Enthalpy-entropy compensation effect on adsorption of light hydrocarbons on monolithic stationary phases.

Enthalpy and entropy of adsorption of light hydrocarbons C1-C4 have been measured for three monoliths of different polarity and for five different carrier gases: helium, hydrogen, nitrogen, carbon dioxide and dinitrogen oxide. Using carrier gas helium the highest values of enthalpy and entropy were observed for monolith based on ethylenedimethacrylate and the lowest values were observed for monolith based on silica, while monolith based on divinylbenzene demonstrated intermediate values. Entropy-enthalpy correlations were observed with carrier gas helium for all thee monoliths and possess similar slope indicating similar adsorption mechanism on all monoliths studied. Comparing different carrier gases entropy-enthalpy correlations within a homological series of solutes were observed for light carrier gases (He, H2 and N2) and were not observed for heavy carrier gases (CO2 and N2O). Instead, entropy-enthalpy correlations for heavy carrier gases were observed with pressure as variable and the higher the carrier gas pressure the lower the values of enthalpy and entropy observed. The observed changes in entropy-enthalpy correlations were explained by competitive adsorption of heavy carrier gas on monoliths.