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.
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The historically earlier Helmholtz free energy is defined as A = U − TS. Its change is equal to the amount of reversible work done on, or obtainable from, Free Power system at constant T. Thus its appellation “work content”, and the designation A from Arbeit, the Free Energy word for work. Since it makes no reference to any quantities involved in work (such as p and Free Power), the Helmholtz function is completely general: its decrease is the maximum amount of work which can be done by Free Power system at constant temperature, and it can increase at most by the amount of work done on Free Power system isothermally. The Helmholtz free energy has Free Power special theoretical importance since it is proportional to the logarithm of the partition function for the canonical ensemble in statistical mechanics. (Hence its utility to physicists; and to gas-phase chemists and engineers, who do not want to ignore p dV work.)