The Phlogistic Role of Heat in the Chemical Revolution and the Origins of Kirwan's ‘Ingenious Modifications… Into the Theory of Phlogiston’

Summary

Contrary to common belief, Lavoisier's greatest phlogistic rival was not Joseph Priestley but Richard Kirwan, a fact that was firmly recognized by both the Lavoisians as well as Priestley himself. During the 1780s, which saw the unprecedented rise of the chemistry of air(s), Kirwan's ‘ingenious modifications…into the theory of phlogiston’, in Mme. Lavoisier's words, became the most dominant alternative to the revisionist pneumatic interpretations of the French. A genealogical contextualization of Kirwan's phlogistic contributions, the circumstances of their emergence and the nature of their evolution and impact, reveals the intricate process of transformation that pneumatic phlogistic thought and practice have undergone during the final years of phlogiston's existence. Originally introduced as an adverse reaction to Scheele's phlogistic reasoning, Kirwan's work evolved as a sophisticated integration between notions of aerial permutations and Adair Crawford's innovative formulation of the phlogistic role of heat, with its origins in the Scottish pneumatic tradition of Black and Irvine. Examining Kirwan's views against the background of metaphysical conflicts over the constitution of pneumatic entities and the role of phlogiston in pneumatic processes traces their origins and advances to a complex interplay between innovation and renovation, proclamation and reclamation, thus depicting the dynamics of (dis-)continuity in the broader phlogistic sphere from which Kirwan's ‘modifications’ have stemmed and which they came to forcefully represent.

An earlier version of this paper was presented at the Canadian Society for the History and Philosophy of Science Annual Meeting, 27–30 May, Saskatoon, Canada.

An earlier version of this paper was presented at the Canadian Society for the History and Philosophy of Science Annual Meeting, 27–30 May, Saskatoon, Canada.

Acknowledgements

I owe special thanks to Trevor Levere for stimulating discussions and insightful commentary. I also wish to thank David Knight and Georgette Taylor for instructive comments and suggestions.

Notes

An earlier version of this paper was presented at the Canadian Society for the History and Philosophy of Science Annual Meeting, 27–30 May, Saskatoon, Canada.

²Kirwan is also known for his geological debate with James Hutton. E.L. Scott, ‘Richard Kirwan, J.H. Magellan, and the Early History of Specific Heat’, Annals of Science, 38 (1981), 141–53 (143 fn. 12).

³See E.L. Scott ‘Richard Kirwan’, in Dictionary of Scientific Biography, 16 Vols., edited by Charles Coulston Gillispie (New York, 1970–1980), Vol. 7, 387–90; E.L. Scott, ‘Kirwan, Richard (1733–1812)’, Oxford Dictionary of National Biography (Oxford, 2004). Both of Scott's entries arise from his doctoral research, which comprises a unique study of Kirwan's life and work and subsequently contains extensive and valuable information. E.L. Scott, The Life and Work of Richard Kirwan (1733–1812) (University of London: Unpublished Ph.D. thesis, 1979). Further details on Kirwan's life and work can be gleaned from J. Reilley and N. O'Flynn, ‘Richard Kirwan, an Irish Chemist of the Eighteenth Century’, Isis 13 (1930), 298–319; James R. Partington, A History of Chemistry, 4 Vols. (London, 1961–1970), Vol. 3, 660–71. For the best account of Kirwan's work on chemical affinities and its relation to the wider context of eighteenth-century chemistry see Mi Gyung Kim, Affinity, That Elusive Dream: A Genealogy of the Chemical Revolution (Cambridge, MA, 2003), esp. 268–77.

⁴The ‘phlogistic camp’ refers broadly to British pneumatic chemists who subscribed, during the 1780s, to phlogistic tenets. Most notable as well as pertinent to the ensuing discussion are Joseph Priestley and Adair Crawford, who shared several fundamental beliefs concerning the constitution of airs (C.W. Scheele, who held different ideas, was also a devout phlogistian and figures prominently throughout the course of this study); Joseph Black and Henry Cavendish are notable, too, although their particular association with phlogistic thought during this transition period is more problematic and difficult to ascertain; additional figures, of slighter repute, are James Keir and William Nicholson.

⁵This is best signalled by the Lavoisians’ detailed responses to Kirwan's Essay on Phlogiston, in which their collaborator (and translator), Mme. Lavoisier, wrote about Kirwan that ‘Among the philosophers who have not yet adopted the new doctrine, he is certainly one of those who is the most capable of producing uncertainty in the minds of such persons as decide by authority’. Richard Kirwan, An Essay on Phlogiston, and the Constitution of Acids … To which are added, Notes, exhibiting and defending the Antiphlogistic theory; and annexed to the French Edition of this Work … With Additional Remarks and Replies, by the Author, translated by W. Nicholson and Mme. Lavoisier (London, 1789), xiv. The term ‘Lavoisians’ is usually taken to include Lavoisier's closest collaborators, C.L. Berthollet, A F. Fourcroy and Guyton de Morveau, his co-authors to the Method of Chymical Nomenclature, translated by James St. John (London, 1788). Lavoisier had also conducted significant collaborations with Pierre-Simon Laplace and with Gaspard Monge. This group is sometimes named the Arsenal group, after their regular place of meeting for scientific discussions. See Kim (note 2), 335–37. For Priestley's acknowledgements, see his post-revolutionary plea, addressed to the Lavoisians, ‘The Surviving Answerers of Mr. Kirwan’ and his reference to Kirwan's ‘pretty large treatise in opposition’ to the French system. Experiments and Observations Relating to the Analysis of Atmospherical Air … To Which Are Added, Considerations on the Doctrine of Phlogiston, and the Decomposition of Water (London, 1796), 33–36. This 1796 plea was reproduced four years later verbatim (and again, in 1803 ‘with additions’) in The Doctrine of Phlogiston Established, and That of the Composition of Water Refuted (Philadelphia, 1800), x–xi; Priestley also reflects solemnly upon Kirwan's conversion (2).

⁶For biographical details on Mme. Lavoisier and her particular involvement in this project as translator, see Denis I. Duveen, ‘Madame Lavoisier, 1758–1836’, Chymia 4 (1953), 13–29 (14–16); Keiko Kawashima, ‘Madame Lavoisier et la traduction française de l'Essay on Phlogiston de Kirwan’, Revue d'Histoire des Sciences 53 (2000), 235–63.

⁷Kirwan (note 4), vi.

⁸A contextual study of the Kirwan–Lavoisians dispute, as arising from the dynamics and rhetoric of the Essay, with particular focus on the loss of ontological and epistemological practices entailed by the renunciation of the phlogistic world-view, in is in preparation by the author.

⁹See, for instance, the excellent historiographic analysis Frederic L. Holmes, ‘The Boundaries of Lavoisier's Chemical Revolution’, Revue d'Histoire des Sciences, 48 (1995), 9–48 (19), in which the author stated that by 1787, the year Kirwan's Essay was first published, ‘the [chemical] revolution was consummated’; he further noted that ‘By that time, the most important experimental and theoretical confrontations on which the issue hung were essentially over’. See also reference to Kirwan's ‘reputation as a stubborn defender of outmoded causes.’ Scott (note 1), 143. Cf. W.H. Brock, The Norton History of Chemistry [Fontana History of Chemistry] (New York, 1993), 93.

¹⁰Two notable recent exceptions are Kim (note 2), 379–83; Seymour Mauskopf, ‘Richard Kirwan's Phlogiston Theory: Its Success and Fate’, Ambix 49 (2002), 185–205. Both authors focus mainly on Kirwan's research into chemical affinities and the way it informed his arguments against the antiphlogistic chemistry.

¹¹The philosophical locus classicus of this view is Thomas Kuhn, The Structure of Scientific Revolutions (Chicago, 1962); the historical one is James B. Conant, The Overthrow of the Phlogiston Theory: The Chemical Revolution of 1775–1789 (Cambridge, MA, 1950). For a historical survey and insightful discussion concerning the historiography of the chemical revolution in the wake of Kuhn and Conant see John. G. McEvoy, ‘Postpositivist Interpretations of the Chemical Revolution’, Canadian Journal of History 36 (2001), 453–69.

¹²See, for instance, Stephen Toulmin and June Goodfield, The Architecture of Matter (Chicago, 1962), esp. 222–28; Alan Musgrave, ‘Why Did Oxygen Supplant Phlogiston? Research Programmes in the History of Chemistry’, in Method and Appraisal in the Physical Sciences, edited by Colin Howson (Cambridge, 1976), 181–209.

¹³Trevor H. Levere and G. L'E. Turner, Discussing Chemistry and Steam (Oxford: Oxford university Press, 2002), 196; Robert Siegfried, ‘The Chemical Revolution in the History of Chemistry’, in Osiris, Volume 4: The Chemical Revolution: Essays in Reinterpretation, edited by A. Donovan (HSS Publications, Philadelphia, PA, 1988), 34–50 (35).

¹⁴Frederic L. Holmes, ‘The “Revolution in Chemistry and Physics”, Overthrow of a Reigning Paradigm or Competition between Contemporary Research Programs?’, Isis 91 (2000), 735–53 (748). In a different study, inspired by ‘Ferdinando Abbri's important study of the chemical revolution, Le terre, l'acqua, le arie’, Holmes suggests a revisionist portrayal of the commonplace historiographic personae of Priestley and Lavoisier, undermining the received view based on ‘Priestley's reputation as a brilliant experimentalist and Lavoisier's reputation as a lesser experimentalist, but greater theorist’. Holmes's study draws on an original reading of the historical actors’ rhetorical devices and reportage, emphasizing how during the late 1770s and early 1780s, far from perceiving himself as leading a revolution, Lavoisier acknowledged Priestley's eminence, while claiming the status of ‘only an able participant in a broader revolution brought about by the new pneumatic chemistry’. Frederic L. Holmes, ‘Phlogiston in the Air’, Nuova Voltiana: Studies on Volta and His Times, edited by F. Bevilaqua and L. Fregonese (Pavia, 2000), 73–113 (75–5, 80); I kindly owe this reference to Georgette Taylor. For various, often divergent, approaches to Priestley's phlogistic endeavours see, for instance, R.E. Schofield, ‘Joseph Priestley, the Theory of Oxidation and the Nature of Matter’, Journal of the History of Ideas, 25 (1964), 285–94; John G. McEvoy, ‘Causes and laws, powers and principles: The metaphysical foundations of Priestley's concept of phlogiston’, in Science, Medicine, and Dissent: Joseph Priestley (1733–1804), edited by R.G.W. Anderson and Christopher Lawrence (London, 1987), 55–71; F. Verbruggen, “How to Explain Priestley's Defense of Phlogiston,” Janus, 59 (1972), 47–69. McEvoy, for example, mentions both Priestley and Kirwan in the context of ‘phlogistic defences’ but Kirwan's efforts are depicted as mere ‘suggestions’, which Priestley had briefly ‘endorsed’ and then ‘rejected’; furthermore, Kirwan's identification of phlogiston with inflammable air is rendered as a sign of the theoretical frailty of phlogistic outlooks: ‘Lavoisier's pragmatic definition of an element as an end product of analysis … did not rob the principle of phlogiston of its substantive identity … [but] it did influence them [phlogistians] in their desire to identify it with a specific [isolable and weighable] substance. John G. McEvoy, ‘Continuity and Discontinuity in the Chemical Revolution’ in Osiris, Volume 4: The Chemical Revolution: Essays in Reinterpretation, edited by A. Donovan (HSS Publications, Philadelphia, PA, 1988), 195–213 (200–201).

¹⁵See, for instance, Stephen Toulmin, ‘Crucial Experiments: Priestley and Lavoisier’, Journal of the History of Ideas, 18 (1957), 205–20. Other momentous experiments in the chemical revolution include the decomposition and synthesis of water.

¹⁶See Michael F. Conlin, ‘Joseph Priestley's American Defense of Phlogiston Reconsidered’, Ambix 43 (1996), 129–45.

¹⁷On Kirwan's 1791 ‘conversion’ see Mauskopf (note 9), 202–204.

¹⁸This point has been most recently argued by Holmes, who suggested a reformulation of our understanding of Priestley's phlogistic interests by situating them within a ‘novel’ pneumatic framework that Priestley himself established and which did not owe its origins to Stahlian precepts; within this framework, Priestley's theoretical commitments to phlogiston were secondary and loosely defined. Holmes (note 13).

¹⁹For Priestley's acceptance of Kirwan's doctrine of phlogiston, on theoretical as well as experimental grounds, see: Joseph Priestley, ‘Experiments relating to Phlogiston, and the seeming Conversion of Water into Air’, Philosophical Transactions 73 (1783), 398–434, esp. 399–414. For Priestley's incessant references to Kirwan's work, see note 4.

²⁰Joseph Priestley, A Scientific Biography of Joseph Priestley, 1733–1804; Selected Scientific Correspondence, edited by R.E. Schofield (Cambridge, MA, 1966), 206–07.

²¹Kirwan (note 4), xv.

²²The ‘continuity’ vs. ‘discontinuity’ debate is open-ended. Cf. J.B. Gough, ‘Lavoisier and the Fulfilment of the Stahlian Revolution’ in Osiris, Volume 4: The Chemical Revolution: Essays in Reinterpretation, edited by A. Donovan (HSS Publications, Philadelphia, PA, 1988), 15–33; McEvoy (note 13).

²⁴Joseph Priestley, ‘An Account of Further Discoveries in Air’, Philosophical Transactions 65 (1775), 384–94 (392).

²³Victor D. Boantza, ‘Collecting Airs and Ideas: Priestley's Style of Experimental Reasoning’, Studies in the History and Philosophy of Science 38 (2007), 506–22.

²⁵It should be noted that ‘table 1’ represents a comparative conceptualization of what I have denominated ‘pneumatic phlogistic sequences’—i.e. these ‘sequences’ do not occur, as such, in the writings of the figures discussed. Rather, they represent a conceptual apparatus extracted and gleaned from the respective texts. In this context, the author owes a substantial intellectual debt to a little known work, which although devised as part of a different argument, exhibits a similar methodological approach. Bernard Langer, Pneumatic Chemistry, 1772–1789: A Resolution of Conflict (Unpublished Ph.D. dissertation, University of Wisconsin, 1971).

²⁶I use ‘transmutation’ to denote the implicit view, endorsed by contemporary phlogistic pneumatic practitioners according to which different airs (or other pneumatic kinds) corresponded to various degrees of phlogistication of a generic pneumatic entity. This process is shown to have followed, theoretically and practically, distinct sequential patterns.

²⁷Joseph Priestley, Experiments and Observations on Different Kinds of Air, and Other Branches of Natural Philosophy: in Three Volumes, Being the Former Six Volumes Abridged and Methodized, with Many Additions (Birmingham, UK, 1790), xvii.

²⁸C.W. Scheele, Chemical Observations and Experiments on Air and Fire, with a Prefatory Introductions by Torbern Bergman; Translated from the German by J.R. Forster, to Which Are Added Notes by Richard Kirwan, with a Letter to Him By Joseph Priestley (London, 1780).

²⁹Joseph Priestley, ‘Observations on Different Kinds of Airs’, Philosophical Transactions 62 (1772), 147–264.

³⁰Scheele (note 27), vii–viii.

³²Scheele (note 27), xxxviii–xl.

³¹Scheele (note 27), viii.

³³Scheele (note 27), 6.

³⁴Scheele (note 27), 10–12.

³⁵Scheele (note 27), 13–14.

³⁶Scheele (note 27), 16.

³⁷Scheele (note 27), 35.

⁴²Scheele (note 27), 33.

³⁸Scheele (note 27), 16.

³⁹Scheele (note 27), 26.

⁴⁰Scheele (note 27), 25–31.

⁴¹Scheele (note 27), 32–33.

⁴³Scheele (note 27), 33–34.

⁴⁶Scheele (note 27), 97–99.

⁴⁴Scheele (note 27), 26.

⁴⁵Scheele (note 27), 77, 97.

⁴⁷Scheele (note 27), 178.

⁴⁸Scheele (note 27), viii, xl.

⁴⁹Priestley (note 26), 181.

⁵⁰Torbern Bergman, A Dissertation on Elective Attractions, translated by Thomas Beddoes (London, 1785; first published in Latin as Disquisitio de attractionibus electives, 1775), 231–34.

⁵¹Pierre J. Macquer, Elements of the Theory and Practice of Chymistry, translated by A. Reid (London, 1764), 7. During the latter third of the eighteenth-century light was assumed, among various chemical practitioners, a chemical–pneumatic identity; although Priestley's reasoning differed from Scheele's he also accorded light such a status. See Victor D. Boantza ‘Light in the Pneumatic Context: Dynamics of Interplay between Theory and Practice in Early Photochemical Research’, Historia Scientiarum 16 (2006), 105–28.

⁵²Joseph Priestley, Experiments and Observations on Different Kinds of Air (London, 2nd. ed. corrected, 1775), 280.

⁵³In the Traité Lavoisier wrote: ‘in the present state of our knowledge, we are unable to determine whether light be a modification of caloric, or if caloric be, on the contrary, a modification of light … [but] we ought provisionally to distinguish, by distinct terms, such things as are known to produce different effects’. Antoine Lavoisier, Elements of Chemistry, in a new systematic order, containing all the modern discoveries, translated by Robert Kerr (New York, 1965; first published in French as Traité élémentaire de chimie, présenté dans un ordre nouveau et d'après les découvertes modernes, Paris, 1789), 4–6.

⁵⁴A.F. Fourcroy, Elements of natural history, and of chemistry, 2nd edition, translated by W. Nicholson (London, 1788; first published in French as Leçons élémentaires d'histoire naturelle et de chimie, 1782), vol. I, 142.

⁵⁵Macquer (note 50), 7.

⁵⁶Fourcroy (note 53), vol. I, 142.

⁵⁷Scheele (note 27), 250.

⁶⁰Scheele (note 27), 196.

⁵⁸Scheele (note 27), 223.

⁵⁹For biographical details on Crawford, see Partington (note 2), Vol. 3, 156–57.

⁶¹Adair Crawford, Experiments and Observations on Animal Heat, and the Inflammation of Combustible Bodies, Being an Attempt to Resolve These Phenomena into a General Law of Nature (London, 1779). The second edition of this essay was published in 1788, under the same title “with very large additions,” and was dedicated to Kirwan “as a mark of respect and esteem, by his most sincere friend, and obliged humble servant, the author. [A. Crawford].” The first 1779 edition consisted of 128 pages; the second edition consisted of 511 pages.

⁶²Some exceptions, mostly descriptive, include Everret Mendelsohn, Heat and Life: The Development of the Theory of Animal Heat (Cambridge, MA, 1964) and J.R. Partington and D. McKie, ‘Historical Studies on the Phlogiston Theory III: Light and Heat in Combustion’, Annals of Science, 3 (1938), 337–71, esp. 345–50. See also D. McKie and N.H. de V. Heathcote, The Discovery of Specific and Latent Heats (New York, 1975), passim.

⁶³The three volumes were published in 1774, 1775 and 1777 and were followed by three additional volumes published in 1779, 1780 and 1786, respectively. The latter three were entitled Experiments and Observations Relating to Various Branches of Natural Philosophy; with a Continuation of the Observations on Air. All of Priestley's pneumatic volumes went through numerous editions.

⁶⁴Arthur Donovan (1975), Philosophical Chemistry in the Scottish Enlightenment (Edinburgh), 273.

⁶⁵Crawford (note 60), 17, in fn; William Irvine (1743–1787) studied medicine and chemistry under Joseph Black (1728–1799) and assisted him in his first experiments on latent heats. In 1766 he was appointed as medical lecturer at the University of Glasgow, a position he held until his death. See Donovan (note 63), 265–66.

⁶⁸Crawford (note 60), 32–33.

⁶⁶Crawford (note 60), 18.

⁶⁷Crawford (note 60), 31–32.

⁶⁹Crawford (note 60), 34; italics mine. Further down the text Crawford is somewhat more explicit, claiming that ‘in the process of respiration, atmospherical air is converted into fixed air’ without mentioning the presence of phlogisticated air (69), by that he meant that the pneumatic transmutation at hand is of common air into fixed air. Dephlogisticated air would be invariably present as part of the aerial mixture. This outlook presumes that further phlogistication of common air would yield, as Priestley suggested, phlogisticated air. Partington and McKie argue along similar lines in interpreting Crawford, thus emphasizing the conceptual underpinning: ‘Phlogiston and pure air combine to form fixed air; the dephlogisticated air is only separated from the atmospheric air.’ Partington and McKie (note 61), 347.

⁷⁰Crawford (note 60), 1–2.

⁷¹Crawford (note 60), 16.

⁷²Crawford (note 60), 17, in fn.

⁷⁴Crawford (note 60), 95.

⁷³R. Fox, The Caloric Theory of Gases: From Lavoisier to Regnault (Oxford, 1971), 20–26; H. Chang, Inventing Temperature: Measurement and Scientific Progress (Oxford, 2004), 64–68.

⁷⁸Crawford (note 60), 67–68.

⁷⁵Crawford (note 60), 34.

⁷⁶Crawford (note 60), 50–53.

⁷⁷Crawford (note 60), 61, 63–64.

⁷⁹Donovan (note 63), 218–19.

⁸⁰Mendelsohn (note 61), 127.

⁸²Crawford (note 60), 74–75.

⁸¹Crawford (1779), 72–73; Joseph Priestley, Experiments and Observations on Different Kinds of Air, Vol. 3 (London, 1777).

⁸³Crawford (note 60), 76–77.

⁸⁴Crawford (note 60), 42.

⁸⁵See Luigi Belloni, ‘Felice Fontana’ in Gillispie (note 2), vol. 5, 55–57.

⁸⁷Scheele (1780), 232–23; It should be noted that the alphabetical listing (A, B, C, D) does not occur in the text but was introduced by the author for the sake of convenience in reference to Kirwan's four different statements. The original text reads: “1st, 2dly, 3dly and 4thly,” respectively.

⁸⁶Scheele (1780), 104–105.

⁸⁸See Scott (note 1), who speculates on the origin of this term and is inclined to attribute it to Kirwan. Scott quotes from Kirwan's 1787 An Estimate of the Temperatures of Different Latitudes: ‘All bodies require a certain quantity of elementary fire or light to heat them to a certain degree, but the quantity requisite to produce this degree varies, according to the nature and species of these bodies, and hence the proportion suited to each is called their specific fire’. (146). For a singular study dealing with the collaboration between Kirwan, Magellan, Crawford and others—as the founder-members of the ‘Coffee House Philosophical Society’—see Levere and Turner (note 12).

⁹⁰Scheele (note 27), 236–37.

⁸⁹Scheele (note 27), 111.

⁹¹Scheele (note 27), 224.

⁹²Priestley (note 51), 282.

⁹³Scheele (note 27), 178–79.

⁹⁴Scheele (note 27), 248–49.

⁹⁵Although he does not argue in favour of a clear connection, Mauskopf mentions in this context Cavendish's 1766 identification between phlogiston and inflammable air. Mauskopf (note 9), 190–93. Cavendish's statement is an isolated instance, not linked to any broader considerations and seems to be a mere fleeting observation upon an experimental phenomenon. Nor does Kirwan make any mention of Cavendish, which evinces the strong circumstantial nature of this association.

⁹⁶Richard Kirwan, ‘Continuation of the Experiments and Observations on the Specific Gravities and Attractive Powers of Various Saline Substances’, Philosophical Transactions 72 (1782), 195–96.

⁹⁷Kirwan (note 95), 196.

⁹⁸Scheele (note 27), 104–105.

⁹⁹Kirwan (note 95), 195–96.

¹⁰⁰Pierre J. Macquer, A Dictionary of Chemistry, Containing the Theory and Practice of that Science, trans. J. Keir (London, 1771), Vol. 2, 516.

¹⁰¹Scheele (note 27), 222–23.

¹⁰²Scheele (note 27), 221; Two years later he repeated: ‘Phlogisticated air consists of fixed air super-saturated with phlogiston’. Kirwan (note 95), 222.

¹⁰⁵Kirwan (note 95), 201.

¹⁰³Kirwan (note 95), 214–15.

¹⁰⁴Kirwan (note 95), 220.

¹⁰⁶Bergman (note 49), 277–78.

¹⁰⁷Henry Cavendish, ‘Experiments on Air’ Philosophical Transactions 74 (1784), 199-53 (123, 129).

¹⁰⁸Bergman (note 49), 352–53.

¹⁰⁹Kirwan (note 4), 4–5.

¹¹⁰Kirwan (note 4), 7–8.