Thermodynamic and kinetic characterization of a bridged-ethylene hybrid C18 stationary phase

In this study, a series of polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic hydrocarbons (NPAHs) is separated on a hybrid stationary phase using methanol and acetonitrile mobile phases. Temperature is varied from 283 to 313 K in order to determine thermodynamic and kinetic parameters of the separation. Thermodynamic behavior is characterized by the retention factor and associated changes in molar enthalpy, whereas kinetic behavior is characterized by the rate constants and associated activation energies. In this study, the retention factors for the NPAHs are smaller than those for the parent PAHs in methanol, while they are more similar to the parent PAHs in acetonitrile. The changes in molar enthalpy are very similar for all solutes, yet are more negative in acetonitrile than in methanol. The rate constants for the NPAHs are smaller than those for their parent PAHs in both mobile phases. Moreover, the rate constants in acetonitrile are one to four orders of magnitude smaller than those in methanol. Based on these thermodynamic and kinetic results, the hybrid stationary phase is compared to traditional silica stationary phases. In addition, the relative contributions from the partition and adsorption mechanisms are discussed.