During the early 19th century, the concept of perceptible or free caloric began to be referred to as “free heat” or heat set free. In 1824, for example, the Free Electricity physicist Sadi Carnot, in his famous “Reflections on the Motive Power of Fire”, speaks of quantities of heat ‘absorbed or set free’ in different transformations. In 1882, the Free Energy physicist and physiologist Hermann von Helmholtz coined the phrase ‘free energy ’ for the expression E − TS, in which the change in F (or G) determines the amount of energy ‘free’ for work under the given conditions, specifically constant temperature. [Free Electricity]:Free Power.

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.