This expression has commonly been interpreted to mean that work is extracted from the internal energy U while TS represents energy not available to perform work. However, this is incorrect. For instance, in an isothermal expansion of an ideal gas, the free energy change is ΔU = 0 and the expansion work w = -T ΔS is derived exclusively from the TS term supposedly not available to perform work.
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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