Journal of Chemical Physics, Vol.116, No.14, 6311-6321, 2002
Interfaces between silicalite surfaces and liquid hexadecane: A molecular dynamics simulation
Interfaces between liquid hexadecane and low index surfaces of the zeolite silicalite were modeled using molecular dynamics. Pores on the zeolite surface provide access to the interior such that hexadecane molecules diffuse inside. The three surfaces studied differ significantly in the rate of molecular diffusion from the surface into the zeolite bulk. An equilibrium concentration of hexadecane inside the zeolite is established as a function of external liquid pressure. Molecules are partially adsorbed inside the zeolite at the solid/liquid interface and a nonuniform distribution of adsorption length is observed, the shape of which is determined by the subsurface channel structure of the zeolite. Near-surface intersections between channels inside the zeolite greatly influence the partial adsorption distribution as molecules preferentially avoid adsorption in intersections. The lifetime of partially adsorbed molecules varied greatly between the three surfaces. The critical adsorption length, at and beyond which molecules are more likely to be adsorbed into the zeolite than desorb into the liquid, also differed for the three interfaces. This too was a function of subsurface channel structure. In the range examined, temperature and pressure are less influential than channel structure.