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On the basis of the principles of non-equilibrium thermodynamics, the following condition was determined: necessary and sufficient for the occurrence of a minimum free energy of a liquid droplet deposited on a solid substrate in a gaseous environment in an isothermal and isochoric system. Only for positive values of the energy of three-phase tension line (shrinking the wetting circumference) for small and large contact angles can the system not reach this minimum. Without exceeding a certain free energy limit, it is not possible for the drop to spontaneously spread over the surface. For zero and negative energy of three-phase tension line (stretching the wetting circumference), the system can always reach a minimum of free energy. The developed equations allow determining the change of free energy occurring between any two stationary states when the droplet volume and physicochemical parameters characterizing energies at the interfaces are known. For a known set of such parameters, the equations allow determining the trajectory of free energy changes in the system as a function of the contact angle from the moment the drop comes into contact with the substrate. The application of the principles of non-equilibrium thermodynamics makes it possible to treat a real system as one in which the drops do not evaporate. However, the system has to be isothermal.

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Analysis of Existing Thermodynamic Models of the Liquid Drop Deposited on the Substrate—A Sufficient Condition of the Minimum Free Energy of the System