Abstract
However one might assess the arguments about the nature of water in the Chemical Revolution (Chap. 1), it may seem that the electrolysis of water (first performed in 1800) must have produced decisive evidence that it was a compound substance. But electrolysis came with a serious puzzle: if the action of electricity was breaking up each particle of water into a particle of oxygen and a particle of hydrogen, how did the oxygen and hydrogen gases emerge at electrodes that were separated from each other by macroscopic distances? The distance problem turned the electrolysis of water into a serious anomaly, rather than positive evidence, for Lavoisierian chemistry. Ritter and his followers argued that electrolysis was in fact a pair of syntheses: water was an element after all, and its combination with positive and negative electricity formed oxygen and hydrogen. This view was dismissed by the majority of post-Lavoisierian chemists, but never conclusively refuted at the time. Those who opposed Ritter proposed a plethora of different solutions to the distance problem, none of them completely convincing. The modern ionic theory only emerged in the last years of the nineteenth century, so there was nearly a whole century of electrochemistry taking place without a consensus on some very basic questions. Nonetheless, electrochemistry made significant progress. Its experimental practices were stabilized and standardized without recourse to agreed-upon fundamental theory. In the theoretical realm there was pluralistic progress, with several competing systems each making its distinctive contributions, in productive interaction with each other.
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Notes
- 1.
“Battery” in later usage, that is. Originally the term was used to refer to a set (battery) of storage-jars for holding static electricity. After Volta’s invention, the term “galvanic battery” was used to describe a collection of cells producing electricity; over time, the term came to refer to single cells as well. In his original paper Volta (1800, 420) very sensibly proposed to call his instrument the electro-motive apparatus (appareil électro-moteur), but this name did not catch on.
- 2.
This is how Priestley put it (1788, 154; emphases original): “That water is decomposed when inflammable air is procured from iron by steam, is not probable; since the inflammable principle [phlogiston] may very well be supposed to come from the iron, and the addition of weight acquired by the iron may be ascribed to the water which has displaced it. Also when the scale of iron, or finery cinder, is heated in inflammable air, it gives out what it had gained, viz. the water.” See also Priestley [1796] (1969), 30–33. To say that the metal absorbs water as it gives up phlogiston is quite like saying that the metal absorbs dephlogisticated water (which is what oxygen was, for Cavendish and Priestley).
- 3.
- 4.
Note his use of the term “incommensurable”, 160 years before Kuhn and Feyerabend! See also Davy [1801] (1839), 206: “The facts relating to the separate production of oxygen and hydrogen acid and alkali in water, are totally incommensurable with the usually received theory of chemistry”.
- 5.
The biographical information on Singer is taken from the Dictionary of National Biography (1897), vol. 52, 211–312.
- 6.
In my references to Ostwald, the latter number cited (131 in this case) is the page number in the original German edition.
- 7.
Ritter may have been anticipated in the synthesis view by one of Nicholson’s anonymous authors, as noted by Ostwald [1896] (1980), 148–149/152–153.
- 8.
This is the experiment with the V-tube arrangement that I will describe in Sect. 2.2.1.2.
- 9.
See Golinski (1992), 213, for a brief discussion of Gibbes’s continuing opposition to Lavoisierian theory.
- 10.
- 11.
This paper is passed over by most historians who discuss Priestley’s work; one exception is a brief discussion given by Schofield (2004), 366.
- 12.
Priestley did use the terms “oxygen” and “hydrogen” (or, “oxigen” and “hidrogen”) interchangeably with “dephlogisticated air” and “inflammable air” in this paper. To be precise: the term “hidrogen” only occurs in the marginal summaries, so Nicholson may have been responsible for that; however, “oxigen” occurs several times in Priestley’s main text, freely mixed in with “dephlogisticated air”.
- 13.
Priestley’s description is ambiguous in this passage, as to whether these measures prevented the production of oxygen gas only, or both gases. On p. 201 he reports an experiment in which an oil-covering on the water also stopped the production of hydrogen (inflammable air). But the key point for the moment, which is clear throughout the paper, is that Priestley thought that the production of the two gases happened independently from each other. See Sect. 2.3.2 for further details.
- 14.
In one place in the article (p. 202, middle) he has the polarity switched, but I think that is a simple error.
- 15.
See also the discussion in Wilkinson (1804), 74–80.
- 16.
Christoph Heinrich Pfaff (1773–1852) taught from 1798 at Kiel University, where he would remain until his death (Hufbauer 1982, 223); on his electrochemical work, see Kragh (2003).
- 17.
- 18.
See Coutts (1959) for some informative details on Cruickshank’s life and work.
- 19.
Coutts (1959, 125) explains the convention in the designation of the parts of the battery used by Cruickshank.
- 20.
On Wilkinson’s life and work, see Thornton (1967).
- 21.
Or that it had so little weight as to be undetectable by the technology of that time (which could in fact be said very fairly about electrons, too).
- 22.
See Brown (1950), 372, and Brown (1979) on Rumford more generally. They also managed to put up sufficiently strong objections to Rumford’s more powerful anti-caloric argument based on the more famous “cannon-boring” argument showing the indefinite production of heat by friction (Chang 2004, 171, and references therein).
- 23.
I have corrected the translation appearing in the English version of Ostwald’s text, which has the terms in square brackets as “potassium sulfate” and “potassium hydroxide”, which is anachronistic in a problematic way, as Berzelius and Hisinger were writing before Davy’s work on the isolation of potassium, when potash was widely regarded as elementary with only an unfounded suspicion that it might be a compound. (Rendering “vitriolic acid” as “sulphuric acid” is not problematic in the same way.)
- 24.
Etienne Gaspard Robertson (1763–1837) in Paris independently advanced a similar view of a galvanic acid (Ostwald [1896] (1980), 209/216). Mottelay (1922, 350–351) explains that Robertson had a personal friendship with Volta, and he was one of the first in Paris to pay proper attention to Volta’s work; curiously, it was through Brugnatelli’s intervention in a lecture given by Robertson that the latter first began his interaction with Volta.
- 25.
Wollaston also found ultraviolet rays, independently of Ritter’s work.
- 26.
For the circumstance of Grotthuss’s death and his legacy, see Gorbunova et al. (1978), 233–234.
- 27.
By this phrase I don’t mean just the electrochemistry of water, but the electrochemical system that took water as a compound.
- 28.
That, too, will become less certain with deeper knowledge.
- 29.
As Faraday meticulously numbered the paragraphs in all of his papers on “Experimental Researches on Electricity” in one consecutive sequence, I will note the paragraph numbers in my citations.
- 30.
So we can see that Cleve was a whole century ahead of Laudan in making the pessimistic meta-induction from the history of science! Laudan’s point is a stronger one, as his examples concern theories that were once well-established, as opposed to Cleve’s ephemera. Cleve may have been wiser than his pupil, but Arrhenius was both the more typical and the more productive player in this game.
- 31.
T. M. Lowry (1936, 270) notes that it was only in 1840 that John Frederic Daniell advanced the general view that a salt was a binary compound of two radicals, not of an acid and an alkali in their entirety.
- 32.
Lowry (1936, 11, 62, 288) states that Davy used caustic potash and caustic soda, and identifies them as the hydroxides of the metals, KOH and NaOH. The non-caustic varieties are the carbonates: K2CO3 and Na2CO3. See Lowry’s explanation (pp. 283–284) on how Davy and others gradually moved away from his initial view that potash and soda were simple oxides.
- 33.
As Knight (1967, 21) explains, this was one reason for which he did not wholly embrace John Dalton’s atomic theory, which postulated a distinct atom for each chemical element recognized as such at the time. While accepting the Lavoisierian operational definition of an element as a hitherto undecomposed substance, Davy focused his effort on effecting new decompositions. One of his motivations for entertaining the revival of phlogiston (see Chap. 1, Sect. 1.2.2) was to see if he could not reduce the number of chemical elements (see Siegfried 1964).
- 34.
- 35.
Many historians and philosophers have criticized Kuhn on this point. For an early example see Toulmin (1970).
- 36.
In this he had two important predecessors. One was Davy, whose conception of the relation between the electrical and chemical forces was more subtle, complex and vague that Berzelius’s. Russell’s view (1959, 12) is that “Faraday was the one to influence the world to look favourably on his master’s theories. And he did this by enshrining them in his own.” The other predecessor I want to highlight is Donovan (1816, 278), who published this insightful view 15 years before Faraday’s work: “it was found that copper lost its affinity for oxygen, by contact with zinc;... the affinity of the zinc for oxygen was much increased by contact with copper. I think therefore there is nothing overstrained in the inference that one has gained what the other lost, or in other words that the copper has transferred a portion of its affinity for oxygen to the zinc.”
- 37.
As usual, the exhaustive treatments by Ostwald [1896] (1980), Mottelay (1922) and Partington (1964) provide very useful exceptions. Another notable exception, though very brief, is Harold Hartley’s discussion of “Faraday’s successors and the theory of electrolytic dissociation” (Hartley 1971, ch. 7); Hartley was not worried about avoiding historiographical whiggism, but his perspective in 1931, when he composed that piece, was that his own current situation resembled that of the rich and uncertain field that Faraday faced, rather than the over-clarity of Arrhenius’s work.
- 38.
Schwab’s focus was on science education. The increasing prevalence of fluid inquiry in science means that it becomes increasingly necessary to train science students for it—in other words, to equip them for critical thinking; see Siegel (1990), 99–102, for further reflections on this point.
- 39.
I carried out these experiments in the electrochemistry lab of Daren Caruana at the Department of Chemistry at University College London. I would like to thank Dr. Caruana and his colleagues most sincerely for the use of the laboratory facilities and all the friendly advice they gave me. I also would like to thank Rosemary Coates, who assisted me most congenially and ably in these and other experiments, and the Leverhulme Trust, whose research grant provided much-needed funds and an authoritative seal of approval.
- 40.
Or is it possible that the application of electricity generates oxygen by decomposing CO2, which will be found dissolved in the water in relative abundance?
- 41.
- 42.
For hosting these experiments, I thank the Department of Chemistry at the University of Cambridge, and Dr. Peter Wothers, Mr. Chris Brackstone, and Mr. Gary Herrington.
- 43.
Darrigol (2000), 266–274, quotation on p. 266, footnote 1.
- 44.
Yet it seems evident that Kuhn had not taken an in-depth look, as he says that “both viewpoints were briefly in the field at once” (p. 23, emphasis added).
- 45.
Partington (1964, 17) also mentions that the Oxford dry pile had continued to work for more than a century.
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Chang, H. (2012). Electrolysis: Piles of Confusion and Poles of Attraction. 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_2
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