If the internal wall of the diffusion column used in the reversed-flow gas chromatography (RFGC) technique is covered with an adsorbent material or a supported liquid, then isotherm determination becomes much simpler.Diffusion and resistance to mass transfer are not neglected, the sorption effect is non-existent and the pressure gradients are negligible along the bed. The method leads directly to independent experimental isotherms over a wide range of concentrations, without specifying a priori an isotherm equation. The isotherm can also be determined in the presence of a surface reaction of the adsorbate. The necessary theoretical analysis has been developed, and the equations derived were applied to benzene and cyclohexane adsorbed on graphitized carbon black, to ethene, ethyne, propene and sulfur dioxide on marble powder, and to propene on silica gel.

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SummaryThe reversed-flow gas chromatographic technique has been applied to the determination of the apparent rate constant and the reaction order of a reaction between two gases or vapors. For seven hydrocarbons (ethane, ethene, ethyne, propene, butene, benzene and toluene) reacting with nitrogen dioxide, the above mentioned kinetic parameters have been determined. For these determinations, the necessary mathematical formulation of the problem has been written and solved, leading to simple expressions which describe the height of the chromatographic sample peaks as a function of time.

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