Theory of Condensation of Liquids of One and Two Components

Cernuschi and Eyring's theory of condensation has been reconsidered, taking account of Kirkwood's criticisms, by the introduction of vibrations in the model. Variation of Einstein's frequency with temperature has been considered, following some works of Raman. With these modification results according with experiment are obtained, overcoming thus Kirkwood's objections. The possibility of extending the model to the case of two components is then examined. The resulting formulas do not allow, because of their complexity, an analytic determination of the critical point. The equations can be simplified supposing that only one of the three previous interactions is different from zero. Numerical calculation has been done for the case of interaction between different particles. The critical curve is found by trial and error. The calculations made for three different concentrations of one of the components (parameter in the theory) shows that the exp(ε/kTc)—ε interaction energy decreases with such concentration.