Use of specific surface areas in inverse gas chromatography studies at zero surface coverage

Inverse gas chromatography (IGC) is frequently used to study adsorption processes at zero surface coverage on microporous activated carbons. This allows to determine the thermodynamic adsorption parameters as equilibrium constants, VS, standard enthalpies of adsorption, ΔHA°, standard free energy of adsorption, ΔGA°, and so on. Nevertheless, the surface areas of the adsorbents (microporous carbons in this case) are needed for this purpose. The experimental determination of the surface areas of microporous solids is not univocal and the results depend on the adsorbate employed in the measurements, usually N2 or CO2. This means that the thermodynamic parameters obtained by IGC are subjected to a degree of uncertainty depending on whether N2 or CO2 is used to determine the surface area values. The aim of this paper is to discuss which of the two surface area values is more appropriate to be used in IGC measurements at zero surface coverage. Experimental and theoretical considerations are supplied in a thorough discussion which supports that CO2 surface area value is more appropriate. Thus, it is proposed that this should be used instead of the more generally extended nitrogen specific surface area obtained by the BET equation.