Abstract
The idea of atoms as forming the ultimate constituents of matter already arose in the great speculative or philosophical minds of the ancient world, although no exact chemical or physical atomic theory actually evolved from it at the time, and although, most importantly, there was no direct evidence for it. The fundamental questions were: What are the chemical elements? What are the basic units which carry the identity of a chemical element? Can matter be divided indefinitely while still preserving its identity?
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- 1.
In some places it is claimed that Aristotle preached that we have to learn from experience. Experience is, however, not the same as an experiment which is carried out under controlled conditions. The ratio between the frequencies of string vibrations was probably found by Pythagoras and his students, and this is considered by many to constitute the first experiment.
- 2.
The so-called razor due to William of Ockham (1285?–1349) is the philosophical principle that, of all possible explanations of a phenomenon, the simplest is most probably the best one. Of course, this principle cannot be proven rigorously. We must ‘take it or leave it’.
- 3.
Even today, an hypothesis is often accepted or rejected by popular vote, i.e., according to the number of scientists who believe it. See, for example, the idea that anthropogenic \(\mathrm{ {CO}}_2\) causes global warming, while no evidence exists to support this quite common conjecture, and one group of scientists even tried to massage the data so as to ‘prove’ it. On the other hand, scientific revolutions are caused just when a single scientist attempts to disclaim a scientific dogma.
- 4.
For more detail on the ancient atomic theory, see Partington, J.R., Annals of Science 4, 245 (1939).
- 5.
Ray, P.C., A History Of Hindu Chemistry V1: From The Earliest Times to the Middle of the Sixteenth Century A.D., Calcutta, The Bengal Chemical and Pharmaceutical Works, Ltd., 1903. The book contains translations of relevant texts from oriental languages to English.
- 6.
Craig, D.H., Ben Johnson: The Critical Heritage, London, Routledge, 1999.
- 7.
Lavoisier, A., Traité Elémentaire de Chimie, Cuchet, Paris, 1789.
- 8.
As scientists could not make a living from doing research alone, Lavoisier, like Fourier after him, became a member of the Fermiers Généraux. This General Farmers association was a private company with 60 members which had at its disposal a fortune of about 100 million pounds. Every 6 years, the company negotiated with the royal treasury the right to collect tax and customs duties. Obviously, this company and its members were not very popular, to put it mildly. Lavoisier’s immense scientific reputation did not save him on Judgement Day, and his job as tax collector cost him his life: he was guillotined in 1794, during the French revolution.
- 9.
There is a controversial claim regarding the extent to which Robert Boyle (1627–1691m) recognized the fundamental nature of a chemical element. See Knight, D., Ideas in Chemistry: A History of the Science, Cambridge University Press, 1992.
- 10.
One sometimes sees erroneous definitions of chemical elements as ‘pure chemical substance’ (see, for example, in Wikipedia). We adopted Lavoisier’s definition here, although we did not define what exactly was meant by ‘a method of chemical analysis’. The atoms of an element are complex systems that exist over a certain range of temperatures and densities, and in certain environments. So a chemical element can exist only if chemistry itself actually exists. In the cores of stars, for example, all atoms are crushed by the pressure, and there is no chemistry to speak of.
- 11.
On the other hand, it is not clear today whether the dark energy and dark matter postulated to explain the structure of galaxies and the expansion of the Universe are matter in the normal sense or merely an expression for our ignorance of some fundamental physical law.
- 12.
Scheele, C.W., Chemische Abhandlung von der Luft und dem Feuer, Upsala und Leipzig, Verlegt von Magn. Swederus, Buchhändler; zu finden bey S.L. Crusius 1777.
- 13.
Wenzel, K.F., Lehre von der Verwandtschaft der Körper, Dresden, 1777.
- 14.
Richter, J.B., Anfangsgründe der Stöchyometrie oder Messkunst chymischer Elemente, Breslau und Hirschberg 1792–1793. Reprint Hildesheim 1968.
- 15.
Note that we stress mass ratios and not number ratios. This is a fundamental point. Fixed mass ratios do not necessarily lead to the atomic hypothesis, but fixed ratios of integers do.
- 16.
Wenzel and later Richter published some inaccurate results and interpretations. This had to do with the conservation of electric charge in the dissociation of salts. See, for example, Wollaston, W.H., Phil. Trans. Roy. Soc. London 104, 1 (1814). Consequently, they lost their credentials as chemists and it was only Berzelius who recognized their achievements about twenty years later. It is not absolutely clear to whom the credit for the discovery of the law of proportionality should go. Does the announcement of a correct law on the basis of incorrect experimental interpretation deserve full recognition? See A History of Chemical Theory, Wurtz, MacMillam and Co. London, 1869. But the idea was good so why was it ignored? Szabadváy (Szabadváy, F., J. Chem. Educ. 39, 267, 1962) suggests that Richter began his book with an attempt to teach chemists simple arithmetic, e.g., explaining things like the simple plus sign. If you treat your fellow practitioners with such disdain, do not be surprised to find they ignore you.
- 17.
In contrast to Lavoisier, Berthollet served the revolutionary government as an adviser and emerged from the French Revolution unharmed. Later he joined Napoleon on his trip to Egypt, where he did the research reported later in his book Essay on Chemical Equilibria.
- 18.
Cato Maximilian Guldberg (1836–1902) and Peter Waage (1833–1900) suggested the law of mass action in 1864 (Forhandlinger: Videnskabs-Selskabet i Christiana 35, 1864). In 1877, van ’t Hoff (1852–1911m) (Berichte der Berliner Chem. Ges. 10, 1877) rediscovered the law without knowing about the earlier discovery by Guldberg and Waage, which was published in Norwegian. In 1879, Guldberg and Waage decided to republish the paper in German (Erdmann’s J. für Prac. Chem. 127, 69, 1879) in order to claim the discovery. The law of mass action says that, when a chemical reaction is in dynamic equilibrium, e.g., \(A+B \rightleftharpoons C\), then \(K(T)=[A][B]/[C]\) is a constant which depends only on the temperature and pressure. Here \([X]\) denotes the concentration of the species \(X\).
- 19.
In conducting this research, Berthollet was assisted by his student Joseph Louis Gay-Lussac, with whom he was engaged in experiments in the laboratory as well as in a balloon flight to a then record height of 23,000 feet. Gay-Lussac and others, including Louis-Jacques Thenard, Jean-Baptiste Biot, Pierre-Louis Dulong, and ultimately Jacques-Etienne Bérard, constituted the active chemical group of the Société d‘Arcueil, all inspired by the older academicians Berthollet and Laplace. The proceedings of the society were published in three volumes between 1807 and 1817 as Mémoires de la Société d‘Arcueil.
- 20.
Gay-Lussac grew up during the French Revolution, and his education was disrupted when his private tutor ran away and his father was imprisoned. However, Gay-Lussac took advantage of the new order when he was chosen to attend the Ecole Polytechnique, the institution that the French Revolution designed to create the leading scientific and technical cadre, especially for the military. Gay-Lussac’s mentors at the Polytechnique, Laplace and Berthollet, urged him to pursue a research-academic career, which he began shortly after graduation in 1800.
- 21.
Gay-Lussac, J.L., Mém. de la Soc. d’Arcueil 2, 207 (1809)
- 22.
von Humboldt, A. and Gay-Lussac, J.F., Ann. der Physik 20, 129, 1805.
- 23.
Thomson, T., A System of Chemistry, Edinburgh, 1807.
- 24.
Thomson had private communication with Dalton, in which Dalton provided him with a copy of A New System of Chemical Philosophy, which he published only a year later. Thomson gave all the credit to Dalton.
- 25.
Proust, J.L., Ann. de Chim. 23, 101 (1797), ibid. 32 (1799).
- 26.
Nonstoichiometric compounds appear mainly among the transition elements which are used in solid-state electronic devices, such as rectifiers, thermoelectric generators, photodetectors, thermistors, and magnets useful in high-frequency circuits.
The existence of nonstoichiometric compounds which led Berthollet astray is related to the presence of defects in the lattice structures of crystalline substances. For example, a sodium chloride crystal in which one of the locations is occupied by a neutral sodium atom rather than a sodium ion. Another example is the FeO crystal with some vacancies (missing oxygen atoms at some location) leading to \(\mathrm{ {Fe}}_{0.95}\mathrm{ {O}}\). Most nonstoichiometric compounds have compositions that are close to those of stoichiometric compounds.
- 27.
Proust, J.L., J. de Phys. 55, 335 (1802).
- 28.
Kapoor, S.K., Berthollet, Proust, and proportions, Chymia 10, 53 (1965).
- 29.
Dalton was also known for his extensive meteorological observations and the rediscovery of the Hadley circulation in the atmosphere, as well as research on color blindness.
- 30.
Richter, J.B., Ueber die Neuren Gegenstande der Chimie, Breslau, 1791, Anfangsgrunden der Stoichiometrie, 1792–1794 (Basics of Stoichiometry).
- 31.
Dalton, J., Memoirs Literary Phil. Soc. Manchester, Second Ser. 1, 271 (1805); reprinted in Foundations of the Atomic Theory: Comprising Papers and Extracts by Dalton, William Wollaston, and Thomas Thomson, Alembic Club Reprints No. 2, The Alembic Club, Edinburgh (1899) p. 15.
- 32.
Hydrogen peroxide, \(\mathrm{ {H}}_2\mathrm{ {O}}_2\), was first discovered by Louis-Jacques Thenard (1777–1857) in 1818. However, it did not change the fact that the ratio of volumes is 2:1 or 1:1, i.e., always a ratio of two integers.
- 33.
Dalton, J., A New System of Chemical Philosophy 1, Manchester, London, printed by S. Russel for R. Bickerstaff, 1808.
- 34.
Berzelius, J.J., Annals of Phil. 2, 443 (1813).
- 35.
There is a long discussion and some surprises in Dumas’ book Lecons sur la Philosophie Chimique, Bechet Jeune, Paris, 1837, based on his lectures at the Collège de France.
- 36.
Another source of conflict was the equation for water. Berzelius said \(\mathrm{ {H}}_2\mathrm{ {O}}\), while Dalton assumed HO.
- 37.
Dalton, J., A New System of Chemical Philosophy, Manchester, 1808.
- 38.
Proust J.L., Ann. de Chim. 28, 213 (1798), and the English abstract Nicholson J. 2, 515 (1799).
- 39.
Thomson, T., A System of Chemistry, 4 vols. Edinburgh, 1802.
- 40.
Dalton, J., Phil. Mag. 14, 169 (1802).
- 41.
Higgins, W., Experiments and Observations on the Atomic Theory and Electrical Phenomena, Graisberry and Campbell, Dublin, 1814.
- 42.
Higgins, W., A Comparative View of the Phlogistic and Antiphlogistic Theories: With Inductions. To which is annexed, An Analysis of the Human Calculus, Publisher Murray, 1789. In this book, Higgins suggested marking the bonding interaction between atoms and within molecules by a straight line. Like Lavoisier, Higgins did not give up the caloric as he hypothesizes that even when two atoms unite, the compound becomes surrounded with one common atmosphere of caloric \({[\ldots ]}\) and this description is continually mixed with the bonding of atoms.
- 43.
At this point Higgins cited the letter he got from the editor: I shall be glad to see your book though I hope you have not taken Lavoisier’s side of the question or else have defended it by arguments totally unlike any thing that has yet appeared. Dr. Priesley’s late admirable experiments have in my opinion totally overset that doctrine and re-established the existence of phlogiston. Yours faithfully, Thos. Beddoes. The editor was ready to publish only what he believed in!
- 44.
Thomson, T., Annal. Phil. 3, 329 (1814).
- 45.
Higgins, W., The Phil. Mag. XLIX, 241, 1817. The letter to the editor is amazing for its strange style of English: It is stated that this paper, referring to Dalton’s paper, was read before the Literary and Philosophical Society of Manchester in the year 1816. That should lie by since is not to be wondered at, as containing nothing new; it relate to a hackneyed subject, which chemists have lately gone over repeatedly. In that part of my paper which appeared in your excellent Magazine for December 1816, I observed that Dr. Thomson stepped forward repeatedly in a very unjust cause, which could never do him credit, as the advocate of Mr. Dalton, while the latter stood silent trembling as the bar of justice. It could easily be part of a play.
- 46.
A list of several tens of articles dealing with Higgins’ claim can be found in Wheeler, T.S., Studies, An Irish Quarterly Review 43, 327 (1954).
- 47.
Wollaston, W.H., Phil. Trans. Roy. Soc. London 104, 1 (1814).
- 48.
But I could find no reference for it in Wollaston’s paper.
- 49.
Wollaston did not explain in the paper why he chose this name for his scale. It is implied in the paper that this number should provide a good explanation for the chemical properties of the elements and compounds.
- 50.
Avogadro, A., J. de Physique 73, 58 (1811). Alembik Club Reprint no 4.
- 51.
Avogadro was born into a well-known family of lawyers and as such, studied law and even started practising. But his soul was in the natural sciences, and in 1800, he began to study physics. In 1809 he started teaching in a high school and it was while serving as a teacher that he announced his discoveries.
- 52.
Ampère, A-M., Ann. de Chim., 1ère serie xc, 43 (1814). There is a mountain ridge called Mons Ampère on the moon.
- 53.
Anonymous, On the relation between the specific gravities of bodies in their gaseous state and the weight of their atoms, Annals of Phil. 6, 321 (1815). The paper was published anonymously. This is a rare phenomenon. Most frequently you find cases were no citation to a previous discovery is made and the author wants to credit himself for it. Such behavior is a testimony to Prout’s standards, i.e., if you are not sure, you publish anonymously.
- 54.
In 1813 Thomson founded and subsequently edited the Annals of Philosophy.
- 55.
Thomson, T., Annal. Phil. 2, 32 (1813). Thomson announced Dalton’s theory in his 1807 book, a year before Dalton himself published it.
- 56.
How times have changed! Can we imagine an anonymous publication today, motivated by the author’s uncertainty regarding an idea?
- 57.
Anonymous, Annals of Philosophy 6, 321 (1815).
- 58.
\(\pi \rho \omega \tau \eta \mathit{ v}\lambda \eta \) means ‘raw material’, from which the term protyle was coined for a hypothetical primitive substance.
- 59.
Dalton, J., Memoirs of the Literary and Phil. Soc. Manchester 1, 244 (1805). Read before the society 12 November 1802.
- 60.
As the molecular weight of hydrogen is 2, this means that 22.4 l of gas weighs 2 g. The weight of the container is then much greater, and manipulations were needed to determine the weight of the gas accurately. Comparison between the results of different researchers gives a good indication of the degree of accuracy in the weights obtained in those days. The fact that hydrogen gas is made up of molecules containing two hydrogen atoms confused the issue, since only one atom of hydrogen participates in some of the molecules, leading to ‘half molecules’.
- 61.
Berzelius, J.J., Pogg. Ann. vii, 397 (1821).
- 62.
Berzelius discovered the elements cerium in 1803, selenium in 1817, silicon in 1824, and thorium in 1828. Lithium salt was discovered by Berzelius’s student Johan August Arfwedson (1792–1841) in his laboratory in 1817 (pure lithium was isolated by Davy). Another student of Berzelius, Nils Gabriel Sefström (1787–1845), discovered vanadium. Berzelius also suggested the way we write chemical reactions today. Dalton for example, used geometrical symbols, while Berzelius suggested using the first letter of the element, for example, \(\mathrm{ {C}} +\mathrm{ {O}}^2 \rightarrow \mathrm{ {CO}}^2\). Later the superscript became a subscript.
- 63.
Berzelius, J.J., Essay upon the Theory of Chemical Proportions, Ann. of Phil. 2, 443 (1813).
- 64.
Berzelius actually got 17.735 times the weight of hydrogen for the atomic weight of chlorine.
- 65.
Petit, A.T. and Dulong, P.L., Ann. Chim. Phys. 2, 395 (1819). Dulong succeeded Petit as professor of physics, and his name is among the 72 mostly French names engraved on the Eiffel tower. Petit, on the other hand, has a mountain on the moon named in his honor.
- 66.
Almost a century later, in 1912, Debye discovered that every solid has a temperature, the Debye temperature, above which, and only above which, the Dulong and Petit law is valid. In their paper, Dulong and Petit did not provide any information about the temperature range of their measurements. But the Debye temperature, which they were unaware of, is very close in many cases to their supposed range of measurement. For example, \(T_\mathrm{ {Debye}}=470\,\mathrm{ {K}}\) for iron, whence the value they got for iron was doubtful. In other cases like gold, \(T_\mathrm{ {Debye}}=165\,\mathrm{ {K}}\) and Petit and Dulong could easily get an accurate measurement.
- 67.
Neumann, F., Poggendorff’s Ann. Phys. 23, 1 (1831).
- 68.
La Rive, A.A. and Marcet, F., Ann. de Chim. et de Phys. 75, 113, 119, 242 (1840). But their work was criticized by Weber, H.F., Phil. Mag. 49, 161 (1875) as not being sufficiently accurate.
- 69.
Thomson, T., Annals of Phil. I, 1 (1821). This was the last volume of the journal edited by Thomson. In the editorial he explained that he was beginning a laborious course of Chemical Lectures with scarcely any previous preparation, and hence had to relinquish the position of editor.
- 70.
Anonymous, Phil. Mag. 4, 450 (1828).
- 71.
Berzelius, J.J., Lehbuch der Chemie, Dresden, 1820. The book first came out in Swedish in 1808–1818, and was later translated to German by Wöhler.
- 72.
von Meyer, E., A History of Chemistry from Earliest Times to the Present Day, translated from German by McGowan, MacMillan and Co., London, 1906. The original book was published in Leipzig in 1888.
- 73.
Leibig (1803–1873) was a well-known chemist, famous for his analysis of many organic compounds and his theory of organic radicals. He is generally considered to be one of the founders of organic chemistry. However, Leibig’s name went before him in his appetite for scientific controversies. As of 1837, he held the powerful position of editor at Anleitung zur Analyse organischer Körper. So Berzelius’ letter was sent hardly a year after Leibeig took the position as editor. The most famous controversies he was involved in were with Mulder, Wöhler, and Pasteur. We may say that Berzelius certainly sent the letter to the right person.
- 74.
The correspondence was published by Carriere, Pub. Lehmann, Munich and Leipzig, 1893.
- 75.
Thomson, T., Annals of Phil. I, 81, 241 (1821).
- 76.
Thomas, T., Annals of Phil. I, 322 (1821).
- 77.
Eilhard Mitscherlich (1794–1863) was a German chemist, best remembered for his law of isomorphism, which states that compounds crystallizing together probably have similar structures and compositions. This relationship was used by Berzelius in early attempts to assign relative masses to the elements.
- 78.
Berzelius, J.J., Lehrbuch der Chemie, Dresden und Leipzig, 1833.
- 79.
Gmelin, L., Handbuch der Theoretischem Chemie, 1827.
- 80.
von Mayer, J.R., Ann. der Chem. und Pharmacie 43, 233 (1842).
- 81.
Unlike Fourier before him, who served the emperor but continued to be creative in science, Dumas largely abandoned his scientific research and in 1848 went to work for the ministry of education under Napoleon III. Dumas became a member of the National Legislative Assembly, a senator, president of the municipal council of Paris, and master of the French mint. His administrative career came to its end with the collapse of the Second Empire.
- 82.
Dumas, J.B.A., Ann. Chim. Phys. 33, 337 (1826), ibid. 50, 337 (1832).
- 83.
Dumas, J.B., Ann. Chim. Phys. 33, 337 (1826).
- 84.
Dumas realized that the reaction is \(\mathrm{ {H}}_2+\mathrm{ {Cl}}_2\rightarrow 2\mathrm{ {HCl}}\) and not \(\mathrm{ {H}}+\mathrm{ {Cl}}\rightarrow \mathrm{ {HCl}}\). In the first reaction, one volume of hydrogen and one volume of chlorine yield two volumes of HCl. The second reaction implies that one volume of hydrogen plus one volume of chlorine yields only one volume of hydrogen chloride.
- 85.
Dumas, J.B., Leçons sur la Philosophie Chimique, Bechet Jeune, Paris, 1837.
- 86.
This is the author’s free translation of Dumas, p. 231.
- 87.
Dumas, J.B.A., Traité de Chimie, appliquée aux arts, Bechet Jeune, Paris, 1828.
- 88.
Dumas, J.B.A., Ann. Chim. Phys. 55, 129 (1859).
- 89.
Gaudin, M.A.A., Ann. Chim. Phys. 52, 113 (1833). See the strange history of Gaudin’s papers in Cole, T.M., Early Atomic Speculations of Marc Antoine Gaudin: Avogadro’s Hypothesis and the Periodic System, Isis 66, 334 (1975).
- 90.
Marignac, J.C., Pr. Ch. 26, 461 (1842), Ibid., Compt. Rend. 14, 570 (1842).
- 91.
Stas, J.S., Bull. de l’Acad. Roy. de Belge. 10, 208 (1860).
- 92.
Note how the English Channel divided the world of chemistry, according to Stas.
- 93.
Turner, E., Phil. Trans. Roy. Soc. London 123, 523 (1833).
- 94.
de Marignac, J.C., Bull. de l’Acad. Roy. de Belgique, 2nd Séries x, no. 8. Reprinted and translated in its entirety in Alembic Club Reprint no. 20, Prout’s Hypothesis from Bibliothèque Universelle (Archives) 9, 97 (1860).
- 95.
On the request of the poet Coleridge in 1833, Whewell invented the term ‘scientist’. Before this time, the terms in use were ‘natural philosopher’ and ‘man of science’.
- 96.
Whewell, W., History of the Inductive Sciences, in two volumes, New York, Appleton Comp., 1857.
- 97.
Dumas, J.B., Compt. Rend. 45, 709 (1857), ibid. 46, 951 (1858), ibid. 47, 1026 (1858).
- 98.
Strecker, A., Theorien und Experimente zur Bestimmung der Atomgewichte der Elemente, Braunschweif, F. Vieweg, 1859.
- 99.
Cannizzaro, S., Il Nuovo Cimento 7, 321 (1858). The origin was a letter Cannizzaro wrote to a colleague in Pisa, Sebastiano de Luca, a professor of chemistry. The paper in the journal is essentially Cannizzaro’s letter. The title was: Sunto di un corso di filosofia chimica fatto nella R. Università de Genova, which means: Sketch of a Course in Chemical Philosophy at the Royal University of Genoa.
- 100.
Friedrich August Kekulé von Stradonitz is known for discovering the structure of the molecule of benzene, \(\mathrm{ {C}}_6\mathrm{ {H}}_6\), in 1865, long before the details of the chemical bond were known. Bull. Soc. Chim. Paris 3, 98 (1865).
- 101.
Wurz, C-A. Account of the sessions of the International Congress of Chemists in Karlsruhe, 3–5 September 1860.
- 102.
The disarray went far beyond the question of atoms and molecules. There were problems in the structure of organic molecules as well as the naming of these molecules. The mid-nineteenth century saw a dramatic growth in the discoveries of organic molecules.
- 103.
Some idea of the personal quarrels that went on in the congress and why no agreement could be achieved can be obtained from Hartley, H., Notes and Records of the Royal Society of London 21, 56 (1966).
- 104.
Kopp found that the molecular heat capacity of a solid compound is the sum of the atomic heat capacities of the elements composing it. The elements with atomic heat capacities lower than those inferred from the law of Petit and Dulong keep these lower values when they are in compounds. Kopp, H., Proc. Roy. Soc. London 13, 229 (1863).
- 105.
Erdmann and Marchand measured atomic weights, in particular those of copper and silver Erdmann, O.L. and Marchand, R.F., Jour. f. Prakt. Chem. xxxi, 389 (1844).
- 106.
Italy was not a country of chemists like France, Germany, or England at that time. Thus, Cannizzaro, an unknown Italian chemist (before the meeting) revived the theory of another unknown Italian, Avogadro. In August 2004, Vincenzo Salerno wrote in the journal Best of Sicily Magazine: His niche is a small but important one. Palermo-born Stanislao Cannizzaro is a special footnote to nineteenth-century physical science. He was, according to some, one of the scientists responsible for bringing chemistry and physics out of the realm of alchemy and into the modern world. The title of the article is: Stanislao Cannizzaro. A Political Physicist.
- 107.
Davy, H., Elements of Chemical Philosophy 1, 273, London: Printed for J. Johnson and Co., 1812. Apparently the second part never appeared. This is the only book on chemistry I have ever seen which discusses gravitation as part of chemistry.
- 108.
Döbereiner, J.W., Ann. Phys. 56, 331 (1817), ibid. 57, 435 (1817), ibid. Ann. der Phys. u. Chem. 15, 301 (1829).
- 109.
Gmelin, L., Hanbuch der Chemie, 4th edn. Heidelberg, Winter, 1843.
- 110.
de Chancourtois, B., Compt. Rend. 54, 757, 840, 967 (1862) ibid. 55, 600.
- 111.
Newlands, J.A.R., Chemical News 7, 70, (1863); ibid. 10, 59 (1864); ibid. 10, 94 (1864); ibid. On the Law of Octaves 12, 83 (1865); ibid. 13, 113 (1866).
- 112.
Bunsen, R.W., Ann. der Chemie und Pharmacie 119, 107 (1861).
- 113.
Crookes, W., Chem. News 3, 193 (1861).
- 114.
Reich, F. and Richter, H.T., J. fur Praktische Chemie 89, 441 (1863), ibid. 90, 172 (1863).
- 115.
Beryllium was discovered in 1789 by Nicolas Louis Vauquelin in the mineral beryl, whence its name beryllium. For some 160 years, the element was called glucinium (from the Greek glykys, meaning sweet), due to the sweet taste of its salts. But note that the metal and its salts are toxic, so it is not advisable to taste the salts, even though they are sweet.
- 116.
Newlands, J.A.R., On the Discovery of the Periodic Law and on Relations among the Atomic Weights, London, Spon, 1884.
- 117.
Odling, W., Phil. Mag. 13, 423 (1857), ibid. 480.
- 118.
Each element has a chemical valence, which is an integer. This number expresses how many univalent atoms of each element are needed to form a chemical compound. For example, the valence of hydrogen is 1 and the valence of oxygen is 2, so two hydrogen atoms are needed for a single atom of oxygen to form a molecule of water.
- 119.
Odling, W., Phil. Mag. 27, 115 (1864); Quarterly J. Sci. 1, 642 (1864).
- 120.
Odling, A., A Course of Practical Chemistry, 2nd edn., Longmans, Green, London, 1865, ibid. 3rd edn., 1868.
- 121.
Meyer, L., Die Moderne Theorien der Chemie, Breslau, 1864. English version: Longman Pub., London, 1888.
- 122.
Meyer, L., The Nature of the Chemical Elements as a Function of Their Atomic Weights, Justus Liebig Annalen der Chemie, Suppl. 7, 354 (1870).
- 123.
Meyer, L., Die Modernen Theorien der Chemie und ihre Bedeutung für die chemische Statik, Breslau, Verlag von Maruschke and Berebdt (1864).
- 124.
Meyer, J.L., Liebig’s Annalen der Chemie, Suppl. 7, 354 (1870).
- 125.
Meyer and Mendeleev were Bunsen’s students, with a five year separation. Interestingly, Bunsen did not trust the work of his students. Bunsen, like most members of the German chemical community, was mainly interested in experimental work and analytical chemistry, as opposed to theoretical work like classification of elements, let alone prediction of the existence of unknown elements. Years later, Meyer commented on the German chemists’ resentment of theoretical papers ‘without any new data’. Brauner, who was also a student of Bunsen and an enthusiastic supporter of Mendeleev’s periodic law, argued that the young members of the editorial board of the journal press for the publication of Mendeleev’s ‘no new data’ paper.
- 126.
Meyer, L., Zur Geschichte des priodischen Atomistik. Ber. Deuts. Chemi. Ges. 13, 259 (1880), ibid. 2043 (1880).
- 127.
Mendeleev, D., Zur Geschichte des priodischen Gesetzes. Ber. Deuts. Chemi. Ges. 13, 1796 (1880).
- 128.
Mendeleev, D.I., J. Russ. Chem. Soc. 1, 35 (1869), ibid. 60; ibid. 3, 25 (1871); Zeit. für Chemie 12, 405 (1869).
- 129.
Thomson, J.J., Phil. Mag. 44, 293 (1897). The discovery of the electron won him the Nobel Prize in 1906.
- 130.
Mendeleev, D., The Principles of Chemistry. The book was written 1868–1870 and translated into English in 1891.
- 131.
Cassebaum, H. and Kauffman, G.B., Isis 62, 314 (1971).
- 132.
Mendeleev, D.I., J. Russian Chemical Soc. 1C, 60 (1869).
- 133.
Lockyer is among the very few astronomers who turned stellar spectroscopy into a science. It led in the end to our understanding the composition of the stars.
- 134.
Janssen, M., AReg 7, 107 (1869). The names Janssen and Lockyer appear together because they independently devised a method to see the corona in broad daylight without the need for an eclipse. Janssen described the spectra, but the courageous hypothesis about a new element is due to Lockyer. Janssen was too enthusiastic about the new instrument to be bothered by an unidentified new element.
- 135.
Argon in 1894, neon in 1898, krypton in 1898, and xenon in 1898. All were found in liquid air. Ramsay, W., Nature 56, 378 (1897).
- 136.
Winkler, who discovered germanium in 1886, the element predicted by Mendeleev as eka-silicon, called Mendeleev’s three predictions ‘bold speculation’ in The Discovery of New Elements During the Last Twenty Five Years, in 1897 [34, p. 136].
- 137.
Beilstein is known for compiling the first Handbuch der organischen Chemie 2, 1880–1883, or Handbook of Organic Chemistry, which contained the chemical properties of about 15,000 organic compounds.
- 138.
In 1893, Mendeleev was appointed Director of the Bureau of Weights and Measures. In this capacity, he was directed to formulate new state standards for the production of vodka. The Vodka Museum in Moscow claims that, in 1894, Mendeleev determined the new standards for vodka as 38% proof. Distilled spirits were taxed according to their alcoholic strength, and consequently the percentage was rounded upwards, to 40%, for simplified taxation calculations. See http://www.russianfoods.com/cuisine/article00016/default.asp. Pravda has a slightly different version (see Pravda, 31 October 2009):
In 1860–1870, private production of vodka in Russia became very popular. It was very difficult for the government to control the quality of vodka and fresh raw material. Soon Russia introduced the state monopoly for vodka production. Chemists got involved in the development of the production process to enable product standardization. The brand ‘Moskovskaya Osobaya’ is directly connected to the name of Dmitry Mendeleev, the inventor of the periodic table of elements. It took the scientist 18 months to find a perfect ratio for volume of spirit to water. Mendeleev published his findings in his doctoral thesis ‘Essay on integration of spirit with water’. This is why Russian vodka is always 40% Alc. by Vol. Mendeleev’s conclusions were appreciated and utilized in alcohol testing and vodka production. His work became the basis for the state comparison standard for the original Russian vodka established in 1894–1896.
- 139.
The discovery of argon is unique as it collected two Nobel prizes in the same year, 1904. Rayleigh (1842–1919) was awarded the Nobel prize in physics for his investigations of the densities of the most important gases and for his discovery of argon in connection with these studies, while Ramsay (1852–1916) was awarded the Nobel prize in chemistry in recognition of his services in the discovery of the inert gaseous elements in air, and his determination of their place in the periodic system.
- 140.
Mendeleev’s view was reported in Nature 51, 543 (1895) under the title Professor Mendeleev on Argon, and it is a report of what Mendeleev said in the meeting of the Russian chemical Society on 14 March 1895. The idea of a new set of elements constituting a new column in the periodic table appeared to Mendeleev too absurd.
- 141.
Mendeleev, D., Popytka khimicheskogo ponimaniia mirovogo efira (in Russian). An English translation appeared as Mendeleff, D. (1904). G. Kamensky (translator): An Attempt Towards a Chemical Conception of the Ether, Longman, Green and Co., New York.
- 142.
Loschmidt, J., Proc. Acad. Sci. Vienna 52, 395 (1865).
- 143.
Maxwell, J.C., Phil. Mag. 19, 28 (1860).
- 144.
A gram mol is the molecular weight expressed in grams. In the case of oxygen, for example, it is \(16\times 2=32\,\mathrm{ {g}}\).
- 145.
von Meyer, E., A History of Chemistry from Earliest Times to the Present Day, translated from German by McGowan, MacMillan and Co., London, 1906. The original book was published in Leipzig in 1888.
- 146.
Gmelin, L., Handbuch der Theoretischen Chemie, Frankfurt am Main, bei Franz Varrwntrapp, 1827.
- 147.
It became clear very early on that the light emitted by each element was characteristic of that element, rather like a ‘finger print’. Thus, by heating the sample in question and carrying out spectroscopic analysis of the light it emitted, it was easy to identify the content of the sample.
- 148.
Wapstra, A.H., Pure and Appl. Chem. 63, 879 (1991). In 1991, a committee decided on criteria for the recognition of new chemical elements.
- 149.
Mendeleev, D., J. Chem. Soc. 55, 634 (1889).
- 150.
Here are some selected quotes:
The most important point to notice is that periodic functions, used for the purpose of expressing changes which are dependent on variations of time and space, have been long known. \([\ldots ]\) This constituted such a novelty in the study of the phenomena of nature that, although it did not lift the veil which conceals the true conception of mass, it nevertheless indicated that the explanation of that conception must be searched for in the masses of the atoms \([\ldots ]\).
If we mark on an axis of abscissae a series of lengths proportional to angles, and trace ordinates which are proportional to sines or other trigonometrical functions, we get periodic curves of a harmonic character. So it might seem, at first sight, that with the increase of atomic weights the function of the properties of the elements should also vary in the same harmonious way. But in this case there is no such continuous change as in the curves just referred to, because the periods do not contain the infinite number of points constituting a curve, but a finite number only of such points \([\ldots ]\).
While connecting by new bonds the theory of the chemical elements with Dalton’s theory of multiple proportions, or atomic structure of bodies, the periodic law opened for natural philosophy a new and wide field for speculation. Kant said that there are in the world ‘two things which never cease to call for the admiration and reverence of man: the moral law within ourselves, and the stellar sky above us’. But when we turn our thoughts towards the nature of the elements and the periodic law, we must add a third subject, namely, ‘the nature of the elementary individuals which we discover everywhere around us’. Without them the stellar sky itself is inconceivable; and in the atoms we see at once their peculiar individualities, the infinite multiplicity of the individuals, and the submission of their seeming freedom to the general harmony of Nature.
From the foregoing, as well as from the failures of so many attempts at finding in experiment and speculation a proof of the compound character of the elements and of the existence of primordial matter, it is evident, in my opinion, that this theory must be classed amongst mere utopias. But utopias can only be combatted by freedom of opinion, by experiment, and by new utopias. In the republic of scientific theories freedom of opinions is guaranteed \([\ldots ]\).
Unfortunately, this is not always so.
- 151.
Mendeleev’s discovery, and his courageous predictions which were soon vindicated, were seminal. But traditional dirty politics was also quick off the mark and mixed itself in liberally with the science. In 1906, Mendeleev was elected by the Nobel prize committee to win the award, but the Royal Swedish Academy of Sciences interfered and the prize went to the Frenchman Henri Moissan (1852–1907) in recognition of the great services rendered by him in his investigation and isolation of the element fluorine, and for the adoption in the service of science of the electric furnace called after him.
The intervention was prompted by the Swedish chemist Svante Arrhenius (1859–1927m), who won the prize in 1903 for his theory of electrolytic dissociation. Mendeleev had been an outspoken critic of Arrhenius (correct!) theory, and the unforgiving Arrhenius played it ugly, seizing the opportunity to take revenge. Arrhenius’ disguised argument was that Mendeleev had made his discovery too many years earlier. This illogical argument, which at best implies the failure of the committee to recognize Mendeleev’s feat sooner, was nevertheless accepted by the prize committee. The attempt to nominate Mendeleev a year later was thwarted once more by Arrhenius. Animosity between chemists apparently has an infinite decay time. For more, see Friedman, R.M., The Politics of Excellence: Behind the Nobel Prize in Science, Times Books, New York (2001). Meyer and Mendeleev, who argued over priority, shared the Davy Medal in 1882.
- 152.
Schützenberger, P., Chem. News 46, 50 (1882). See also Schützenberger, in a discussion of the variability of the law of definite proportions before the Chemical Society of Paris in 1883, as quoted in the Proc. Am. Acad. Arts Sci. May, 1888.
- 153.
Butlerow, A., Ber. 16, 1559 (1882), ibid. The Inconsistency of the Atomic Weights, Am. Chem. J. 5, 137 (1883).
- 154.
Richards, T.W., Proc. Am. Acad. Arts and Sci. XXIII, 177 (1887).
- 155.
Landolt, H.H., Sitzunsb. d. K. pr. Akad. Wiss. 16, 354 (1908).
- 156.
We know today that the chemical binding energy is smaller than \(10^{-8}mc^2\), whence Landolt’s careful experiment was not that accurate, although in 1906, a year after the theory of special relativity, this could have been figured out.
- 157.
Baxter, G.P. and Thorvaldson, T., J. Am. Chem. Soc. 33, 337 (1911), Baxter, G.P. and Parsons, L.W., J. Am. Chem. Soc. 43, 507 (1921).
- 158.
Crooke, J.P., Memoirs Am. Acad. Arts Sci. 5, 23 (1854), ibid. Nature 34, 423 (1886).
- 159.
Theodore William Richards won the Nobel prize in chemistry in 1914, in recognition of his exact determinations of the atomic weights of a large number of the chemical elements. Generations of chemists had improved the measurements and, at long last, the one who was most accurate and made measurements for a sufficiently long time was finally Nobelized.
- 160.
One of the tragedies of science happened when the brilliant scientist Moseley was killed on the battle field of Gallipoli, Turkey, in 1915.
- 161.
Moseley, H., Phil. Mag. 26, 1024 (1913), ibid. 27, 703 (1914).
- 162.
Moseley looked for the highest X-ray frequency emitted by the element.
- 163.
Moseley, H.G.J., Phil. Mag. XX, 1024 (1913).
- 164.
In some textbooks you may find it claimed that, when Moseley arranged the elements according to the atomic number, he got a nice periodicity. The truth is, however, the other way round. Moseley invented the atomic number.
- 165.
Moseley used \(N\) to denote the location in the table. Today we use \(Z\) to denote the number of elementary charges in the nucleus, and \(Z\equiv N\).
- 166.
The element nipponium was discovered in 1908 by Ogawa. It later became clear that nipponium is actually rhenium. See Yoshihara, H.K., Proc. Jpn. Acad. Ser. B, Phys. Biol. Sci. 84, 232 (2008).
- 167.
Bohr, N., Nature 107, 104 (24 March 1921).
- 168.
Lindemann, F.A., Nature 92, 631 (5 February 1914). Lindemann was the one who proved that you cannot ‘square the circle’ by a ruler and compass construction, since he proved that \(\pi \) is a transcendental number. This great proof did not prevent him from publishing several incorrect proofs of Fermat’s last theorem See Bell, E.T., Men of Mathematics, Simon and Schuster, New York 1986.
- 169.
Moseley, H., Nature 92, 554 (15 January 1914). Moseley and Bohr replied to Lindemann just a week later. Bohr’s letter preceded Moseley’s. Lindemann was wrong.
- 170.
It was strange to uncover such an error in the article by the scientist who was the first to prove that \(\pi \) is transcendental. Lindemann, who was essentially a mathematician, also worked on the theory of the electron, and had engaged in controversy over this with Arnold Sommerfeld (1868–1951), one of his PhD students. Sommerfeld was known as the Prince of German Physics. He was nominated a record 81 times for the Nobel Prize in Physics, and served as PhD supervisor for more Nobel prize winners in physics than any other supervisor before or since. However, he never actually got the award.
- 171.
See Shaviv, G., The Life of Stars, Magnes and Springer, 2009.
- 172.
Moseley, H.G.J., Phil. Mag., Ser. 6, 27, 703 (1914).
- 173.
Aston, F.W., Nature 104, 383 (1919) and Phi. Mag. Ser. 6, 39, 611 (1920), ibid. Nature 104, 393 (1919).
- 174.
There are several calculations in electrodynamics which yield \(E=\alpha mc^2\), where \(\alpha \) is of the order of unity.
- 175.
Söderbaum was a chemist, the secretary of the Swedish Academy of Sciences and a member of the Nobel committee for chemistry as of 1900. (He must therefore have been involved in the Mendeleev case.) In his later years, Söderbaum became interested in the history of chemistry and in particular the biography of Berzelius, about whom he wrote several books. It is an irony of history that the Swedish Söderbaum awarded the Nobel prize to the physicists who spoiled Berzelius’ arguments against Prout’s hypothesis.
- 176.
Brown, R., Miscellaneous Botanical Works 1, London, Royal Society. Ibid. Edinburgh New Phil. J. 5, 358 (1828). Ibid. Phil. Mag. 4, 161 (1828).
- 177.
van der Pas, P.W., The Discovery of Brownian Motion. Scientiarum Historia 13, 17 (1971).
- 178.
Brongiart, A-T., Ann. Sci. Naturelles 12, 41 (1827).
- 179.
In many writings on Brownian motion, it is claimed that, in 1877, J. Desaulx hypothesized that the phenomenon was due to thermal motion of molecules. The texts even supply a quote from Desaulx. However, I failed to find any article by an author with this name, let alone a hypothesis. See also the footnote on Einstein’s paper.
- 180.
Gouy, L.G, Compt. Rend. 109, 102 (1889).
- 181.
Exner, F.M., Ann. Phys. 2, 843 (1900). Exner became famous because he was assisted for a while by Erwin Schrödinger.
- 182.
Fick, A., Ann. Phys. 94, 50 (1855). This is a purely phenomenological approach. There is no physics in it. Smoluchowski, M., Ann. Phys. 21, 756 (1906). This paper was published shortly after Einstein’s paper.
- 183.
Einstein, A., Ann. Phys. 17, 549 (1905), ibid. 19, 289, 371 (1906). This was part of Einstein’s dissertation at Zürich University. Einstein gave no reference in his paper, save one to Kirchhoff’s lectures. In Ann. de Physik 19, 371 (1906), there is a paper by Einstein in which he tells the reader that Seidentopf informed him that he (Seidentopf) and Gouy (J. de Phys. 7, 561, 1888) carried out experiments on Brownian motion and had data. Einstein remarked that he found agreement between his theory and the experimental data of Gouy. There is no reference to Desaulx, and nor does such a reference appear in Exner’s paper. Apparently, the heros of Brownian motion did not know about Desaulx.
- 184.
Perrin, J., The Brownian Motion in Atoms, D. van Nostrand, 1916. Ibid. Compt. Rendu, May 1908. Perrin, J. and Donau, J., Fortschritt. über Kolloide u. Polymere 1, no. 6–7, April 1910.
- 185.
The accurate value is \(6.022\times 10^{23}\). Reasonable values were obtained in the late nineteenth century using the sedimentation equilibrium of colloidal particles. Millikan’s oil drop experiment in the 1900s gave even better accuracy and was cited in most chemistry text books till about 50 years ago.
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Shaviv, G. (2012). Order in the Chemical Elements. In: The Synthesis of the Elements. Astrophysics and Space Science Library, vol 387. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-28385-7_1
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