Simulation studies of retention in isotropic or oriented liquid n-octadecane

In gas-liquid chromatography with liquid-crystalline stationary phases and in liquid-liquid chromatography with polymeric bonded phases, the retention selectivity has been linked to the orientation of the retentive phase. In an effort to explore the nature of this effect, molecular simulations utili zing the configurational-bias Monte Carlo technique in the Gibbs ensemble w ere performed. Through this simulation technique, the partition coefficient s of benzene, naphthalene, n-heptane, and n-dodecane were calculated when p artitioning takes place between an oriented or an isotropic liquid n-octade cane phase of equal density and a helium gas phase. The calculated partitio n coefficients demonstrate that the n-alkane solutes prefer the oriented n- octadecane phase over the isotropic one, while the opposite behavior (but t o a smaller extent) is observed for benzene and naphthalene solutes. The n- alkane solute transfer into the oriented n-octadecane phase is favored by a smaller entropic penalty and a minor enthalpic gain compared to that into the isotropic phase. While the entropic cost for partitioning into the liqu id phases increases by about 40% from n-heptane to n-dodecane, there is onl y a small increase of about 8% from benzene to naphthalene. Minor preferent ial alignment was observed for n-dodecane and naphthalene in the oriented l iquid phase, but no significant differences are observed for the solutes' c onformational properties in the two solvent environments.