KRAGH, Helge - Julius Thomsen and Classical Thermochemistry

British Society for the History of Science
Cambridge University Press

Julius Thomsen and Classical Thermochemistry
Author(s): Helge Kragh
Source: The British Journal for the History of Science, Vol. 17, No. 3 (Nov., 1984), pp. 255-272
Published by: Cambridge University Press on behalf of British Society for the History of
Science
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B3HS, 1984, 17
Julius Thomsen and classical

thermochemistry
Helge Kragh*
Classical thermochemistry is inextricably bound up with the problem of

chemical affinity. In 1851, when Julius Thomsen began his career in
thermochemistry, the concept of chemical affinity had been in the centre of
chemical enquiry for more than a century.' In spite of many suggestions,
preferably to explain affinity in terms of electrical or gravitational forces,
almost nothing was known about the cause and nature of affinity. In this
state of puzzling uncertainty some chemists felt it more advantageous to
establish an adequate experimental measure of affinity, whatever its
nature was. One way of providing affinity with a quantitative description
was by means of the heats evolved in chemical processes.
A thermochemical measure of affinity was first suggested by Germain
Henri Hess who believed that the proper measure of chemical affinity was
given by heats of dilution.2 The most important of Hess' results was his
generalization known as the law of constant heat summation, orjust Hess'
law, that the amount of heat developed in a chemical reaction is constant,
regardless of whether the reaction proceeds directly or through a number
of intermediate steps. Remarkably, this conclusion was announced at a
time when the energy principle was not yet stated and the mechanical
theory of heat was still in its infancy. In fact, Hess' results were based on a
caloric conception of heat. In the early forties the idea of a general
correlation and conservation of the forces of nature gained a strong appeal,
until it was formulated in definite terms through the mechanical theory of
heat. Helmholtz, in his classical work on energy conservation, pointed out
that Hess' law is a simple consequence of the principle of conservation of
energy.3 But apart from rather casual remarks the energy principle was not
immediately applied to chemistry and was not well known to chemists in
the late forties. Although the rising conviction of a basic unity between the
forces of nature, including affinity, naturally stimulated interest in a
*Address: Magnolievangen 41, 3450 Aller0d, Denmark.
' T. L. Levere, Affinityand matter.Elements of chemicalphilosophy 1800-1865, Oxford, 1971. Of relevance
to the present subject are also V. M. Schelar, 'Thermochemistry and the third law of thermodynamics,'
Chymia, 1966, 11, 99-124, and V. V. Raman, 'The permeation of thermodynamics into nineteenth
century chemistry,' Indianjournal of history of science, 1975, 10, 16-37.
2 H. M. Leicester, 'Germain Henri Hess and the foundation of thermochemistry,' Y. chem. ed., 1951,
28, 581-583. Hess' papers are reprinted in Ostwald's Klassiker der exakten Wissenschaften, no. 9, Leipzig,
1921.
3 H. Helmholtz, Uber die Erhaltung der Kraft, Berlin, 1847, 32.
256
HelgeKragh
thermochemical conception of affinity, Hess' calorimetric studies were not

followed up to any extent. Consequently the thermochemical conception of
affinity did not at once benefit from the new mechanical theory of heat.
The first large-scale series of calorimetric determinations of heats
involved in chemical reactions, after those of Hess, were carried out in Paris
by Pierre Antoine Favre and Johann Theobald Silbermann.4 They
collected a large amount of thermochemical data, reporting hundreds of
accurate measurements which in the two decades to follow constituted the
main body of data for thermochemistry. But they hesitated in connecting
their measurements with theoretical notions and did not succeed in
providing affinity with a general and operational thermochemical definition. They ended up with identifying affinity with chemical stability,
measured by the quantity of heat evolved by formation of a chemical
compound from its constituents. Although the mechanical theory of heat
was fully developed in 1852, Favre and Silbermann did not make use of it
in their works. The mechanical theory of heat diffused slowly to France
where it was generally accepted only from the mid fifties and applied in
chemistry only a decade later, with the works of Berthelot.
At about the time when Favre and Silbermann made their measurements the relations between heat and chemical processes were also studied
by a few other chemists. In England thermochemical studies were pursued
by Thomas Graham, Thomas Andrews and Thomas Woods.5 However,
the most important contributions to thermochemistry came from France
and Denmark.
Julius Thomsen's early interest in thermochemistry may have been
the result of the influence exerted by Ludwig August Colding and was
perhaps also indebted to H. C. Orsted's general view of the forces of nature.
Thomsen was, like Colding, a protege of Orsted6 who for years had
conceived chemical affinity to be a force intimately correlated with other
forces of nature, such as light, electricity and heat. Colding was a friend of
Thomsen with whom he collaborated in matters of administration and
technology. Probably Colding's occupation with the equivalent of heat
and mechanical force had an impact on Thomsen's initiation of his
research programme in which the principle of energy conservation was for
the first time incorporated in chemical theory.
Thomsen published his system of a new thermochemistry in 1852-54.7
His ambition was to determine the absolute values of chemical forces by
4 P. A. Favre and J. T. Silbermann, 'Recherches sur les quantites de chaleur degagees dans les
actions chimiques et moleculaires,' Ann.chim.phys., 1853, 37, 406-508.
5 Levere, op. cit. (1), 202. J. R. Partington, A historyof chemistry,
4 vols., London 1961-1970, IV,
608-612.
6H. Kragh, 'Julius Thomsen and 19th century speculations on the complexity of atoms,' Annalsof
science,1982, 39, 37-60. For Colding and his debt to Orsted, see P. F. Dahl, 'Ludwig A. Colding and the
1963, 8, 174-188. Extractsof Colding's work of 1851 is translated in
conservation of energy,' Centaurus,
B. Bruce Lindsay (ed.), Energy: historical developmentof the concept, Stroudsburg (Pennsylvania),
1975,
36 1-364.
7 J. Thomsen, 'Bidragtil et thermochemisksystem,' Kgl. Da. Vid.Selsk.Skr.,Mat.-Nat.Afd.(5), 1852,
Julius Thomsenand Classical Thermochemistry
257
means of thermochemical measurements and thus supply the vague

concept of affinity with a new quantitative and operational meaning. In
1861 he stated his programme as follows:
By considering the amount of heat involved by the formation of a
chemical compound as a measure of affinity, as a measure of the work
required again to resolve the compound into its component parts, it
must be possible to deduce general laws for the chemical processes,
and to exchange the old theory of affinity, resting on an uncertain
foundation, for a new one, resting on the sure foundation of numerical
value.8
For the energy involved in a reaction Thomsen used various names; in his
publications of 1852-54 he changed between 'affinity', 'chemical force'
and 'thermodynamic equivalent'. Thomsen adopted as a fundamental
assumption that the heat of combination of a compound has to equal the
difference between the thermal affinities of the compound and those of its
constituents; that is, the thermal affinity of energy is conserved. In his first
series of papers he succeeded in showing, among other things, that Hess'
law followed from his thermochemical theory, thus changing its status from
an empirical generalization to a deduction from higher principles.
The basic principles of thermochemistry, as Thomsen saw them, were
stated in 1854. First he proposed a new definition of affinity: 'The force
which unites the component parts of a chemical compound is called
affinity.... In order to split up a compound, to overcome the affinities, a
force is necessary the quantity of which can be measured as the amount of
heat evolved in the formation of the compound from its constituents in
question.'9 Conceiving a chemical process to be an exchange of affinities in
which the weaker affinities are replaced by stronger ones, Thomsen
concluded that 'Every simple or complex action of a purely chemical
nature is accompanied by evolution of heat."0 This general statement,
known as Thomsen'sprinciple, became the much discussed backbone of
thermochemistry in the decades to follow. The phrase 'of a purely chemical
nature' was crucial in Thomsen's formulation, introduced as a protection
against the objection that although most chemical processes evolve heat,
some do not and thus seem to contradict the principle. In 1854
endothermic processes were well known and Thomsen discussed himself a
number of processes which are followed by absorption of heat. He argued
however that these processes were not of a 'purely chemical nature' and
hence outside the realm of his principle. 'I see only chemical actions in such
3, 115-165; 'Die Grundzuge eines thermochemisches Systems,' [Poggendorf's]Annalen, 1853, 88,
349-362; 90, 261-288; 91, 83-104; 92, 34-57.
8J. Thomsen, 'Om de chemiske processers almindelige character og en pa denne bygget
affinitetslaere,'Kgl. Da. Vid.Selsk. Oversigter,1861, 100-134, on 104.
9'Grundzuge,' op. cit. (7), 1854, 92, 34.
'0 Ibid., 36.
258
Helge Kragh
processes where the substances combine in definite proportions, according

to their number of equivalence, and I will only consider these in order to
test the theory by experience."' Thomsen's attempt to protect his principle
by means of the rather vague and arbitrary criterion of what a chemical
action is, was much criticized later on. Many chemists felt that it was
plainly ad hoc, tending to make the principle irrefutable and hence
unscientific. Indeed, Thomsen's criterion for what should be counted as a
purely chemical action was not only vague, but he also stated it in
incompatible versions.'2
In later publications Thomsen often stressed that his system of
thermochemistry was an empirical generalization and hence independent
of the nature of matter and affinity. But Thomsen was always a firm
proponent of atomism and believed that ultimately the nature of affinity
would find its explanation in the mechanics of atoms.'3 In 1853 he offered a
tentative explanation of affinity in terms of atomic motions, based on the
principle of energy conservation.'4 In his later works he was however
careful to stress that such atomic theories were still premature. As the
dynamical laws of atoms were still unknown, the task would have to be left
for the future, he concluded.
It was only from 1866, when Thomsen was appointed professor at the
University of Copenhagen, that he was able to continue his work of
1852-54 and develop it experimentally. From 1866 to about 1886
Thomsen performed an extensive research programme in experimental
and theoretical thermochemistry, publishing a steady flow of papers to
Danish and German journals. The bulk of Thomsen's results was collected
in the monumental four-volume work ThermochemischeUntersuchungen,
published 1882-86. Thomsen wrote his most important papers in German
language and felt at home in the German scientific tradition. Among his
more than 230 publications, 140 were published in German periodicals,
only one in an English journal and none in French scientific journals.
Thomsen's thermochemical measurements covered most groups of
organic and inorganic substances and resulted in a wide range of
applications. Of particular importance was his confirmation of 1869 of
Guldberg and Waage's recently developed law of mass action. 5 Thomsen
was able to show that in the case of partial decomposition of salts, Guldberg
"Ibid.
12 In the Danish version of 1852 a purely chemical action was stated to

be one which is 'solely caused
by the innate forces of the substances' (p. 157). Thirty years later the criterion read that the process
'proceeds without the expenditure of external energy and is accomplished only through striving of the
atoms towards more stable equilibrium.' J. Thomsen, ThermochemischeUntersuchungen,4 vols., Leipzig,
1882-1886, I, 16.
3 See Kragh, op. cit. (6).
14'Grundzuge,' op. cit. (7), 1853, 90.
15J. Thomsen, 'Thermochemische Untersuchungen. I, Uber die Bertholletsche Affinitatstheorie,'
[Poggendorf's]Annalen, 1869, 138, 65-102. C. M. Guldberg and P. Waage, Etudes sur les affinitis chimique,
Christiania (Oslo), 1867. E. W. Lund, 'Guldberg and Waage and the law of mass action,'J. chem. ed.,
1965, 42, 548-550.
Julius ThomsenandClassicalThermochemistry 259

and Waage's theory was in good agreement with thermochemical
measurements as interpreted in accordance with Thomsen's own ideas of
thermochemistry.Although Thomsen's work did much to make the law of
mass action accepted, Guldberg and Waage did not agree with Thomsen's
thermochemical theory of affinity. The work of Guldberg and Waage was
originally addressed to an understanding of chemical affinity. But during
their work they realized that affinity is only one component among others
determining the behaviour of a chemical processand that current effortsto
provide a single measure of affinity, that being electrical, gravitational or
thermal, were not satisfactory.In 1867 they criticized Thomsen's theory of
affinity, though not mentioning their Danish colleague by name. 'The heat
evolved during the reactionsdepends not only on the molecular heats of the
reacting substancesbut also on the circumstancesunder which the reaction
proceeds. ... if the circumstances can change the result of the reaction,
then they necessarily cause, at the same time, changes in the evolved
heat."6 Guldberg and Waage asked how the thermochemical concept of
affinity could possibly account for the fact that in most reversible
decompositions there is no net heat evolution.
II
Ten years after Thomsen had completed his system Marcellin Berthelot in
Paris began his extensive research in thermochemistry.'7Berthelot's first
study was followed by several book-length articles'8and the whole work,
experimental and theoretical, was collected in his Essai de mecanique
chimique,published two years before the appearance of Thomsen's
In these and later publications'9Berthelot represented the
Untersuchungen.
science of thermochemistryas a French invention with himself as the chief
inventor, an account which was bound to cause a collision with Thomsen
in Copenhagen.
Berthelot's own experiments in thermochemistrystarted in 1873. At
that time he had already formulated the basic principles of thermochemistry, using as experimental evidence the investigations of Favre and
Silbermann. The number and formulations of Berthelot's principles were
subject to changes in his various publications but in their essence they
affected two statements both of which were shown to be consequences of
the mechanical theory of heat. According to Berthelot's 'principle of
molecular work' the measureof chemical affinity was given by the quantity
of heat evolved. In processeswhere external energy does not intervene this
16Etudes, op. cit. (15), 15.
17 M. Berthelot, 'Recherches de thermochimie,' Ann. chim. phys., 1865, 6, 290-464. M. P. Crosland,
'Berthelot, Pierre Eugene Marcellin,' in C. C. Gillispie (ed.), Dictionary of scientificbiography,New York,
1970-80, II, 63-72.
18 M. Berthelot, 'Nouvelles recherches de thermochimie,'
Ann. chim. phys., 1869, 18, 5-201;
des corps dans les dissolutions,' Ann. chim.phys., 1873,29,433-514;
'Recherches calorimetriquesurl'etat
'Sur les principes generaux de la thermochimie,' Ann. chim. phys., 1875, 4, 5-131, 141-213.
260
Helge Kragh
quantity is a constant, depending only on the terminal states of the system.

The principle of molecular work, a generalization of Hess' law of constant
heat summation, was stated by Berthelot in 1865.20 The second principle
which Berthelot considered the proper foundation of rational thermochemistry, was first stated in 186421 and, in greater detail, in 1869 and
1875. This 'principle of maximum work' or 'third principle of thermochemistry' states that 'Every chemical change accomplished without the
intervention of external energy tends to the production of that body, or
system of bodies, which disengages most heat.'22 The validity of Berthelot's
principle of maximum work was, in its earlier formulations, restricted to
certain classes of chemical reactions (e.g., only very fast ones) but from
1875 and later on he stated it as a very general principle which had to apply
by necessity. He declared, for example, that the principle implies that
'every chemical change which can be accomplished without the aid of a
preliminary work, and without the intervention of foreign energy,
necessarily happens if it disengages heat.'23 Berthelot shared Thomsen's
view that thermal processes were the result of energetic transformations.
Affinity was conceived to be an innate attractive force, the heat of reaction
due to a transformation of its energy from potential to kinetic form. This
was the general view of classical thermochemistry, stated, for example, also
by Dumas in 1868.24
The striking similarity between Berthelot's principles and those stated
by Thomsen in 1853-54 was, according to Berthelot, a coincidence as he
was not aware of Thomsen's works until years after he started his own
research in thermochemistry.25 Thomsen felt however obliged to assert his
own priority and to protest against Berthelot's claim of being the founder of
the laws of thermochemistry. In 1872 he subjected Berthelot's work to a
devastating criticism, bluntly characterizing it as 'fraud' based on
'uncritical armchair works'. The sad result of Berthelot's efforts was,
Thomsen said, merely to have 'loaded the scientific journals with a
countless number of false and totally unusable numerical values.'26 Though
not directly accusing Berthelot of plagiarism, he concluded that Berthelot
had done no more than restate the results found by himself twenty years
earlier.27 Thomsen's attack resulted in a vehement response from Berthelot
who maintained that his thermochemical principles were quite different
19 M. Berthelot, Essai de micaniquechimiquefondie sur la thermochimie,2 vols., Paris, 1879; Thermochimie:
donnies et lois numerique,2 vols., Paris, 1897.
20 Berthelot, op. cit. (17).
21 M. Berthelot, Lecons sur les mithodesgenirales de synthise, Paris, 1864, on 399.
22 Berthelot, op. cit. (18), 1875, 52.
23 Ibid., 212.
24 M. Dumas, 'Remarques sur Faffinite,' Compterendu,1868, 67, 597-614, on 607.
25 Micanique chimique, op. cit. (19), I, X.
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.
261
from those stated by Thomsen.28 Berthelot declared that Thomsen's

principle, that every purely chemical action is usually accompanied by an
evolution of heat, was a banality known for a century. His dismissal of
Thomsen's principle as being of no scientific originality was also addressed
to his compatriot Henri Saint-Claire Deville who in 1860, years before
Berthelot, had proposed a thermochemical notion of affinity similar to that
of Thomsen.29 The exchange of views of 1872-73 was only the beginning of
a long and embittered controversy between the two chemists, lasting for
more than twenty years. The real subject of the controversy concerned
which of the two scientists should be credited as the founder and doyen of
thermochemistry. Both Thomsen and Berthelot felt that this honour could
not be divided between them.
Berthelot exerted a great influence on French chemistry in the later
part of the nineteenth century.30 A little prior to Berthelot's first works in
thermochemistry a special chair was created for him at the Collge de France
and in the years to follow he worked hard to build up the image he wanted
of himself, as the unrivalled pioneer within key branches of modern
chemistry. In France, at least, the propaganda bore fruit, leaving the
impression that thermochemistry was a creation of French chemists,
headed by Berthelot and founded upon his principle of maximum work.
Berthelot's principle and his conception of thermochemistry came to be
associated with the prestige of French science.
Thomsen was from a small country without a great scientific and
patriotic tradition; contrary to Berthelot, he was not at all interested in
forming a school around him and his work in thermochemistry. Thomsen's
scientific ambition was to gain recognition as the one who had provided
thermochemistry with a solid theoretical foundation supported by reliable
experiments. He liked to emphasize that his theoretical considerations as
well as his thousands of calorimetric measurements were his own works,
indebted to nobody but himself. By personality Thomsen was a fighting
character, often arrogant and fiery and highly critical of views which
differed from his own.3' He was unwilling to accept that other researchers
could substantially improve the knowledge of thermochemistry which, he
was inclined to think, was virtually completed with his own investigations.
Thomsen's first contribution to thermochemistry was purely theoretical,
28 M. Berthelot, 'Sur la reclamation de priorite elevee par M. J. Thomsen relativement aux

principes
de la thermochimie,' Bul. soc. chim.Paris, 1873, 19, 485-489.
29 According to A. Wurtz (ed.), Dictionnaire
de chimie,Paris, 1869-1870, II, 824.
30 See, e.g., the views of Paul Sabatier, Victor Grignard and Pierre Duhem as quoted in M. J.
Nye,
'Berthelot'santi-atomism: a 'matter of taste'?'Annalsof science,1981, 38, 585-590. Also in A. Metz, 'La
notation atomique et la theorie atomique en France a la fin du XiXe siecle,' Revued'historiedessciences,
1963, 16, 233-239, on 236.
31 In obituary articles the personality of the deceased is often idealized. In Edward Thorpe's
memorial lecture one reads however about Thomsen's 'cold and unsympathetic nature [which] evoked
no warmer feelings.' E. Thorpe, 'Thomsen memorial lecture,'7. Chem.Soc.London,1910, 97, 161-172,
on 165. Similarly Niels Bjerrum,a student of Thomsen: 'Thomsen was of a vehement and fiery nature.
He could rise against his opponents quite without self-command . . .,' N. Bjerrum, 'Julius Thomsen',
Chem.Ber., 1909, 42, 4971-4988, on 4977.
262
Helge Kragh
making use of hypotheses and imaginative reasoning. But he soon

developed a predilection for the art of experimenting and took a pride in
performing very accurate measurements. Indeed, Thomsen often
expressed a strong, and sometimes naive, confidence in the value of
experiments in deciding crucially between competing theories. He did not
recognize that his own experiments were far from pure observations and
that any conclusion derived therefrom involved in fact a complicated
network of theoretical assumptions. Thomsen's 'experimenticist' predilection32 and mistrust of hypotheses in chemistry is reflected in his controversies with Berthelot and other chemists over the significance of thermochemical measurements.
Thomsen's attack of 1872-73 on Berthelot's methods and scientific
credibility was reiterated in 1878.33 Thomsen claimed that Berthelot was
not only a bad experimenter but also a biased scientist who judged
experimental values according to whether they agreed or not with his own
doubtful hypotheses. Berthelot, on his side, not unexpectedly criticized
Thomsen's measurements for being inaccurate and uninteresting.34 Favre,
the Parisian veteran in thermochemistry, assisted Berthelot's cause by
hinting that Thomsen's confirmation of the variation of the heat of reaction
with temperature (Kirchoff's equation) was not an original work as it
illegitimately relied on results first found by Favre.35 The persistent rivalry
between Thomsen and Berthelot can be followed through many of their
publications in the period 1872-1886. Neither of the two chemists wasted
an occasion to point out the bad methods, illegitimate conclusions and
inaccurate measurements of the other; or, conversely, to claim their own
priority and competence. Instead of applying the results and methods of
each other they jealously stuck to their own works and referred to the other
mainly for the purpose of criticism. As a result of Thomsen's anti-French
feelings Berthelot's bomb calorimeter for combustion in oxygen was never
introduced in Thomsen's laboratory. Despite its advantages Thomsen
would not accept the use of an apparatus developed by his Parisian rival.
While Thomsen was aggressive and published several anti-Berthelot
papers, the powerful Berthelot could afford the more discrete tactics of
almost ignoring his colleague in Copenhagen. In Berthelot's voluminous
writings on thermochemistry, Thomsen appears only as a very secondary
and provincial figure.
In France Thomsen's case was supported by Pierre Duhem who had
32 Experimenticism is the extreme empiricist doctrine that experiments and accurate measurements
have absolute priority in the analysis of scientific work. The term was introduced and exemplified by
Gerald Holton in 'Einstein and the 'crucial' experiment,' Am.j. phys., 1969, 37, 968-982.
33 J. Thomsen,
'Ueber Genauigkeit thermochemischer Zahlenresultate,' Chem. Ber., 1878, 11,
2183-2188.
34 M. Berthelot, 'Sur la chaleur de dissolution du sulfate de soude,' Ann. chim.phys., 1878, 14, 445-452.
35 M. P. A. Favre, 'Reclamation relative a une note de M.J. Thomsen,' Bul. soc. chim. Paris, 1874, 21,
487.
263
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.
264
HelgeKragh
closely linked to German science; all of his major publications, including

the attacks on Berthelot, appeared in German.
III
A major part of Thomsen's thermochemical programme was directed to
the problems of structural chemistry, in particular in organic chemistry.4'
The general idea was to establish a connection between, on one hand, the
assumed structure of a compound and, on the other hand, its heat of
formation. Thomsen argued that when such a connection was established,
comparison between the calculated value and the experimental value of
the heat of formation of the compound in question would provide a test for
theories of molecular structure. In order to work out this idea Thomsen
made use of the general principles of thermochemistry and assigned
definite thermal values, or strengths of affinity, to the various types of
chemical bonds, irrespective of their position in the molecule. These
thermal values were determined from the heats of formation of molecules of
known structure which again were based on the experimentally known
heats of combustion. For example, the heats of formation at constant
volume of ethane and methane were found to be, in Thomsen's notation,
(C2,H6) - 104 2 kcal and (C,H4) = 59-6 kcal. Denoting the thermal value of
a single bond between two carbon atoms with v, and that of a bond
between carbon and hydrogen with r, Thomsen assumed that (C,H4) = 4r
and (C2,H6)= 6r+v, which leads to the result that v, is 14 8 kcal.
Following this kind of reasoning Thomsen concluded that the amounts of
heat which correspond to a single and a double bond are approximately
the same and furthermore close to the thermal value of the C-H bond. The
thermal value of the triple bond was found to be almost zero. This led to the
rather strange conclusion that if two carbon atoms are united by two
bonds, no energy is required to break one of the bonds; and in triply bound
carbon atoms no energy is set free by their union. Thomsen thus thought to
have shown that compounds which contain double or triple bonds
according to the usual view, are, in fact, saturated. He also thought that his
thermochemical method was able to settle the question of the structure of
benzene.
This was one of the most discussed questions of structural chemistry,
especially after 1866 when Kekule published his famous hexagon formula
with alternating double and single bonds.42 Although Kekule's proposal
remained the most favoured throughout the century it was contested from
many sides. One of the alternatives which attracted considerable interest
was due to Albert Ladenburg who in 1869 proposed a prismatic structure
41 J. Thomsen, 'Thermochemische
Untersuchungen
uber die Theorie der Kohlenstoffverbindungen,' Chem. Ber., 1880, 13, 1321-1334; ThermochemischeUntersuchungen,op. cit. (12), IV.
42
A. Kekule, Lehrbuchder organischenChemie, 2 vols., Erlangen, 1866, II, 496.
265
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.
266
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.
267
In a sharp and detailed criticism Bruhl characterized Thomsen's theory as

biased and totally out of contact with chemical reality.56
Thomsen's reputation, and with it his conception of thermochemistry,
was shaken by the negative reception of his thermo-structural theory.
Wilhelm Ostwald was indebted to Thomsen's works in thermochemistry
which he ranked highly; he now asked if Thomsen's science had met its
Waterloo in its attack on organic molecules.57 Ostwald thought yes.
Naturally Thomsen was deeply affected by the criticism of Stohmann,
Bruhl and others, especially as his competence as an experimenter was
questioned while the organo-thermochemical measurements of Berthelot
and his group did not meet with a similar criticism. But Thomsen was
unwilling to accept any shortcomings of his own. He continued to claim his
superiority also in the theory and practise of organic thermochemistry,
complaining that his results were ignored while those of Stohmann and
Berthelot and his pupils were accepted.58 When the American Frank W.
Clarke in 1903 proposed a new thermochemical theory of organic
substances which differed from Thomsen's, the ageing Thomsen rejected it
as speculative, biased and useless.59His rejection had the character of a deja
vu as it contained the very same methodological objections which were
raised against his own theory some twenty years earlier.
Thomsen's conservatism was nourished by his unfriendly character
and preference for isolation. None of the younger generation of chemists
had much contact with Thomsen who did not at all like the new wave in
chemistry which threatened to make his life-work obsolete. For example, in
1887 Ostwald and Walther Nernst were able to point out a serious error
in Thomsen's old determination of the heat of formation of mercury
compounds.60 Ostwald argued from general and theoretical reasons that
Thomsen's determination had to be wrong and asked Nernst to redetermine the heat developed when mercury unites with bromine. Nernst
obtained a result which differed substantially from Thomsen's which was
based on his theory of thermal affinity. Although Thomsen at once
56J. W. Bruhl, 'Kritik der Grundlagen und Resultate der sogenannten Theorie der Bildungswarme
organischer Korper,' J. prakt.Chemie,1887, 35, 181-204, 209-236.
57 W. Ostwald, Zs. phys.Chemie,1887,1,201. Most of Ostwald's early contributions to chemistrywere
in the tradition of Thomsen whose approach to the problem of affinity inspired him much. For
3 vols., Berlin,
EineSelbstbiographie,
Ostwald's indebtedness to Thomsen, see W. Ostwald, Lebenslinien.
1926.
58Thomsen sought, apparently in vain, to convince Ostwald that his thermochemical data on
organic substances were superior to those of Berthelot and Stohmann and ought to be republished in
Chemie.Referring to the omission of his organic data in the third edition of
Zeitschriftfirphysikalische
TabellenThomsen protestedagainst 'such an outrageous treatment from
physikalisch-chemischen
Landolt's
the side of one of the main worksin German literature.' Letter from Thomsen to Ostwald, January 27,
1905. I am grateful to the Wilhelm-Ostwald-Archiv for sending me copies of the Thomsen-Ostwald
correspondence.
59 F. W. Clarke, 'A new law in thermochemistry,' Proc. Washington
Acad. sci., 1903, 5, 1-37; J.
Thomsen, 'F. W. Clarkes neues thermochemischesGesetz,' Zs.phys.Chemie,1903, 43, 487-493.
60J. Thomsen, 'Thermochemische Untersuchungen, XVII,' J. prakt.Chemie,1874, 11, 261-283; W.
Nernst, 'tYberdie Bildungswarme der Quecksilberverbindungen,'Zs. phys.Chemie,1888, 2, 23-28.
268
Helge Kragh
admitted his error6' he was much annoyed to see his thermochemical

method defeated by the new physical chemistry. In a letter to Ostwald,
Svante Arrhenius reported: 'I have recently received a small letter from
Nernst; he will now travel even farther away from the seriously assaulted
Thomsen. I had hoped that at least his inorganic works could rest in peace,
but it seems not to be so.'62 At the time of the publications of Berthelot's
the high-spots of classical
CChimique
mecaniqueand Thomsen's Untersuchungen,
thermochemistry, several other textbooks on thermochemistry appeared,
signifying what must have seemed the maturing of a successful branch of
chemistry. However, the success was only apparent. In fact classical
thermochemistry, as developed by Thomsen and Berthelot, was a
degenerating research tradition already from about 1880, when it was met
with insurmountable difficulties and increasing criticism. Ten years later
the once so progressive Thomsen-Berthelot approach had virtually
vanished from the research front. In the first volume of Zeitschriftfur
physikalischeChemieLothar Meyer read the epitaph over the approach of
Thomsen and Berthelot. Meyer summarized: 'One has to recognize that
the fundamental hypotheses of the thermal theory of affinity have not been
supported by observation....
Many of the admirers of the thermal theory
of affinity, until a few years ago throned in undisputed majesty far above all
facts, will perhaps find it hard to see it fade away.'63
The concept of chemistry upon which classical thermochemistry
rested was essentially that of mechanical reductionism: i.e., the goal of
chemistry was considered to be the reduction of chemical phenomena to a
level where they could be explained in terms of Newtonian mechanics. By
means of the mechanical theory of heat and the associated theory of affinity
thermochemistry was thought to provide an effective instrument in
reaching that goal. Both Thomsen and Berthelotjustified their thermochemical theories by linking them to the Newtonian ideal. Similar views were
held by other leading thermochemists: strongest, perhaps, by Alexander
Naumann, professor at the university of Giessen, who published the first
textbook in thermochemistry in 1869. Naumann based his account very
closely on the mechanical theory of heat and Berthelot's principle of
maximum work. He stated that 'The mechanical theory of heat seems
.. . to be the most appropriate path in order to make chemistry approach
its final goal, to formulate it as a mechanics of atoms.'64 A similar view was
61 Thomsen,
Zs. phys.Chemie,1888, 2, 21-22; letter from Thomsen to Ostwald, December 12, 1887
(Wilhelm-Ostwald-Archiv).
62 H-G. Korber (ed), Aus demwissenschaftlichen
BriefwechselWilhelmOstwald,2 vols., Berlin(GDR),
1961, II, 41.
63 L. Meyer, 'Die bisherigen
der
Entwickelung
Affinitatslehre,'Zs. phys.Chemie,1, 1887, 134-144, on
140 and 143.
64 A. Naumann, Grundriss
der Thermochemie,
Braunschweig, 1869, 2. An extended and updated
version of Naumann's work, much in use in Germany, appeared in 1882 as Lehr-undHandbuchder
Thermochemie.
Friedrich Mohr wrote on chemical affinityin the same vein, see his Mechanische
Theorieder
chemischen
Affinitdt,Braunschweig, 1868.
269
expressed by Jahn, whose exposition of thermochemistry was strongly

indebted to the works of Thomsen. However, although Jahn saw
thermochemistry as a method for explaining affinity in terms of a
mechanics of atoms, he considered atoms to be methodological entities, not
ontological ones. 'Atomism is not a dogma; it by no means states anything
about the real constitution of matter but is a view which allows a
description of the phenomena in complete correspondence with observations.'65 Jahn's anti-ontological atomism shows that classical thermochemistry, although founded upon the mechanical theory of heat, could
well be conceived as indifferent as to the reality of atoms. That, in any case,
was the view of Berthelot. He was a staunch advocate of mechanical
chemistry but did not accept atoms as the ultimate building blocks of
matter and certainly not as the precondition for a rational thermochemistry.66
Atomism or not, the foundation of classical thermochemistry was the

Thomsen-Berthelot principle which gradually turned out to be untenable.
Already in 1864 the Dutch scientist Schroder van der Kolk argued that
many chemical processes are not in accordance with the Thomsen-Berthelot principle and that the energy is only one component among others in
the measure of chemical affinity. Van der Kolk demonstrated that the
results of Sainte-Claire Deville on incomplete thermal dissociation of
compounds67 were incompatible with the thermochemical concept of
affinity and concluded that 'affinity and heats of combination are
impossible to deduce from each other.'68 The objections of van der Kolk
made no more impact on thermochemical orthodoxy than did other
contemporary criticism, such as the arguments of Guldberg and Waage. In
the seventies other critical voices were raised with increasing intensity.
Lord Rayleigh pointed out that the thermochemical theory of affinity did
not accord with the theory of energy dissipation, and criticized chemists for
not recognizing the importance of the second law of thermodynamics.69
The Russian chemist Alexei Potilitzin, an assistant to Mendeleev, attacked
the Thomsen-Berthelot principle from an empirical position, arguing that
it could not possibly account for the existence of endothermic and
reversible reactions.70 In the early eighties the weight of these and other
objections were generally acknowledged and the confidence in the
thermochemical theory of affinity rapidly faded away. Pattison Muir
expressed a general view when passing the following sentence over the
65Jahn, op. cit. (50), 205.
66 M. Berthelot, 'Atomes et equivalents,' Comptesrendus, 1877, 84, 1269-1276. M. J. Nye, Molecular
reality, London, 1972, 7. See also Levere, op. cit. (1), 207-211 and Nye, op. cit. (30).
67 H. Sainte-Claire Deville, Lecons sur la dissociation, Paris, 1866.
68 H. W. Schroder van der Kolk, 'Ueber die mechanische Energie der chemischen Wirkungen,'
[Poggendorf's] Annalen, 1864, 122, 439-454, on 452.
69 Lord Rayleigh, 'On the dissipation of energy,' Nature, 1875, 11, 454-455 (Royal Institution
lecture).
70 A. Potilitzin, Chem. Ber., 1879, 12, 2369-2374.
270
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
For a decade or so thermochemical orthodoxy sought to maintain its

former authority, coexisting with its young progressive alternative,
physical chemistry, but keeping to its own standards.76 Eventually the
71 Pattison Muir, op. cit. (37), 446. For other contemporary criticism, see B.
Rathke, 'Ueber die
Principien der Thermochemie,' Abhandl.d. Naturf. Ges. zu Halle, 1882, 15, 197-227; L. Meyer, Die
modernen
Theorien
derChemie,4th edn., Breslau, 1883; P. Duhem, Lepotentielthermodynamique,
Paris, 1886.
72 Thomsen, op. cit. (27), 428.
73 In particular through the works of Helmholtz and van't Hoff. H. Helmholtz, 'Zur Thermodynamik chemischer Vorgange,' Sitzungsber.
Akad. Wiss. Berlin, 1882, 1, 21-39, 825-836. J. H. van't Hoff,
Etudesde dynamique
chimique,Amsterdam, 1884.
74 Thermochemische
Untersuchungen,
op. cit. (12), II, 1883, 428.
75 In 1894 Berthelot admitted that the principle of maximum work has no general validity; he argued
that it was a primitive version of the law of entropy. M. Berthelot, 'Le principe du travail maximum et
l'entropie,' Comptesrendus,1894, 118, 1378-1392.
76 The controversybetween thermochemistryand thermodynamically based physical chemistrywill
be the subject of a forthcoming paper of R. G. A. Dolby. I am grateful to Dr. Dolby for his critical
remarks to earlier versions of the present paper.
J7ulius Thomsenand Classical Thermochemistry
271
inadequacy of classical thermochemistry was realized even by the few

chemists who still worked within the tradition founded by Thomsen and
Berthelot. Writing in 1903 Clarke tersely remarked that 'Few general
conclusions of unimpeachable validity have been developed by thermochemical research, and so, of late years, the entire subject has fallen somewhat
in disfavor.'77 Considered as front research classical thermochemistry had
ceased to exist at about 1910.
V
In retrospect the history of classical thermochemistry is the history of the
successful emergence, less successful defense and then gradual decline of a
scientific idea until it was transformed and, in a new context, incorporated
in a new powerful paradigm. Eventually the thermochemical concept of
affinity disappeared without much ado. Evidence incompatible with it had
been known for decades but the theory was not rejected simply as the result
of counter-evidence and no crucial experiment was accepted as a falsifying
instance. Rather the theory gradually lost its power and scientific interest
under the combined pressure of accumulated empirical counter-evidence,
conceptual criticism and new forms of scientific style. The thermochemical
theory of affinity was not given up because it was replaced by another and
better theory of affinity. The entire concept of affinity, for a century and a
half regarded as a crucial problem in chemistry, seemed to have lost its
magic; at the turn of the century it was no longer considered interesting to
search for measures or models of chemical affinity.
The transformation of classical thermochemistry into chemical
thermodynamics is in many respects representative for scientific change.
Chemical thermodynamics a la Duhem or Gibbs was not merely a critical
development of thermochemistry a la Thomsen or Berthelot but, conceptually and stylistic, rather its negation. The change was not abrupt or
complete but a process, or conflict, which lasted several years; and it was, at
the same time, a generational conflict in which the younger generation
developed its own paradigm which the older thermochemists would
neither understand nor accept. Leading thermochemists like Thomsen and
Berthelot had invested too much of their scientific prestige in orthodox
thermochemistry to change to a new rival paradigm. Like most other
chemists they lacked the mathematical background which could have
helped them in appreciating the works of e.g. Gibbs. There were,
furthermore, significant differences between the scientific world views of
classical thermochemistry and the emerging physical chemistry. Thus the
ideas of physical chemistry were based on an anti-mechanist and
anti-reductionist programme which was opposed to the Newtonian ideal of
the Thomsen-Berthelot approach. As regards Thomsen, the anti-atomism
77 Clarke, op. cit.
(59), 2.
272
Helge Kragh
of many physical chemists was contrary to his deep-rooted belief in the

reality of atoms. Although Berthelot shared the anti-atomism-but
not the
anti-mechanism
of Ostwald, Duhem and others, his view on chemistry
was incompatible with that of physical chemistry. According to Berthelot
physics and chemistry were separate sciences, with separate aims and
methods.78 He believed that progress in chemistry could be ensured by
widening the gulf between physics and chemistry; not by narrowing it as
was the programme of physical chemistry. A programme to which
Thomsen, for his part, had no objections.
78
Nye, op. cit. (30).
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Cambridge University Press

Julius Thomsen and classical

Classical thermochemistry is inextricably bound up with the problem of

thermochemical conception of affinity, Hess' calorimetric studies were not

Julius Thomsenand Classical Thermochemistry

means of thermochemical measurements and thus supply the vague

processes where the substances combine in definite proportions, according

12 In the Danish version of 1852 a purely chemical action was stated to

Julius ThomsenandClassicalThermochemistry 259

quantity is a constant, depending only on the terminal states of the system.

Julius Thomsenand Classical Thermochemistry

from those stated by Thomsen.28 Berthelot declared that Thomsen's

28 M. Berthelot, 'Sur la reclamation de priorite elevee par M. J. Thomsen relativement aux

making use of hypotheses and imaginative reasoning. But he soon

Julius Thomsenand Classical Thermochemistry

closely linked to German science; all of his major publications, including

Julius Thomsenand Classical Thermochemistry

Julius Thomsenand Classical Thermochemistry

In a sharp and detailed criticism Bruhl characterized Thomsen's theory as

admitted his error6' he was much annoyed to see his thermochemical

Julius Thomsenand Classical Thermochemistry

expressed by Jahn, whose exposition of thermochemistry was strongly

Atomism or not, the foundation of classical thermochemistry was the

For a decade or so thermochemical orthodoxy sought to maintain its

J7ulius Thomsenand Classical Thermochemistry

inadequacy of classical thermochemistry was realized even by the few

of many physical chemists was contrary to his deep-rooted belief in the

Nye, op. cit. (30).

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