Themodynamics of Adsorption and Patterns of the Gas-Chromatographic Retention of Cyclic Amines on Surfaces of Graphitized Thermal Carbon Black

The thermodynamic characteristics of adsorption (TCA) of aniline, cyclohexylamine, and some of their derivatives on surfaces of graphitized thermal carbon black (GTC) are experimentally determined under conditions of gas-adsorption chromatography. It is concluded that the TCA values for the studied compounds depend to a large extent on the features of the geometrical and electronic structure of molecules in the gas phase. The effect of the sp(3)-sp(2)-rehybridization of nitrogen atoms upon moving from molecules of unsubstituted aniline to N-methyl- and N,N-dimethylanilines are determined, along with the ortho-effects in 2-methyl and 2,6-dimethylanilines on the TCA values. It is shown that the above intramolecular effects result in nonadditive contributions to the energy of adsorption of the NH2-group in the a number of the studied compounds. Values of the thermal component of adsorption entropy are calculated, allowing conclusions on the physical state of the molecules of the studied compounds in the field of GTC adsorption forces. The mobility of adsorbate molecules is estimated using models of delocalized and localized adsorption. It is shown that in the series of ortho-meta-para-substituted anilines, the para-isomer is characterized by the highest values of retention on GTC, while the relative order of ortho- and meta-isomer elution is determined by the Van der Waals sizes of substituents in aromatic rings. A conclusion is reached on the high structural selectivity of a GTC surface in respect to positional isomers in the series of studied aniline derivatives.