Everything about On The Equilibrium Of Heterogeneous Substances totally explained
In the
history of thermodynamics,
On the Equilibrium of Heterogeneous Substances is a 300-page paper written by American mathematical-engineer
Willard Gibbs. It is one of the founding papers in
thermodynamics, along with German physicist
Hermann von Helmholtz's 1882 paper "
Thermodynamik chemischer Vorgange". Together they form the foundation of
chemical thermodynamics as well as a large part of
physical chemistry.
Gibbs's
Equilibrium marks the beginning of chemical thermodynamics by integrating
chemical, physical,
electrical, and
electromagnetic phenomena into a coherent system. It introduced concepts such as
chemical potential,
phase rule, and others, which form the basis for modern physical chemistry. American writer
Bill Bryson describes Gibbs's
Equilibrium paper as "the
Principia of
thermodynamics".
On the Equilibrium of Heterogeneous Substances, was originally published in a relatively obscure American journal, the
Transactions of the Connecticut Academy, in several parts, during the years 1875 to 1878 (although most cite "1876" as the key year). It remained largely unknown until translated into German by
Wilhelm Ostwald and into French by
Henry Louis Le Chatelier.
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 changes, among others. As stated by
Henri Louis Le Chatelier, it "founded a new department of chemical science that's 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.
The comprehension of the laws which govern any material system is greatly facilitated by considering the
energy and
entropy of the system in the various states of which it's capable. As the difference of the values of the energy for any two states represents the combined amount of
work and
heat received or yielded by the
system when it's brought from one
state to the other, and the difference of entropy is the limit of all possible values of the integral:
»
But it isn't only in respect to the external relations of a system that its energy and entropy are of predominant importance. As in the case of simple mechanical systems, such as are discussed in theoretical mechanics, which are capable of only one kind of action upon external systems, namely the performance of mechanical work, the function which expresses the capability of the system of this kind of action also plays the leading part in the theory of equilibrium, the condition of equilibrium being that the variation of this function shall vanish, so in a thermodynamic system, such as all material systems are, which is capable of two different kinds of action upon external systems, the two functions which express the twofold capabilities of the system afford an almost equally simple criterion for equilibrium.
Collector value
The value of Gibbs'
Equilibrium can't be over-estimated. This paper alone has produced at least four
Nobel Prize winners. Original copies of Gibbs' paper sell for 1,000 US dollars. One example is shown below:
» Gibbs, Josiah Willard
On the Equilibrium of Heterogeneous Substances...Abstract by the author, New Haven: 1878. pp. 441-58 in The American Journal of Science and Arts (Eds. James D. & E.S. Dana, and B. Silliman), Third Series, Vol. XVI, No. 96, December 1878. 8vo, orig. printed wrappers (spine frayed & text leaves loose in wrappers). New Haven: 1878. Abstract of Gibbs' contribution which originally appeared in its entirety in the Transactions of the Connecticut Academy of Arts and Sciences. Roberts & Trent, Bibliotheca Mechanica, p. 138. Good copy preserved in a slip case. Ex Bibliotheca Mechanica.
[Cost= $US1000]
Further Information
Get more info on 'On The Equilibrium Of Heterogeneous Substances'.
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