Thermodynamic analysis of ordered and disordered monolayer of argon adsorption on graphite

We presented a detailed thermodynamic analysis of argon adsorption on a graphitized carbon black with a kinetic Monte Carlo scheme. In this study, we particularly paid attention to the formation of a hexagonal two-dimensional molecular layer on a graphite surface and discuss conditions of its stability and thermodynamic properties of the adsorbed phase as a function of loading. It is found that the simulation results are substantially affected by the dimensions of the simulation box when the monolayer forms a hexagonal ordered structure. This is due to the fact that the lattice constant is constrained by the dimensions of the surface. To circumvent this, we presented a thermodynamic technique, which allows for the variation of the box size as a function of loading, to determine the "intrinsic" lattice constant (rather than apparent average value because of the fixed dimensions of the simulation box) and the thermodynamic functions for the adsorbed phase: the Helmholtz free energy, the chemical potential, and the surface tension. The tangential and normal pressures as a function of the distance from the surface are also discussed.