There is apparently growing interest in the use of direct chromatographic methods to study the equilibrium properties of gas-solid systems. Direct methods, in contrast to methods which merely use chromatography for analysis of phase composition, have two basic characteristics: the chromatographic column is the experimental system, and experiments are locally transient in nature, although equilibrium properties are the desired goal.The residence time of pulses at infinite dilution in a carrier gas has been used to calculate gas-solid interaction potentials (6, 7), adsorption site energy distribution ( 1 5 ) , and relative adsorbability of hydrocarbons on acid catalysts ( 1 2 ) . Elution and displacement curves have been analyzed by a number of authors to determine adsorption isotherms, surface areas, and apparent heats of adsorption (2 to 4 , 1 4 ) .Radioactive tracers have been used in the pulse residence time procedure by Stalkup (16), Helfferich ( 9 ) , Koonce (11), Gilmer ( 5 ) , and Haydel (8). The theory and practice of using a multicomponent carrier gas have been discussed by several of these authors (8,11,13,16); in each case the simplification produced by the use of radioactive tracers was noted.Applications of pulse chromatography to the study of chemically reactive mixtures has been rather limited.Tamaru (17) studied reacting mixtures in a steady state tubular reactor by pulsing the input concentration, but his columns were far removed from equilibrium conditions. Klinkenberg ( 1 0 ) gives a theoretical analysis of the reaction A G
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