- The most complete account of the cryolite industry is Topp Niels-Henrik Kryolitindustriens Historie 1847–1990 Copenhagen 1990 unfortunately only published in few copies and with no English summary. The present paper relies to a considerable extent on this carefully researched work. Other valuable secondary sources include C. F. Jarl, Fabrikken Øresund 1859–1909: Kryolitindustriens Historie og Udvikling (Copenhagen, 1909); and Sophus M. Jørgensen, ‘Zur Geschichte des Kryoliths und der Kryolith-Industrie’, in Beiträge aus der Geschichte der Chemie dem Gedächtnis von Georg W. A. Kahlbaum, edited by Paul Diergart (Leipzig, 1909), 500–8. Together with other historical cases from Danish technical chemistry, the cryolite industry is also treated in Helge Kragh and Hans J. Styhr Petersen, En Nyttig Videnskab: Episoder fra den Tekniske Kemis Historie i Danmark (Copenhagen, 1995).
- Schumacher , C.F. 1795 . Fortegnelse og Beskrivelse over Nogle Grønlandske Mineralier . Skrivter af Naturhistorie-Selskabet , 4 ( 2 ) : 206 – 233 .
- 1798 . Scherer's Allgemeine Journal der Chemie , 2 : 502 – 502 . where Abildgaard's results are briefly mentioned and the name cryolite first appears. The name was often spelled in its Danish forms, kryolith or kryolit.
- Giesecke , K.L. 1910 . Bericht über einer mineralogischen Reise in Grönland . Meddelelser om Grønland , 35 : 1 – 478 . (227).
- Abildgaard , P.C. 1800 . Om Norske Titanertser og om en Nye Steenart fra Grönland . Kongelige Danske Videnskabernes Selskab, Skrifter , : 305 – 316 . Andrada reported his and Abildgaard's results the same year, adding that cryolite, apart from alumina and fluorspar acid, also contained ‘a bit of kali’, i.e. ‘vegetable’ soda or potash. J. B. Andrada, ‘Kurze Angabe der Eigenschaften und Kennzeichen einiger neuen Fossilien aus Schweden und Norwegen’, Scherer's Allgemeine Journal der Chemie, 4 (1800), 28–39. On Abildgaard, see S. Andersen, P. C. Abildgaard (1740–1801): Biography & Bibliography (Copenhagen, 1985).
- Klaproth , M.H. 1801 . Chemische Untersuchung des Kryoliths . Neue Schriften der Gesellschaft Naturforschender Freunde zu Berlin , 3 : 322 – 328 . A preliminary announcement of Klaproth's results appeared in Journal de Physique, 51 (1800), 473. See also M. H. Klaproth, Beiträge zur Chemischen Kenntniss der Mineralkörper, 6 vols (Berlin, 1802), III, 207–14; and L. N. Vauquelin, Sur la Présence de la Soude dans la Chryolite du Groënland, annonceé par M. Klaproth’, Annales de Chimie, 37 (1800), 89–93. The reported percentages of alumina, soda, and fluorspar acid were: 24:36:40 (Klaproth), and 21:33:46 (Vauquelin). Abildgaard acknowledged the progress made by Klaproth and Vauquelin in his ‘Mineralogiske Efterretninger’, Nyt Bibliothek for Physik, Medicin og Oeconomie, 1 (1801), 274–76. For other early literature on cryolite, see Ove B. Bøggild, The Mineralogy of Greenland (Copenhagen, 1953), 74–77.
- Berzelius , Jöns J. 1824 . Undersökning af Flusspatsyran och dess Märkvärdigaste Föreningar 31 – 32 . Stockholm The report on cryolite first appeared in Svenska Vetenskaps Akademiens Handlingar, 1823 (315). Translated into values for aluminium, sodium, and fluor, Berzeliur' figures correspond to 12·91% Al, 32·83% Na, and 54·26% F (determined as rest), whereas today's values are 12·85% Al, 32·85% Na, and 54·30% F.
- Giesecke , C. 1822 . On Cryolite . The Edinburgh Philosophical Journal , 6 : 141 – 144 . Giesecke's travel diary was published in 1910; see Giesecke (note 4). For a biographical sketch of Giesecke, see K. J. V. Steenstrup, ‘Einleitung und Biographische Mitteilungen’, i–xxxvii in the same volume of Meddelelser om Grønland. Apart from his mineralogical career, Giesecke is also known for his artistic contributions, in particular for being the author of Mozart's famous opera Die Zauberflöte. (The official author, Emanuel Schikaneder, merely changed Giesecke's version.)
- Giesecke . 1822 . On Cryolite . The Edinburgh Philosophical Journal , 6 : 142 – 142 . Cryolite may have been useful for this purpose not only because of its softness but also because it has a refractive index of 1·33, the same as water, which means that it is almost invisible as weight on an angling line.
- Topp , N.-H. 1990 . Kryolitindustriens Historie 1847–1990 3 – 3 . Copenhagen
- For Thomsen, see Bjerrum N. Julius Thomsen Berichte der Deutsche Chemische Gesellschaft 1909 42 4971 4988 and H. Kragh, ‘Julius Thomsen and 19th-Century Speculations on the Complexity of Atoms’, Annals of Science, 39 (1982), 37–60.
- On Owen and his factory, see Nyrop Camillus Fredens Mølle: Et Stykke Industrihistorie Copenhagen 1905 and H. Kragh and H. J. Styhr Petersen (note 1).
- Thomsen did not publish his method nor did he reveal how he arrived at his invention. His only published account of soda manufacture from cryolite dates from 1862, in an article that also appeared in French and German translations Thomsen J. Nogle Meddelelser Angaaende Kryolithindustrien Tidsskrift for Physik og Chemi 1862 1 321 332 The present account of the invention is mainly based on an unpublished report Thomsen made in connection with his patent application in 1852 (here referred to as ‘Report’). Extracts of the report, now at the Danish National Business Archives in Aarhus, are given in N.-H. Topp (note 1), 6–9.
- The basic idea of Thomsen's thermochemical theory of affinity was that the heat evolved in a chemical reaction is a measure of the affinity, a statement sometimes known as the Thomsen-Berthelot principle. It is tempting to speculate that Thomsen used thermochemical reasoning to infer or predict the alkaline decomposition of cryolite, i.e. that his invention was theoretically grounded. However, this seems not to have been the case. The strong affinity between calcium and fluor was known at the time, and Thomsen did not perform thermochemical measurements with cryolite or other of the substances active in the process leading to soda. Thomsen first published his theory of thermochemistry in Bidrag til et Thermochemisk System Kongelige Danske Videnskabernes Selskab, Skrifter, Matematisk-Naturvidenskabelig Afdeling 1852 3 115 165 series 5 which contains no reference relevant to cryolite soda. For Thomsen's thermochemical theory, see H. Kragh, ‘Julius Thomsen and Classical Thermochemistry’, British Journal for the History of Science, 17 (1984), 255–72.
- Topp , N.-H. 1990 . Kryolitindustriens Historie 1847–1990 4 – 6 . Copenhagen Axel Garboe, Geologiens Historie i Danmark, 2 vols (Copenhagen, 1959) II, 213–21.
- With modern atomic weights, the figure is 408·5 tons of soda. Thomsen's value of 392 tons, as given in his patent document, was presumably due to inaccurate atomic (or equivalent) weights. Eleven years later, he corrected his earlier figure to 408 tons. Thomsen J. Der Kryolith-Sodaofen Polytechnisches Journal 1863 167 362 370 [Dingler's] (366).
- Goldschmidt , M. 1857 . Et Industrielt Billede fra Danmark . Nord og Syd , II : 249 – 261 . where Mining Journal (4 October 1856), 670, is quoted. According to the journal, the cryolite was sold to ‘some parties in Staffordshire’.
- Deville , H.E. Sainte-Claire . 1859 . De l'Aluminium: Ses Propriétés, sa Fabrication et se Applications Paris
- Deville , H.E. Sainte-Claire . 1859 . De l'Aluminium: Ses Propriétés, sa Fabrication et se Applications 91 – 95 . Paris A method to prepare aluminium chloride and, electrolytically, pure aluminium from the fused chloride was also described by Robert Bunsen, ‘Notiz über die Elektrolytische Gewinnung der Erd- und Alkalimetalle’, Annalen der Physik und Chemie, 92 (1854), 648–51. In 1857, Thomsen experimented with electrolytic decomposition of cryolite, not in molten from but suspended in water. Although initially optimistic, Thomsen had to conclude that the method was unsatisfactory and he never published his results. Thomsen's experiments are referred to in a letter from C. F. Tietgen of May 1857, reproduced in N.-H. Topp (note 1), 91.
- Rose did not acknowledge Thomsen's suggestion, but there is strong evidence for the connection in the form of a letter from Howitz to the Danish Ministry of Internal Affairs of 1856, quoted in Topp N.-H. Kryolitindustriens Historie 1847–1990 Copenhagen 1990 44 44 and also from the description in M. Goldschmidt (note 19).
- Rose , H. 1855 . Ueber eine Neue und Vortheilhafte Darstellung des Aluminiums . Annalen der Physik und Chemie , 96 : 152 – 163 . (161).
- Dick , A. 1855 . On the Preparation of Aluminium from Kryolite . Philosophical Magazine , 10 : 364 – 365 .
- Wöhler , F. 1856 . Ueber die Reduction des Aluminiums aus Kryolith . Annalen der Chemie und Pharmacie , 99 : 255 – 256 . Wöhler obtained his cryolite from Forchhammer in Copenhagen.
- For sources and further information, see Hall M. Boas The Strange Case of Aluminium History of Technology 1976 1 143 158 Joseph W. Richards, Aluminium: Its History, Occurrence, Properties, Metallurgy and Applications, Including its Alloys (Philadelphia, 1887); and Paul Morel, ed., Histoire Technique de la Production d'Aluminium (Grenoble, 1992), 22–29.
- Deville , H.E. Sainte-Claire . 1856 . Mémoire sur la Fabrication du Sodium et de l'Aluminium . Annales de Chimie et de Physique , 46 : 415 – 458 . Deville began his experiments with cryolite, small amounts of which he had been provided with by Rose in Berlin and by Hofmann in London, in late 1855; Deville, ‘Nouveau Mode de Préparation de l'Aluminium et de Quelques Corps Simple, Métalliques et non Métalliques’, Comptes Rendus, (1855), 1053–57.
- Deville , H.E. Sainte-Claire . 1859 . De l'Aluminium: Ses Propriétés, sa Fabrication et se Applications 110 – 110 . Paris where excerpts of Chancourtois' report (Notice Scientifique sur la Géologie du Groênland) are included.
- See the patents listed in Gmelins Handbuch der Anorganischen Chemie, no. 35 A1 Berlin 1934 106 107
- Thoinsen , J. 1862 . Zur Geschichte der Kryolithindustrie . Polytechnisches Journal , 166 : 441 – 443 . [Dingler's]
- Tissier , C. 1859 . Recherches sur la Composition des Aluminates Déduite de celle des Fluorures . Comptes Rendus , 48 : 627 – 631 . For Deville, see note 20, 113–15.
- Persoz , J. 1859 . De la Formation du Sulfate Aluminique et d'un Nouveau Procédé Industriel pour la Fabrication de l'Alun . Annales de Chimie et de Physique , 56 : 102 – 106 . A similar process was patented by F. G. Spilsbury, British Patent No. 1443 (1856). This is according to J. W. Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry, 16 vols (London, 1924), v, 303-11, where other early patents for use of cryolite are also mentioned.
- For business details and the complicated relationship to the state-owned Royal Greenland Trading Company, see Topp N.-H. Kryolitindustriens Historie 1847–1990 Copenhagen 1990 where details about the extraction of cryolite in Greenland can also be found. The account in this article of the technical processes is primarily based on C. F. Jarl (note 1): J. Thomsen (note 13); M. Goldschmidt (note 19); and the manuscript ‘Kryolithens Techniske Anvendelse og Bearbeidelse’ in the cryolite archive (National Business Archives). This manuscript, a detailed 78-page account dated December 1863, was written by Vilhelm Storch, a chemical engineer at the ‘Øresund’ factory who later became a leading dairy chemist and, in 1892, Professor of Chemistry at the Agricultural University (Landbohøjskolen).
- Thomsen , J. 1862 . Nogle Meddelelser Angaaende Kryolithindustrien . Tidsskrift for Physik og Chemi , 1 : 321 – 332 . and 17); and J. W. Richards (note 26), 146–50. The superiority of Thomsen's kiln over the traditional kiln used in Christiansdal and also in Harburg was questioned by the technical manager of the Harburg work. C. Dittmar, ‘Über den Ofen des Harburger Alaunwerks' [Dingler's] Polytechnisches Journal, 167 (1863), 199–201.
- Thomsen developed a titrimetric method to determine the composition of clay soil products with the aim of standardizing the sulphuric clayey soil produced by the cryolite factory. Thomsen J. Quantitativ Bestemmelse af Leerjord ved Titrering Tidsskrift for Physik og Chemie 1863 2 225 233 Other specially developed titrimetic methods were used to determine the strength of the soda lye, which could not be reliably determined by the standard titration with sulphuric acid and litmus as indicator (‘Kryolithens Techniske Anvendelse’, note 33).
- A detailed description is given in Wagner J.R. Alaun und Andere Thonerdesalze Jahres-Bericht der Chemischen Technologie 1862 8 291 304
- Topp , N.-H. 1990 . Kryolitindustriens Historie 1847–1990 337 – 337 . Copenhagen
- The works were Gebrüder Giulini (Ludwigshafen), Hirschmann, Kijewski & Scholtze (Warsaw), Gebrüder Löwig (Breslau), and Koninklijke Chemische Fabriek (Uithoorn). According to Thomsen, writing in 1862, the cryolite works in Prague was directed by a Mr Rademacher (note 30, 442). The Ludwigshafen works, founded in 1837, was one of Germany's main producers of sulphuric acid, (Leblanc) soda, sulphuric clay soil, and nitric acid. 150 Jahre Giulini-Chemie Ludwigshafen 1973 Walter Wetzel, Naturwissenschaften und Chemische Industrie in Deutschland (Stuttgart, 1991), 58.
- Schwarz , H. 1862 . Die Harburger Kryolithfabrik . Polytechnisches Journal , 166 : 283 – 289 . [Dingler's]
- I am grateful to Ernst Homburg for having provided me with information about the Uithoorn factory. A brief description appears in Serrurier L. Over de Soda-Fabriekekatie Tijdschrift der Nederlandsche Matschappij ter Bevordering van Nijverheid 1866 29 241 274
- Leavitt , R.K. 1950 . Prologue to Tomorrow: A History of the First Hundred Years in the Life of the Pennsylvania Salt Manufacturing Company Philadelphia
- Haber , L.F. 1958 . The Chemical Industry During the Nineteenth Century 41 – 41 . Oxford 47.
- Pedersen , J. and Petersen , O. Strange . 1938 . An Analysis of Price Behaviour During the Period 1855–1913 86 – 86 . Copenhagen For the cryolite industry up to 1873, see Alfred Benzon, ‘Über den Kryolith von Grönland und die darauf Gegründete Industrie’, in Bericht über die Entwickelung der Chemischen Industrie Während des Letzten Jahrzehends, edited by August W. Hofmann (Braunschweig, 1875), 660–77.
- Gillespie , C.C. 1957 . The Discovery of the Leblanc Process . Isis , 48 : 152 – 170 . (170); idem, The Natural History of Industry’, ibid., 398–405 (399).
- For example, Holmes Frederic L. Eighteenth-Century Chemistry as an Investigative Enterprise Berkeley 1989 85 102 Although Gillespie implicitly used as a criterion of science-based industry the entrance of significant chemical theory, he also warned explicitly against ‘the tendency of modern historical writers to suppose that … if science was related to industry, it must have been through the medium of advancing theory’. Gillespie, ‘Natural History’ (note 43), 404. For an excellent historiographic review of the question, see N. McKendrick, The Role of Science in the Industrial Revolution: A Study of Josiah Wedgwood as a Scientist and Industrial Chemist’, in Changing Perspectives in the History of Science: Essays in Honour of Joseph Needham, edited by Michael Teich and Robert Young (London, 1973), 274–319.
- De Solla Price , D.J. 1965 . Is Technology Historically Independent of Science? A Study in Statistical Historiography . Technology and Culture , 6 : 553 – 568 . Another example of the weak coupling, from an entirely different part of technology, is analysed in H. Kragh, ‘The Krarup Cable: Invention and early Development’, Technology and Culture, 35 (1994), 129–57.
- Donnely , J. 1994 . Consultants, Managers, Testing Slaves: Changing Roles for Chemists in the British Alkali Industry, 1850–1920 . Technology and Culture , 35 : 100 – 128 .
- Meyer-Thurow , G. 1982 . The Industrialization of Invention: A Case Study From the German Chemical Industry . Isis , 73 : 363 – 381 . E. Homburg, ‘The Emergence of Research Laboratories in the Dyestuffs Industry’, British Journal for the History of Science, 25 (1992), 91–112.
Annals of Science
Volume 52, 1995 - Issue 3