The inverse gas chromatographic method of reversed-flow gas chromatography is extended to the measurement of the probability density function f( ) for the adsorption energies on heterogeneous surfaces, as a function of the experimental time. The values of f( ) are not found from the solution of an integral equation, but by their direct calculation from experimental data in a very simple way. The method is applied to the adsorption of (CH 3 ) 2 S on CaCO 3 and CaCO 3 + C, in the presence and in the absence of NO 2 , at two temperatures around 303 and 323 K. The kinetic physicochemical parameters for the adsorption/desorption phenomena are also calculated for the above systems. The normalization of the f( ) found, with respect to time, is easily done.

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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.