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KRAGH, Helge - Julius Thomsen and Classical Thermochemistry
KRAGH, Helge - Julius Thomsen and Classical Thermochemistry
KRAGH, Helge - Julius Thomsen and Classical Thermochemistry
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B3HS, 1984, 17
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HelgeKragh
1975,
36 1-364.
7 J. Thomsen, 'Bidragtil et thermochemisksystem,' Kgl. Da. Vid.Selsk.Skr.,Mat.-Nat.Afd.(5), 1852,
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Helge Kragh
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Helge Kragh
26J. Thomsen, 'Die vollige Unguldigkeit der von Berthelot ... berechneten Zahlenwerte,' Chem.
Ber. 1872, 5, 181-185, on 185.
2ij. Thomsen, 'Eine Prioritatsfragebezuglich einiger Grundsatze der Thermochemie,' Chem.Ber.,
1873, 6, 423-428.
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Helge Kragh
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his own reasons for doing so.36 Duhem felt that his career was blocked by
the repressive authority associated with Berthelot's principle of which he
always was a fervent critic. With the sole exception of Duhem, Berthelot's
claim to be the founder of rational thermochemistry was accepted in
France. In Germany and England Thomsen's merits were fully recognized.37 When the Royal Society in 1883 awarded the Davy Medal for
pioneering contributions to thermochemistry,38 the honour was shared
between Thomsen and Berthelot, no doubt to the dissatisfaction of both
chemists.
The controversy between Thomsen and Berthelot was to some extent
due to differences in scientific style and perspective. Both scientists
advocated an empiricist method, emphasizing that scientific laws should
be the result of observations and that hypotheses should be used very
cautiously and only if they were closely linked to experiments. Thomsen
tended to conceive the exact determination of thermochemical quantities
as an end in itself and consequently judged experimental accuracy as the
prime virtue of thermochemistry. Berthelot's attitude was less experimenticist. For him thermochemical measurements were interesting primarily
because of their relevance for theoretical notions such as the principle of
maximum work.39 Berthelot's positivistic outlook led him to deny the
reality of atoms and molecules. Although Thomsen too held positivistic
virtues in high esteem, he did not share Berthelot's anti-atomism. On the
contrary, Thomsen was a firm believer in the reality of atoms and their
significance in thermochemistry.
The rivalry between Thomsen and Berthelot may have been related
to the political situation in Europe after the Franco-Prussian war. In
France there was a widespread hostility against German science and what
was felt to be Germany's attempt to obtain a monopoly in science. The
prestige of French science was a constant preoccupation of leading French
scientists, among them many chemists.40 A part of this prestige was
Berthelot's principle of maximum work and French thermochemistry in
general. Although Thomsen was not a German his thermochemistry was
36 P. Duhem, 'Thermochimie,' Revuedesquestions
1897, 12, 361-392, on 363-364 and 368.
scientifique,
Reviewing Berthelot's Thermochimie
Duhem took the opportunity to launch a strongly worded attack on
Berthelot and his position in French chemistry. According to Duhem, Berthelot's principle was a
'ridiculous tautology' (370). In 1884 Duhem's doctoral dissertationwhich contained an attack on the
principle of maximum work was rejected as a resultof its questioning thermochemicalorthodoxy; it was
published as a book two years later as Lepotentiel
thermodynamique
(Paris, 1886). See D. G. Miller, 'Pierre
Duhem', Physicstoday,December 1966, 47-53.
37 M. M. Pattison Muir, Principlesof chemistry,
London, 1884; W. Ostwald, Lehrbuch
derallgemeinen
Chemie,2 vols., Leipzig, 1892-1893, 11/1, 64; E. von Meyer, Geschichte
derChemie,Leipzig, 1889, 383.
38 Proc.Roy.Soc.London,1883, 36, 74.
39 HarryJones, an American chemist of the Ostwald school, described Thomsen as 'the type of mind
that delights in accurate experimental work';while Berthelot was 'not the type of mind to be limited to
fine experimental work.... Berthelot made thermochemical measurementsfor a definite purpose, and
that was to see to what far-reaching conclusions they would lead.' H. C. Jones, A newerain chemistry,
New York, 1913, 36.
40 H. W. Paul, The sorcerer'sapprentice.The Frenchscientist'simage of Germanscience1840-1919,
Gainesville (Florida), 1972.
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HelgeKragh
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in which the six carbon atoms were held together by single bonds only.43
Thomsen now applied his new method of calculating heats of formation of
hypothetical organic structures to the case of benzene. In 1880 he
concluded that Kekule's formula was all wrong.4 Thomsen claimed that
his thermochemical arguments against the double bond theory were
conclusive, constituting a crucial test as to the structure of benzene and
related compounds. 'The question concerning the constitution of benzol
can now be given a decisive answer by means of experiments ... It can be
decided with certainty whether a hydrocarbon contains only single bonds
or partly single and multiple bonds.'45 Thomsen argued that according to
his theory the heat of combustion of benzene would be 846 kcal if Kekule's
structure was assumed. On the other hand, on Ladenburg's structure the
heat of combustion was calculated to 802-3 kcal. In order to compare the
two theoretical results with the actual heat of combustion of benzene,
Thomsen redetermined this quantity with great care and found it to be
805-8 kcal, agreeing well with Ladenburg's formula but not with Kekule's.
Consequently he concluded that 'The six carbon atoms of benzol are
united to each other by nine single bonds, and the previous assumption of a
structure of benzol with three single and three double bonds is not
supported by experiment.'46
In 1887 Thomsen published his own model of benzene, based on an
octahedral structure.47 Thomsen placed the six carbon atoms at the corners
of a regular octahedron, each of the carbon atoms being connected to three
others by one axial and two peripheral bonds. In that way he retained the
symmetry and the nine single bonds the presence of which he thought to
have proved experimentally. Thomsen's proposal did not win much
support. With the one exception of Henry Edwards Armstrong no chemists
of significance seem to have paid attention to it.48
Thomsen's ambitious programme of applying thermochemistry as a
key to structural chemistry aroused considerable interest. Lothar Meyer
wrote approvingly to Thomsen that 'if your experiments in mass action, in
neutralization etc. have already shown that thermochemistry is suitable for
something else than just the lengthy conversions a la Berthelot of negative
heats of reaction into positive ones, then your structural researches now
43 A. Ladenburg, 'Ueber Benzolformeln,'Chem.Ber., 1869,2, 272-274. A diagonal structure, similar
undderen
Betrachtungen
to that proposed by Ladenburg, was forwarded by A. Claus in his Theoretische
derorganischen
Chemie,Freiburg, 1867, 207-208. For other candidates and
Anwendungen
zur Systematik
background to the problem of the structureof benzene, see C. A. Russell, Thehistoryof valency,Leicester,
1971, ch. 9.
44J. Thomsen, 'Die Constitution des Benzols,' Chem.Ber., 1880, 13, 1808-1811; 'Zur Benzolformel,'
Chem.Ber., 1880, 13, 2166-2168.
45 Ibid., 1810.
46 Ibid., 1811.
1886, 179-186.
47J. Thomsen, 'Om benzolmolekylets konstitution,' Kgl. Da. Vid.Selsk. Oversigter,
48 H. E. Armstrong, 'The determination of the constitution of carbon compounds from thermochemical data,' Phil. mag., 1887, 23, 73-109. Armstrongproposeda 'centric' formulawhich agreed with the
nine single bonds suggested by Thomsen.
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Helge Kragh
open up a very wide perspective which even the most dense aromatic fog of
colour will not be able to obscure.'49 However, with few exceptions, such as
Hans Jahn at the university of Vienna,50 the chemists did not accept
Thomsen's thermo-structural theory.
In an extensive review of 1881 the American chemist J. P. Cooke
judged Thomsen's work as 'a bold push beyond the beaten tracks of
science.'5' But he concluded that chemical evidence, if taken together,
supported Kekule's formula rather than Ladenburg's and that Thomsen's
arguments did not prove the fallacy of Kekule's theory. Other chemists,
such as D. I. Mendeleev and M. M. Pattison Muir, criticized Thomsen's
confidence in his method and objected to the logic of his argumentation.52
In England, Thomsen's theory was also criticized by Armstrong and S. U.
Pickering both of whom argued that Thomsen's conclusions tended to
destroy the accepted bond theory of organic constitution.53 In contrast to
their German colleagues, Cooke, Pattison Muir, Armstrong and Pickering
did not dismiss Thomsen's reasoning completely; they found his theory
important and suggestive and sought rather to modify it in order to bring it
into accordance with accepted views.
Untersuchungen
After the appearance of volume four of Thermochemische
F. Stohmann
from
was
launched
criticism
Germany.
a much sharper
which
of
of
benzene
of
the
heat
combustion
published new measurements
Berthelot's
with
but
were
in
Thomsen's
agreement
from
good
differed
value.54 Thomsen at once objected to Stohmann's measurements but
Stohmann continued to criticize Thomsen's accuracy.55 Stohmann was
clearly irritated over what he considered as Thomsen's stubbornness; he
claimed that Thomsen was not willing to discuss matters impartially.
Stohmann was supported byJ. W. Bruhl in Freiburg who not only argued
forcibly against Thomsen's conclusions concerning the structure of
benzene but dismissed his entire thermo-structural theory as 'speculations'.
49 Quoted from Bjerrum, op. cit. (31), 4983. This letter, as well as most other letters and unpublished
materials which Thomsen left at his death, seems to have been lost. The archive of the Royal Library in
Copenhagen includes eight boxes with source materials on Thomsen but nothing of particular interest
to the history of chemistry. The Wilhelm-Ostwald-Archiv
in Berlin(GDR) owns a small number of
letters from Thomsen to Ostwald.
50 H. Jahn, Die Grundsatzeder Thermochemie,Vienna, 1882, 147.
51
J. P. Cooke, 'Notice ofJulius Thomsen's thermochemical investigation of the molecular structure
of the hydrocarbon compounds,' Am. j. sci., 1881, 21, 87-98, on 98.
52 Pattison Muir, op. cit. (37), 174f and 303f; D. I. Mendeleev, 'Ueber die Verbrennungswarme
der
Kohlenwasserstoffe,' Chem. Ber., 1882, 15, 1555-1559.
53 Armstrong, op. cit. (48); S. U. Pickering, 'Note on the foregoing communication,'
Phil. mag., 1887,
23, 109-112; 'On thermochemical constants,' Phil. mag., 1888, 26, 53-62.
54 F. Stohmann,
P. Rodatz and H. Herzberg, 'Ueber den Warmewerthe des Benzols,' J. prakt.
Chemie, 1886, 33, 241-260. Stohmann adopted the calorimetric technique developed by Berthelot and
his pupils; in 1887 he worked in Berthelot's laboratory where he was introduced to the bomb
calorimeter.
55J. Thomsen, 'Ueber die Verbrennungswarme des Benzols,'Y. prakt. Chemie, 1886, 33, 564-567; F.
Stohmann, 'Entgegnung zu vorstehender Abhandlung des Herrn Thomsen,' ibid., 568-576; 'Zur
weiteren Beleuchtung der Untersuchungen des Herrn Julius Thomsen,' Y. prakt. Chemie, 1887, 35,
136-141. Exchange of views between Thomsen and Stohmann in _'.prakt. Chemie, 1886, 34, 55-56.
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Helge Kragh
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Helge Kragh
theory: 'Until there is a more definite kinetic theory of affinity than has yet
been proposed, it will not be possible to apply thermal methods, except in a
general and broad way, to the questions suggested by the term affinity.'7' A
contributory cause to the declining confidence in the thermochemical
theory of affinity was no doubt its failure in elucidating the structure of
organic compounds.
The experimental objections to the Thomsen-Berthelot principle,
such as incomplete dissociation, reversibility, and spontaneous endothermic processes, had been known for many years but were for a long time
disregarded by orthodox thermochemists. Although Thomsen and Berthelot claimed that the principle was derived from, and justified by,
observations, in reality they took it to be self-evident. Experiments which
did not agree with the Thomsen-Berthelot principle were explained away,
either by classifying them as exceptions, lying outside the range of the
principle, or by forcing them to agree with it by means of more or less
artificial assumptions. However, the attempts to rescue the universality of
the Thomsen-Berthelot principle could not help to appear more and more
unsatisfactory and ad hoc as counter-evidence and other objections
accumulated. In 1873 Thomsen reluctantly admitted that probably his
theory had no general or absolute validity.72 In the early eighties the true
nature of the Thomsen-Berthelot principle was explained within the
framework of the new chemical thermodynamics.73 It was proved that the
principle can only claim validity as an idealization under extreme
conditions, viz. at the temperature of absolute zero. Thomsen now stated
without reservation that his original view was only an approximation to
the truth. 'The release of the affinities usually appears as a development of
heat; however, the evolved heat of reaction often is not a reliable expression
of the quantities of the released affinities.'74 The other champion of
thermochemistry, Berthelot, was less inclined to give up his principle of
maximum work the general validity of which he maintained for several
years.75
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Helge Kragh
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