Generalized Gibbs' approach in heterogeneous nucleation.

Heterogeneous nucleation (condensation and boiling) on planar solid surfaces is described taking into account changes of the state parameters of the critical clusters in dependence on supersaturation. The account of the variation of the state parameters of the cluster phase on nucleation is performed in the framework of the generalized Gibbs' approach. One-component van der Waals fluids are chosen as a model for the analysis of the basic qualitative characteristics of the process. The analysis is performed for both hydrophobic and hydrophilic surfaces and similarities and differences between condensation and boiling processes are discussed for the two different cases. It is shown that, in the generalized Gibbs' approach, contact angle and catalytic factor for heterogeneous nucleation become dependent on the degree of metastability (undercooling or superheating) of the fluid. For the case of formation of a droplet in supersaturated vapor on a hydrophobic surface and bubble formation in a liquid on a hydrophilic surface the solid surface has only a minor influence on nucleation. In the alternative cases of condensation of a droplet on a hydrophilic surface and of bubble formation in a liquid on a hydrophobic surface, nucleation is significantly enhanced by the solid. Effectively, the existence of the solid surface results in a significant shift of the spinodal to lower supersaturations as compared with homogeneous nucleation. Qualitatively the same behavior is observed now near the new (solid surface induced) limits of instability of the fluid as compared with the behavior near to the spinodal curve in the case of homogeneous nucleation.