Multilayer adsorption of C₂H₄ and CF₄ on graphite: Grand Canonical Monte Carlo simulation

Highlights: • Finite number of layers, at saturated pressure, is found for low temperatures. • A layer is represented by a sharp step which is a first order phase transition. • A thin film to thick film transition around the triple point is observed. • Temperatures and relative pressures of layers formation and phase diagrams are given. - Abstract: We study the phase transitions in adsorbed multilayers by Grand Canonical Monte Carlo simulations (GCMC) of the lattice-gas model. The focus will be on ethylene (C₂H₄) and tetrafluoromethane (CF₄) on a homogeneous graphite surface. Earlier simulations of these systems investigated structural properties, dynamical behaviors of adsorbed films and thermodynamic quantities such as isosteric heat. The main purpose of this study is to consider the adsorbed multilayers by the evaluation of the layering behavior, the wetting phenomena and the critical temperatures. The isotherms obtained for temperature from 50 K to 170 K reproduce a number of interesting features observed experimentally: (i) we observe an important number of layers in contrast with previous simulations, (ii) a finite number of layers at saturated pressure for low temperatures are found, (iii) the isotherms present vertical steps typical of layer-by-layer growth, at higher temperatures these distinct layers tend to disappear signifying that the film thickness increases continuously, (iv) a thin film to thick film transition near the triple point temperature is noticed. In addition to this qualitative description, quantitative information are determined including temperatures and relative pressures of layers formation, layer-critical-point temperatures and phase diagrams. Comparing the two systems, ethylene/graphite and tetrafluoromethane/graphite, we observe a qualitatively similar behavior.