solvent loading, in accordance with theory and with the known facts about the distribution of a polar solvent on Celite. The zero-flowrate B12 values are effectively the same with all columns. These values of B12 at 50°C are, for benzene + nitrogen, –98 ± 9 cm3 mole–1, and for benzene + carbon dioxide, –250 ± 15 cm3 mole–1, both being in fair agreement with theoretical predictions for systems of non-spherical molecules of different sizes. The activity coefficient for benzene at infinite dilution in glycerol at 50°C is logγ13= 2.084 ± 0.005.

Article information

Article type
Paper

Trans. Faraday Soc., 1969,65, 1014-1031

Gas-liquid chromatographic determination of cross-term second virial coefficients using glycerol. Benzene + nitrogen and benzene + carbon dioxide at 50°C

A. J. B. Cruickshank, B. W. Gainey, C. P. Hicks, T. M. Letcher, R. W. Moody and C. L. Young, Trans. Faraday Soc., 1969, 65, 1014 DOI: 10.1039/TF9696501014

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