The young J.H. van't Hoff: The background to the publication of his 1874 pamphlet on the tetrahedral carbon atom, together with a new english translation

Annals of Science

Volumn 58, Issue 1, 2001, Pages 51-74

  Ramberg, Peter J ^a   Somsen, Geert J ^b  

^a University of Maastricht   (Netherlands)

^b MAASTRICHT UNIVERSITY   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0035240884     PISSN: 00033790     EISSN: None     Source Type: Journal    
DOI: 10.1080/000337901457696     Document Type: Article

References (78)

1. According to Dutch spelling rules, a space is required between the 'van' and ''t' portions of Van 't Hoff's name, and the V is capitalized when no first name or initials are present. The lower case v is used otherwise, for example 'J. H. van 't Hoff' and 'Van 't Hoff'. Because these changes can result in a change in pronunciation, we have elected to follow the Dutch rules, except in titles of references where the American or German spelling conventions were followed.
2. Jacobus Henricus van 't Hoff, Voorstel tot uitbreiding der tegenwoordig in de scheikunde gebruikte structuur-formules in de mimte; benevens een daarmee samenhangende opmerkung omtrent het verband tusschen optisch actief vermogen en chemische constitutie van organische verbindingen (Utrecht, 1874). Fischmann mentions that the printing of this pamphlet was financed by Van 't Hoff's father, but he offers no source for this information, and it does not appear in any other biography of Van 't Hoff. E. Fischmann, 'A reconstruction of the first experiments in stereochemistry: letters from Van't Hoff to Bremer in a new chronological sequence', Janus, 72 (1985), 131-56.
3. George M. Richardson (editor), The Foundations of Stereochemistry: Memoirs by Pasteur, van't Hoff, Le Bel, and Wislicenus (New York, 1901);
4. Henry M. Leicester and Herbert S. Klickstein (editors), A Sourcebook in Chemistry, 1400-1900 (Cambridge, Massachusetts, 1952);
5. Otto T. Benfey (editor), Classics in the Theory of Chemical Combination (New York, 1963).
6. Ernst Cohen, Jacobus Henricus van't Hoff: Sein Leben und Werken (Leipzig, 1912).
7. A short English synopsis of Van 't Hoff's contribution to physical chemistry is given in Chapter 1 of John W. Servos, Physical Chemistry from Ostwald to Pauling: The Making of a Science in America (Princeton, 1990).
8. Robert Scott Root-Bernstein, 'The ionists: founding physical chemistry, 1872-1890', PhD Thesis, Princeton University (1980).
9. Those studies that have proved most helpful in our analysis are Bastiaan Willink, Origins of the second golden age of Dutch science after 1860: intended and unintended consequences of educational reform', Social Studies of Science, 21 (1991), 503-26;
10. A. Y. Kipnis, B. E. Yavelov and J. S. Rowlinson, Van der Waals and Molecular Science (New York, 1996);
11. Klaas van Berkel, Albert van Helden and Lodewijk Palm, (editors), A History of Science in The Netherlands: Survey, Themes, and References (Leiden, 1999). The Berkel volume contains an extensive bibliography of Dutch-language studies of Dutch science.
12. Enrolment was not automatic, as graduates of the HBS were required to pass examinations in those subjects - Latin and Greek - treated in the Gymnasium, but not at the HBS.
13. Pieter Boekholt, 'Classical or modern? university-preparatory education', A History of Science in The Netherlands: Survey, Themes, and References, edited by Klaas van Berkel, Albert van Helden and Lodewijk Palm (Leiden, 1999), 279-310 (306).
14. A fourth university would be created in 1877, when the Atheneum in Amsterdam, an academy created in 1632 but subsequently unable to acquire the status of a university, would finally be converted into the University of Amsterdam. Van 't Hoff would become appointed to the newly created Chair in Chemistry, Mineralogy and Geology. A brief description of the Atheneum is given by Kipnis et al. (note 6), 70-1, and Cohen (note 4), 139-140.
15. The precise grounds for Van 't Hoff's admission to Leiden are unclear. Cohen says that Van 't Hoff received a dispensation from a pending law admitting HBS students to the University, but he was mistaken, in that there was no such law, active or pending, until 1917. Van 't Hoff may have been one of the exceptions, but he also may have learned enough Greek and Latin to pass at the Gymnasium level. Cohen (note 4), 24.
16. Emil Fischer, 'Gedächtnisrede auf Jacobus Henricus van't Hoff', Gesammelte Werke. Untersuchungen aus verschiedenen Gebieten: Vorträge und Abhandlungen Allgemeinen Inhalts, edited by Max Bergmann (Berlin, 1924), 891-902 (892); Kipnis et al. (note 6), 9, 23.
17. Van 't Hoff to his parents, 1872, translated from Dutch into German in Cohen (note 4), 46. Translation from the German by Fischmann (note 2), 143.
18. Richard Anschütz, August Kekulé, 2 vols (Berlin, 1929), II, 437-8.
19. Kekulé's indifference to Van 't Hoff continued through the 1870s. He ignored Van 't Hoff's request for a recommendation letter in his application to the University of Amsterdam and, in his 1877 Rectorat given at the University of Bonn, he incorrectly stated that Van 't Hoff had elaborated on Le Bel's ideas. For a discussion of the relationship between Van 't Hoff and Kekulé, see Jost Weyer, 'Van't Hoff, Kekulé, und die Stereochemie: Zwei unveröffentliche Briefe von J. H. van't Hoff an A. Kekulé', Janus, 64 (1977), 217-30.
20. Cohen (note 4), 57.
21. Klaas van Berkel, 'The legacy of Stevin. A chronological narrative', A History of Science in The Netherlands: Survey, Themes, and References, edited by Klaas van Berkel, Albert van Helden and Lodewijk Palm (Leiden, 1999), 3-235 (113-121).
22. On Buys-Ballot, see Frans van Lunteren, 'De oprichting van het Koninklijk Nederlands Meteorologisch Instituut: Humboldtiaanse wetenschap, Internationale Samenwerking en Praktisch Nut', Gewina 22 (1999), 216-43;
23. on Donders, see L. T. G. Theunissen, 'F. C. Donders en de wetenschappelijke bril', Beroep op de Wetenschap. Utrechtse Geleerden Tussen Universiteit en Samenleving 1850-1940, edited by L. J. Dorsman (Utrecht, 1999);
24. on Harting, see L. T. G. Theunissen, 'Een warm hart en een koel hoofd. Pieter Harting over wetenschap, de natie en de vooruitgang', Bijdragen en Mededelingen Betreffende de Geschiedenis der Nederlanden, 110 (1995), 473-98.
25. The available evidence does not offer any concrete suggestions about the seemingly fortuitous meeting of Van 't Hoff and Le Bel in Wurtz' laboratory. They certainly became friends during that time, as they began a correspondence (of unknown extent) afterwards. We can only speculate on the events in Wurtz' laboratory during the winter and spring of 1874. Although they may not have spoken directly of the tetrahedron together, it seems unlikely that they never discussed the subject in general. Perhaps Van 't Hoff used something like the Kekule models (discussed in Section 3) with Le Bel or other members of the group at some point, which eventually triggered the idea in Le Bel's mind. On the other hand, it may have been Le Bel who introduced Van't Hoff to the concept of molecular asymmetry (from crystallography) that then clarified Van 't Hoff's original idea, until then only a foggy idea of a tetrahedral arrangement.
26. J. H. van 't Hoff, Bijdrage tot de kennis van cyanzijnzuur en malonzuur (Utrecht, 1874). Under Eduard Mulder, chemistry at Utrecht would lose the prestige acquired by his father and would not regain it until after 1900. When Van 't Hoff matriculated in 1873, it seems likely, however, that Utrecht still possessed a better laboratory (or a better reputation) than Groningen or Leiden.
27. Adolph von Baeyer to Emil Fischer, 12 June 1911, Emil Fischer papers, Bancroft Library, Berkeley, California.
28. Although located in Paris, Wurtz was strongly sympathetic to the German structuralist view. See Alan J. Rocke, The Quiet Revolution: Hermann Kolbe and the Science of Organic Chemistry (Berkeley, California, 1993).
29. The relationship between the French crystallographic tradition and its relationship to nineteenth-century chemistry is given in Seymour H. Mauskopf, Crystals and Compounds: Molecular Structure and Composition in Nineteenth Century French Science (Philadelphia, Pennsylvania, 1976).
30. Peter J. Ramberg, 'Theory and methodology in the early history of stereochemistry', PhD Thesis, Indiana University (1993); Rocke (note 19);
31. Alan J. Rocke, Chemical Atomism in the Nineteenth Century: From Dalton to Canizarro (Columbus, Ohio, 1984);
32. Mary Jo Nye, From Chemical Philosophy to Theoretical Chemistry: The Dynamics of Matter and the Dynamics of Disciplines (Berkeley, California, 1993).
33. The use of the word 'cultural' here is intentional. Molecular modelling techniques, whether using physical hand-held molecular models of those drawn on paper, do not depict the molecule as it 'really' is, but only certain aspects that are important at the moment. Although they represent what chemists considered as real objects, such models are conventional and defined by the current theoretical culture of chemistry, used by tacit or explicit agreement among chemists. See Eric Francoeur, 'The forgotten tool: the design and use of molecular models', Social Studies of Science, 27 (1997), 7-40;
34. 'Beyond dematerialization and inscription: does the materiality of molecular models matter?,' HYLE: An International Journal for the Philosophy of Chemistry, 6 (2000), 63-84.
35. Other studies on the use of physical modelling during the 1860s and 1870s are by O. Bertrand Ramsay, 'Molecular models in the early development of stereochemistry: I. The van't Hoff model. II. The Kekule models and the Baeyer strain theory', Van't Hoff-Le Bel Centennial, edited by O. Bertrand Ramsey (Washington, DC, 1974), 74-96;
36. Stereochemistry (London: Heyden, 1981);
37. 'The early history and development of conformational analysis', Essays on the History of Organic Chemistry, edited by J. G. Traynham (Baton Rouge, Louisiana, 1987), 54-77;
38. Christoph Meinel, 'Modelling a visual language for chemistry, 1860-1875', unpublished manuscript. We thank Professor Meinel for making this essay available.
39. N. W. Fisher, 'Wislicenus and lactic acid: the chemical background to van't Hoff's hypothesis', Van't Hoff-Le Bel Centennial, edited by O. B. Ramsey (Washington, DC, 1974), 33-54.
40. Meinel (note 21).
41. Van 't Hoff himself did not regard his ideas in the Ansichten very highly and later called the book 'hardly worth knowing' but, as Root-Bernstein argued, the Ansichten does bridge well the organic and physical chemistry in Van 't Hoff's career. J. H. van 't Hoff, Ansichten über die organische Chemie, 2 vols (Braunschweig, 1878-81).
42. Cohen (note 4), 57.
43. J. H. van 't Hoff, Die Lagerung der Atome im Raume, 2nd edn (Braunschweig, 1894), 1. Our translation from the original German.
44. Translated from the original Dutch into German in Cohen (note 4), 85, 514. Our translation from the German.
45. Scientists' own recollections of the discovery process are notoriously difficult to evaluate, and there is a distinct possibility that Van 't Hoff was embellishing his own memory when he recounted these events in order to make his own contribution all the more profound in relation to Le Bel's. We are not aware, however, of any other sources that would directly contradict Van 't Hoff's public statements or indicate that he exaggerated or mispresented the story. Van 't Hoff was notoriously taciturn and not prone to self-aggrandization and, unlike his closest colleagues in physical chemistry, Arrhenius and Ostwald, did not write any lengthy autobiographical accounts (a fact that may be due to his premature death). It also seems significant that Le Bel was silent about any priority claims with Van 't Hoff, and there has never been any indication of a priority dispute between Van 't Hoff and Le Bel. As early as 1875, largely because Van 't Hoff himself cited Le Bel's paper, they were considered as 'coauthors' of the theory of the tetrahedral carbon atom.
46. Cohen (note 4), 83-84.
47. We thank an anonymous referee of an earlier draft of this article for this suggestion.
48. E. H. Baumhauer, 'Avant-propos', Archives Néerlandaises des Sciences Exactes et Naturelles Publiee's par la Societé Hollandaise de Sciences a Harlem, 1 (1866), xiii-xiv.
49. J. H. van 't Hoff, 'Sur les formules de structure dans l'espace', Archives Néerlandaises des Science Exactes et Naturelles, 9 (1874), 445-54.
50. H. A. M. Snelders, 'The reception of J. H. Van't Hoff's theory of the asymmetric carbon atom', Journal of Chemical Education, 51 (1974), 2-7.
51. According to Van Berkel (note 15), 116, this poor reception was in large part due to the dominance of Mulder over Dutch chemistry. On Buys-Ballot, see H. A. M. Snelders, 'Het materiebegrip bij Buys-Ballot', Scientiarum Historiae, 10 (1968) 152-72;
52. H. A. M. Snelders, 'De reactie van Buys-Ballot op Van 't Hoff's Voorstel', Scientiarum Historiae, 15 (1973) 27-37;
53. Harold L. Burstyn, 'C. H. D. Buys-Ballot', Dictionary of Scientific Biography, 24 vols, edited by Charles Gillispie (New York, 1973), II, 628.
54. Buys-Ballot's own theory, which he had published in his Schets eener physiologie van het onbewerktuigde rijk der natuur (Utrecht, 1849), in fact resembled Van 't Hoff's ideas in more than one respect. It was also mathematical in nature and equally aimed at establishing atomic affinities but, while Van 't Hoff expressed these in a geometric model, Buys-Ballot had represented them in a graph, displaying the atom's attraction and repulsion as a function of the distance (and not of the angle). Moreover, Buys-Ballot never related physical properties, such as the optical rotating power, to the atom's geometric properties.
55. James Walker, 'Van't Hoff memorial lecture', Chemical Society Memorial Lectures, 2 vols (London, 1913), II, 255-71 (258).
56. The stellingen are virtually unknown in the literature about Van 't Hoff. Cohen mentions Van 't Hoff's dissertation and the stellingen only briefly, without mentioning the unique role that the stellingen played in Dutch dissertations. To our knowledge, only two English language articles (one very obscure) have mentioned them and offered four of the theses in English translation: Theses 14 and 15 appear in H. A. M. Snelders, 'The reception of J H. Van't Hoff's theory of the asymmetric carbon atom', Journal of Chemical Education, 51 (1974), 2-7;
57. Theses 7 and 32 appear in H. S. van Klooster, 'van't Hoff (1852-1911) in retrospect', Proceedings of the International Symposium on the Reactivity of Solids, 1952 (Göteborg, 1954), 1095-100 (1096).
58. G. J. W. Bremer, 'Vorläufige Mittheilung über eine neue Aepfelsäure, welche die Polarisationsebene rechts dreht', Berichte der deutschen chemischen Gesellschaft, 8 (1875), 861-3;
59. G. J. W. Bremer, Een rechtsdraaiend appelzuur (Utrecht, 1875). Bremer's experiments are recounted in Fischmann (note 2).
60. Cohen (note 4), 72, 83-4.
61. The most significant addition was the incorporation of Le Bel's ideas on molecular asymmetry, which has been recognized in two articles: R. B. Grossman, 'Van't Hoff, Le Bel, and the development of stereochemistry: a reassessment', Journal of Chemical Education, 66 (1989), 30-3;
62. Leonello Paoloni, 'Stereochemical models of benzene, 1869-1875', Bulletin for the History of Chemistry, 12 (1992), 10-24.
63. Cohen (note 4), 72.
64. Very little information is available about Richardson's life and career. From the biographical information in his doctoral dissertation, Richardson was born in Ohio in 1863, studied chemistry at LeHigh University and pursued graduate work with Ira Remsen at Johns Hopkins University. He completed his PhD in 1890, writing a dissertation on double salts of tin. He is identified on the title page of Foundations as Professor of Organic Chemistry at Stanford University but, after 1901, his fate remains a mystery. He is not listed in American Men of Science or Poggendorf's Handwörterbuch, nor is he listed as an author in the early volumes of Chemical Abstracts. George M Richardson, Stannous Double Halide Salts of Tin, with a Few Notes Upon the Cuprous Double Halide Salts (Baltimore, Maryland, 1890).
65. A site on the World-Wide Web (The ChemTeam : http://dbhs.wvusd.k12.ca.us/Chem-History/Van't-Hoff-1874.html) has posted Richardson's translation of the Voorstel,
66. also citing that it is a translation of the Archives article and does not mention at all that it was originally written in Dutch.
67. J. H. van 't Hoff, 'Sur les formules de structure dans l'espace', Bulletin de la Societé de Chimique de France (Paris), 23 (1875), 295-301.
68. The only reproductions of the original diagrams, to our knowledge, were in a 1974 centennial reprint of the pamphlet, and (greatly reduced in size) in O. Bertrand Ramsay, 'The early history and development of conformational analysis', (note 21), 54-77.
69. There is also a later basis for considering the word 'congruent' in a translation. The appendix to the first German edition of the Voorstel, Die Lagerung der Atome im Raume (Braunschweig, 1877) gave templates for creating cardboard tetrahedra to represent how the shape of the carbon atom changed when different groups were added. When all four groups on the carbon atom were different, there would be four different bond lengths. The resulting enantiomorphic tetrahedra would then, as geometrical shapes, be 'incongruent' in the true sense of the word.
70. Van 't Hoff used in the title and throughout the text the phrase 'actief vermogen', a common phrase, also used in German (aktives Vermögen), to describe what today we would call optical activity. Richardson, indeed, translated the phrase 'optisch actief vermogen' from the title as simply 'optical activity'. In 1973, Snelders translated parts of the Voorstel into English, also using the phrase 'optical activity': H. A. M. Snelders, 'The birth of stereochemistry: an analysis of the 1874 papers of J. H. van't Hoff and J. A. Le Bel', Janus, 60 (1973), 261, 278. As Van 't Hoff used elsewhere the different phrase 'optisch actieve' or 'optically active', we have elected to translate the phrase 'actief vermogen' as ''activating power', meaning 'the capacity to produce optical activity', which is slightly different from 'optical activity'. The term 'activating power' also gives a nineteenth-century ring to the text.
71. Van 't Hoff's initial choice of a planar arrangement of the carbon atoms has never been explained (that is why not simply introduce the tetrahedron initially?) but, if we consider the culture of physical modelling that developed in the 1860s, these are none other than Hofmann's 'glyptic' formulae, in which the valences were coplanar. It seems likely, therefore, that Van 't Hoff was comparing the relative plausibility of the models used by Hofmann and Kekule for counting spatial isomers.
72. 4, as it does in the Voorstel and in the Archives translation. This error is repeated in both Benfey's (note 3) and Leicester and Klickstein's (note 3) reprints.
73. This is a spelling error on Van 't Hoff's part, as he is referring to Gustav Charles Bonaventure Chancel (1822-90), Charles Gerhardt's successor at the Montpelier Academy. This error is repeated in Richardson (note 3).
74. Van 't Hoff used here a peculiar Dutch word, 'waarschijnlijkheidsband', that is difficult to translate. Translated literally, it would mean a 'relationship of probability' or 'a connection of likelihood'. Richardson translated it as 'probable relation'. The best way of conveying the meaning in English would then be 'probable connection'.
75. Richardson (note 3) did not translate the last clause of this sentence.
76. 2.COOH.
77. 3. CCl=CH.COOH. Richardson corrected both this and the previous formula without comment.
78. This is incorrect, as Van 't Hoff (or perhaps a typesetter) miscopied the letters from his own diagram. He wrote ACB, but the corners of the tetrahedron involved in bonding in the diagram are clearly labelled ABD (C is the central carbon atom). Here Richardson (note 3) did not spot the error and also wrote ACB. This error is repeated in the Archives and Cohen (note 4) translations, and subsequently in the Leicester and Klickstein (note 3) and the Benfey (note 3) volumes.