Nucleation Gibbs thermodynamic approach

The above kinetic equations, developed based on the thermodynamic approach of Gibbs (1928), Volmer and Weber (1926), and Becker and Doring (1935), belong to the so-called classical nucleation theories. They have been criticized for the use of surface energy (interfacial tension), cr, which is probably of little physical significance when applied to small molecular assemblies of the size of critical nucleus. 

The nucleation process has been discussed above in terms of the so-called classical theories stemming from the thermodynamic approach of Gibbs and Volmer, with the modifications of Becker, Doring and later workers. The main criticism of these theories is their dependence on the interfacial tension (surface energy), 7, e.g. in the Gibbs-Thomson equation, and this term is probably meaningless when applied to clusters of near critical nucleus size. 

The given approach allows us to differentiate the influence of thermodynamic constraints on hysteresis (related to the Gibbs free energy dependence on size and nucleation barrier) from the influence of kinetic constraints on hysteresis (related to the activation energy for the diffusion across the parent phase-nucleus interface). At high T the hysteresis is related to thermodynamic control of the process, whereas at low T the hysteresis is related to kinetic control of the process. 

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