10— The Theory of Chemical Structure and the Structure of Chemical Theory
1. A useful review of the literature on this subject by John Brooke can be found in C. A. Russell, ed., Recent Developments in the History of Chemistry (London: Royal Society of Chemistry, 1985), pp. 107-109; the classic analysis is Brooke, "Wöhler's Urea and its Vital Force? A Verdict from the Chemists," Ambix , 15 (1968), 84-114. See also C. A. Russell, "The Changing Role of Synthesis in Organic Chemistry," Ambix , 34 (1987), 169-180. [BACK]
2. Wöhler to Berzelius, 22 February 1828, in Wallach, BWB , 1 , 205-208; Berzelius to Wöhler, 7 March 1828, ibid., pp. 208-209; Wöhler to Liebig, 13 October 1863, in Hofmann, LWB , 2 , 145-146. Isomerism was indeed a hot topic in the years after 1828, but the phenomenon was by no means completely novel; at least seven instances of organic isomerism (and several more in the inorganic realm) had been studied during the years 1811-1826 (A. J. Rocke, Chemical Atomism in the Nineteenth Century [Columbus: Ohio State Univ. Press, 1984], pp. 167-174). Berzelius coined the word isomer in 1830 in response to Wöhler's and several other recent discoveries. [BACK]
3. Hermann Kopp, Geschichte der Chemie , 1 (Braunschweig: Vieweg, 1843), 442; the assertion is repeated in the same work, 4 (1847), 244. [BACK]
4. Brooke, "Verdict," pp. 109-113. [BACK]
5. For example, in Kolbe, Lehrbuch (1854), pp. 3-4. Kolbe, who joined Wöhler just ten years after the synthesis, believed in a strong version of the claim (Kolbe to Vieweg, 26 January 1864, VA 198). [BACK]
6. For the former attitude, see Thomas Thomson, The History of Chemistry , 2 vols. (London: Colburn and Bentley, 1830-1831), 2 , 317; Wöhler and Liebig, "Untersuchungen über die Natur der Harnsäure," Annalen , 26 (1838), 241-340 (on p. 340) (in a letter of 24 July 1837, Liebig urged that Wöhler should add to one of their joint papers "some clever comments" asserting that it will prove possible to create sugar from "charcoal and rainwater" (Hofmann, LWB , 1 , 112); and J. E. Schlossberger, Lehrbuch der organischen Chemie , 3d ed. (Stuttgart: Müller, 1854), pp. 27-28. For examples of doubts, see ibid.; and V. Regnault, ed. A. Strecker, Kurzes Lehrbuch der Chemie (Braunschweig: Vieweg, 1851), p. 576. [BACK]
7. A. Strecker, "Über die künstliche Bildung der Milchsäure und einen neuen, dem Glycocoll homologen Körper," Annalen , 75 (1850), 27-45 (on p. 28); Kolbe, Über die chemische Constitution organischer Verbindungen (Marburg: Elwert, 1858), p. 6. [BACK]
8. Kolbe, "Über die chemische Constitution der Isäthionsäure und des Taurins," Annalen , 112 (1859), 241-243; idem, "Über die chemische Constitution und künstliche Bildung des Taurins," Annalen , 122 (1862), 33-47. [BACK]
9. Kolbe, "Über die Rückbildung des Alanins aus Milchsäiure," Annalen , 113 (1860), 220-223. [BACK]
10. J. Volhard, "Über Sarkosin," Annalen , 123 (1862), 261-265. [BACK]
11. Kolbe and Schmitt, "Directe Umwandlung der Kohlensäure in Ameisensäure," Annalen , 119 (1861), 251-253. [BACK]
12. Kolbe and Schmitt, "Rother Farbstoff aus dem Kreosot," Annalen , 119 (1861), 169-172. They had first encountered this reaction in February 1859
(Kolbe's laboratory notebook, unpaginated, SSDM 3812). [BACK]
13. The anecdote is told by Wilhelm Ostwald, regarding his only conversation with Kolbe, in January 1883: Lebenslinien: Eine Selbstbiographie , 3 vols. (Berlin, 1926-1927), 1 ,190-191. Kolbe "was at that time in his own estimation the decisive personality in chemical affairs not only for Germany, but for the entire world. Accordingly he acted dignified and reserved." [BACK]
14. Kolbe indicated to Varrentrapp (28 February 1870, VA 266) that a synthesis of indigo had long been his great desire. [BACK]
15. N. W. Fisher, "Organic Classification Before Kekulé," Ambix , 20 (1973), 106-131, 209-233; M. J. Nye, "Berthelot's Anti-Atomism: A 'Matter of Taste'?" Annals of Science , 31 (1981), 585-590; idem, "Explanation and Convention in Nineteenth-Century Chemistry," in R. Visser, et al., eds., New Trends in the History of Science (Amsterdam: Rodopi, 1989), pp. 171-186. Nye's book, From Chemical Philosophy to Theoretical Chemistry: Dynamics of Matter and Dynamics of Discipline, 1800-1950 (Berkeley: Univ. of California Press, 1993), treats many of the same issues as this section. [BACK]
16. Larry Laudan has written a history of the "method of hypothesis" during the eighteenth and nineteenth centuries: Science and Hypothesis: Historical Essays on Scientific Methodology (Boston: Reidel, 1981); a discussion of this subject specific to chemistry is A. J. Rocke, "Methodology and Its Rhetoric in Nineteenth-Century Chemistry: Induction versus Hypothesis," in Elizabeth Garber, ed., Beyond History of Science: Essays in Honor of Robert E. Schofield (Bethlehem, P.A.: Lehigh Univ. Press, 1990), pp. 137-155.è [BACK]
17. J. B. Dumas, Leons sur la philosophie chimique , 2d ed. (Paris, 1878), pp. 66-67. (lecture delivered on 23 April 1836). An explicit reference to the predictive function of theories is also contained in his Traité de chimie appliquée aux arts , 8 vols. (Paris, 1828-1846), 5 (1835), 72. [BACK]
18. L. Pearce Williams, "André-Marie Ampère," Scientific American , January 1989, pp. 90-97: [BACK]
19. John F. W. Herschel, A Preliminary Discourse on the Study of Natural Philosophy (London: Longman, Green, 1830), pp. 29-34, 150, 186-188, and 197-212. [BACK]
20. Rocke, "Methodology," pp. 149-151. [BACK]
21. Kenneth Caneva, "From Galvanism to Electrodynamics: The Transformation of German Physics and Its Social Context," Historical Studies in the Physical Sciences , 9 (1978), 63-159, esp. 95-122. [BACK]
22. Kolbe, "Beiträge zur Kentniss der gepaarten Verbindungen," Annalen , 54 (1845), 145-188 (on pp. 160, 183, and 188). [BACK]
23. This is a principal thesis of my Chemical Atomism in the Nineteenth Century: From Dalton to Cannizzaro (Columbus: Ohio State Univ. Press, 1984). [BACK]
24. For a detailed study exemplifying these trends, see Kathryn M. Olesko, Physics as a Calling: Discipline and Practice in the Königsberg Seminar for Physics (Ithaca, N.Y.: Cornell Univ. Press, 1991). [BACK]
25. Today elemental analyses are done by specialized commercial laboratories, not by individual chemists. I also ignore here instrumental methods of analysis developed during the twentieth century, which are indeed based
on high technology, mathematical theory, physical properties and precision measurements. That is a story that does not enter into our narrative. [BACK]
26. These examples and quotes are taken from John Servos, Physical Chemistry from Ostwald to Pauling: The Making of a Science in America (Princeton, N.J.: Princeton Univ. Press, 1990), pp. 48-51 and 321-324; quotes are from the years 1926-1927. [BACK]
27. Details of this story can be found in Rocke, Chemical Atomism . [BACK]
28. Wurtz, in Répertoire de chimie pure , 3 (1861), 419. [BACK]
29. Hofmann, Introduction to Modern Chemistry (London: Walton and Maberley, 1865), p. v. [BACK]
30. On Erlenmeyer, see especially Otto Krätz, "Das Portrait: Emil Erlenmeyer, 1825-1909," Chemie in unserer Zeit , 6 (1972), 52-58; idem, Beilstein-Erlenmeyer: Briefe zur Geschichte der chemischen Dokumentation und des chemischen Zeitschriftenwesens (Munich: Fritsch, 1972); and Rita Meyer, "Emil Erlenmeyer (1825-1909) als Chemietheoretiker und sein Beitrag zur Entwicklung der Strukturchemie," Ph.D. dissertation, University of Munich, 1984. [BACK]
31. Kekulé to Erlenmeyer, 29 January 1859, in Richard Anschütz, August Kekulé , 2 vols. (Berlin: Verlag Chemie, 1929), 1 , 150-151; Kekulé to Erlenmeyer, 6 August 1859, August-Kekulé-Sammlung. [BACK]
32. Kekulé to Liebig, undated, in Anschütz, Kekulé , 1 , 130. [BACK]
33. Erlenmeyer, ZfC , 3 (1860), 1-3. The next year Erlenmeyer noted that the study of chemistry had become "positively fashionable" (ibid., 4 [1861], 217). [BACK]
34. The originals of these letters do not seem to have survived, but the content is clear from the replies: Kolbe to Erlenmeyer, 19 February 1860, and Wurtz to Erlenmeyer, 22 February 1860, Dingler Nachlass. [BACK]
35. Kolbe to Erlenmeyer, 19 November and 6 and 11 December 1863, Dingler Nachlass. [BACK]
36. Kolbe to Erlenmeyer, 17 December 1863, Dingler Nachlass. [BACK]
37. Erlenmeyer, Die Aufgabe des chemischen Unterrichts (Munich: Akademie-Verlag, 1871), p. 27. [BACK]
38. Erlenmeyer, "Vorläufige Notiz über eine etwas abgeänderte Betrachtungsweise der Alkohole und ihrer Derivate," ZfC , 4 (1861), 202-204; ibid., p. 197. In another passage from about this time, Erlenmeyer adds another warning against the effort to judge "the true constitution of a compound" (ibid., pp. 167-168). [BACK]
39. Erlenmeyer, "Die Theorie," ZfC , 5 (1862), 18-32 (on p. 27-31). [BACK]
40. A. J. Rocke, "Subatomic Speculations and the Origin of Structure Theory," Ambix , 30 (1983), 1-18. [BACK]
41. Erlenmeyer, "Bemerkungen zu der vorstehenden Abhandlung [by Heintz]," ZfC , 5 (1862), 218-223. [BACK]
42. Erlenmeyer, "Vorläufige Notiz über das Verhältniss der Kolbe'schen Betrachtungsweise zu der sog. Typentheorie," ZfC , 6 (1863), 728-735. [BACK]
43. Kolbe to Erlenmeyer, 12 February and 22 November 1864, Dingler Nachlass. [BACK]
44. Krätz, "Erlenmeyer," p. 55; idem, Beilstein-Erlenmeyer , pp. 16-18. [BACK]
45. Erlenmeyer to Kolbe, 28 June 1871, SSDM 3551. [BACK]
50. Kolbe to Varrentrapp, 1 October 1871, VA 268; the article was "Moden der modernen Chemie," JpC , 112 (1871), 241-271. [BACK]
51. Kolbe to Vieweg, 4 October 1871, VA 269. [BACK]
52. Kolbe to Volhard, 22 June 1873 and 20 November 1874, SSDM 3662 and 3673. [BACK]
53. Alexander Vucinich, Science in Russian Culture, 1861-1917 (Stanford, Calif.: Stanford Univ. Press, 1970); Nathan M. Brooks, "The Formation of a Community of Chemists in Russia, 1700-1870," Ph.D. dissertation, Columbia Univ., 1990. [BACK]
54. G. V. Bykov, "A. M. Butlerov," DSB ; A. J. Rocke, "Kekulé, Butlerov, and the Historiography of the Theory of Chemical Structure," British Journal for the History of Science , 14 (1981), 27-57; Brooks, "Formation," pp. 257-281. [BACK]
55. Jean Jacques, "Boutlerov, Couper et la Société Chimique de Paris (Notes pour servir à l'histoire des théories de la structure chimique)," BSC , 1953 , 528-530. [BACK]
56. Butlerov, "Einiges über die chemische Structur der Körper," ZfC , 4 (1861), 549-560. [BACK]
57. Erlenmeyer to Butlerov, 4 May 1862, in G. V. Bykov and L. M. Bekassova, "Beiträge zur Geschichte der Chemie der 60-er Jahre des XIX. Jahrhunderts: I: Briefwechsel zwischen E. Erlenmeyer und A. M. Butlerov," Physis , 8 (1966), 185-198 (on pp. 187-188). Bykov and Bekassova suggest (p. 186) that the two probably first met at Speyer, but this is not consistent with the passage just cited. It is more probable that they first became acquainted when Butlerov visited Heidelberg (twice) in 1857-1858. [BACK]
58. G. V. Bykov and Z;. I. Sheptunova, "Nemetskii 'Zhurnal khimii' (1858-1871) i russkie khimiki (k istorii khimicheskoi periodiki)," Trudy instituta istorii estestvoznaniia i tekhniki , 30 (1960), 97-110; O. Krätz, "Iwan Turgenjew und die russischen Chemiker in Heidelberg," Chemie in unserer Zeit , 21 (1987), 89-99; idem, "Erlenmeyer," pp. 54-55. [BACK]
59. For example, Butlerov, "Ueber die Verwandtschaft der mehraffinen Atome," ZfC , 5 (1862), 297-304; idem, "Ueber die verschiedenen Erklärungsweisen einiger Fälle yon Isomerie," ZfC , 6 (1863), 500-534; idem, "Ueber die systematische Anwendung des Princips der Atomigkeit zur Prognose von Isomerie und Metameriefällen," ZfC , 7 (1864), 513-532. [BACK]
60. Butlerov, "Erklärungsweisen," pp. 501-506 and 509-514; "Systematische Anwendung," p. 513.
61. Ibid., p. 504-505 and 520. [BACK]
60. Butlerov, "Erklärungsweisen," pp. 501-506 and 509-514; "Systematische Anwendung," p. 513.
61. Ibid., p. 504-505 and 520. [BACK]
62. Kolbe to Frankland, 9 July 1867, Frankland Archive 01.04.1374. [BACK]
63. Kekulé, Annalen , 130 (1864), 12; idem, C.r ., 58 (1864), 510. [BACK]
64. Rocke, "Historiography of Chemical Structure;" C. A. Russell, History of Valency (Leicester: Leicester Univ. Press, 1971). [BACK]
65. Kekulé to Erlenmeyer, 6 August 1859, and Kekulé to Meyer, 23 Octo-
ber 1860, both in the August-Kekulé-Sammlung, the latter also printed in Anschütz, Kekulé , 1, 204; ibid., p. 290 (citing Kekulé's 1866 benzene theory paper). [BACK]
66. Kolbe to Vieweg, 1 March and 16 October 1860, 9 November 1863, and 15 May 1866, VA 155, 160, 197, and 244. [BACK]
67. Kekulé, "Beiträge zur Kenntniss der Salicylsäure und der Benzoësäure," Annalen , 117 (1861), 145-164 (on p. 164). [BACK]
68. Kekulé, "Zwei Berichtigungen zu Kolbe's Abhandlung: 'Ueber die chemische Constitution der Mellithsäure, des Paramids u.s.w.,'" Annalen , 125 (1863), 375-376; Kolbe, "Constatirung eines Irrthums," Annalen , 126 , 125-126, with editorial note by Kopp. [BACK]
69. Kolbe, "Vermischte Notizen," Annalen , 113 (1860), 238-244 (on p. 244). The details in this paragraph are derived from Kolbe's explanatory note in his Das chemische Laboratorium der Universität Marburg (Braunschweig: Vieweg, 1865), pp. 109-111. [BACK]
70. Kekulé, "Elektrolyse zweibasischer Säuren," ZfC , 7 (1864), 293. [BACK]
71. Kolbe to Erlenmeyer, 26 May and 2 July 1864, Dingler Nachlass. [BACK]
72. Kolbe, Laboratorium , pp. 110-111. [BACK]
73. Albert Ladenburg, Lebenserinnerungen (Breslau: Trewendt & Granier, 1912), pp. 38-39. [BACK]
74. This thesis is defended in Rocke, "Historiography of Chemical Structure." [BACK]
75. Kekulé, Lehrbuch der organischen Chemie , 2 vols. (Erlangen: Enke, 1859-1866), 2, 244-249 (fascicle written and published in 1864). [BACK]
76. Wurtz to Butlerov, 19 February 1864, in G. V. Bykov and J. Jacques, "Deux pionniers de la chimie moderne, Adolphe Wurtz et Alexandre M. Boutlerov, d'après une correspondance inédite," Revue d'histoire des sciences , 13 (1960), 115-134 (on pp. 121-122).
77. ibid. Butlerov to Wurtz, no date, but ca. March 1864, in ibid., pp. 123-124. [BACK]
76. Wurtz to Butlerov, 19 February 1864, in G. V. Bykov and J. Jacques, "Deux pionniers de la chimie moderne, Adolphe Wurtz et Alexandre M. Boutlerov, d'après une correspondance inédite," Revue d'histoire des sciences , 13 (1960), 115-134 (on pp. 121-122).
77. ibid. Butlerov to Wurtz, no date, but ca. March 1864, in ibid., pp. 123-124. [BACK]
78. Butlerov, Vvedeniie k polnomu izucheniiu organicheskoi khimii (Kazan, 1864-1866); Lehrbuch der organischen Chemie zur Einführung in das specielle Studium derselben (Leipzig, 1867-1868); Beilstein to Baeyer, 31 January 1864, Baeyer Collection. Butlerov had completed about 100 pages of manuscript by this date and had enlisted Beilstein's help (who was then in Göttingen) to find a German publisher. [BACK]
79. Butlerov, Lehrbuch , pp. 75-78. [BACK]
80. Beilstein to Butlerov, 14 December 1862, in Bykov and Bekassova, "Beiträge zur Geschichte der Chemie der 60-er Jahre des XIX. Jahrhunderts: II. F. Beilsteins Briefe an A. M. Butlerov," Physis , 8 (1966), 267-285 (on p. 268). [BACK]
81. Erlenmeyer to Butlerov, 9 July 1864, in Bykov and Bekassova, "Briefwechsel," p. 192. [BACK]