Kirwan, Richard

(b. Cloughballymore, County Galway, Ireland, 1733[?]; d. Dublin, Ireland, 1 June 1812)

chemistry, mineralogy, geology, meteorology.

The second son of Martin Kirwan, of Cregg Castle near Corrandulla, and Mary French, of Cloughbally-more near Kilcolgan, Richard Kirwan was descended from two prominent landed familes. Little is known for certain about his early years; he was apparently a precocious, bookish child. After his father’s death in 1741 he was brought up at his mother’s home, where he had been born.

In about 1750 Kirwan enrolled at the University of Poitiers, to which his elder brother, Patrick, had gone earlier, their religion virtually excluding them from British universities. A letter from his mother written at about this time indicates that he had already developed an interest in chemistry, for which he was neglecting his specified curriculum; he nevertheless seems to have become proficient in Latin. His mother died soon afterwards, and in 1754 Kirwan left the university but remained in Europe and became a Jesuit novice.

Upon the death of Patrick and his consequent inheritance of the family estates Kirwan abandoned his novitiate and returned to Ireland. In 1757 he married Anne Blake, daughter of Sir Thomas Blake of Menlough Castle, just north of Galway; they had two daughters. Kirwan seems to have spent most of his married life at the home of the Blakes, where he fitted up a laboratory and amassed a library. His wife died in 1765 while he was in London studying law.

The motives for Kirwan’s turning to law are not clear. He renounced his Catholic beliefs in 1764 as a prerequisite of his being called to the Irish bar in 1766, but practiced for only about two years, finding the profession uncongenial and the rewards inadequate. During the next eight or nine years, about three of which were spent in London (ca. 1769-1772), he increased his knowledge of science and languages; and in 1777 he returned to London, where he stayed for ten years. His house became a well-known meeting place for those distinguished by birth, position, or achievement—particularly in science.

In 1787 Kirwan returned to Ireland. He was one of the original members of the Royal Irish Academy, to which he presented a large number of papers on a remarkable variety of subjects, and of which he was president from 1799 until his death. Much of Kirwan’s work in chemistry was done during the decade he spent in London. He was admitted to the Royal Society in 1780 and awarded the Copley Medal for his work on chemical affinity.

Although by some the term “affinity” was used in preference to “attraction” to avoid the implications of the latter, Kirwan had no such reservations: “Chymical affinity or attraction is that power by which the invisible particles of different bodies intermix and unite with each other so intimately as to be inseparable by mere mechanical means.” It differed from nonchemical forms of attraction in that it caused “a body already united to another to quit that other and unite with a third, and hence it is called elective attraction.” He coined the terms “quiescent” and “divellent” (afterwards generally adopted) to denote, respectively, those affinities which resisted decomposition and those which tended to effect decomposition and bring about a new union.

Kirwan began his three-part paper (1781-1783) by referring to the “recent great improvement in the subject by the excellent Mr. Bergman.”¹ But up until then, he felt, only the order of affinities had been attended to (the first table showing this had been published by E. F. Groffroy in 1718); and none except “Mr. Morveau of Dijon” had thought of ascertaining the actual degrees of attraction between one substance and others, or between the same two substances in different circumstances. Kirwan, how ever, had already “bestowed much pains” on this problem.²

He set out to determine the weights of various bases and metals that neutralized or dissolved in a given weight of each of the three mineral acids, believing these weights to be proportional to the affinities of the particular acid with the given bases or metals. His preliminary problem, however, was to find the weight of “real acid” in an aqueous solution. He believed that Priestley’s discovery of “marine acid air” (hydrogen chloride)—that is, the acid freed from all water—had shown him how to do this. Knowing the specific gravity of the air and that of any solution, the weight of real acid in the solution could be found. For other acids, he made use of the assumption (presumably derived from Homberg) that the same weights of different acids neutralized a given weight of a particular alkali.

The measurements of affinity which Kirwan obtained were, of course, equivalents. His findings, translated and published in France and Germany, must have contributed to the formulation of the law of reciprocal proportions explicated by Richter. In two later papers on the composition of salts, read in 1790 and 1797 and published in Ireland, he revised some of his results and criticized some of those obtained by Richter and others. The first of these papers was translated by Mme. Lavoisier, who earlier had translated Kirwan’s best-known work, the Essay on Phlogiston.³

First published in 1787, the Essay defended the phlogiston theory against the views then being promulgated in France by Lavoisier and his followers. Kirwan identified phlogiston with “inflammable air” (hydrogen), comparing it with “fixed air”(carbon dioxide); the latter, Black had shown, could exist “fixed, concrete and unelastic” in solids and in a “fluid, elastic and aëeriform” state. He did not deny the observations on which Lavoisier had based his rejection of phlogiston, but believed them to be explicable in terms of the older theory, which on the whole, accorded best with known chemical facts.

Kirwan’s arguments hinged on his belief that inflammable air and “dephlogisticated air” (oxygen), although they had been shown to form water at red heat, formed fixed air at lower temperatures, and that the fixed air contained a greater proportion of phlogiston than did water. Thus, for example, he was able to explain the gain in weight of metals when calcined: this was due to the fixed air formed from dephlogisticated air and the phlogiston in the metal, and then absorbed. In the French translation of the Essay (1788), lengthy comments on each section were added by leading “antiphlogistians” (including Lavoisier); these, translated by William Nicholson, were included, with brief replies by Kirwan, in the second English edition (1789). A detailed refutation of the Essay was published in the same year by Kirwan’ countryman William Higgins, whom he afterwards befriended.⁴

Kirwan abandoned the phlogiston theory in 1791 because he failed to show conclusively the formation of fixed air from phlogiston and oxygen. In spite of his conversion, Kirwan was not overly enthusiastic about the new nomenclature. He forbore using it in the second edition of his Elemnets of Mineralogy and employed some terms of his own, earning a reproof from Guyton de Morveau.⁵ Following Cronstedt, Kirwan based his classification on qualitative chemical tests. Commenting on the vast increase of mineralogical information in Europe during the decade following his first edition, Kirwan said he would have despaired of assimilating it had it not been for the acquisition of the Leskean collection of minerals. He negotiated the purchase of this collection for the Royal Dublin Society and used his influence to obtain a grant from the Irish Parliament of £1,200 toward its cost.

Much has been written regarding Kirwan’ intemperate attack on James Hutton’s geomorphological theory. Although he was by no means alone in opposing Hutton, it was apparently his paper (1793), “Examination of the Supposed igneous Origin of Stony Substances,” that led Hutton to expand his ideas in his Theory of the Earth (1795). It has iften been overlooked, however, that Kirwan’s attack, if forthright, was less acrimonious than either Hutton’ reply in the second chapter of his book or John Playfair’s later defense of Hutton.⁶ Kirwan also challenged the experimental support of Hutton’s theories given by Sir James Hall.⁷ In his Geological essays and papers published in the Transactions of the Royal Irish Academy, he attempted to reconcile his observations with the history of the earth as related in Genesis.,⁸

Kirwan’s defense of outmoded ideas has tended to overshadow his more positive contributions to science. In particular, his pioneering work in meteorology has only recently claimed much attention. From records of Irish weather covering forty-one years, complied by John Rutty, he worked out a system of probabilities with a view to forecasting the weather for seasons ahead. His predictions were more often right than wrong and were much valued by farmers; though the sequences he observed have not persisted in Ireland, methods of autocorrelation similar to Kirwan’s are today proving successful elsewhere. Noteworthy, too, is his concept of air masses (redeveloped independently during the present century), his terms for which— polar” and “dquatorial,” “supra-marine” and “supra-terrene”—anticipated modern classification.⁹

Kirwan was interested in the application of science to industry and wrote informatively on coal mining, manures, and bleaching (he probably introduced chlorine bleaching to Ireland). ¹⁰ In the last decade of his life, however, he virtually abandoned science for other interests. He published volumes on logic and metaphysics, and in one paper tried to prove that man’s first language was a primitive form of Greek. He developed a number of eccentricities, particularly in later life, which were the subject of many anecdotes in the literature of the period.

NOTES

1. Bergman had a high opinion of Kirwan as a chemist, and on his proposal Kirwan was elected a member of both the Royal Society of Sciences in Uppsala and the Royal Academy of Sciences in Stockholm (see the introduction [pp. xlvii-li] to G. Carlid and J. Nordströom, eds., Torbern Bergman’s Foreign Correspondence (Stockholm, 1965), which contains eleven letters from Kirwan to Bergman (1782-1784)).

2. He later mentioned the attempts by Guyton de Morveau and C. F. Wenzel to quantify affinities, but pointed out their limited application. For an account of their methods see W. A. Smeaton, “Guyton de Morveau and Chemical Affinity,” in Ambix, 11 (1963), 55-64.

3. See D. I. Duveen, “Madame Lavoisier, 1758-1836,” in Chymia, 4 (1953), 13-29.

4. T. S. Wheeler and J. R. Partington, The Life and Work of William Higgins (Oxford, 1960), which contains a facs. reper. of A Comparative View of the Phlogistic and Antiphlogistic Theories, 2nd ed. (London, 1791), analyzes the arguments and gives much information about Kirwan.

5. In a review of the first volume (Annales de chimie, 23 ) [1791], 102-106), Kirwan thought highly of Guyton, and they were regular correspondents (see Smeaton, “L. B. Guyton de Morveau and His Relations with British Scientists,” in Notes and Records. Royal Society of London, 22 (1967), 113-130.

6. In Illustrations of the Huttonian Theory of the Earth (Edinburgh, 1802), passim. Playfair disparaged Kirwan’s reputation as a mineralogist (p. 481).

7. See C. S. Smith, “Porcelain and Plutionism,” in C. J. Schjeer, ed. Towards a History of Geology (Cambridge, Mass.-London, 1969), pp. 317-338.

8. A good account of his theory is in G. L. Davies, The Earth in Decay (London, 1969), pp. 142-145.

9. For a apprasia buy meterlosts see F. E. Dixon in Dublin Historical Record, 24 (1971), 58-59, and in Weather, 5 (1950), 63-65; also W. E. Knowles, Middleton, A History of the Theories of Rain (London, 1965), p.86.

10. See A. E. Musson & E. Robinson, Science and Technology in the Industrial Revolution (Manchester, 1969), pp. 186, 259-260, 289, 319-320.

BIBLIOGRAPHY

I. Original Works. Kirwan’s books are Elements of Mineralogy (London, 1784; 2nd ed., rev. and much enl.: I, London, 1794; II, Dublin, 1796); a 3rd ed., virtually a repr. of the 2nd ed., was published in Dublin in 1810, appearently “against his approbation”: Kirwan had “declined for some time previously the further cultivation of the science” (see R. Bakewell, An Introduction to Mineralogy [London,. 1819]. p iv); An Essay on Phlogiston andthe Constitution of the Acids (London, 1787; 2nd ed. [with notes from the French ed.], London, 1789; a facs. repr. of 2nd ed., London, 1968).

See also An Estimate of the Temperature of Different Latitudes (London, 1787), an early work in comparative climatology; An Essay on The Analysis of Mineral Waters (London, 1799), a good account of the qualitative and quantitative methods available; Geological Essays (London, 1799); Logick, 2 vols. (London, 1807); Metaphysical Essays (London, 1809) was styled “Vol. I” in its 1st ed., but this was omitted from the title page of a repr. in 1811.

The list of Kirwan’s papers in the Royal Society’s Catalogue of Scientific Papers, 3 (1969), 665-667, omits those in Philosophical Transactions of the Royal Society: almost complete lists are given by M. Donovan in Proceedings of the Royal Irish Academy, 4 (1850), xcv-xcvii, and by J. Reilly and N. O’Flynn in Isis, 13 (1930), 316-317, although a few articles and reprs. in periodicals are omitted.

In order of their treatment in the text, Kirwan’s most important papers on chemistry are “Experiments and Observations on the Specific Gravities and Attractive Powers of Various Saline substances,” in Philosophical Transactions of the Royal Society, 71 (1781), 7-41; 72 (1782), 179-236; and 73 (1783),15-84; “Experiments onHepatic Air,” ibid., 76 (1786), 118-154 (this gives a good account of hydrogen sulfide, and describes Kirwan’s discovery—independently of P. Gengembre—of hydrogen phosphide, which he called “phosphoric hepatic air”).

“Of the Strength of Acids, and the Proportions of Ingredients in Neutral Salts,” in Transactions of the Royal Irish Academy, 4 (n.d.), 3-84, read in 1790; “Additional Observations on the Proportion of Real Acid in the Three Ancient Known Mineral Acids, and on the Ingredients in Various Neutral Salts and Other Compounds,” ibid., 7 (1800), 163-297.

Kirwan’s geological publications include “Examination of the Supposed lgneous Origin of Stony substances,” ibid., 5 (n.d.), 51-81, read in 1793, his first attack on Hutton’s theory; “On the Primitive State of the Globe and its Subsequent Catastrophe,” ibid., 6 (1797), 233-308; “Observations on the Proofs of the Huttonian Theory of the Earth, Adduced by Sir James Hall, Bart.,” ibid., 8 (1802), 3-27; “An Illustration and Confirmation of Some Facts Mentioned in an Essay on the Primitive State of the Globe,” ibid., 29-34; “An Essay on the Declivities of Mountains,” ibid., 35-52.

On meteorology, see “A Comparative View of Meteorological Observations Made in Ireland Since the Year 1788, With Some Hints Towards Forming Prognostics of the Weather,” ibid., 5 (n.d.), 3-29, rad in 1793; “Essay on the Variations of the Barometer,” ibid., 2 (1788), 43-72; “Of the Variations of the Atmosphere,” ibid., 8 (1802), 269-507 (his concept of “air masses” is in these last two).

Kirwan’s papers on applied science include “Observations on Coal Mines,” ibid., 2 (1788), 15-170; “On the Composition and Proportion of Carbon in Bitumens and mineral coal,” ibid., 6 (1797),141-167; “What are the Manures Most Advantageously Applicable to the Various Sorts of soils, and What Are the Causes of Their beneficial Effect in Each Particular Instance,” ibid., 5 (n.d.) 129-198, read in 1794 (this was repr. separately and rev. several times); “Experiments On the Alkaline Substances Used in Bleaching, and On the Colouring Matter of Linen-Yearn,” ibid., 3 (1789), 3-47.

II. Secondary Literature. The main biography of Kirwan is by M. Donovan, who said he had access to family records, in Proceedings of the Royal Irish Academy, 4 (1850), lxxxi-cxviii; biographies since 1850 have relied heavily on this. Using it in conjunction with other sources, and providing a historical background, P. J. McLaughlin gives a very readable account in Studies, 28 (1939), 461-474, 593-605, and 29 (1940), 71-83, 281-300.

Other biographies are J. O’Reardon, “The Life and Works of Richard Kirwan,” in National Magazine [Dublin], 1 (1830), 330-342, 469-475; J. R. O’Flanagan, in Dublin Saturday Magazine, 2 (1865), 242-244, 254-256, 266-269; C. J. Brockman, “Richard Kirwan, chemist, 1733-1812,” in Journal of Chemical Education, 4 (1927), 1275-1282; J. Reilly and N. O’Flynn, “Richard Kirwan, An Irish Chemist of the Eighteenth century,” in Isis, 13 (1930), 298-319; F. E. Dixon, “Richard Kirwan the Dublin Philosopher,” in Dublin Historical Record, 24 (1971), 53-64.

On Kirwan’s chemistry, see J. R. Partington, History of Chemistry, III (1962), 660-671 and passim. On Kirwan and Hutton, see C. C. Gillispie, Genesis and Geology (Cambridge, Mass., 1951), pp.49-56 and passim; and E. B. Bailey, James Hutton, the Founder of Modern Geology (London-New York, 1967), 69-73.

E. L. Scott