Visible work: The role of students in the creation of Liebig's Giessen research school

Notes and Records of the Royal Society

Volumn 62, Issue 1, 2008, Pages 31-49

  Jackson, Catherine M ^a  

^a UNIVERSITY COLLEGE LONDON   (United Kingdom)

Author keywords

Analysis; Giessen; Laboratory; Liebig; Technicians; Training

Indexed keywords

EID: 38949204419     PISSN: 00359149     EISSN: 17430178     Source Type: Journal    
DOI: 10.1098/rsnr.2007.0032     Document Type: Article

References (135)

1. J. Liebig, footnote to H. Hess, 'Ueber die Wasserstoffbestimmung bei der Analyse organisher Substanzen', Annln Pharm. 26, 189-194 (1839), p. 192,
2. in the translation by W. Gregory in J. Liebig, Instructions for the chemical analysis of organic bodies, footnote, pp. 28-30 (Griffin, Glasgow; Tegg, London, 1839), p. 30.
3. J. B. Morrell, 'The chemist breeders: the research schools of Liebig and Thomas Thomson', Ambix 19, 1-46 (1972).
4. F. L. Holmes, 'Justus Liebig', Dictionary of scientific biography, vol. 8, pp. 329-350 (Scribner, New York, 1973).
5. S. Shapin, 'The invisible technician', Am. Scient. 77, 554-563 (1989), p. 561.
6. A. W. Hofmann, The life-work of Liebig. The Faraday Lecture for 1875 (Macmillan, London, 1876).
7. The Faraday lecture was delivered on 18 March 1875. J. Volhard, Justus von Liebig (Barth, Leipzig, 1909).
8. Quantitative organic analysis involved the determination of the percentage by mass of the elements carbon, hydrogen, and (sometimes) nitrogen in organic substances. The percentage of oxygen was then calculated by difference.
9. Hofmann, op. cit. (note 5), p. 8.
10. Hofmann, op. cit. (note 5), pp. 45-46.
11. W. H. Brock, Justus Liebig: the chemical gatekeeper (Cambridge University Press, 1992).
12. Morrell, op. cit. (note 2),
13. and Holmes, op. cit. (note 3), helped to establish this view of Liebig, which remains widespread.
14. F. L. Holmes, 'The complementarity of teaching and research in Liebig's laboratory', Osiris 5, 121-164 (1989).
15. J. S. Fruton, 'The Liebig research group - a reappraisal', Proc. Am. Phil. Soc. 132, 1-66 (1988).
16. M. C. Usselmann, C. Reinhardt, K. Foulser and A. J. Rocke, 'Restaging Liebig: a study in the replication of experiments', Ann. Sci. 62, 1-55 (2005).
17. G. Holton, 'Subelectrons, presuppositions, and the Millikan-Ehrenhaft dispute', in The scientific imagination: case studies, pp. 25-83 (Cambridge University Press, 1978), pp. 52-54 and 71-72.
18. J. Earman and C. Glymour, 'Relativity and eclipses: the British eclipse expeditions of 1919 and their predecessors', Hist. Stud. Phys. Biol. Sci. 11, 49-85 (1980), at p. 85.
19. Liebig's paper introducing the Kaliapparat included analyses of a number of substances whose composition was well known, as well as of six alkaloids, including morphine. Justus Liebig, 'Ueber einen neuen Apparat zur Analyse organischer Körper, und über die Zusammensetzung einiger organischen Substanzen', Annln Phys. Chem. 21, 1-43 (1831).
20. Usselmann et al., op. cit. (note 11), p. 14. Italics in original.
21. Usselmann et al., op. cit. (note 11), p. 24.
22. Some of these forms of feedback were documented in J. Liebig, Anleitung zur Analyse organischer Körper (Vieweg, Braunschweig, 1837).
23. Usselmann et al., op. cit. (note 11), p. 28. Achieving 'replicative consistency' depended on obtaining consistent weights of carbon dioxide and water from all analyses of the same substance.
24. Usselmann et al., op. cit. (note 11), pp. 32-33.
25. See also M. C. Usselmann, 'Liebig's alkaloid analyses: the uncertain route from elemental content to molecular formulas', Ambix 50, 71-89 (2003), pp. 74 and 82.
26. Liebig's letter to his parents, March 1823, cited in Holmes, op. cit. (note 10), p. 125,
27. from E. Berl (ed.), Briefe von Justus Liebig: Nach neuen Funden (Liebig-Museum-Gesellschaft, Giessen, 1928), pp. 51-53. The emphasis has been added.
28. Volhard, op. cit. (note 5), p. 58.
29. See also J. Liebig, Eigne biographische Aufzeichnungen (Liebig-Museum-Gesellschaft, Giessen, 1926), pp. 18-20.
30. Holmes, op. cit. (note 10), pp. 128 and 133-134.
31. Holmes, op. cit. (note 3), p. 331.
32. Usselmann et al., op. cit. (note 11), p. 12, noted the significance of Liebig's brief visit to Paris in October 1828, where he learnt glassblowing skills sufficient to enable him 'to make any kind of glass apparatus himself.
33. F. L. Holmes, 'Analysis by fire and solvent extractions: the metamorphosis of a tradition', Isis 62, 129-148 (1971).
34. U. Klein, 'Shifting ontologies, changing classifications: plant materials from 1700 to 1830', Stud. Hist. Phil. Sci. 36, 261-329 (2005), p. 261. See especially pp. 313-320 on 'expert substances and the classification of carbon compounds circa 1830'.
35. Usselmann et al., op. cit. (note 11), p. 2. Throughout this paper, I use 'formula' to refer to the molecular formula of a substance. The combining mass was a concept equivalent to molecular mass.
36. J. Liebig, 'Ueber die Constitution des Aethers und seiner Verbindungen', Annln Phys. Chem. 31, 321-326 (1834), p. 321. 'Man kennt schon längst mit Gewissheit die procentische Zusammensetzung des Aethers, des Weingeistes und ihrer Verbindungen, aber über die Art, wie die Elemente derselben mit einander vereinigt sind, hat man nur, mehr oder weniger wahrscheinliche, Vermuthungen.'
37. J. Liebig, 'Nachricht, das chemisch-pharmaceutische Institut zu Giessen betreffend', Mag. Pharm. 20, 98-99 (1827);
38. also in Jb. Chem. Phys. 21, 376 (1827).
39. Extracted from the translation in Holmes, op. cit. (note 10), pp. 127-128.
40. H. Buff, 'Ueber Indigsäure und Indigharz', Jb. Chem. Phys. 21, 38-59 (1827).
41. Holmes, op. cit. (note 10), pp. 128 ('isolated') and 130 ('possibilities').
42. J. Liebig, 'Ueber die Säure welche in dem Harn der grasfressenden vierfüssigen Thiere enthalten ist', Annln Phys. Chem. 17, 389-399 (1829).
43. J. Liebig and F. Wöhler, 'Ueber die Zusammensetzung der Honigsteinsäure', Annln Phys. Chem. 18, 161-164(1830).
44. J. Liebig, 'Ueber die Analyse organischer Substanzen', Annln Phys. Chem. 18, 357-367(1830).
45. J. Liebig, 'Ueber die Zusammensetzung der Kamphersäure und des Kamphers', Annln Phys. Chem. 20, 41-47 (1830).
46. Liebig's joint work with Wöhler was J. Liebig and F. Wöhler, 'Untersuchungen über die Cyansäuren', Annln Phys. Chem. 20, 368-400 (1830).
47. F. Kodweiss, 'Ueber die Zusammensetzung der Harnsäure und über die Producte, welche durch ihre Zersetzung mit Salpetersäure erzeugt werden', Annln Phys. Chem. 19, 1-25 (1830).
48. The term Kaliapparat was in widespread use by about 1833.
49. Liebig, op. cit. (note 14).
50. J. B. Dumas and P.-J. Pelletier, 'Recherches sur la composition élémentaire et quelques propriétés charactéristiques des bases salifiables organiques', Annls Chim. Phys. 24, 163-191 (1823).
51. A major and persistent problem (discussed at greater length in note 54) was that nitrogen tended to be oxidized to nitrogen oxides under the conditions of the analysis, thereby seeming to increase the amount of carbon dioxide produced.
52. Liebig, op. cit. (note 14), pp. 7-8, direct quotation from p. 8.
53. For substances of high molecular mass, a relatively small error in the percentage composition could significantly affect the formula assigned to the compound. This difficulty was exacerbated with the alkaloids, which not only have high molecular masses but also contain only a tiny percentage of nitrogen.
54. Fruton, op. cit. (note 10), p. 11.
55. Fruton, op. cit. (note 10), Appendix I. The seventh, Karl Winkelblech, matriculated in chemistry in 1832, having worked on cobalt oxides, and went to Marburg to study for his doctorate.
56. Liebig became a co-editor with Geiger of the Magazin für Pharmacie, which he renamed when he became sole editor in 1832.
57. C. Oppermann, 'Ueber die Zusammensetzung des Terpenthinöls und einiger von demselben entstehenden Producte', Annln Phys. Chem. 22, 193-207 (1831).
58. As Usselmann et al., op. cit. (note 11), p. 9, noted, Liebig analysed morphine by both methods but did not publish the comparison.
59. Liebig, op. cit. (note 1), p. 30. Italics in original.
60. See A. J. Rocke, 'Origins and spread of the "Giessen model" in university science', Ambix 50, 90-115 (2003);
61. A. J. Rocke, Nationalising science: Adolphe Wurtz and the battle for French chemistry (MIT Press, Cambridge, MA, 2001);
62. Usselmann et al., op. cit. (note 11);
63. and C. M. Jackson, 'Re-examining the research school: August Wilhelm Hofmann and the re-creation of a Liebigian research school in London', Hist. Sci. 44, 281-319 (2006), on the spread of analysis using the Kaliapparat.
64. Liebig himself no longer referred to the method from 1833 onwards.
65. J. Liebig, 'Analyse der Harnsäure', Annln Pharm. 10, 47-48 (1834), p. 47.
66. R. Blanchet and E. Sell, 'Ueber die Zusammensetzung einiger organischer Substanzen', Annln Pharm. 6, 259-308 (1833), pp. 259-260.
67. Usselmann et al., op. cit. (note 11), p. 14.
68. F. L. Holmes, 'Scientific writing and scientific discovery', Isis 78, 220-235 (1987).
69. For example, by Morrell, op. cit. (note 2).
70. Fruton, op. cit. (note 10), p. 19, cited Vogt's recollections.
71. Blanchet and Sell, op. cit. (note 46), pp. 304-305.
72. Liebig was also able to use analyses carried out by his students to challenge published results. For example, in 1834 Liebig used work carried out by Ettling in a critical editorial note to a paper by Dumas in Liebig's Annalen der Pharmacie concerning the analysis of clove oil. See Liebig footnote to J. Dumas, 'Organisch-chemische Untersuchungen', Annln Pharm. 9, 65-85 (1834), p. 68.
73. Blanchet and Sell, op. cit. (note 46), p. 260.
74. Qualitative analysis measured the ratio of the volumes of carbon dioxide and nitrogen, but the formation of nitrogen oxides under the oxidizing conditions of the combustion often led to significant errors in this ratio (see note 35). Making a separate determination of the mass of carbon dioxide using the Kaliapparat gave independent evidence as to whether nitrogen had been oxidized during the analysis. The production of nitrogen oxides increased the apparent carbon dioxide to nitrogen ratio, making the determination of carbon from the qualitative analysis too high and that of nitrogen too low. See J. Liebig, 'Ueber einige Stickstoff-Verbindungen', Annln Pharm. 10, 1-47 ( 1834), p. 20, for a description of this method applied to melamine.
75. See also Usselmann et al., op. cit. (note 11), pp. 35-42, for a description of both methods.
76. Liebig, op. cit. (note 45), p. 47, emphasis added. 'Die Ursache davon liegt darin, dass diese Chemiker den Kohlensroff dieser Säure nicht direkt bestimmt haben, wodurch sie einer Controle für die Stickstoffbestimmungen entbehren, welche der Apparat, den ich beschrieben habe, jetzt mit Zuverlässigkeit anzuwenden erlaubt.'
77. Even in the absence of nitrogen, fitting a formula to a substance of high molecular mass might require similar controls for carbon and hydrogen, namely comparing the outcome of analyses performed in different ways to check that the results were consistent. These controls are described in Liebig, op. cit. (note 16), pp. 53-55;
78. translated by W. Gregory as Liebig, op. cit. (note 1), pp. 42-43.
79. Liebig, op. cit. (note 54), pp. 2-3.
80. Liebig, op. cit., pp. 1-2. 'Wir sind in diesem Theile der Chemie noch weit von dem scharf begrenzten Standpunkte der anorganischen entfernt.'
81. Liebig, op. cit., p. 2: 'sie [organische Körper] sind Glieder einer und derselben Kette, von welcher wir bis jetzt nur hier und da eine kleine Strecke verfolgen konnten'.
82. F. Wöhler and J. Liebig, 'Untersuchungen über das Radical der Benzoësäure', Annln Phys. Chem. 26, 465-479(1832), p. 472.
83. See, for example, Liebig's critique of Döbereiner's analysis of acetal in J. Liebig, 'Ueber Acetal (Sauerstoffäther), Holzgeist und Essigäther', Annln Phys. Chem. 27, 605-618 (1833).
84. Liebig to Berzelius, 10 March 1839, in W. Lewicki (ed.), Berzelius und Liebig: ihre Briefe 1831-1845, mit gleichzeitigen Briefen von Liebig und Wöhler (Cromm, Göttingen, 1991), p. 182: 'grenzlose Wandelbarkeit'.
85. W. C. Zeise, 'Neue Untersuchungen über das entzündliche Platinchlorür', Annln Pharm. 23, 1-11 (1837).
86. Zeise, then Professor of Chemistry in Copenhagen, had first published analyses of this unusual substance (now called Zeise's salt) in 1831. See U. Klein, Experiments, models, paper tools: cultures of organic chemistry in the nineteenth century (Stanford University Press, 2003), pp. 180-182, on Liebig's response to those earlier analyses.
87. Liebig to Berzelius, 21 December 1837, in Lewicki, op. cit. (note 62), p. 140.
88. Liebig, 'Ueber die Aethertheorie, in besonderer Rücksicht auf die vorgehende Abhandlung', Annln Pharm. 23, 12-42 (1837), p. 13: 'Diess ist nicht der Gang der heutigen Chemie'.
89. Liebig, op. cit., p. 16. This was a reference to the constant error of between 0.2% and 0.23% in hydrogen determination identified by Liebig and Wöhler.
90. See F. Wöhler and J. Liebig, 'Ueber die Bildung des Bittermandelöls', Annln Pharm. 22, 1-24 (1837), p. 13.
91. Liebig, op. cit. (note 65), pp. 18-19. 'Hr. Zeise geht in seinen Arbeiten von dem Gesichtspunkte aus, dass man mit Wahrhaftigkeit und Aufrichtigkeit alle seine Versuche beschreiben und angeben müsse, grade so wie man sie erhalten habe, selbst die, an deren Richtigkeit man zu zweifeln Ursache habe; desshalb hat er denn auch diejenigen Wasserstoffbestimmungen mitgetheilt, die seine theoretische Formel weit übersteigen.'
92. This wording is from J. Liebig, 'Bemerkungen zu vorstehenden Berichtigung', Annln Chem. Pharm. 33, 117-125 (1840), p. 118, but the sentiment is often expressed in Liebig' s publications throughout this period.
93. Liebig, op. cit. (note 65), p. 19.
94. Oppermann, op. cit. (note 41), p. 197. 'Die gelungensten Analysen ... sind folgende'.
95. For example, Liebig's published determination of the percentage by mass of carbon in the alkaloid morphine was 72.340%. This result was based on two gravimetric analyses performed using the Kaliapparat that appear at folios 68v and 63v in his 1830 laboratory notebook. Liebig, however, made a total of five further gravimetric determinations of the carbon content of morphine (at folios 43v, 44v, 45v and 53v), all of which gave significantly lower percentages of carbon and which he chose not to publish. See Liebig, op. cit. (note 14), p. 17.
96. Usselmann et al., op. cit. (note 11), p. 45.
97. Usselmann, op. cit. (note 18), pp. 72 and 74.
98. Wöhler and Liebig, op. cit. (note 66), p. 13: 'die Grenze der Genauigkeit'.
99. J. Liebig, 'Bemerkungen zu vorstehenden Abhandlung', Annln Pharm. 26, 41-60 (1838), p. 43: 'ob zwei Atome Wasserstoff mehr oder weniger darin enthalten sind, darüber kann die Analyse keinen Aufschluss geben'.
100. See also V. Regnault, 'Neue Untersuchungen über die Zusammensetzung der organischen Basen', Annln Pharm. 26, 10-41 (1838).
101. Liebig, op. cit., p. 59.
102. Liebig emphasized the importance of combining weight in the conversion of analytical data to formula, but did not regard this alone as capable of distinguishing between his formula for morphine and that proposed by Regnault. See Liebig, op. cit., pp. 42-43.
103. Usselmann, op. cit. (note 18), p. 82.
104. Usselmann et al., op. cit. (note 11), pp. 32-33.
105. Usselmann, op. cit. (note 18), p. 85.
106. Liebig's samples of morphine were obtained from two different pharmacists: Carl Wittstock in Berlin, and Emanuel Merck in Darmstadt. See Liebig, op. cit. (note 14), p. 16.
107. Usselmann, op. cit. (note 18), p. 87.
108. Usselmann et al., op. cit. (note 11), p. 32.
109. Usselmann et al., op. cit., p. 2.
110. See, for example, Liebig, op. cit. (note 16), p. 37,
111. or in English translation, Liebig, op. cit. (note 1), p. 28, on the correct procedure for handling the 'excess of hydrogen over the truth' of 0.14-0.2%. 'In publishing the weights obtained in an analysis, we must... give the numbers as they occur.'
112. See, for example, A. J. Rocke, 'Organic analysis in comparative perspective: Liebig, Dumas, and Berzelius, 1811-1837', in Instruments and instrumentation (eds F. L. Holmes and T. H. Levere), pp. 275-310 (MIT Press, Cambridge, MA, 2002).
113. Hess, op. cit. (note 1). Liebig responded in an extended footnote covering pages 192-194.
114. Direct quotations are from p. 192 in the translation by W. Gregory in Liebig, op. cit. (note 1), pp. 28-29. Despite Liebig's use of the word 'friend', Hermann Hess had not studied with Liebig in Giessen.
115. Liebig, op. cit. (note 1), p. 193.
116. H. Hess, 'Ueber die Zusammensetzung der Zuckersäure', Annln Pharm. 26, 1-9 (1838).
117. H. Hess, 'Ueber die Constitution der Zuckersäure', Annln Chem. Pharm. 30, 302-313 (1839), p. 310.
118. J. Liebig, 'Ueber die vorstehende Notiz des Hrn. Akademikers Hess in Petersburg', Annln Chem. Pharm. 30, 313-319 (1839), p. 314.
119. H. Hess, 'Berichtigung zu meinem Aufsatze über die Constitution der Zuckersäure', Annln Chem. Pharm. 33, 116-117 (1840).
120. Liebig, op. cit. (note 68), p. 118. 'Der wahre wissenschaftliche Werth einer chemischen Untersuchung besteht also nicht darin Zahlenresultate aufzufinden und sie nebeneinander zu stellen, es gehört noch dazu, dass diese Zahlen einen geistigen Ausdruck in sich schliessen.' Liebig had expressed a very similar opinion to Zeise in 1837.
121. See Liebig, op. cit. (note 65), p. 13.
122. Liebig, op. cit. (note 68), pp. 121-122. 'Ist Thaulows Erklärung richtig, so sind seine Analyse wahr, ist sie falsch, so können seine Analysen demungeachtet zuverlässig seyn, aber sie bedürfen alsdann einer anderen Interpretation.'
123. Liebig, op. cit. (note 68), p. 121. 'Die Richtigkeit einer Zahl hängt von Zufälligkeiten ab, die Auffindung der Wahrheit, welche daraus entspringt, ist die Aufgabe der Wissenschaft, aber durch Kupferoxyd, Spirituslampen und Sauerstoffgas allein wird sie nicht gefunden.'
124. Liebig, op. cit. (note 68), pp. 123-124. 'Je schlechter alsdann der Chemiker, desto schärfer der Beweis!!'
125. Liebig, op. cit. (note 88), p. 319.
126. Liebig was by no means the first person to consider this important. For example, A. E. Shapiro, 'Newton's optical notebooks: public versus private data', in Reworking the bench: research notebooks in the history of science (eds F. L. Holmes, J. Renn and H.-J. Rheinberger), pp. 43-65 (Kluwer, Dordrecht, 2003), p. 61, has suggested that Newton had presented his experimental observations on optics 'as unambiguously agreeing with experimental laws' in a 'quest to establish a more certain science'.
127. A. W. Hofmann, 'A page of scientific history', Q. J. Sci. 8, 145-153 (1871), p. 146.
128. Holton, op. cit. (note 12), p. 53.
129. Usselmann et al., op. cit. (note 11), p. 45.
130. Shapin, op. cit. (note 4), p. 563.
131. That this is the case is borne out by the numerous eminent scientists who began their careers in very junior laboratory positions. In the field of organic chemistry, one example that comes readily to mind is that of the late Charles W. Rees FRS, who became Hofmann Professor of Organic Chemistry at Imperial College, London, having begun his working life as what he termed a 'laboratory boy '. See also D. Phillips, 'Obituary: Charles Rees, CBE, FRS (1927-2006)', in Chemistry World (Royal Society of Chemistry, Cambridge, November 2006).
132. Liebig was outraged by Dumas's contemporary attempts to build a research group supported by personal patronage, which he regarded as retrogressive. According to Liebig, 'the times when Berthollet could gather a circle of eminently-talented young men around him at Arcueil are past'. J. Liebig, Annln Pharm. 2, 19-30 (1832),
133. cited in J. R. Partington, A history of chemistry, vol. 3 (Macmillan, London, 1962), p. 299: 'die Zeiten, wo Berthollet zu Arcueil, einen Kreis von jungen, eminenten Talenten um sich zu versammeln wusste, sind vorbei'. On Dumas' s research group,
134. see L. J. Klostermann, 'A research school of chemistry in the nineteenth century: Jean Baptiste Dumas and his research students', Ann. Sci. 42, 1-40 (1985).
135. Rocke, op. cit. (note 43), p. 85, has noted Liebig's 'aggressive' use of 'budding young chemists' as assistants in his research programme, whereas (p. 115) Dumas bore the cost of his students' research, creating a research group 'predicated on expanded personal patronage'.