Thermodynamic Free Energy - History

History

The quantity called "free energy" is a more advanced and accurate replacement for the outdated term affinity, which was used by chemists in previous years to describe the force that caused chemical reactions. The term affinity, as used in chemical relation, dates back to at least the time of Albertus Magnus in 1250.

From the 1998 textbook Modern Thermodynamics by Nobel Laureate and chemistry professor Ilya Prigogine we find: "As motion was explained by the Newtonian concept of force, chemists wanted a similar concept of ‘driving force’ for chemical change. Why do chemical reactions occur, and why do they stop at certain points? Chemists called the ‘force’ that caused chemical reactions affinity, but it lacked a clear definition."

During the entire 18th century, the dominant view with regard to heat and light was that put forth by Isaac Newton, called the Newtonian hypothesis, which states that light and heat are forms of matter attracted or repelled by other forms of matter, with forces analogous to gravitation or to chemical affinity.

In the 19th century, the French chemist Marcellin Berthelot and the Danish chemist Julius Thomsen had attempted to quantify affinity using heats of reaction. In 1875, after quantifying the heats of reaction for a large number of compounds, Berthelot proposed the principle of maximum work, in which all chemical changes occurring without intervention of outside energy tend toward the production of bodies or of a system of bodies which liberate heat.

In addition to this, in 1780 Antoine Lavoisier and Pierre-Simon Laplace laid the foundations of thermochemistry by showing that the heat given out in a reaction is equal to the heat absorbed in the reverse reaction. They also investigated the specific heat and latent heat of a number of substances, and amounts of heat given out in combustion. In a similar manner, in 1840 Swiss chemist Germain Hess formulated the principle that the evolution of heat in a reaction is the same whether the process is accomplished in one-step process or in a number of stages. This is known as Hess' law. With the advent of the mechanical theory of heat in the early 19th century, Hess’s law came to be viewed as a consequence of the law of conservation of energy.

Based on these and other ideas, Berthelot and Thomsen, as well as others, considered the heat given out in the formation of a compound as a measure of the affinity, or the work done by the chemical forces. This view, however, was not entirely correct. In 1847, the English physicist James Joule showed that he could raise the temperature of water by turning a paddle wheel in it, thus showing that heat and mechanical work were equivalent or proportional to each other, i.e., approximately, . This statement came to be known as the mechanical equivalent of heat and was a precursory form of the first law of thermodynamics.

By 1865, the German physicist Rudolf Clausius had shown that this equivalence principle needed amendment. That is, one can use the heat derived from a combustion reaction in a coal furnace to boil water, and use this heat to vaporize steam, and then use the enhanced high-pressure energy of the vaporized steam to push a piston. Thus, we might naively reason that one can entirely convert the initial combustion heat of the chemical reaction into the work of pushing the piston. Clausius showed, however, that we must take into account the work that the molecules of the working body, i.e., the water molecules in the cylinder, do on each other as they pass or transform from one step of or state of the engine cycle to the next, e.g., from (P₁,V₁) to (P₂,V₂). Clausius originally called this the “transformation content” of the body, and then later changed the name to entropy. Thus, the heat used to transform the working body of molecules from one state to the next cannot be used to do external work, e.g., to push the piston. Clausius defined this transformation heat as dQ = TdS.

In 1873, Willard Gibbs published A Method of Geometrical Representation of the Thermodynamic Properties of Substances by Means of Surfaces, in which he introduced the preliminary outline of the principles of his new equation able to predict or estimate the tendencies of various natural processes to ensue when bodies or systems are brought into contact. By studying the interactions of homogeneous substances in contact, i.e., bodies, being in composition part solid, part liquid, and part vapor, and by using a three-dimensional volume-entropy-internal energy graph, Gibbs was able to determine three states of equilibrium, i.e., "necessarily stable", "neutral", and "unstable", and whether or not changes will ensue. In 1876, Gibbs built on this framework by introducing the concept of chemical potential so to take into account chemical reactions and states of bodies that are chemically different from each other. In his own words, to summarize his results in 1873, Gibbs states:

In this description, as used by Gibbs, ε refers to the internal energy of the body, η refers to the entropy of the body, and ν is the volume of the body.

Hence, in 1882, after the introduction of these arguments by Clausius and Gibbs, the German scientist Hermann von Helmholtz stated, in opposition to Berthelot and Thomas’ hypothesis that chemical affinity is a measure of the heat of reaction of chemical reaction as based on the principle of maximal work, that affinity is not the heat given out in the formation of a compound but rather it is the largest quantity of work which can be gained when the reaction is carried out in a reversible manner, e.g., electrical work in a reversible cell. The maximum work is thus regarded as the diminution of the free, or available, energy of the system (Gibbs free energy G at T = constant, P = constant or Helmholtz free energy F at T = constant, V = constant), whilst the heat given out is usually a measure of the diminution of the total energy of the system (Internal energy). Thus, G or F is the amount of energy “free” for work under the given conditions.

Up until this point, the general view had been such that: “all chemical reactions drive the system to a state of equilibrium in which the affinities of the reactions vanish”. Over the next 60 years, the term affinity came to be replaced with the term free energy. According to chemistry historian Henry Leicester, the influential 1923 textbook Thermodynamics and the Free Energy of Chemical Reactions by Gilbert N. Lewis and Merle Randall led to the replacement of the term “affinity” by the term “free energy” in much of the English-speaking world.