Journal of Chemical Physics, Vol.109, No.22, 10004-10010, 1998
Critical embryo phase transitions in the nucleated binary glycerin carbon dioxide system
In order to develop a consistent nucleation theory, the main assumptions of the theory should be revised. One of the questionable problems is the role of the carrier gas in nucleation and the surface tension for the critical embryo as a function of cluster size. Using a flow diffusion chamber, the vapor nucleation rates were measured with high precision and phase transitions in critical embryos containing two and more dozen molecules were detected. Phase transitions in critical embryos were used as markers to detect that the new phase critical embryos contain two components. Phase transitions of the first order related with critical point second-order phase transitions in the pure CO? carrier-gas were used as markers to demonstrate the presence of CO2 in critical embryos of condensate. Results of this research, in our opinion, very clearly demonstrate that vapor nucleation in a gaseous atmosphere is a binary process and must be interpreted from the point of view of nucleation theory within a binary system. "Supercritical" nucleation is a virtual term born by interpretation of binary vapor-gas nucleation by using the nucleation model of a single component. A critical condition for the binary system could be a higher level for the single component critical pressure and/or temperature, which can produce the illusion of supercritical nucleation. One component interpretation can be used far from the critical condition. On the other hand, the Laplace pressure practically always is able to approach the nucleation condition to the critical pressure. This level of detail is a problem for future studies. The traditional application of classical nucleation theory for vapor-gas nucleation should be modified to consider the nucleation conditions in pressure-temperature-composition space.
Keywords:HOMOGENEOUS NUCLEATION