Determination of diffusion coefficients by gas chromatography

Gas chromatography (GC), apart from the qualitative and quantitative analysis of gaseous mixtures, offers many possibilities for physicochemical measurements, among which the most important is the determination of diffusion coefficients of gases in gases and liquids and on solids. The gas chromatographic techniques used for the measurement of diffusion coefficients, namely the methods based on the broadening of the chromatographic elution peaks, and those based on the perturbation of the carrier gas flow-rate, are reviewed from the GC viewpoint, considering their running though the history, the experimental arrangement and procedure, the appropriate mathematical analysis and the main results with brief discussions. The experimental data on diffusion coefficients, determined by the various gas chromatographic techniques, are compared with those quoted in the literature or estimated by the known empirical equations predicting diffusion coefficients. This comparison permits the calculation of the precision and accuracy of the techniques applied to the measurement of diffusion coefficients. (C) 2004 Elsevier B.V. All rights reserved.