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The strange case of Dr. Petit and Mr. Dulong Roberto Piazza Dipartimento di Chimica, Materiali ed Ingegneria Chimica Politecnico di Milano, Piazza Leonardo da Vinci, 32 - 20133 Milano Abstract Petit (DP) limiting law for the (vibrational) specific heat was one of Boltzmann’s great achievements. The Dulong-Petit limiting law for the specific heats On the other hand, evidence of the crushing failure of solids, one of the first general results in thermo- of the DP law at low temperatures, besides giving dynamics, has provided Mendeleev with a powerful support to Nernst’s Third Law of thermodynamics, tool for devising the periodic table and gave an im- motivated Einstein to introduce quantum concepts portant support to Boltzmann’s statistical mechan- in condensed matter physics and Debye to develop a ics. Even its failure at low temperature, accounted consistent vibrational theory of the heat capacity of for by Einstein, paved the way to the the quantum solids [2]. Even today, the study of the anomalous mechanical theory of solids. These impressive con- behavior of the specific heat close to a quantum sequences are even more surprising if we bear in critical point has granted the DP law a “second mind that, when this law was announced, thermal wind” [3]. phenomena were still explained using Lavoisier’s The accomplishment of Dulong and Petit is even concept of caloric and Dalton’s atomic theory was more remarkable when framed within the histori- in its infancy. Recently, however, bitter criticisms cal and geographical context in which it was ob- charging Dulong and Petit of ‘data fabrication’ and tained. At that time thermodynamics, still in its fraud, have been raised. This work is an attempt infancy, was based in France on the caloric theory to restore a more balanced view of the work per- of Lavoisier and Laplace, Dalton had introduced his formed by these two great scientists and to give atomic theory less than two decades earlier, and Ja- them back the place they deserve in the framework cob Berzelius had published a first table of atomic of the development of modern science. weights only six years before [4, 5]. Besides, quan- titative values of the “capacity for heat” of bod- ies, a concept that had slowly developed in the late 1 Introduction XVIII century from the discovery of latent heat by the (French–born) Scottish chemist Joseph Black, On 19 April 1819 Pierre–Louis Dulong appeared were still rather inaccurate. Indeed, the advance- before the Acad´emie des Sciences in Paris to read ments both in the experimental methods and in a paper, jointly prepared with Alexis-Th´er`ese Petit, data interpretation that, as we shall see, paved the which was going to stand as a fundamental step in way to the final discovery by these two young scien- statistical physics [1]. What Dulong and Petit had tists (Dulong was 34, and Petit just 27), are truly found was, in their own words, that “the atoms of impressive. And yet. arXiv:1807.02270v1 [physics.hist-ph] 6 Jul 2018 all simple bodies have exactly the same capacity Yet, in the data presented by Petit and Dulong to for heat”1 or, more specifically, that the product of support their revolutionary finding there is some- the specific heat of 13 chemical elements times their thing odd, something that does not line up com- atomic mass (hence the molar specific heat) was pletely. Elusive concerns in contemporary accounts approximately constant. As a matter of fact, the and even in authoritative studies of their life and justification of what is now known as the Dulong– work [6, 7, 8] recently progressed to the stage of 1“Les atomes de tous les corps simples ont exactement la questioning the scientific integrity of the two scien- mˆeme capacit´epour la chaleur”. tists, even of blaming them of fraud and “data fab- 1 rication” [9]. To be true, these harsh remarks seem to give you a couple of hints, you should find out to have been confined to a rather restricted audi- that: ence2. So, I regarded as useful to bring it to the 1. Even the most trivial check, namely that Col- attention of physicists, perhaps from the slightly umn 1 × Column 2 = Column 3 fails in one different perspective that I may have of the devel- case; opment of scientific ideas. 2. Much worse, even if the value of the atomic weight of at least two of the elements is largely wrong, the corresponding molar specific heats in Column 3 are quite close to modern values. Which means of course that there are com- pensating errors in the experimental values of Column 1. There are also some additional puzzling values that, with a deeper investigation, you may have discover and that we shall discuss later. In any case, if you have done the exercise, you may understand why it did not take me long before falling in a state of deep consternation, concluding that either a) there was something fishy, or b) my neurons have already sub- Figure 1: Data used by Petit and Dulong to derive limated more than I am aware of. Although the sec- their law (for convenience of the English readers, I ond possibility could not definitely be excluded, I plot the version published in the contemporary trans- went into a rather frustrating bibliographical search lation of Ref [1] that appeared in the Annals of Philos- that lead me to discover just a single paper written ophy [10]). in 2002 by Carmen Giunta, a professor in chem- istry at Le Moyne College in Syracuse, with the Before venturing into this enterprise, rather de- rather severe and accusatory title “Dulong and Pe- manding for a physicist on the job who does not tit: a case of data fabrication?” [9]. Although, as pretend at all to be a professional in historical is- you will see, I do not share Giunta’s bitter criti- sues, let me however tell you how I became aware cism, I think that this work has not attracted the of this strange story. While teaching statistical attention it deserves3. To avoid jumping to rushed physics in my university I have always found ex- conclusions, I had to embark upon a rather long in- tremely helpful to complement my technical pre- vestigation that arguably provided me with a more sentation of a subject with some historical remarks balanced perspective of this story, and which I hope that students generally appreciate. The very early you may wish to follow. Let us first introduce the stage at which the DP law was obtained has always two main characters we shall deal with. intrigued me, hence I decided, while writing the En- glish version of my notes [11], to investigate a bit more the matter by reading the original paper by 2 A hapless physician and a Petit and Dulong. As an experimentalist, the first thing I did was of course checking the data that boy wonder they presented in the table reproduced in Fig. (1), Life was not kind to Dulong, at least at the be- comparing at the same time their values for atomic 4 ginning. Born in Rouen on February 13, 1785 , or- weights and molar specific heats (at constant pres- phaned at the age of four, he was raised by his aunt sure) with modern ones. As an appetizer, my read- ers may want to to repeat the same exercise. Just 3Giunta’s paper was actually presented at the 221st Na- tional ACS Meeting with the (not much lighter) title “Du- 2So far, I have not found any colleagues aware of this long and Petit: a Case of Scientific Misconduct?”. diatribe, with the exception of Albert Philipse, a valuable 4Most biographical accounts, and Wikipedia too, state Dutch chemist at the van ‘t Hoff Laboratory in Utrecht, with that Dulong was born on February 13, but this is a long- whom I share the curiosity for the history of science. standing historical mistake. See the results of the detailed 2 and godmother Mme Faurax in Auxerre, where she Laplace included among its members great physi- took care of his education “with all the tenderness cists such as Biot, Gay–Lussac, Arago and Pois- of a mother” [13]. Mostly by dint of his own efforts, son, was at that time a stronghold of Lavoisier’s he prepared himself for the Ecole´ Polytechnique at caloric theory, where the “vibrational” (kinetic) Paris and matriculated at sixteen, the minimum theory of heat was strongly opposed and Dalton’s entrance age. Yet, his studies at the Ecole´ were atomic theory was still far from being generally ac- plagued by sick leaves that prevented his admis- cepted [8, 4]: The discovery by Dulong and Petit sion to the artillery corps, so that he was eventually was going to change this mood drastically. In Ar- forced to abandon the Ecole´ without completing cueil Dulong performed his first important chemi- the course. Dulong’s impaired physical condition cal study in which he extended Berthollet’s studies turned his attention to medicine, which in those of salt decomposition to show that also insoluble days did not require lengthy or deep studies5. Yet, salts are capable of exchanging constituents with this did not turn out to be a good choice, at least soluble electrolytes [15], a study that fostered the financially. He started practicing medicine in one of development of the law of mass action [6, 16]. Du- the poorest neighborhoods of Paris 12th arrondisse- long began to gain a reputation as a brilliant and ment, where, according to Arago [14], extremely careful experimentalist swiftly.

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