Skip to main content
SpringerLink
Log in

A historical/epistemological account of the foundation of the key ideas supporting chemical equilibrium theory

  • Published:
Foundations of Chemistry Aims and scope Submit manuscript

Abstract

In this paper it is performed a historical account of the theoretical roots that grounded the following four key basic ideas of chemical equilibrium: ‘incomplete reaction’, ‘reversibility’, ‘equilibrium constant’ and ‘molecular dynamics’. These notions developed in nineteenth-century as a consequence of the evolution of the concept of chemical affinity. The discussion begins with the presentation of the earliest affinity table [‘Table des rapports’] published in 1718 by Geoffroy. Afterwards, it is examined Bergman’s compilation. The theory supporting this arrangement assumed that chemical displacement reactions were complete and could not be reversed. It is analysed how Berthollet’s model showed the inadequacy of this view. His new conceptual considerations established that the amount of the substances involved in a reaction was an essential factor determining its direction, which accounted for the early concepts of incomplete reaction and reversibility. Guldberg and Waage specified the role of mass in chemical equilibrium reactions as they considered the concentrations of the chemicals involved, formulating the first chemical equilibrium mathematical equation that approximates what is called nowadays chemical equilibrium constant. Finally, it is presented how Pfaundler was the first to consider the kinetic theory in the interpretation of the macroscopic properties of equilibrium reactions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Similar content being viewed by others

Notes

  1. Pages 380–381.

  2. Two English translations are available: (a) Concerning the different affinities observed in chemistry between different substances In: Leicester, H. M., Klickstein, H.S. A Source Book in Chemistry, 1400–1900. Harvard University, Cambridge, MA, 67–75 (1963); (b) Geoffroy, E.F.: Table of the different relations observed in chemistry between different substances. Science in Context 9, 313–319 (1996).

  3. Page 203.

  4. Page 203.

  5. Page 203.

  6. Page 202.

  7. Page 11.

  8. Pages 6–7.

  9. Pages 11–12.

  10. Page 4.

  11. Pages 2–3.

  12. Page 3.

  13. Pages 1–2.

  14. Pages 35–36.

  15. Page 1046.

  16. The reference given corresponds to an English translation of the original work published in 1864.

  17. Page 1044.

  18. Page 74.

  19. Page 1045.

  20. Page 4.

  21. Page 1046.

  22. Page 7.

  23. Page 7.

  24. Page 10.

  25. Page 74.

  26. Page 21.

  27. Page 555.

  28. Page 74.

  29. Page 303.

  30. Page 303.

  31. Page 27.

  32. Page 91.

  33. Page 24.

  34. Translated: Pfaundler, L.: A Contribution to Chemical Statics. Bull. Hist. Chem. 36(2), 87–97 (2011). The quotations given in this paper refer to this recent translation.

  35. Page 88.

References

  • Bensaude-Vicent, B., Strengers, I.: Histoire de la Chimie. La Découverte, Paris (1993)

    Google Scholar 

  • Berger, J.: Chemische Mechanik und Kinetik: Die Bedeutung der Mechanischen Wärmetheorie für Die Theorie Chemischer Reaktionen. Ann. Sci. 54, 567–584 (1997)

    Article  Google Scholar 

  • Bergman, T.: A Dissertation on Elective Attractions, 2nd edn. Frank Cass & Co Ltd., London (1785)

    Google Scholar 

  • Berthollet, C.L.: Recherches sur la loi de l’affinitté. Baudouin, Paris (1801)

    Google Scholar 

  • Berthollet, C.L.: Essai de Statique Chimique. Demonville, Paris (1803)

    Google Scholar 

  • Brock, W.H., Knight, D.M.: The atomic debates: “memorable and interesting evenings in the life of the chemical society”. Isis 56, 1–29 (1965)

    Article  Google Scholar 

  • Clausius, R.: The nature of motion which we call heat. Philos. Mag. 14, 108–127 (1857)

    Article  Google Scholar 

  • Cohen, B.R.: The element of the table: visual discourse and preperiodic representation of chemical classification. Configurations 12, 41–75 (2004)

    Article  Google Scholar 

  • Deltete, R.J.: Wilhelm Ostwald energetics 1: origins and motivation. Found. Chem. 9, 3–56 (2007)

    Article  Google Scholar 

  • Dolby, R.G.A.: Thermochemistry versus thermodynamics: the nineteenth century controversy. Hist. Sci. 22, 375–400 (1984)

    Article  Google Scholar 

  • Duncan, A.M.: Some theoretical aspects of eighteenth-century tables of affinity-I. Ann. Sci. 18, 177–194 (1962a)

    Article  Google Scholar 

  • Duncan, A.M.: Some theoretical aspects of eighteenth-century tables of affinity-II. Ann. Sci. 18, 217–234 (1962b)

    Article  Google Scholar 

  • Duncan, A.M.: The functions of affinity Tables and Lavoisier’s list of elements. Ambix 37, 26–42 (1970)

    Google Scholar 

  • Duncan, A.M.: Laws and Order in Eighteenth-Century Chemistry. Clarendon Press, Oxford (1996)

    Google Scholar 

  • Ganaras, K., Dumon, A.: La construction du concept d’Équilibre chimique. L’actualité Chimique 266, 38–46 (2003)

    Google Scholar 

  • Gay-Lussac, L.J.: Observations sur l’Oxydation de Quelques Métaux. Crochard, Paris (1816)

    Google Scholar 

  • Gay-Lussac, L.J.: Considerations sur les Forces Chimiques. Ann Chim Phys 70, 407–434 (1839)

    Google Scholar 

  • Geoffroy, E.F.: Table des Differents Rapports Observés en Chimie entre Differentes Substances. Memoires de l’Académie Royale des Sciences, pp. 202–212 (1718)

  • Gladstone, J.H.: On circumstances modifying the action of chemical affinity. Philos Trans 145, 179–223 (1855)

    Article  Google Scholar 

  • Gladstone, J.H.: Some experiments illustrative of the reciprocal decomposition of salts. Q J Chem Soc 9, 144–156 (1857)

    Article  Google Scholar 

  • Goupil, M.: Du Flou au Clair?. Histoire de l’Affinité Chimique. CTHS, Paris (1991)

    Google Scholar 

  • Grapí, P.: Study of some conditions involved in the construction of the concept of chemical reversibility. In: History and Philosophy of Science in Science Education, vol. 1, pp. 449–457. Queen’s University, Kingston (1992)

  • Grapí, P.: The marginalization of Bertholet’s chemical affinities in the french textbook tradition at the beginning of nineteenth century. Ann. Sci. 58, 111–135 (2001)

    Article  Google Scholar 

  • Grapí, P., Izquierdo, M.: Berthollet’s conception of chemical change in context. Ambix 44, 113–130 (1997)

    Article  Google Scholar 

  • Guggenheim, E.A.: More about the laws of reaction rates and of equilibrium. J. Chem. Educ. 33, 554–555 (1956)

    Article  Google Scholar 

  • Guldberg, C.M., Waage, P.: Études sur les Affinités Chimiques. Christiania University, Oslo (1867)

    Google Scholar 

  • Guldberg, C.M., Waage, P.: Über Die Chemische Affinität. J. Prakt. Chem. 127, 69–114 (1879)

    Article  Google Scholar 

  • Harris, J., Brock, W.H.: From Giessen to Gower Street. Towards a biography of Alexander William Williamson (1824–1904). Ann. Sci. 31, 95–130 (1974)

    Article  Google Scholar 

  • Holmes, F.L.: From elective affinities to chemical equilibria: Berthollet’s law of mass action. Chymia 8, 105–145 (1962)

    Article  Google Scholar 

  • Holmes, F.L.: Eighteenth-Century Chemistry as an Investigative Enterprise. University of California Press, Berkeley (1989)

    Google Scholar 

  • Holmes, F.L.: The communal context for Etienne-François Geoffroy’s “Table des Rapports”. Sci. Context 9, 289–311 (1996)

    Google Scholar 

  • Horstmann, A.F.: Theorie der Dissociation. Ann. Chem. Pharm. 170, 192–210 (1873)

    Article  Google Scholar 

  • Jensen, W., Kulhman, J.: Leopold Pfaundler and the origins of the kinetic theory of chemical reactions. Bull. Hist. Chem. 37, 29–41 (2012)

    Google Scholar 

  • Joly, B.: Etienne-François Geoffroy, entre la Royal Society et l’Académie Royale des Sciences: ni Newton, ni Descartes. Methodos (on line) 12 (2012). https://doi.org/10.4000/methodos.2855

  • Joly, B.: Etienne-François Geoffroy (1672–1731), a chemist on the frontiers. Osiris 29, 117–131 (2014)

    Article  Google Scholar 

  • Kapoor, S.C.: Berthollet, Proust, and proportions. Chymia 10, 53–110 (1965)

    Article  Google Scholar 

  • Kim, M.G.: Practice and representation: investigative programs of chemical affinity in the nineteenth century. Ph.D. Thesis, University of California, Los Angeles (1990)

  • Kim, M.G.: The layers of chemical language, I: constitution of bodies v. structure of matter. Hist. Sci. 30, 69–96 (1992)

    Article  Google Scholar 

  • Kim, M.G.: Affinity. That Elusive Dream. The MIT Press, Cambridge, MA (2003)

    Book  Google Scholar 

  • King, M.C.: Experiments with time: progress and problems in the development of chemical kinetics. Ambix 28, 70–82 (1981)

    Article  Google Scholar 

  • Klein, U.: E.F. Geoffroy’s Table of different “Rapports” observed between different chemical substances—a reinterpretation. Ambix 42, 79–100 (1995)

    Article  Google Scholar 

  • Laidler, K.J.: Chemical kinetics and the origin of physical chemistry. Arch. Hist. Exact Sci. 32, 43–75 (1985)

    Article  Google Scholar 

  • Laidler, K.J.: The World of Physical Chemistry. Oxford University Press, Oxford (1995)

    Google Scholar 

  • Lefèvre, W.: Viewing chemistry through its ways of classifying. Found. Chem. 14, 25–36 (2012)

    Article  Google Scholar 

  • Lemay, P., Oesper, R.E.: Claude Louis Berthollet (1748–1822). J. Chem. Educ. 23(158–165), 230–236 (1946)

    Google Scholar 

  • Lemoine, M.G.: Études sur les Équilibres Chimiques. In: Fremy. M. (ed.) Encyclopédie Chimique, Tome I, pp. 69–372. Dunod, Paris (1882)

  • Levere, T.H.: Affinity and Matter. Elements of Chemical Philosophy 1800–1865. Clarendon Press, Oxford (1971)

    Google Scholar 

  • Lindauer, M.W.: The evolution of the concept of chemical equilibrium from 1775 to 1923. J. Chem. Educ. 39, 384–390 (1962)

    Article  Google Scholar 

  • Lund, E.W.: Guldberg and Waage and the law of mass action. J. Chem. Educ. 42, 548–549 (1965)

    Article  Google Scholar 

  • Lund, E.W.: Activated complex—a centenarian? J. Chem. Educ. 45, 125–128 (1968)

    Article  Google Scholar 

  • Lund, E.W., Hassel, O.: Guldberg and Waage and the law of mass action. In: Bastiansen, O. (ed.) The law of mass action. A centenary volume, 1864–1964, pp. 37–46. Det Noske Videnskaps-Akademi Oslo, Oslo (1964)

    Google Scholar 

  • Malaguti, M.J.: Exposition de Quelques Faits Relatifs a l’Action Réciproque des Sels Solubles. Ann. Chim. Phys. 37, 198–206 (1853)

    Google Scholar 

  • Mellor, J.W.: Chemical Statics and Dynamics. Longmans Green, London (1914)

    Google Scholar 

  • Muir, M.M.P.: Chemical affinity. Philos. Mag. 8, 181–203 (1879)

    Article  Google Scholar 

  • Muir, M.M.P.: A History of Chemical Theories and Laws. Arno Press, New York (1907–1975)

  • Newton, I.: Optics or a Treatise of the Reflections, Refractions. Inflections and Colours of Light. Dover, New York (1979)

    Google Scholar 

  • Øhrstrøm, P.: Guldberg and Waage on the influence of temperature on the rates of chemical reactions. Centaurus 28, 277–286 (1985)

    Article  Google Scholar 

  • Ostwald, W.: L’Évolution d’une Science: la Chimie. Flamarion, Paris (1914)

    Google Scholar 

  • Ostwald, W.: Outlines of General Chemistry. MacMillan, London (1980)

    Google Scholar 

  • Partington, J.R.: A History of Chemistry. MacMillan, London (1970)

    Google Scholar 

  • Pasdeloup, M., Laugier, A.: Le concept de reaction Chimique en Gestation. Entre les Affinités Électives et l’Attraction Universelle. Aster 18, 165–182 (1994)

    Google Scholar 

  • Paul, E.R.: Alexander W. Williamson on the atomic theory: a study of nineteenth-century British Atomism. Ann. Sci. 35, 17–31 (1978)

    Article  Google Scholar 

  • Petit, A.: Associating physics and chemistry to dissociate molecules: the history of the Clausius–Williamson hypothesis. Hist. Stud. Nat. Sci. 46, 360–391 (2016)

    Article  Google Scholar 

  • Pfaundler, L.: Beiträge zur Chemischen Statik. Ann. Phys. 131, 55–85 (1867)

    Article  Google Scholar 

  • Quílez, J.: The role of theories in early studies of chemical equilibrium. Bull. Hist. Chem. 31, 45–57 (2006)

    Google Scholar 

  • Quílez, J.: From chemical forces to chemical rates: a historical/philosophical foundation for teaching chemical equilibrium. Sci. Educ. 13, 1203–1251 (2009)

    Article  Google Scholar 

  • Roth, E.: Etienne Francois Geofroy’s Table of relations and the concept of affinity. Fresenius J. Anal. Chem. 337, 188–203 (1990)

    Article  Google Scholar 

  • Sadoun-Goupil, M.: Le Chimiste Claude-Louis Berthollet 1748-1822: Sa Vie-Son Oeuvre. Vrin, Paris (1977)

    Google Scholar 

  • Servos, J.W.: Physical Chemistry from Ostwald to Pauling. Princeton University Press, Princeton (1990)

    Google Scholar 

  • Smeaton, W.A.: Guyton de Morveau and Chemical Affinity. Ambix 11, 55–64 (1963)

    Article  Google Scholar 

  • Smeaton, W.A.: Geoffroy was not a Newtonian chemist. Ambix 18, 212–214 (1971)

    Article  Google Scholar 

  • Smeaton, W.A.: Tobern Olof Bergman: from natural history to quantitative chemistry. Endeavour 8, 71–74 (1984)

    Article  Google Scholar 

  • Snelders, H.A.M.: Dissociation, darwinism and entropy. Janus 64, 51–75 (1977)

    Google Scholar 

  • Stengers, I.: L’Affinité Ambiguë: le Rêve Newtonien de la Chimie du XVIIIe Siècle. In: Serres, M. (ed) Élements d’Histoire des Sciences, pp. 297–319. Bordas, Paris (1989)

    Google Scholar 

  • Taylor, G.N.L.: Variations on a theme: patterns of congruence and divergence among 18th century chemical affinity theories. Ph.D. Thesis, University College London, London (2006)

  • Taylor, G.: Choice or no choice? Affinity and theory choice. In: Tobin, E., Ambrosio, C. (eds.) Theory choice in the history of chemical practices, pp. 29–54. Springer, Berlin (2016)

    Chapter  Google Scholar 

  • Thackray, A.: Atoms and Powers: An Essay on Newtonian Matter-Theory and the Development of Chemistry. Harvard University Press, Cambridge (1970)

    Book  Google Scholar 

  • Van’t Hoff, J.H.: Études de Dynamique Chimique. Frederik Muller, Amsterdam (1884)

    Book  Google Scholar 

  • Waage, P., Guldberg, C.M.: (Translated by Abrash, H.I.) Studies concerning affinity. J. Chem. Educ. 63, 1044–1047 (1986)

    Article  Google Scholar 

  • Weller, S.W.: Napoleon Bonaparte, French Scientists, chemical equilibrium, and mass action. Bull. Hist. Chem. 24, 61–65 (1999)

    Google Scholar 

  • Williamson, A.W.: Theory of Ætherification. Philos. Mag. 37, 350–356 (1850)

    Google Scholar 

  • Williamson, A.W.: Suggestions for the dynamics of chemistry derived from the theory of etherification. In: Notices of the Proceedings at the Meetings of Members of the Royal Institution, vol. 1, pp. 7–24 (1851–1854)

Download references

Author information

Authors and Affiliations

  1. Department of Education, Universitat Jaume I, 12071, Castelló de la Plana, Spain

    Juan Quílez

Authors
  1. Juan Quílez
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Juan Quílez.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Quílez, J. A historical/epistemological account of the foundation of the key ideas supporting chemical equilibrium theory. Found Chem 21, 221–252 (2019). https://doi.org/10.1007/s10698-018-9320-0

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10698-018-9320-0

Keywords

Search

Navigation