‘Ueber die künstliche Bildung des Harnstoffs,’ pp. 253-256 in: Annalen der Physik und Chemie, Folge 2, Band 12.

Leipzig: Johann Ambrosius Barth, 1828.

First edition, complete journal volume, of this foundation work of organic chemistry. “In 1828, Wöhler succeeded in effecting an artificial synthesis of urea by heating ammonium cyanate. This was the first time that an organic substance had ever been built up artificially from the constituents of an inorganic substance without any intervention of vital processes, and it soon became clear that there is no essential difference between the structural chemistry of life and that of inanimate nature” (GM). “This was the first synthesis of an organic compound, and this accomplishment is generally regarded as the beginning of organic chemistry” (Sparrow, p. 37). “The discovery destroyed the vitalistic theory which held that organic compounds could be produced only by living organisms, and led eventually to the brilliant results that have been achieved in attempts to synthesize other organic compounds” (Dibner). “In 1828, Friedrich Wöhler (1800-1882) published a short article in which he described the unexpected formation of urea from ammonium cyanate. The appearance of urea as a product was entirely unexpected, because theory predicted that cyanic acid and ammonia should produce a compound with the properties of a salt. Urea was not a salt, and it did not possess any of the properties expected for cyanates. In the article, Wöhler repeatedly noted the novelty of the artificial synthesis, but he and his mentor, the well-known Swedish chemist Jöns Jacob Berzelius (1779-1848), were most intrigued by the formation of a nonsalt from a salt, and that ammonium cyanate and urea had the same elemental composition. Neither Wöhler nor Berzelius commented, as the epigraphs might suggest, on how the synthesis influenced the doctrine of vitalism, but within a few decades, chemists came to regard Wöhler’s experiment as an ‘epochal’ discovery that would mark both the death of vitalism and the birth of organic chemistry as a sub-discipline of chemistry. The myth has proved remarkably enduring – a survey of modern organic chemistry textbooks has revealed that 90 per cent of them mention some version of the Wöhler myth” (Ramberg, p. 60).

“Wöhler, the son of an agronomist and veterinarian, attended the University of Marburg and then the University of Heidelberg, from which he received a medical degree with a specialty in obstetrics (1823). However, his passion always was chemistry. The eminent professor of chemistry at Heidelberg, Leopold Gmelin, judged Wöhler to be already too advanced to profit from his courses, so he sent him to study with the world-famous Swedish chemist Jöns Jacob Berzelius. A year of mineral analysis in Stockholm not only provided Wöhler with the best chemical training then available but also cemented a close lifelong bond between the two men. Wöhler quickly mastered the Swedish language and subsequently served as Berzelius’s translator and advocate in Germany” (Britannica).

Wöhler became acquainted with his lifelong friend Liebig as a result of what seemed in 1825 to be a minor squabble over the interpretation of analytical results but became a classic example of a new phenomenon that Berzelius in 1830 called isomerism: both silver cyanate and silver fulminate correspond to the empirical formula AgCNO. Liebig had studied the explosive fulminate and at first rejected Wöhler’s 1824 results for the stable cyanate. In the 1820’s most chemists assumed that only one chemical compound corresponded to one set of analytical percentages. Wöhler and Liebig exchanged letters, often visited each other, and sometimes took vacations together from 1829 until Liebig’s death in 1873.

“Wöhler’s interest in cyanates led to a historic preparation of ‘artificial’ urea, the circumstances of which are best described in his letter to Berzelius of 22 February 1828:

‘I can no longer, as it were, hold back my chemical urine; and I have to let out that I can make urea without needing a kidney, whether of man or dog: the ammonium salt of cyanic acid is urea.

‘Perhaps you can remember the experiments that I Performed in those happy days when I was still working with you, when I found that whenever one tried to combine cyanic acid with ammonia a white crystalline solid appeared that behaved like neither cyanic acid nor ammonia. . . . I took this up again as a subject that would fit into a short time interval, a small undertaking that would quickly be completed and – thank God – would not require a single weighing.

‘The supposed ammonium cyanate was easily obtained by reacting lead cyanate with ammonia solution . . . Four-sided right-angled prisms, beautifully crystalline, were obtained. When these were treated with acids, no cyanic acid was liberated, and with alkali, no trace of ammonia. But with nitric acid lustrous flakes of an easily crystallized compound, strongly acid in character, were formed; I was disposed to accept this as a new acid because when it was heated, neither nitric nor nitrous acid was evolved, but a great deal of ammonia. Then I found that if it were saturated with alkali, the so-called ammonium cyanate reappeared; and this could be extracted with alcohol, Now, quite suddenly I had it! All that was needed was to compare urea from urine with this urea from a cyanate.’

“The letter goes on to describe how the discovery adds to the pairs of substances of similar composition but of different properties already known. ‘It is noticeable that in making cyanates (and in making ammonia) we always have to start with an organic substance …’

“In his published paper [offered here] Wöhler referred to his work of 1823, in which he had shown that cyanogen and aqueous ammonia yielded oxalic acid and a white crystalline solid that he now realized was urea. This, and his new method, he considered to be remarkable examples of the preparation ‘by art’ of a substance of animal origin from inorganic materials” (DSB).

“As early as the 1840s, Wöhler’s supporters began to tout his discovery as the ‘death knell’ of vitalism—and it is still usually described that way—but recent historical inquiry has shown that the situation was more complex; Wöhler’s own antivitalist claims were necessarily muted and qualified. His discovery was at least as important for the history of isomerism as for vitalism, since very few cases were then known of two distinct compounds having identical compositions. Two years after Wöhler’s synthesis of urea, Berzelius defined the concept and introduced the new word isomerism” (Britannica).

The urea myth can be conveniently condensed into three components: (1) that Wöhler synthesized urea from the elements; (2) that the synthesis unified organic and inorganic chemistry under the same laws; (3) that the synthesis destroyed, or at least weakened, the idea of a ‘vital force’ in living organisms. As historians have extensively documented, however, each of these three parts is highly problematic. First, Wöhler’s synthesis could be, and was, rejected as artificial, because there may have been a residual ‘vital force’ in his starting materials [Wöhler had started with organic matter, derived inorganic elements from it, and used those to produce urea]. Second, well before the urea synthesis, chemists had operated under the assumption, promoted by Berzelius, that organic and inorganic chemistry should follow the same laws of chemical combination. Third, ‘vitalism’ was not a single theory but a variety of related ideas about the nature of life that continued well after Wöhler’s synthesis in both chemical and biological contexts …

“In most versions of the myth, vitalism is assumed to be a theory that supposes the existence of a mystical, nonmaterial entity that is present in living things but absent in inorganic systems – a ‘rational soul’ that is responsible for maintaining the complex systems found in living organisms … [However,] vitalism was not a single comprehensive theory but a variety of theories about biological systems. Berzelius himself had developed a version of vital materialism as early as 1806, which he incorporated into the section on organic chemistry in the 1827 edition of his textbook; he never substantially revised the entry in subsequent editions. Similarly, Justus von Liebig (1803-1873) described vital force in Animal Chemistry (1842) as ‘a peculiar property, which is possessed by certain material bodies, and becomes sensible when their elementary particles are combined in a certain arrangement or form.’ This force, analogous to gravity or electricity, arose from the complexity of the system. Because the synthesis of a single compound could have had little effect on vitalistic theories about an organized system, it should not be surprising that Wöhler and Berzelius failed to discuss the impact of the synthesis of urea on vitalism in their correspondence and that early textbooks on organic chemistry did not mention Wöhler or the urea synthesis …

“The Wöhler myth shows no signs of fading away, because it serves several specific purposes. For organic chemists, it provides a hero who accomplished a specific datable task that assumed great significance. The myth became widespread after Wöhler’s death in 1882, in part to validate the theoretical autonomy of organic chemistry as a discipline that no longer required concepts from either biology or physics, and in part because German chemists wished to place the origins of the powerful German chemical community, in which synthesis played a central role, squarely in their own country. For biologists, the myth’s simplistic image of vitalism provides a convenient foil for depicting how physiologists adopted the rigorous mechanistic and quantitative methods of chemistry and physics in the process of making biology more ‘scientific’ by ridding it of ‘pseudoscientific’ entities such as vital forces” (Ramberg, pp. 60-66).

“All that said, with respect to the insignificance claim for Wöhler’s urea, there is a danger in proving too much. Wöhler obviously thought that he had done something rather dramatic in his excited letter of 22 February 1828 to his mentor Berzelius, stressing that he could make urea without a kidney, or even a living creature. Berzelius’ reply two weeks later is just as enthusiastic and just as focused on the issue of organic synthesis; Wöhler had produced a ‘jewel’ for his ‘laurel-wreath’ that would ‘immortalize’ his name. Wöhler clearly noted in his letter that his accomplishment would fail to convert a committed sceptic, and his published article did not assert that vitalism had been refuted. Moreover, both Wöhler and Berzelius recognized that the reaction was very relevant to a separate issue, the emergent study of isomerism, for Wöhler had simultaneously discovered that urea and ammonium cyanate had identical compositions. However, these qualifications do not negate the fact that both men regarded the new reaction to be important for an evaluation of vitalist beliefs … The ‘myth’ of Wöhler’s overthrow of vitalism in 1828 (and myth it surely was) was not created, as has been argued, in the spate of celebratory articles published during the centennial year, nor even in Hofmann’s 1882 obituary of Wöhler. It was created in the immediate aftermath of the event itself. As early as 1843, Hermann Kopp, writing as a historian, urged that this was the deed that destroyed vitalist belief, and ignored the reaction’s relevance for isomerism; Kopp’s portrayal became an important source for later writers … Relevant it was; a refutation of vitalism it was not. However, by the early 1850s, if not before, the myth of a definitive refutation had become ensconced in the German textbook literature” (Rocke, pp. 240-241).

Ironically, the modern understanding of the mechanism of production of urea in the mammalian liver seems to retain a certain ‘vitalistic’ aspect, although it would certainly not be described in that way today. “… the chemical synthesis observed by Wöhler does not represent the reaction which is employed in the mammalian liver for urea synthesis. The mechanism of this process was elucidated by the German physician Hans A. Krebs and his medical student Kurt Henseleit in 1932 and was shown to include the ornithine cycle. This ‘urea cycle’ is only observed in living cells; this apparently vitalistic phenomenon is caused by the compartmentalization of the various enzymatic reactions in mitochondria and cytosol, respectively” (Kinne-Safran & Kinne).

Dibner, Heralds of Science 45; Garrison-Morton 671; Sparrow, Milestones of Science 197; DSB XIV, pp. 474 et seq. Kinne-Safran & Kinne, ‘Vitalism and synthesis of urea. From Friedrich Wohler to Hans A. Krebs,’ American Journal of Nephrology 19 (1999), pp. 290-294. Ramberg, ‘Myth 7. That Friedrich Wöhler’s synthesis of urea in 1828 destroyed vitalism and gave rise to organic chemistry,’ pp. 59-66 in: Newton's apple and other myths about science, Numbers & Kampourakis (eds.), Harvard University Press, 2015. Rocke, The quiet revolution: Hermann Kolbe and the science of organic chemistry, 1993.

8vo (199 x 122 mm), pp. viii, 632. Contemporary speckled boards, paper spine label lettered in manuscript (binding a little rubbed). A very good copy. Stamp of Carl Alexander Bibliothek in Eisenach. Preserved in a custom leather box.

Item #4840

Price: $2,800.00

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