Abstract

AbstractTo account for the effect of condensation heat on the condensation coefficient (α), a semiempirical model is proposed. The model contains two free parameters: a characteristic size of the “hot spot” where the heat release occurs and its lifetime. At reasonable values of the parameters, the model agrees well with experimental and computer‐simulated data for both simple and associating liquids. For nonequilibrium conditions, the model leads to the Hertz–Knudsen equation with α dependent not only on characteristics of the liquid but also on those of ambient vapor. This offers an explanation for the existing scattering of experimental data in α. Among other things, the expression for α obtained shows that for the net evaporation process α is always higher than that for the net condensation, and moreover, α = 1 for all liquids if evaporation occurs in vacuum. The model also indicates that for complex associating liquids like glycerol α may be quite sensitive to peculiarities of the liquid state under consideration.

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