On The Equilibrium of Heterogeneous Substances - Overview

Overview

Gibbs first contributed to mathematical physics with two papers published in 1873 in the Transactions of the Connecticut Academy on "Graphical Methods in the Thermodynamics of Fluids," and "Method of Geometrical Representation of the Thermodynamic Properties of Substances by means of Surfaces." His subsequent and most important publication was "On the Equilibrium of Heterogeneous Substances" (in two parts, 1876 and 1878). In this monumental, densely woven, 300-page treatise, the first law of thermodynamics, the second law of thermodynamics, the fundamental thermodynamic relation, are applied to the predication and quantification of thermodynamic reaction tendencies in any thermodynamic system in a visual, three-dimensional graphical language of Lagrangian calculus and phase transitions, among others. As stated by Henri Louis Le Chatelier, it "founded a new department of chemical science that is becoming comparable in importance to that created by Lavoisier." This work was translated into German by W. Ostwald (who styled its author the "founder of chemical energetics") in 1891 and into French by H. le Chatelier in 1899.

Gibbs's "Equilibrium" paper is considered one of the greatest achievements in physical science in the 19th century and one of the foundations of the science of physical chemistry. In these papers Gibbs applied thermodynamics to the interpretation of physicochemical phenomena and showed the explanation and interrelationship of what had been known only as isolated, inexplicable facts.

Gibbs' papers on heterogeneous equilibria included:

• Some chemical potential concepts
• Some free energy concepts
• A Gibbsian ensemble ideal (basis of the statistical mechanics field)
• A phase rule