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Is the Size of a Small System a Thermodynamic Parameter?

  • CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY
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Abstract

A corollary of the molecular equilibrium theory of small systems is considered for the Clausius–Clapeyron equation with regard to experimentally measured periods of relaxation of momentum and processes of mass transfer. It is shown that in accordance with the phase rule, the heat of the phase transition for small drops does not depend on their radii; i.e., the size of a small system is not a thermodynamic parameter. This conclusion contradicts the existing interpretations that follow from thermodynamic approaches based on metastable Gibbs droplets, in which the ratio of momentum and mass relaxation times is violated and the droplet size is considered a thermodynamic parameter. This contradiction is explained by variation in the size of the equilibrium small phase changing the surface tension, which is not an intrinsic property of a small phase. In thermodynamics, however, varying the radius of a droplet alters the internal state of a small phase. Consideration is given to the Hill approach based on the possibility of using metastable states in small systems to derive the Clausius–Clapeyron equation, and to the correctness of using equilibrium equations of thermodynamics to describe the melting of small crystals.

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  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991, Moscow, Russia

    Yu. K. Tovbin

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Translated by L. Chernikova

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Tovbin, Y.K. Is the Size of a Small System a Thermodynamic Parameter?. Russ. J. Phys. Chem. 96, 1647–1657 (2022). https://doi.org/10.1134/S0036024422080258

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  • DOI: https://doi.org/10.1134/S0036024422080258

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