Selling a theory: The role of molecular models in J. H. van 't Hoff's stereochemistry theory

Annals of Science

Volumn 63, Issue 2, 2006, Pages 157-177

  Van Der Spek, Trienke M ^a  

^a Boerhaave Museum   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

MOLECULAR STRUCTURE; MOLECULES; STEREOCHEMISTRY;

MATERIAL MODELS; MOLECULAR MODELS; PHYSICAL ENTITIES; THREE-DIMENSIONAL STRUCTURE;

PROFESSIONAL ASPECTS;

EID: 33646779142     PISSN: 00033790     EISSN: 1464505X     Source Type: Journal    
DOI: 10.1080/00033790500480816     Document Type: Article

References (80)

1. U. Klein, 'The Creative Power of Paper Tools in Early Nineteenth-Century Chemistry', in Tools and Modes of Representation in the Laboratory Sciences, edited by U. Klein (Dordrecht, 2001), 13-35 (28).
2. P. J. Ramberg, 'Paper Tools and Fictional Worlds: Prediction, Synthesis and Auxiliary Hypotheses in Chemistry', same publication, 61-79 (62).
3. E. Francoeur, 'Molecular Models and the Articulation of Structural Constraints in Chemistry', same publication, 95-117 (96-98).
4. See also U. Klein, Experiments, models, paper tools: cultures of organic chemistry in the nineteenth century (Stanford, CA, 2003) on the use of paper tools in organic chemistry. Eric Francoeur wrote several articles on the use of molecular models in the late nineteenth and twentieth centuries, but he did not include the earliest models.
5. The history of these molecular models is described in C. Meinel, 'Molecules and Croquet Balls', in Displaying the Third Dimension: Models in Science, Technology, and Medicine, edited by S. H. de Chadarevian and N. Hopwood (Stanford, CA, 2004), 242-76.
6. Jacobus Henricus van 't Hoff (1852-1911) studied mathematics and physics at the University of Leiden and received his doctoral degree in chemistry at the University of Utrecht on 22 December 1874. He subsequently worked as a teacher at the Veeartsenijschool in Utrecht (1877) and as a lector and subsequently professor in Amsterdam (1878-1892) and in Berlin (1892-1911). In 1893, he shared the Royal Society's Davy medal with J. le Bel for his contribution to stereochemistry. In 1901, he was awarded the Nobel Prize for Chemistry for his work on physical chemistry. More biographical information can be found in: E. Cohen, Jacobus Henricus van 't Hoff: sein Leben und Wirken (Leipzig, 1912).
7. Deutsches Museum inventory number 4680; Museum Boerhaave inventory numbers 31272 and 10239. Museum Boerhaave has a large amount of 'Van 't Hoffiana' in its collection, including his molecular models, various personal belongings and the major part of his archive (archive 208). Another part of his archive is kept at the John Hopkins University in Baltimore, USA.
8. J. A. le Bel, 'Sur les relations qui existent entre les formules atomiques des corps organiques, et le pouvoir rotatoire de leurs dissolutions', Bulletin de la Société Chimique de France, (2), 22 (1874) 337-47.
9. J. H. van 't Hoff, Voorstel tot uitbreiding der tegenwoordig in de scheikunde gebruikte structuur-formules in de ruimte: benevens een daarmee samenhangende opmerking omirent het verband tusschen optisch actief vermogen en chemische constituie van organische verbindingen (Utrecht, 1874).
10. A full, revised English translation of this pamphlet was published in 2001: P. J. Ramberg, and G. J. Somsen, 'The Young J. H. van 't Hoff: The Background to the Publication of his 1874 Pamphlet on the Tetrahedral Carbon Atom', Annals of Science, 58 (2001) 51-74.
11. An extensive reading of this period and especially the settings in which Van 't Hoff wrote his theory and made his models can be found in: Stereochemistry, edited by O. B. Ramsay (London, 1981)
12. and P. J. Ramberg, Chemical Structure, Spatial Arrangement, The Early History of Stereochemistry, 1874-1914 (Aldershot, UK, 2003).
13. C. Ritter, 'An early history of Alexander Crum Brown's graphical formulas', in: Tools and Modes of Representation in the Laboratory Sciences, edited by U. Klein (Dordrecht, 2001), 35-46.
14. This was the Friday Evening Discourse, 7 April 1865, Royal Institution, London. C. Meinel, 'Molecules and Croquet Balls', in Displaying the Third Dimension: Models in Science, Technology, and Medicine, edited by S. H. de Chadarevian and N. Hopwood (Stanford, CA, 2004), 242-76.
15. F. R. Japp, 'Kekulé Memorial Lecture', in Memorial lectures delivered before the Chemical Society 1893-1900 (London, 1901), 97-138. Citation: The four units of affinity of the carbon atom, instead of being placed in one plane, radiate from the sphere representing the atom in the direction of hexahedral axes, so that they end in the faces of a tetrahedron (. . .) A model of this description permits of the union of 1, 2 and 3 units of affinity, and, it seems to me, does all that a model can do.
16. J. H. van 't Hoff, Die Lagerung der Atome im Raume, 2nd edition (Brunswick, 1894), 2.
17. C. Meinel (note 7). P. Ramberg (note 5), 56.
18. J. H. van 'Hoff (note 9), 1-2.
19. P. J Ramberg (note 5), 50-52.
20. P. J. Ramberg, G. Somsen (note 4), 63.
21. J. H. van 't Hoff, 'Sur les formules de structure dans l'espace', Archives Néerlandaises des Sciences Exactes et Naturelles, 9 (1874), 445-54.
22. 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. Only Professor Buys Ballot in Utrecht wrote a public reaction.
23. The text of his open letter to Van 't Hoff is published in E. Cohen, Jacobus Henricus van 't Hoff: sein Leben und Wirken (Leipzig, 1912), 94-104.
24. J. H. van 't Hoff, La chimie dans l'espace (Rotterdam, 1875).
25. J. H. van 't Hoff (note 15).
26. J. H. van 't Hoff (note 15). As far as we know, none of these sets has survived.
27. J. H. van 't Hoff (note 15), 7, footnote 1.
28. See note 3.
29. The Leiden 2 set of 69 models has only ever been mentioned in a footnote to a Dutch article in 1924: W. P. Jorissen, 'Eenige Brieven van Van 't Hoff (1874-1875)', Chemisch Weekblad, (21), 43 (1924), 495-501 (497).
30. The German set in the Deutsches Museum in Munich was described by O. B. Ramsay, 'Molecular Models in the Early Development of Stereochemistry', in Van 't Hoff-Le Bel Centennial, edited by O. B. Ramsay (Washington, DC, 1975), 74-96. Ramsay's article contains several observations that need adjustment, for instance the numbering of the models. Therefore, some discrepancies may exist between Ramsay's description and that given in this article.
31. The Leiden 1 set was described by 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.
32. An administration copy of the letter of thanks, dating from 2 April 1906, is kept in the archive of letters of the Deutsches Museum ('Chemie', VA-1252, subletter H). In this letter, the museum director described the models as 'Originalen ihrer Modellen'. The acquisition is described in the annual report of the Deutsches Museum, 1906. See also a calligraphed letter dated 7 January 1909, in archive 208, Museum Boerhaave, Leiden.
33. The manual is described in the letter of thanks that Oscar von Millar sent to Van 't Hoff on 2 April 1906 (see note 21) but could not be traced in the archives of the Deutsches Museum.
34. J. H. van 't Hoff (note 15)
35. See note 21.
36. Gustav Bremer's widow donated the set to the Chemistry Department of the University of Leiden after his death in 1909, where it was kept until recently.
37. J. H. van 't Hoff (note 15), 16, including footnotes. Sec models no. XIII-XVII, present in the German set and the Leiden 2 set.
38. J. H. van 't Hoff, Die Lagerung der Atome im Raume (Brunswick, Vieweg, 1877), 46-53.
39. In a letter to W. P. Jorissen on 12 May 1911, Bremer's widow described the close contact between her late husband and Van 't Hoff in the 1870s and the fact that the molecular models in her husband's legacy were produced by Van 't Hoff only (Museum Boerhaave, archive of 'Bremer' letters, arch 1).
40. Ten cardboard models, inventory number 10239. Eight letters from Van 't Hoff to Bremer, written in late 1874 and 1875 (archive of 'Van 't Hoff letters, arch 1). The eight letters were published by W. P. Jorissen, 'Eenige brieven van Van 't Hoff (1874-1875)', Chemisch Weekblad, (21), 43 (1924), 495-501.
41. Chronological rearrangement of these letters by E. Fischmann, 'A reconstruction of the First Experiments in Stereochemistry', Janus, 72 (1985), 131-56. Letter number 3, dating from 13 July 1875, contains a 'manual' for the use and meaning of the cardboard objects. Surprisingly, Jorissen reported the ten molecular models comprising the Leiden 1 set missing in 1924. Obviously, they were rediscovered, because they came to the museum after Bremer's widow died in 1936.
42. For instance, O. B. Ramsay (note 20), 85.
43. Letter no. 7 according to E. Fischmann (note 29). Gustav Bremer published part of his experimental results in his dissertation Een rechtsdraaiend appetzuur (Assen, 1875). He received his doctoral degree in Utrecht on 15 October 1875.
44. Date based on Van 't Hoff's remark that he was surrounded by the papers of his dissertation when he wrote this letter. He received his doctoral degree on 22 December 1874. Unfortunately, the ink of this letter is strongly bleached.
45. Van 't Hoff had already suggested in his Dutch publication (see note 4) that a compound with more than one asymmetric carbon atom must have many stereoisomers, but he did not explain this statement any further with examples or calculations. In the letter to Bremer dating from December 1874, he became more specific on this point.
46. W.P Jorissen and E. Fischmann (note 29).
47. Despite the fact that Van 't Hoff urged him to do so, Bremer seems not to have used the 'interactive' feature of the drawing: the letter shows no signs of having been folded.
48. J. H. van 't Hoff (note 27), 46-53. This publication dates from February 1877.
49. The colour code on the surviving models consists of 'white' (transparent), yellow, red and blue. See: J. H. van 't Hoff (note 15), 7 and 11. In 1877, the code changed to white, black, red, and blue, and had to be applied with sheets of coloured paper.
50. A detailed description of this technique can be found in: J. H. van 't Hoff, Die Lagerung der Atome im Raume (Brunswick, 1877), 46-53.
51. Sec note 8.
52. P. J. Ramberg (note 5), 81-84; O. B. Ramsay (note 5), 85-87.
53. J. H. van 't Hoff's Dutch publication dating from September 1874 (note 4) contains the first illustrations of apex-centred tetrahedrons, while the first face-centred example is found in a drawing dating from December of the same year; see section 2.4.
54. 2H - blue (. . .).
55. J. H. van 't Hoff (note 27), 46-47.
56. J. H. van 't Hoff (note 15), 7, footnote 1.
57. Letter no. 3 according to E. Fischmann (note 29).
58. J. H. van 't Hoff (note 4).
59. The precursor of Van 't Hoff's models is described in section 2.4.
60. O. B. Ramsay (note 20), 82.
61. Model XX (figure XXIX in the text).
62. O. B. Ramsay (note 20), 82.
63. J. H. van 't Hoff (note 15), 7, footnote 1; J. H. van 't Hoff (note 27), 5, footnote. Original phrase: für den Zweck der Anschauligkeit is unerlässlich die Contraction von Modelten aus Cartonpapier.
64. Anonymous, 'Vorstellung über die räumliche Lagerung der Atome', Der Naturforscher, 9, 19 (1876). Article kept in Museum Boerhaave (arch 208). Original citation: der Brochüre des Herrn van 't Hoff ist eine grosse Anzahl aus Pappe gefertigter Modelle beigegeben, welche das Verständniss wesentlich erleichtern.
65. P. J. Ramberg (note 5), 87-101.
66. P. J. Ramberg, 'Paper Tools and Fictional Worlds: Prediction, Synthesis and Auxiliary Hypotheses in Chemistry', in: Tools and Modes of Representation in the Laboratory Sciences, edited by U. Klein (Dordrecht, 2001), 61-79 (62-69).
67. Van 't Hoff had already postulated this hypothesis in early 1875 (letter no. 2, according to E. Fischmann) (note 29) but worked it out in more detail with the help of models in the letter of 13 July (letter no. 3, according to E. Fischmann).
68. The two single tetrahedron models of tartaric acid can be combined to make a double tetrahedron model of the same compound because the structural formula of tartaric acid is symmetrical. The two single tetrahedrons are placed against each other with the face that represents the largest chemical group, which is identical on both models. The single tetrahedrons thus exactly replace the written formula on the shared face by its spatial representation and combine to make a model that illustrates the spatial surrounding of two adjacent asymmetric carbon atoms. The possible combinations are: models VIII and IX combining to make model I, models VIII and II combining to make model VI, and models II and III combining to make model VII.
69. The magnitude A is of opposite sign for stereoisomers. Models II and III are mirror images of the models VIII and IX, so their optical activity is symbolized by -A, resulting in -A - A = -2A for model VII.
70. The conversion of tartaric acid into malic acid can take place at either of the two asymmetric carbon atoms because of the symmetrical structural formula of tartaric acid.
71. E. Fisher, 'Gedächtnisrede auf Jacobus Henricus van 't Hoff, Gedächtnisrede Jahrgang 1911, 1 (Berlin, 1911), 5. Original citation: Was van 't Hoff an der Hand seines Modells auch für solche komplizierten Fälle inbezug auf Konfiguration, optisches Drehungsvermögen, Anzahl der Formen usw. vorausgeschaut, ist dann in geradezu staunenderregender Weise bestätigt worden.
72. J. H. van 't Hoff (note 15), 7, footnote 1.
73. C. Meinel (note 1).
74. See note 7.
75. Arthur Henninger, a friend of Van 't Hoff who worked in the laboratory of Adolphe Wurtz in Paris, presented Van 't Hoff's theory to a French audience on 19 March 1875.
76. The letter is published in E. Cohen (note 2), 114-15.
77. J. Wislicenus addressed the Zürich chemical club on 2 November 1869. Citation: Die Thatsachen zwingen dazu die Verschiedenheit isomerer Molecule von gleicher Structurformel durch verschiedene Lagerung ihrer Atome im Raum zu erklären. Reported in: O. Meister, Berichte der Deutschen Chemischen Gesellschaft, 2 (1869), 620.
78. Original citation in E. Fisher (note 59), 5, English translation by P. J. Ramberg (note 5), 88.
79. See note 55. P. J. Ramberg (note 5), 87-101.
80. J. H. van 't Hoff (note 27), 5, footnote. Original phrase see note 54.