Journal of Chemical Physics, Vol.114, No.12, 5180-5193, 2001
Kinetics of condensation of gases: A new approach
A recently developed new approach for the determination of the work of critical cluster formation in nucleation is applied here to the description of the kinetics of condensation of gases. This method is a generalization of the classical Gibbs' approach retaining its advantages and avoiding its shortcomings. For an illustration, the method is developed here for the case of condensation in a one-component van der Waals gas. The surface tension between liquid and gas is described by a modification of Macleods equation. However, any other relationships specifying the state of the system under consideration, which may be considered eventually as more appropriate, can be employed as well. For relatively small supersaturations, the classical Gibbs' results (employing the capillarity approximation) are retained as a special case. However, similarly to the van der Waals-Cahn and Hilliard and more recent methods of density functional calculations in the determination of the work of critical cluster formation, for initial states, approaching the spinodal curve, the work of critical cluster formation is shown to tend to zero. In the intermediate range of supersaturations, it leads to smaller values of the work of critical cluster formation as predicted by the classical theory. The method can be extended also straightforwardly to the description of condensation in multicomponent gases as well as to bubble formation in liquids. (C) 2001 American Institute of Physics.