In most cases of interest there are internal degrees of freedom and processes, such as chemical reactions and phase transitions, which create entropy. Even for homogeneous “bulk” materials, the free energy functions depend on the (often suppressed) composition, as do all proper thermodynamic potentials (extensive functions), including the internal energy.
Free energy is that portion of any first-law energy that is available to perform thermodynamic work at constant temperature, i. e. , work mediated by thermal energy. Free energy is subject to irreversible loss in the course of such work. [Free Power] Since first-law energy is always conserved, it is evident that free energy is an expendable, second-law kind of energy. Several free energy functions may be formulated based on system criteria. Free energy functions are Legendre transforms of the internal energy.
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