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NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=2b20bebb-858a-4d0c-86bb-5281afea97c5 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=2b20bebb-858a-4d0c-86bb-5281afea97c5 ABSTRACT: The geometry of phenanthridine, benzothiophene, tetralin, and naphthalene representative of the heterocyclic, naphthenic, and aromatic components of bitumen adsorbed on kaolinite is optimized using density functional theory and periodic boundary conditions in gas phase. These bitumen model compounds preferentially adsorb on the aluminum hydroxide surface of kaolinite with energy decreasing in the order phenanthridine > naphthalene > tetralin ∼ benzothiophene. The adsorption of phenanthridine is strengthened by hydrogen bonding between the pyridinic N atom and an axial hydroxyl group of kaolinite, while the rest of the molecules adsorb through van der Waals interactions. The mechanism of solvation in CO 2 and the effect of liquid and supercritical CO 2 on the adsorption thermodynamics are studied using the three-dimensional reference interaction site model theory with the closure approximation of Kovalenko and Hirata (3D-RISM-KH) molecular theory of solvation at 293−333 K and 10−30 MPa. The CO 2 solvent interacts with the aluminum hydroxide surface of kaolinite by hydrogen bonding, with the pyridinic N atom of phenanthridine by electrostatic interactions, and with the rest of the bitumen model compounds by hydrophobic interactions, as inferred from the 3D site density distribution functions of CO 2 . The molecule−kaolinite potentials of mean force in CO 2 show that the adsorption of naphthalene and tetralin on kaolinite is substantially weakened as the pressure is increased and the temperature is decreased. Benzothiophene adsorption is the least sensitive to CO 2 temperature and pressure changes. In liquid CO 2 at 30 MPa and 293 K, the hydrocarbon molecules are weakly adsorbed and can be desorbed by CO 2 , while the heterocycles wo...