Thermochemistry versus Thermodynamics: The Nineteenth Century Controversy

This point, widely appreciated by historians of science, has now become a research site for sociologists of knowledge. See, for example, Latour B. Woolgar S. , Laboratory life: The social construction of scientific facts (London, 1979).

Schelar V. M. , “Thermochemistry and the third law of thermodynamics”, Chymia, xi (1966), 99–124.

Ibid., 99.

Ibid., 99.

Ibid., 107–11.

Ibid., 112–15.

Ibid., 112. This judgement repeats word for word (without acknowledgement) a comment of E. Thorpe in his “Thomsen memorial lecture”, Memorial lectures delivered before the Chemical Society, ii (1914), 166.

Schelar , op. cit., 115.

Parkes G. S. , “Some notes on the history of thermochemistry”. Journal of chemical education, xxviii (1949), 262–6; Raman V. V. , “The permeation of thermodynamics into nineteenth century chemistry”, Indian journal of history of science, x (1975), 16–37; Kragh H. , “Julius Thomsen and classical thermochemistry”, The British journal for the history of science (forthcoming).

Levere T. H. , Affinity and matter: Elements of chemical philosophy 1800–1865 (Oxford, 1971), ch. 7, takes an account of the earlier theories in chemistry up to the work of Berthelot.

See, for example, Hiebert E. N. , “Developments in physical chemistry at the turn of the century”, in Science, technology and society in the time of Alfred Nobel , ed. by Bernhard C. G. (Oxford, 1982), 97–115.

Hiebert E. , “The energetics controversy and the new thermodynamics”, in Roller D. H. (ed.), Perspectives in the history of science and technology (Norman, Oklahoma, 1971), 67–86. Nye M. J. , “Berthelot's anti-atomism: A matter of taste?”, Annals of science, xxxviii (1981), 585–90.

Ostwald Wilhelm , for example, who became the focus of the drive towards institutionalization in the new discipline in 1887, wrote textbooks with full discussion of recent historical developments, and also edited the important series of reprints, “Klassiker der exacten Naturwissenschaften”. Among his American students, H. C. Jones wrote a semi-popular historical account of the origins of physical chemistry, A new era in chemistry (London, 1913), which was strongly loyal to the new physical chemists. A number of English chemists with interests in physical chemistry who were active at the beginning of the century also wrote on the history of science, giving full importance to physical chemistry. They include T. M. Lowry, M. M. P. Muir, W. A. Tilden, W.C. D. Whetham, and, somewhat later, J. R. Partington.

See especially Partington J. R. , A history of chemistry, iv (London, 1963), ch. 19.

Duhem's influence on the modern historians is clear. For example, Schelar does not merely cite Duhem, but takes over aspects of the historical framework he offers. It is unlikely that Schelar or any other modern historian would pay much attention to J. Moutier (especially while misspelling his name as Schelar does) had not Duhem paid fulsome tribute to his teacher.

Stallo J. B. , The concepts and theories of modern physics (Cambridge, Mass., 1960), ch. 16.

Jungfleisch E. , “Notice sur la vie et les travaux de Marcellin Berthelot”, Bulletin de la Société Chimique de France (1913), especially ch. 3.

Duhem P. , Introduction à la mécanique chimique (Paris, 1893), preface.

Thomsen J. , “Die Grundzüge eines thermochemischen Systems”, Poggendorff's Annalen, xcii (1854), 34, as quoted by Schelar , op. cit. (ref. 2), 110.

Berthelot M. , “Sur la statique des dissolutions salines”, Bulletin de la Société Chimique de Paris, xix (1873), 160. The same statement is given in many later publications, and in particular in Essai de mécanique chimique fondée sur la thermochimie (Paris, 1879), i, 24.

Thomsen J. , “Eine Prioritätsfrage bezüglich einiger Grundsätze der Thermochemie”, Sitzungsberichte der Deutschen chemischen Gesellschaft, vi (1873), 423. Kragh , op. cit. (ref. 9), discusses the exchange.

Berthelot M. , “Sur un réclamation de priorité élevée par M. J. Thomsen relativement aux principes de la thermochimie”, Bulletin de la Société Chimique de Paris, xix (1873), 485–9, especially 487–9.

Duhem's fullest accounts are in Duhem , op. cit. (ref. 18), and in “Thermochimie. A propos d'un livre récent de M. Marcelin Berthelot”, Revue des questions scientifique, xlii (1897), 361–92, especially pp. 363–4.

Berthelot M. , Essai de mécanique chimique fondée sur la thermochimie (2 vols, Paris, 1879), i, p. xxiii.

Ibid., p. xxiv.

Ibid., 7.

The German ancestry of physical chemistry in the mid-nineteenth century acknowledged by Ostwald and his school is mainly populated by those who studied with or were at some stage under the influence of R. W. Bunsen and his circle of associates at Heidelberg, which included H. Kopp. In addition to Horstmann, there were Landolt H. H. Meyer J. L. Rathke H. B. ,.

Duhem , op. cit. (ref. 18). See also Duhem P. , “Une science nouvelle. La chimie physique”, Revue philomatique de Bordeaux et du Sud-Ouest , (1899), 205–19 and 260–80, especially p. 262.

Rayleigh Lord , “On the dissipation of energy”. Nature, xi (1875), 454–5.

Duhem , op. cit. (refs 18 and 23).

Gibbs J. W. , “On the equilibrium of heterogeneous substances”, Transactions of the Connecticut Academy, iii (1875–78), 108–248, 343–524. Reprinted in Gibbs J. W. , Scientific papers (London, 1906), i, 55–353.

von Helmholtz H. , “Die Thermodynamik der chemischer Vorgänge”, Sitzungsberichte der Königlich Preussischen Akademie der Wissenschaften zu Berlin, 2nd ser., i (1882), 22–39, and later papers.

Armstrong H. E. , “Marcelin Berthelot”, Nature, cxx (1927), 659–63.

Jahn H. , Die Grundsätze der Thermochimie (Vienna, 1882); Naumann A. , Lehr- und Handbuch der Thermochimie (Braunschweig, 1882). These developments are reviewed in Kragh, op. cit. (ref. 9).

For example, W. Nernst castigated the Berthelot school for its “almost inconceivable ignorance of foreign literature”, in Theoretical chemistry, from the standpoint of Avogadro's rule and thermodynamics (1st English edn, London, 1895), 581.

Rathke B. , “Die Principien der Thermochemie und ihre Andwegung”, Abhandlungen der Naturforschenden Gesellschaft zu Halle, xv (1882), 197–224, 225–7.

Fisher N. , “Avogadro, the chemists and historians of chemistry: Part 2”, History of science, xx (1982), 212–30, especially pp. 220–4.

Partington , op. cit. (ref. 14), 596.

See, for example, Muir M. M. P. , Nature, xx (1879), 8–10; xxi (1879), 516–17; xxii (1880), 285–8.

Muir M. M. P. , Nature, xxi (1879), 517.

Muir M. M. P. , Nature, xxii (1880), 286.

Muir M. M. P. , assisted by D. M. Wilson, Elements of thermal chemistry (London and Cambridge, 1885), 174–82.

Meyer L. , Modern theories of chemistry (London, 1888; translation of the 5th edn), 434.

There are, for example, allusions to its limitations in Ostwald W. , Lehrbuch der physikalische Chemie (2 vols, Leipzig, 1885–87), ii, 19–22.

Nernst , op. cit. (ref. 35), ch. 5.

See for example, Duhem P. , “Notation atomique et hypothèses atomistiques”, Revue des questions scientifiques, xxxi (1892), 391–454, especially p. 453.

Duhem P. , Le potentiel thermodynamique et ses applications à la mécanique chimique et à l'étude des phénomènes electriques, submitted 1884 (Paris, 1886).

Duhem , op. cit. (ref. 18), 51.

Jungfleisch , op. cit. (ref. 17), 100.

Berthelot M. , letter to Le Chatelier, 3 May 1894, quoted in Jungfleisch, op. cit. (ref. 17), 101.

Berthelot M. , Comtes rendus de l'Académie des Sciences, cxviii (1894), 1378–92, and later appearing as the first chapter of Thermochimie: Données et lois numériques (2 vols, Paris, 1897).

In his “Berthelot memorial lecture”, H. B. Dixon offered an example of such a practical application. “Was not Deacon inspired by Berthelot's ideas when he sought and finally found a practical method of liberating chlorine from hydrochloric acid by the oxygen of the air?”, Memorial lectures delivered before the Chemical Society 1901–1913, ii (1914), 192. I am not convinced of the historical influence as Henry Deacon's patent for his process was dated 29 April 1868 (see Miall S. , A history of the British chemical industry London, 1931), 89), at which time Berthelot's work was at a very early stage. But Dixon clearly thought that this was an example of an industrial process for which Berthelot's Principle is a helpful guide. Dixon's comment was brought to my attention by an anonymous History of science referee of this paper.

Duhem , op. cit. (ref. 23).

Ibid., 370.

Ibid., 389.

Ibid., 390.

Ibid., 392.

Berthelot M. , “Remarques sur quelques règles thermochimiques relativement à la prévision des réactions”, Comtes rendus de l'Académie des Sciences, cxxxix (1904), 1005–9.

Jungfleisch , op. cit. (ref. 17).

Miller D. G. , “Ignored intellect: Pierre Duhem”, Physics today, xix (1966), 47–53, p. 49.

Berthelot M. , letter of 13 May 1894, quoted by Jungfleisch, op. cit. (ref. 17), 100.

Berthelot , op. cit. (ref. 51).

Berthelot , for example, claimed that his Principle was in accordance with the facts to the same order of accuracy as such laws of physicists as that of the uniform compressibility of gases. Berthelot , op. cit. (ref. 51, 1894), 1380.

See, for example, Dolby R. G. A. , “Debates over the theory of solution: A study of dissent in physical chemistry in the English-speaking world in the late nineteenth and early twentieth centuries”, Historical studies in the physical sciences, vii (1976), 297–404.

On Perrin's role, see Nye M. J. , Molecular reality: A perspective on the scientific work of Jean Perrin (London and New York, 1972). See also Guéron J. Magat M. , “A history of physical chemistry in France”, Annual review of physical chemistry, xxii (1971), 1–23, especially pp. 3–4.