On the Equilibrium of Heterogeneous Substances



In the physical chemistry.[1][2]

Gibbs's Equilibrium marks the beginning of chemical thermodynamics by integrating thermodynamics".[3]

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).[4] It remained largely unknown until translated into German 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 chemical energetics") in 1891 and into French by H. le Chatelier in 1899.[6]

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 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:

Opening section

“ Die Energie der Welt ist constant. ”
(The energy of the universe is constant).

“ Die Entropy der Welt strebt einem Maximum zu. ”
(The entropy of the universe tends to a maximum)
Clausius[7]

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 is capable. As the difference of the values of the energy for any two states represents the combined amount of work and state to the other, and the difference of entropy is the limit of all possible values of the integral:

\int \frac{\delta Q}{T}

in which dQ denotes the element of heat received from external sources, and T is the temperature of the part of the system receiving it, the varying values of energy and entropy characterize in all that is essential the effect producible by the system in passing from one state to another. For by mechanical and thermodynamic contrivances, supposedly theoretically perfect, any supply of work and heat may be transformed into any other which does not differ from it either in the amount of work which does not differ from it either in the amount of work and heat taken together or in the value of the integral:

\int \frac{\delta Q}{T}

But it is not 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 cannot 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:[8]

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]

References

  1. ^ Ott, Bevan J.; Boerio-Goates, Juliana (2000). Chemical Thermodynamics – Principles and Applications. Academic Press. ISBN 0-12-530990-2. 
  2. ^ a b Servos, John, W. (1990). Physical Chemistry from Otwald to Pauling. Princeton University Press. ISBN 0-691-08566-8. 
  3. ^ Bryson, Bill (2003). A Short History of Nearly Everything. Broadway Books, 116-17,121. ISBN 0-7679-0818-X. 
  4. ^ Gibbs, Willard, J. (1876). Transactions of the Connecticut Academy, III, pp. 108-248, Oct. 187-May, 1876, and pp. 343-524, May, 1877-July, 1878.
  5. ^ Gibbs, J. Willard (1993). The Scientific Papers of J. Willard Gibbs - Volume One Thermodynamics. Ox Bow Press. ISBN 0-918024-77-3. 
  6. ^ Josiah Willard Gibbs - Britannica (1911).
  7. ^ Clausius, R. (1865). The Mechanical Theory of Heat – with its Applications to the Steam Engine and to Physical Properties of Bodies. London: John van Voorst, 1 Paternoster Row. MDCCCLXVII.
  8. ^ On the Equilibrium of Heterogeneous Substances - Jonathan A. Hill, Bookseller Inc.
 
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