Abstract
Quine, taking the molecular constitution of matter as a paradigmatic example, offers an account of the relation between theory confirmation and ontology. Elsewhere, he deploys a similar ontological methodology to argue for the existence of mathematical objects. Penelope Maddy considers the atomic/molecular theory in more historical detail. She argues that the actual ontological practices of science display a positivistic demand for “direct observation,” and that fulfillment of this demand allows us to distinguish molecules and other physical objects from mathematical abstracta. However, the confirmation of the atomic/molecular theory and the development of scientists’ ontological attitudes towards atoms was more complicated and subtle than even Maddy supposes. The present paper argues that the history of the theory in fact supports neither Quine’s and Maddy’s accounts of scientific ontology. There was no general demand from scientists to “see” atoms before they were reckoned to be real; but neither did the indispensable appearance of atoms in the best theory of chemical combination suffice to convince scientists of their reality.
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Notes
See Quine (1955, pp. 252–254).
See Quine (1955, p. 247).
It is probably not enough that T be the best theory; likely, it must also meet some minimum threshold of confirmation. That is: T must not be just the best of uniformly bad alternatives, it must be a good theory. In what follows, I will suppose that any theory that is the best is also good.
See Field (1980) for an example of this strategy applied to the case of numbers.
See Maddy (1997, pp. 143–152).
Maddy isn’t alone in drawing lessons about the ontological and evidential practices of science from the history of the atomic theory—see, e.g., Glymour (1975), Gardner (1979), Salmon (1984), and Chalmers (2011); and most such philosophical accounts also assign Perrin a central role in the story. Needham (2004a, pp. 200–215), though skeptical of other aspects of the history of atomism as usually told, likewise identifies Perrin’s experiments as the “turning point for the atomic theory” (p. 215). Indeed, the belief that Perrin finally succeeded in establishing the existence of atoms is widespread enough that van Fraassen (2009) has characterized it as philosophical “lore.” van Fraassen, of course, rejects the lore; but he does claim that Perrin was instrumental in turning the kinetic theory—and so, by extension, atomism—into “a truly empirical theory” (van Fraassen 2009, p. 23).
Various historians of science have also explored the diversity of attitudes towards chemical (and physical) atomism during the 19th century. See, e.g., Nye (1972), Brush (1976a, b), and Rocke (1984), though my aims—and some of my historiographical conclusions—depart from theirs. Note, too, that these sources don’t always agree amongst themselves about the details.
See Duhem (1991, pp. 31–32).
The puzzles that inorganic chemistry presented for the atomic theory arose from the fact that the transition metals readily take on various different oxidation states and so display multiple valencies. These puzzles were eventually solved with the development of Alfred Werner’s coordination theory—see his (1893) and (1898)—and the rise of the quantum mechanical account of the atom.
See Klein (1994, pp. 170–171) for a detailed elaboration of this view of matter and chemical combination, though as situated in the 17th century. (Thanks to an anonymous reviewer for directing me to the Klein.) The view is later mentioned by Wurtz (1898, p. 307) and discussed at length—indeed advocated—by Duhem (1902).
The law of definite proportions states that substances combine chemically only in fixed ratios (by weight)—chemical composition does not vary continuously; the law of multiple proportions states that substances may combine in several different ratios, each ratio being an integer multiple of the smallest.
Dalton used a system of patterned circles as chemical symbols for the elements; the modern alphabetic chemical symbols are based on those of Berzelius.
See Cannizzaro (1858).
For both atomic and equivalent weights, a standard—e.g., \(H=1\), or \(O=10\), or \(C=12\) (the modern standard)—must be conventionally set.
The term ‘equivalent’ was introduced by Wollaston (1814), and his system of equivalent weights was widely adopted. Wollaston standardized the weights so that \(O = 10\) and determined (among other elemental and compound weights) \(H = 1.32\) and \(C = 7.54\); he assigned water the formula HO, giving it a weight of 11.32. In presenting his system, Wollaston insisted that though equivalent weights could be interpreted as the proportional weights of atoms and molecule, they need not be, and that the determination and utility of the weights were independent of Dalton’s atomic hypothesis. Rocke (1984, pp. 61–66) has persuasively argued that, despite this disclaimer—and despite the uptake of the equivalent notation by many anti-atomists—Wollaston was himself an atomist.
For more on the nature of equivalents, see Sub-Sect. 3.2 below.
Berthelot denied this, but even if he hadn’t, it is not clear that he would have recognized it as an advantage for the atomic notation—he and Marignac disagreed fundamentally on the proper role of physical properties in chemical theorizing.
Duhem advocates the same course in his (1892). Such a strategy abandons the prospect of an explanation of why physical properties consistently correspond to a single system of equivalents. This was no bother to Duhem, of course, since he denied that explanation was a proper goal of science.
Brodie (1869) reports the subsequent discussion.
Note that Marignac freely used this proportionality to set “atomic” wieghts, but did not admit it as evidence of the existence of atoms.
Victor Meyer proposed two such syntheses—of isomers of bromochloronitroethane—in 1876, although it is unknown whether he carried them out; see Ramberg (2003, p. 160). Tantalizingly, Mach (1896, p. 390) claims, “The atomistic philosophy has recently gained ground again owing to the advances made in stereochemistry.” Alas, he does not elaborate.
Needham (2004a, b, 2008) argues that, in fact, atomism contributed little to nothing in the way of chemical explanation till the early 20th century, and in particular denies that 19th century atomism successfully explained either the law of definite proportions or optical activity. Needham claims (2004b, p. 1041; 2004a, p. 203) that the atomists’ proposed explanation of the law definite proportions amounts to insisting that quantities of chemical species combine in definite proportions simply because smaller quantities of those species combine in definite proportions; and this is no real explanation because it “merely repeats what has to be explained on a smaller scale” (2004b, p. 1041). But this seems to mistake the explanans: definite proportions are to be explained, not by the combination of smaller quantities, but by the combination of discrete, smallest possible quantities of chemical species. Atoms thus provide a constitutive explanation of the law of definite proportions: macroscopic combinations are constituted by (very) many individual instances of combination of discrete atoms; the proportions of the macroscopic combinations necessarily recapitulate the proportions of the combination of atoms. It’s true, as Needham argues, that there was no good theory of the mechanism of chemical combination in the 19th century, since the nature of chemical bonding was only elucidated by the quantum mechanical account of the atom. But the explanation of the law of definite proportions doesn’t require a fully worked out mechanistic picture. Indeed, the details of chemical bonding are irrelevant to this explanation: it matters only that, however they combine, chemical species do so in discrete, minimal chunks of fixed mass. Similar remarks hold for Needham’s (2004a, p. 210) contention that without a mechanistic theory of the interaction of light with matter, the proposed explanation of optical activity via molecular asymmetry is nothing more than a posited correlation between “a difference in representation” and a “difference in laevo- and dextrorotary isomers.” This characterization elides the entire substance of the explanation. The atomist theory posits a property of some molecules, asymmetric spatial structure, which can be characterized independent of the target phenomenon, optical activity, and assigns it a causal role in the rotation of plane-polarized light. The explanation is only partial until the mechanism of light rotation can be explicated, but partial explanation isn’t the same thing as no explanation. (Compare: I can perfectly well explain—at least partially—that my car won’t run because its engine was submerged in a flood, even if I have no idea of how water interferes with an internal combustion engine.)
See Nye (1984, p. 242).
See van’t Hoff (1898).
Noyes delivered this remark at an address in September, 1909—the same month Perrin’s pamphlet announcing his results on Brownian motion appeared in French, and many months before it was translated into English (Perrin 1910).
These explicit defenses of atomism are in fact somewhat unusual for the time period. For the most part, chemists just didn’t take atoms to need much defending; they simply put them to work without comment. See also Brush (1976a, p. 94).
Ostwald and Duhem, of course, worked in both physics and chemistry—Ostwald won the chemistry Nobel in 1909 for his work on catalysis—and were important figures in the emergence of physical chemistry during this period. Though a mainstream, if minority view, in physics, their anti-atomism was highly idiosyncratic among chemists (even, it seems, among physical chemists). Nye (1993, p. 139), in a careful study of the early development of physical and theoretical chemistry, calls Duhem “primarily a physicist.” Berthelot—who also had positivist leanings (see Nye 1981; Dolby 1984)—was the only other prominent chemist who denied the existence of atoms at the end of the century. (Frantisek Wald also denied atomism, but he was known primarily for that denial, rather than for his contributions to chemical research.) Though he died in 1907, Berthelot was from an earlier generation than Ostwald and Duhem, and he had been active in the mid-century debates over the atomic notation; his skepticism about atoms was, to some extent, a holdover from this earlier period. It is perhaps also notable that Ostwald, Duhem, and Berthelot were all deeply involved in the development of thermochemistry and chemical thermodynamics. Dolby (1984) provides an excellent overview.
The most comprehensive overview of the energeticist program is Helm (1898). Mach was not himself an energeticist, though he was generally sympathetic; see, for example, Mach (1883, pp. 455–456 and 607). Poincaré expresses support for the energeticist program in Chapter VIII of his (1902)—see especially p. 129. Planck rejected energeticism, and instead believed that a mechanistic account of thermodynamic phenomena ought to be reconciled with a continuum view of matter. See Kuhn (1978, pp. 11–29), as well as the preface to the first edition of Planck (1897).
Duhem relates thermodynamics to chemical mechanics in Chapter 10 of his (1902).
For a recent technically detailed account of the reverisibility paradox and its consequences for the foundations of statistical mechanics and thermodynamics, see Callender (2011).
See, e.g., Mach (1896, p. 335; 1910, p. 137), Poincaré (1902, pp. 178–179), and Planck as quoted in Kuhn (1978, p. 25). The preference for a universal interpretation of the second law of thermodynamics was, perhaps, in part due to the seeming irreversibility of all observable macroscopic processes. There thus seemed to be some empirical evidence for the universal interpretation, and (as we shall see below) this evidence was drawn from precisely that realm that many positivist opponents of the kinetic theory regarded as the only proper domain of scientific investigation.
Duhem here appeals to Poincaré and quotes him thus: “The mechanism is incompatible with Clausius’ theorem.”
van Fraassen (2009) also makes this point and provides additional quotes and references.
Kundt and Warburg (1875) measured \(\gamma \) for Mercury vapor to be 1.67. This was the only specific heat measurement in agreement with the kinetic theory until Rayleigh and Ramsay (1895) determined that \(\gamma \) for their newly discovered Argon was 1.66, and Lockyer (1895) determined that for Helium (also first isolated by Rayleigh) \(\gamma = 1.65\). For a roughly contemporaneous compilation of specific heats of other common substances, see Clausius (1879, p. 59).
See, for example, William Thomson (1891), who argues that the equipartition theorem fails for some systems, and Jeans (1901), who argues that equipartition does not apply to molecules in interaction with the ether. The discrepancy between derived and measured specific heats is, in fact, due to the quantization of the internal modes of energy of the molecule, and so the equipartition paradox was only solved with the development of quantum mechanics.
See, for example, Duhem (1895, p. 186) and Stallo (1884, pp. 67–68). Stallo’s criticisms of the kinetic theory were endorsed by Mach, who saw him as a philosophical ally and who wrote the introduction to the German edition of Stallo’s attack on atomism. Duhem also raised a variety of further empirical and theoretical worries about atomism; see Needham (2008).
Brush (1976a, p. 245) shares this judgment: “In retrospect it seems clear that the criticisms of kinetic theory in this period were motivated not primarily by technical problems...but, rather, by a general philosophical reaction against mechanistic or ‘materialistic’ science and a preference for empirical or phenomenological theories, as opposed to atomic models.”
Though see Needham (2008) for doubts about throwing Duhem in with the positivists.
So, for example, Avagadro’s law—since it pronounces on the number of (unobservable) particles in a given sample of gas—is not an experimental law.
Note that in Duhem’s view (and contra Quine’s) this power and fecundity do not speak to the truth of the system.
Needham (2004a) is surely right—as I, too, have argued above—that the case pressed against atomism in this period was not entirely positivistic. But he is just as surely wrong in claiming: “The unobservability of atoms was as irrelevant for the opponents of atomism... as it was to Dalton and his followers” (p. 202). Mach and Ostwald, at least, explicitly draw connections between their anti-atomism and preference for energetics, on the one hand, and their philosophical views, on the other. And it can be no coincidence that the anti-atomists were nearly one-and-all empiricists of some stripe.
Quoted in Solov’ev and Petrov (1968, p. 305).
Quoted in Solov’ev and Petrov (1968, pp. 305–306).
See Perrin (1910, p. 90) for a tabular summary.
Quoted in Nye (1972, p. 157).
Quoted in Nye (1972, p. 151).
Although the German journals neither reviewed nor abstracted new books.
For an example of the latter, see the passage—quoted above, p. 13—from Bevan (1904, p. 111).
See especially Mach (1896, p. 334), who dismisses the protestations of the few kinetic theorists who claimed to hold an instrumentalist view of atomism.
Maddy (1997, p. 142).
Quoted in Nye (1972, p. 7).
See Maddy (1997, p. 142).
At least this criticism does. Maddy (1997, pp. 143–152) also argues—persuasively—that the practice of idealization causes trouble for indispensability arguments.
Recall, for example, Marignac and Odling, discussed above.
It may be, of course, that the chemical transformations cannot be carried out directly, but must proceed through intermediate chemical species.
Following the idiom of 19th c. chemistry, I’m using ‘weight’ and ‘mass’ interchangeably.
In equivalent systems that incorporate Gay-Lussac’s law, chemical equations also provide volumetric information by allowing parts to given in units of volume. In such cases, certain formulas must be modified to take account of the empirical data. So, for example, (2) becomes
$$\begin{aligned} 2\hbox {H}_{2} + \hbox {O}_{2} \rightarrow 2\hbox {H}_{2}\hbox {O} \end{aligned}$$(3)Parts by volume are read directly off the coefficients: two volumes of hydrogen combine with one volume of oxygen to yield two volumes of water vapor. The subscripts in ‘H\(_{2}\)’ and ‘O\(_{2}\)’ indicate that one part by volume corresponds to two (normalized) parts by weight for both hydrogen and oxygen. When parts are given by weight directly, (3) simplifies to (2).
Note, however, that the interpretations carry distinct theoretical commitments—even beyond their different ontologies. Since, on the anti-atomist schematic interpretation, any amount of substance is eligible to enter into chemical reactions, one part by weight can take on any value and every instance of (2) read schematically is true. By contrast, on the atomistic interpretation, the schema has to be restricted because the masses entering into chemical reactions are quantized: \(m\) in (2**) can only take on values that are integer multiples of \(n\). Thus, on the schematic interpretation,
$$\begin{aligned} n\,\hbox {g} \,\hbox {H} + 8\,n \,\hbox {g}\, \hbox {O} \rightarrow 9\,n\, \hbox {g} \,\hbox {H}_{2}\hbox {O} \end{aligned}$$(2b)is true; but on the atomistic interpretation, it represents a physical impossibility since it would require half-particles of oxygen and water. The quantization predicted by the atomistic interpretation is not directly observable under ordinary conditions due to limits on the sensitivity and accuracy of mass measurement. A single atom of hydrogen has a mass of approximately 2 \(\times \) 10\(^{-24}\) g. Even today, the best balances are accurate to roughly 10\(^{-10}\) g, and so can only reliably distinguish samples of hydrogen that differ by on the order of a thousand billion atoms.
Imagine a paraphrase that replaces each occurrence of ‘atom’ with an occurrence of ‘atom*’. Is there a clear ontological difference between the original theory and the paraphrase?
Rocke (1984) argues that advocates of equivalents were tacitly, if unknowingly, committed to chemical atomism because systems of equivalents, such as Wollaston’s, were “operationally identical” (p. 64) to chemical atomism: equivalent weights were (generally) set based on the same experimental data and techniques—including non-stoichiometric data—used to determine atomic weights, both atomic and equivalent weights required chemists to employ assumed formulas for some compounds, etc. (p. 12.) Rocke makes a compelling case for extensive operational overlap between the equivalent and atomist notations. But it’s not clear to me that this operational similarity—however strong—shows that equivalents were really mis-named atoms, since the concepts played quite different theoretical roles. Atomists could justify the use of “two-volume” formulas on ontological grounds; in equivalent systems, the use of two-volume or four-volume formulas was justified pragmatically. Atomists willingly hypothesized about the arrangements and groupings of atoms within molecules, as atoms were taken to have stable identities; such speculation was foreclosed within equivalent systems, since equivalents are not entities. To this last point, it is significant that Wollaston frequently wrote of the spatial positions and physical interactions of atoms, but not of equivalents—see Rocke (1984, pp. 64–65) for examples and references.
In any event, even if we acquiesce to Rocke’s operationalism, his notion of chemical atomism is quite thin. According to Rocke (p. 13), all that chemical atomism consists in is (a) the positing of “invariant elemental weights to explain the inelegant variability of empirical combining proportions,” and (b) using “these chemical building blocks to construct schematically all known compounds.” Note that the “chemical building blocks” are the “atomic weights” themselves, not elemental particles or fixed portions of matter. Rocke’s chemical atomism, then, is a commitment to each chemical species having a certain intrinsic and invariable characteristic property that is systematically—perhaps causally—related to its macro-level chemical behavior, to its dispositions to enter into chemical reactions. Such atomism is not ontological: it does not involve a commitment to the discreteness of matter, to each chemical species having an ultimate particle—or even some smallest amount of continuous substance—that bears its characteristic property, to atoms retaining their identities throughout chemical transformations, etc. In short, Rocke’s chemical atomism does not entail that atoms are things. Rocke reserves the phrase “physical atomism” for the ontological thesis, and he agrees that chemical and physical atomism can come apart. (Thanks to an anonymous reviewer for encouraging me to elaborate on the anti-atomist interpretation of chemical equations and to engage Rocke’s argument.)
Quine, in various places, walks back these strong statements of holism—and even expresses regret that he ever stated it so strongly—characterizing holism instead as the claim that statements are confirmed only en masse, in collections large enough to have observable entailments. (See, for example, his 1991, p. 57.) Collections much smaller than the whole of science itself may meet this criterion. Such weak holism, however, won’t support the weight of the indispensability argument, at least in its classical form, for its not clear what’s to stop us from walling off some part of our scientific conceptual scheme—say, the non-observational part—as “non-ontological.” Indeed, the mid-19th-century chemists, such as Marignac, who adopted the atomic notation but denied the reality of atoms appear to be engaging in such a strategy at the level of theory: experimental results confirmed various empirical laws (e.g., the law of multiple proportions, the periodicity of various physical properties) and justified an instrumental or heuristic use of the atomic notation, but forced no “metaphysical” conclusions. This buttresses Maddy’s argument that the practice of idealization undercuts indispensability.
Thanks to an anonymous reviewer for encouraging me to address this response.
No individual seems to have adopted atomism in chemistry but rejected it in physics. Such a position seems logically possible: although a discrete structure of matter accounts for the phenomena of chemical combination, there are purely energetic (rather than kinetic) explanations of thermodynamic phenomena.
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Acknowledgments
Thanks to Jody Azzouni, Larry Sklar, Jamie Tappenden, and especially to Penelope Maddy for useful discussion and comments on various drafts of this paper. Thanks also to a number of anonymous reviewers whose comments and criticisms helped to significantly strengthen the paper.
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Brown, J.D.K. Chemical atomism: a case study in confirmation and ontology. Synthese 192, 453–485 (2015). https://doi.org/10.1007/s11229-014-0581-4
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DOI: https://doi.org/10.1007/s11229-014-0581-4