Abstract
Water served as an emblematic locus for debates on the atomic constitution of matter. Today it is taken as common sense that water is H2O, but this was a highly disputed hypothesis for the first half-century of atomic chemistry. In Dalton’s original formulation of the atomic theory published in 1808 water was presented as HO, and consensus on the H2O formula (first proposed by Avogadro) was not reached until after the mid-century establishment of organic structural theory based on the concept of valency. The main epistemic difficulty was unobservability: molecular formulas could be ascertained only on the basis of the knowledge of atomic weights, and vice versa. There were multiple self-consistent sets of molecular formulas and atomic weights, which were employed in at least five different systems of atomic chemistry that flourished in the nineteenth century, each with its distinctive set of aims and methods and in productive mutual interaction. At the heart of the distinctive systems of atomic chemistry were different ways of operationalizing the concept of the atom (weighing, counting, and sorting atoms). It was operationalization that enabled atomic theories to become more than mere hypotheses that may or may not be consistent with observed phenomena. If we examine the crucial phase of development in which the consensus on H2O was achieved, the key was not the revival of Avogadro’s ideas by Cannizzaro, but the establishment of good atom-counting methods in substitution reactions. This, too, was a triumph of operationalization. We also need to keep in mind that the H2O consensus was not a straightforward unification of all systems of atomic chemistry; rather, it was a reconfiguration of the field which resulted in a new pluralistic phase of development.
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Notes
- 1.
- 2.
As prophecy goes, this is the best I have found, from Berzelius (1813, 449): “It is in the study of the composition of organic bodies that our knowledge of the laws of chemical proportions, and of the electrochemical theory, will one day reach that degree of perfection which the human mind is capable of giving it.”
- 3.
For a collection of informative articles on Dalton’s life and work, see Cardwell (1968).
- 4.
See Chap. 1, Sect. 1.2.3, on “compositionism” in eighteenth-century chemistry.
- 5.
See Dalton (1808, 215) and Dalton (1810, 316–368). Figure 3.1 is a reproduction of Dalton’s Plate 5, opposite p. 560; note that he was using the Lavoisierian French term “azote” for nitrogen. Modern formulas for these compounds match Dalton’s, except that his NO3 would be our N2O5, nitric anhydride (see Lowry 1936, 209).
- 6.
One interesting exception was Dalton’s early supporter Thomas Thomson, who still gave an account of atomic volumes even in 1831 in the 7th edition of his System of Chemistry, ranging from 1 for carbon to 28 for potassium (Thomson 1831, vol. 1, 14).
- 7.
Dalton (1808, 215) and Dalton (1810, 275). But he does briefly acknowledge that it is possible that water may be H2O (Dalton 1810, 276). In my exposition in the current section (Sect. 3.1), I will sacrifice historical accuracy and use modernized atomic-weight numbers (rather than Dalton’s own), in order to avoid confusing the modern reader.
- 8.
Thomson took the idea of physical atoms as prevalent common sense, and in fact even used the term “atom” freely in his text before the section where he introduced Dalton’s ideas; in fact the same is done in Dalton’s own text (e.g., Dalton 1808, 125).
- 9.
Priestley never agreed, and maintained that it was a phlogiston-rich inflammable air (see, e.g., Priestley [1796] 1969, 37–38).
- 10.
The second series is similar to Dalton’s formulas.
- 11.
The following simple exercise demonstrates one way in which the latter statement is true: take the system of atomic weights and molecular formulas that you accept; pick any element in that system and halve its atomic weight, and double the number of that atom in every molecular formula; then we have a whole new system that is self-consistent. For example, if we said that the atomic weight of oxygen was 8 instead of 16, we would end up with water as H2O2, carbon dioxide as CO4, etc. This can be done to any element we like, as often as we like.
- 12.
These include (in roughly chronological order) Ida Freund, T. M. Lowry, Joshua Gregory, J. R. Partington, Colin Russell, David Knight, Aaron Ihde, William H. Brock, John Hedley Brooke, Evan Melhado, Arnold Thackray, Mary Jo Nye, Trevor Levere, Alan Rocke, Christoph Meinel, Ursula Klein, Joseph Fruton, Peter Ramberg, and Alan Chalmers.
- 13.
For Dalton, who envisaged the atoms and molecules of gases stacked up without unnecessary gaps between each other, EVEN amounted to the same thing as what Dalton said he had rejected: “At the time I formed the theory of mixed gases, I had a confused idea, as many have, I suppose, at this time, that the particles of elastic fluids are all of the same size” (Dalton 1808, 188).
- 14.
For extensive details on Avogadro’s life and work, see Morselli (1984).
- 15.
It seems that some authors did ignore Avogadro, whether they were aware of his ideas or not; Joseph Fruton (2002, 56) notes that Berzelius chose not to discuss Avogadro in his annual reviews, and that Hermann Kopp’s history of chemistry (1843–1847) makes no mention of Avogadro’s name.
- 16.
See Mauskopf (1969) on Ampère and Gaudin.
- 17.
See Mauskopf (1970) on Haüy’s work and its connection with atomism.
- 18.
- 19.
Hartley (1971), 188–192, provides a lively account of Cannizzaro’s interventions at the Karlsruhe Congress.
- 20.
Liebig (1851, Letters 6 and 7) is an interesting exception, though it is not really a textbook.
- 21.
In the second installment of the same paper (Berzelius 1814, section IV) he presented considerations on the “weight of elementary volumes compared with that of oxygen gas”.
- 22.
In modern American usage the standard term to use is “valence”, but “valency” is more faithful to the usage closer to the time of the events discussed here.
- 23.
This gives a clear pointer toward pluralism, as I will discuss further in Chap. 5.
- 24.
In Chap. 2 it was noted that not everyone doing electrochemistry with the Voltaic pile shared this electrostatic view; however, the dualists within atomic chemistry all seem to have thought electrostatically.
- 25.
See Servos (1990), ch. 1, for an exposition of the motivations that gave rise to physical chemistry.
- 26.
- 27.
Otherwise, what is the point of secondary literature? For a list of authors I have found most helpful, even if I don’t cite them extensively, see footnote 12.
- 28.
- 29.
I do have a view on that issue, which is expressed in Chang (2005).
- 30.
See Sect. 3.3.1 C1 for a further discussion of the different between definition and meaning.
- 31.
- 32.
See Lowry (1936), 310–311, for these brief descriptions.
- 33.
In acid–base neutralization one is dealing with “compound atoms” rather than elementary atoms, but the conceptual structure is the same. In fact, from Dalton until the middle of the century it was perfectly routine for chemists to speak of the “atoms” of radicals and other compound units; see, for instance, the work in organic chemistry discussed in Klein (2001). The modern usage of “molecule” did not take universal hold till later.
- 34.
This is just the kind of productive theory-ladenness of observation that Norwood Russell Hanson spoke of (see Chap. 2, Sect. 2.2.1).
- 35.
Modern measurements would give these weights as 28:44, instead of Dalton’s 12:19.
- 36.
Dalton does not seem to have been entirely consistent in usage; in another context he would only call “binary” what is strictly made up of only two elementary atoms.
- 37.
It should be noted that Dalton’s reasoning takes it for granted that after clumping together the composite atom made up of carbonic oxide and oxygen does not sub-divide; interestingly, that sort of post-combination division was precisely what Avogadro felt compelled to assume.
- 38.
- 39.
- 40.
And not “Daltonism”, which refers to the red–green color-blindness, which Dalton suffered from and published a paper about.
- 41.
- 42.
- 43.
- 44.
This, in my view, constituted premature unification at the start, which we should not necessarily praise just because it turned out well in the end. But that is certainly not to deny that it did not make a promising and productive avenue of inquiry.
- 45.
See Partington (1964), 218f.
- 46.
- 47.
- 48.
See Lowry (1936), 422–423, on the ammonia type.
- 49.
In this I follow Chalmers (2009), ch. 10.
- 50.
In modern terms, the reaction is HCN + Cl2 → ClCN + HCl.
- 51.
Laurent, however, still took pains to distinguish his own view from Dumas’s.
- 52.
In the modern formula for acetic acid, we halve the number of all the atoms, to get C2H4O2 (or, more structurally, CH3.COOH). For oxalic acid we have kept Berzelius’s C2H2O4, but we parse that out as (COOH)2.
- 53.
This is where Hermann Kolbe’s struggle on behalf of electrochemical dualism becomes so valuable, because he was attempting to extend the operational basis of dualism by electrolytically isolating organic radicals.
- 54.
Crum-Brown had expressed a very similar view, less colorfully, in 1874. See Levere (1971), 195.
- 55.
- 56.
- 57.
This can be distinguished from pluralism motivated by exploratory or iconoclastic sentiments. All will be brought together in Chap. 5.
- 58.
Quoted in Brock (1992), 226.
- 59.
This is a better image than that of surreptitiously or violently extracting her secrets.
- 60.
- 61.
One might indeed argue that there is no such thing as entirely passive observation. That may well be, but that does not pose a difficulty for operationalism, only for standard empiricism.
- 62.
In his Nobel Lecture, speaking of his other major contribution to science, Van’t Hoff expressed the view that molecular collisions only provided “an anyway hypothetical conception of the cause of [osmotic] pressure” (quoted in Nye 1976, 259).
- 63.
- 64.
To be precise, I should say “the tendency to occupy certain volumes”, as it was undetermined whether atoms themselves took up all the volume occupied by a body, or there was space between atoms contributing to the volume.
- 65.
On Wittgenstein as a pragmatist, see Putnam (1995), ch. 2.
- 66.
This demand for operability is applied to all concepts, including philosophical ones. In Chap. 4, Sect. 4.3.1, I will give a pragmatist–operationalist analysis of the concept of truth.
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Chang, H. (2012). HO or H2O? How Chemists Learned to Count Atoms. In: Is Water H2O?. Boston Studies in the Philosophy and History of Science, vol 293. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-3932-1_3
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